Coated steel sheet having excellent corrosion resistance and method for producing the same

Abstract

A coated steel sheet having excellent corrosion resistance comprises: a zinc or a zinc alloy plated steel sheet or an aluminum or an aluminum alloy plated steel sheet; a composite oxide coating formed on the surface of the plated steel sheet; and an organic coating formed on the composite oxide coating. The composite oxide coating contains a fine particle oxide and a phosphoric acid and/or a phosphoric acid compound. The organic coating has thickness of from 0.1 to 5 μm.

Description

TECHNICAL FIELD

The present invention relates to a coated steel sheet having excellent corrosion resistance and a method for producing the same.

BACKGROUND ART

Steel sheets for household electric appliances, for buildings, and for automobiles have widely used zinc based or aluminum based plated steel sheets treated on their surface with chromating using a solution consisting mainly of chromic acid, bichromic acid, or their salts in order to improve the corrosion resistance (white-rust resistance and rust resistance). The chromate treatment is an economical treatment method providing excellent corrosion resistance under a relatively simple procedure.

The chromate treatment uses hexavalent chromium which is a substance under regulation of pollution control laws. The hexavalent chromate substantially does not pollute environment nor attack human bodies, because it is perfectly handled in a closed system over the whole treatment process, thus it is completely reduced and recovered within the process. Therefore, it is never emitted to natural environment, and the sealing function of organic coatings reduces the chromium elution from the chromate coatings to nearly zero. Nevertheless, recent concern about global environment increases the independent movements to diminish the use of heavy metals including hexavalent chromium. In addition, there has begun a movement to eliminate or minimize the heavy metals in products to avoid contamination of environment when shredder scrap of wasted products is discarded.

Responding to those movements, many non-polluting treatment technologies without applying chromating have been introduced to prevent generation of rust and white-rust on zinc base plated steel sheets. Among them, several methods using organic compounds and organic resins have been proposed. Examples of these methods are the following.

(1) A method using tannic acid, (for example, JP-A-51-71233), (the term “JP-A” referred to herein signifies “Unexamined Japanese Patent Publication”).

(2) A method using a thermosetting paint prepared by blending an epoxy resin, an amino-resin, and tannic acid, (for example, JP-A-63-90581).

(3) A method using chelation force of tannic acid, such as a method using a mixed composition of a water-type resin and a polyhydric phenol carboxylic acid, (for example, JP-A-8-325760).

(4) A method using surface treatment to coat an aqueous solution of a hydrazine derivative onto the surface of tin plate or zinc plate, (for example, JP-B-53-27694 and JP-B-56-10386), (the term “JP-B” referred to herein signifies “Examined Japanese Patent Publication”).

(5) A method using an inhibitor containing an amine-added salt which is prepared by adding amine to a mixture of acylsarcosine and benzotriazole, (for example, JP-A-58-130284).

(6) A method using a treatment agent prepared by blending tannic acid with a heterocyclic compound such as benzothiazole compound, (for example, JP-A-57-198267).

These conventional technologies, however, have problems described below.

The methods (1) through (4) have a problem in corrosion resistance and other characteristics. That is, the method (1) gives insufficient corrosion resistance, and fails to give uniform appearance after the treatment. The method (2) does not aim to form a rust-preventive coating in a thin film form (having thicknesses of from 0.1 to 5 μm) directly on the surface of zinc base or aluminum base plating, thus the method fails to attain sufficient corrosion-protective effect even it is applied in a thin film form onto the surface of zinc base or aluminum base plating. The method (3) also gives insufficient corrosion resistance.

The method (4) is not applied to a zinc base or aluminum base plated steel sheet. Even if the method (4) is applied to those types of steel sheets, the formed coating has no network structure so that it has no satisfactory barrier performance, which results in insufficient corrosion resistance. JP-B-23772 (1978) and JP-B-10386 (1081) disclose blending of an aqueous solution of hydrazine derivative with a water-soluble polymer (such as polyvinylalcohol, a maleic acid ester copolymer, an acrylic acid ester copolymer) aiming to improve the uniformity of coating. However, that kind of mixture which simply blends an aqueous solution of hydrazine derivative with a water-soluble polymer compound cannot give satisfactory corrosion resistance.

Also the methods (5) and (6) do not aim to form a rust-preventive coating on the surface of a zinc base or aluminum base plated steel sheet in a short time. And, even when a treatment agent is applied onto the surface of the plated steel sheet, lack of barrier performance against corrosive causes such as oxygen and water fails to provide excellent corrosion resistance. The method (6) describes also about the additives in terms of mixing with resins (such as epoxy resin, acrylic resin, urethane resin, nitrocellulose resin, and polyvynilchloride resin). However, simple mixture of resin with a heterocyclic compound such as a benzothiazole compound cannot give sufficient corrosion resistance.

Under a practical condition that alkaline degreasing is applied at a pH range of from about 9 to about 11 using spray method or the like to remove oil which was applied onto the surface during press-working or other steps, all of the methods (1) through (6) have a problem that the alkaline degreasing induces peeling or damaging the coating, thus failing to sustain corrosion resistance. Therefore, all of these methods referred above are not suitable for practical uses as a method for forming rust-preventive coatings.

DISCLOSURE OF THE INVENTION

It is an object of the present invention to provide a coated steel sheet which does not contain heavy metals such as hexavalent chromium within the coating, and which is safe and non-toxic in manufacturing process and on using thereof, while attaining excellent corrosion resistance, and to provide a method for manufacturing thereof.

To attain the object, firstly, the present invention provides a coated steel sheet having excellent corrosion resistance, which comprises a zinc or a zinc alloy plated steel sheet or an aluminum or an aluminum alloy plated steel sheet, a composite oxide coating formed on the surface of the plated steel sheet, and an organic coating having a thickness in a range of from 0.1 to 5 μm formed on the composite oxide coating.

The composite oxide coating contains:

(α) fine particles of oxide;

(β) at least one metal selected from the group consisting of Mg, Ca, Sr, and Ba (including the case that the metal is in a form of compound and/or composite compound); and

(γ) phosphoric acid and/or phosphoric acid compound.

The composite oxide coating has a thickness in a range of from 0.005 to 3 μm, or has a total coating weight of the component (α), the component (β) converted to metal concerned, and the component (γ) converted to P 2 O 5 , in a range of from 6 to 3,600 Mg/m 2 .

The organic coating contains a product of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) comprises a hydrazine derivative (C) containing active hydrogen.

Secondly, the present invention provides a coated steel sheet having excellent corrosion resistance, which comprises a zinc or a zinc alloy plated steel sheet or an aluminum or an aluminum alloy plated steel sheet, a composite oxide coating formed on the surface of the plated steel sheet, and an organic coating having a thickness in a range of from 0.1 to 5 μm formed on the composite oxide coating.

The composite oxide coating contains:

(α) fine particles of oxide; and

(β) phosphoric acid and/or phosphoric acid compound.

The composite oxide coating has a total coating weight of the component (α) and the component (β) converted to P 2 O 5 , in a range of from 5 to 4,000 mg/m 2 .

The organic coating contains a product of reaction between a film-forming organic resin (A) and an active hydrogen-laden compound (B), a part or whole of which compound (B) comprises a hydrazine derivative (C) containing active hydrogen.

Thirdly, the present invention provides a coated steel sheet having excellent corrosion resistance, which comprises a zinc or a zinc alloy plated steel sheet or an aluminum or an aluminum alloy plated steel sheet, a chemical conversion treatment coating formed on the surface of the plated steel sheet, and an organic coating having a thickness in a range of from 0.1 to 5 μm on the chemical conversion treatment coating.

The organic coating contains a product of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) comprises a hydrazine derivative (C) containing active hydrogen.

Fourthly, the present invention provides a coated steel sheet having excellent corrosion resistance, which comprises a zinc or a zinc alloy plated steel sheet or an aluminum or an aluminum alloy plated steel sheet, and an organic coating having a thickness in a range of from 0.1 to 5 μm on the surface of the plated steel sheet.

The organic coating contains a product of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) comprises a hydrazine derivative (C) containing active hydrogen.

Fifthly, the present invention provides a coated steel sheet having excellent corrosion resistance, which comprises a zinc or a zinc alloy plated steel sheet or an aluminum or an aluminum alloy plated steel sheet, a composite oxide coating formed on the surface of the plated steel sheet, and an organic coating having a thickness in a range of from 0.1 to 5 μm formed on the composite oxide coating.

The composite oxide coating contains:

(α) fine particles of oxide;

(β) at least one metal selected from the group consisting of Mg, Ca, Sr, and Ba (including the case that the metal is in a form of compound and/or composite compound); and

(γ) phosphoric acid and/or phosphoric acid compound.

The composite oxide coating has a thickness in a range of from 0.005 to 3 μm, or has a total coating weight of the component (α), the component (β) converted to metal concerned, and the component (γ) converted to P 2 O 5 , in a range of from 6 to 3,600 mg/m 2 .

The organic coating contains, as a base resin, an organic polymer resin (A) having OH group and/or COOH group.

Sixthly, the present invention provides a coated steel sheet having excellent corrosion resistance, which comprises a zinc or a zinc alloy plated steel sheet or an aluminum or an aluminum alloy plated steel sheet, a composite oxide coating formed on the surface of the plated steel sheet, and an organic coating having a thickness in a range of from 0.1 to 5 μm formed on the composite oxide coating.

The composite oxide coating comprises (α) fine particles of oxide and (β) phosphoric acid and/or a phosphoric acid compound.

The composite oxide coating has a total coating weight of the component (α) and the component (β) converted to P 2 O 5 , in a range of from 5 to 4,000 mg/m 2 .

The organic coating contains, as a base resin, an organic polymer resin (A) having OH group and/or COOH group.

Seventhly, the present invention provides a method for manufacturing a coated steel sheet having excellent corrosion resistance, which comprises the steps of:

preparing a zinc or a zinc alloy plated steel sheet or an aluminum or an aluminum alloy plated steel sheet; treating the prepared plated steel sheet in an acidic aqueous solution within a pH range of from 0.5 to 5, which acidic aqueous solution contains

(a) silica and/or silica sol in a range of from 0.001 to 3 mole/liter as SiO 2 ,

(b) phosphoric acid ion and/or phosphoric acid compound in a range of from 0.001 to 6 mole/liter as P 2 O 5 , and

(c) at least one substance selected from the group consisting of: either one metallic ion selected from the group consisting of Al, Mg, Ca, Sr, Ba, Hf, Ti, Y, Sc, Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Ni, Co, Fe, and Mn; a water-soluble ion containing at least one of the above-given metals; an oxide containing at least one of the above-given metals; an oxide containing at least one of the above-described metals; and a hydroxide containing at least one of the above-given metals, in a range of from 0.001 to 3 mole/liter as the total of above-given metals converted to the metal concerned; and

forming a chemical conversion treatment coating having a thickness in a range of from 0.005 to 2 μm on the surface of the plated steel sheet by heating and drying the processed plated steel sheet.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing the relation between molar ratio [Mg/Si] and white-rust resistance in an acidic aqueous solution.

BEST MODE FOR CARRYING OUT THE INVENTION

Best Mode 1

According to a finding of the inventors of the present invention, an organic coating steel sheet inducing no pollution problem and providing excellent corrosion resistance is obtained without applying chromate treatment which may give bad influence to environment and human body, through the steps of: forming a specific composite oxide coating as the primary layer coating on the surface of a zinc base plated steel sheet or an aluminum base plated steel sheet; then forming a specific chelating resin coating as the secondary layer coating on the primary layer coating; further preferably blending an adequate amount of a specific rust-preventive agent into the chelating resin coating.

The organic coating steel according to the present invention is basically characterized in that a composite oxide coating as the primary layer coating comprising (α) fine particles of oxide, (β) one or more of metal selected from the group consisting of Mg, Ca, Sr, and Ba (including the case that the metal is in a form of compound and/or composite compound), and (γ) phosphoric acid and/or phosphoric acid compound, is formed on the surface of a zinc base plated steel sheet or an aluminum base plated steel sheet, that, further on the primary coating layer, an organic coating containing a chelating resin is formed as the secondary coating layer as the product of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, thus applying the hydrazine derivative (C) as a chelating group to the film-forming resin (A).

Preferably the above-described composite oxide coating as the primary layer coating contains: SiO 2 fine particles as the component (α) at a specific coating weight; one or more substance (magnesium component) selected from the group consisting of Mg, a compound containing Mg, a composite compound containing Mg, as the component (α) at a specific coating weight; and phosphoric acid and/or phosphoric acid compound as the component (γ) at a specific coating weight.

The above-described primary layer coating and the secondary layer coating provide excellent rust-preventive effect even when they are used independently from each other compared with conventional chromate base coatings. Nevertheless, according to the present invention, a thin coating provides corrosion resistance equivalent to that of chromate coating by adopting dual layer coating structure consisting of primary and secondary layers to give a synergy effect.

Although the mechanism of corrosion resistance in the dual layer coating structure consisting of a specific composite oxide coating and a specific organic coating is not fully analyzed, the corrosion-preventive effect of the dual layer coating structure presumably comes from the combination of corrosion-suppression actions of individual coatings, which is described below.

The corrosion preventive mechanism of the composite oxide coating as the primary layer coating is not fully understood. The excellent corrosion-preventive performance, supposedly, owes to that the dense and slightly soluble composite oxide coating acts as a barrier coating to shut off corrosion causes, that the fine particles of oxide such as silicon oxide (SiO 2 ) form a stable and dense barrier coating along with an alkali earth metal such as Mg and phosphoric acid and/or phosphoric acid compound, and that, when the fine particles of oxide are those of silicon oxide (SiO 2 ), the silicic acid ion emitted from the silicon oxide forms basic zinc chloride under a corrosive environment to improve the barrier performance. Even when defects occur on the coating, it is supposed that a cathodic reaction generates OH ion to bring the interface to alkali side, and Mg ion and Ca ion, which are soluble matter in alkali earth metal, precipitates as Mg(OH) 2 and Ca(OH) 2 , respectively, which act as the dense and slightly soluble reaction products to seal the defects, thus resulting in suppressing the corrosion reactions. Also it is assumed that phosphoric acid and/or phosphoric acid compound contributes to the improvement of denseness of the composite oxide coating, further that the phosphoric acid component catches the zinc ion which is eluted during an anodic reaction as a corrosion reaction in the coating-defect section, then the phosphoric acid component is converted to a slightly soluble zinc phosphate compound to form a precipitate at that place. As described above, alkali earth metals and phosphoric acid and/or phosphoric acid compounds should perform self-repair action in the coating-defect section.

That kind of work effect appears particularly when the composite oxide coating contains, as described before, SiO 2 fine particles as the component (α) at a specific coating weight; a magnesium component as the component (β) at a specific coating weight; and phosphoric acid and/or phosphoric acid compound as the component (γ) at a specific coating weight.

The corrosion-preventive mechanism of the organic coating as the above-described secondary layer coating is also not fully analyzed. The mechanism is, however, presumably the following. By adding a hydrazine derivative, not applying a simple low molecular weight chelating agent, to the film-forming organic resin, (1) the dense organic polymer coating gives an effect to shut-off corrosion causes such as oxygen and chlorine ions, (2) the hydrazine derivative is able to form a stable passive layer by strongly bonding with the surface of the primary layer coating, and (3) the free hydrazine derivative in the coating traps the zinc ion which is eluted by a corrosion reaction, thus forming a stable insoluble chelated compound layer, which suppresses the formation of an ion conduction layer at interface to suppress the progress of corrosion. These work effects should effectively suppress the development of corrosion, thus giving excellent corrosion resistance.

Particularly when a resin containing epoxy group is used as the film-forming organic resin (A), a dense barrier coating is formed by the reaction between the epoxy-group-laden resin and a cross-linking agent. Thus, the formed barrier coating has excellent penetration-suppression performance against the corrosion causes such as oxygen, and gains excellent bonding force with the base material owing to the hydroxyl group in the molecule, which results in particularly superior corrosion resistance.

Further excellent corrosion resistance is obtained by using an active-hydrogen-laden pyrazole compound and/or an active-hydrogen-laden triazole compound as the hydrazine derivative (C) containing active hydrogen.

As in the case of prior art, blending simply a hydrazine derivative with the film-forming organic resin gives very little improvement in corrosion-suppression. The reason is presumably that the hydrazine derivative which does not enter the molecules of the film-forming organic resin forms a chelate compound with zinc which is eluted under a corrosive environment, and the chelate compound cannot form a dense barrier layer because of low molecular weight. To the contrary, introduction of a hydrazine derivative into the molecules of film-forming organic resin, as in the case of present invention, provides markedly high corrosion-suppression effect.

According to the organic coating steel sheet of the present invention, further high anti-corrosive performance (self-repair work at coating-defect section) is attained by blending adequate amount of ion-exchanged silica (α) with an organic coating consisting of above-described specific reaction products. The corrosion-preventive mechanism which is obtained by blending the ion exchanged silica (α) with the specific organic coating is speculated as follows. First, under a corrosion environment, the zinc ion which is eluted from the plating coating is trapped by the above-described hydrazine derivative, thus suppressing the anode reaction. On the other hand, when cation such as Na ion enters under the corrosion environment, the iron exchange action emits Ca ion and Mg ion from the surface of silica. Furthermore, when OH ion is generated by the cathode reaction under the corrosive environment to increase pH value near the plating interface, the Ca ion (or Mg ion) emitted from the ion-exchanged silica precipitates in the vicinity of the plating interface in a form of Ca(OH) 2 or Mg(OH) 2 , respectively. The precipitate seals defects as a dense and slightly soluble product to suppress the corrosion reactions.

There may given an effect that the eluted zinc ion is exchanged with Ca ion (or Mg ion) and is fixed onto the surface of silica. By combining both the anti-corrosive actions of hydrazine derivative and ion exchanged silica, particularly strong corrosion-preventive effect would appear.

Also in the case that an ion-exchanged silica is blended with a general organic coating, corrosion-preventive effect is obtained to some extent. Nevertheless, when an ion exchanged silica is blended with an organic coating consisting of a specific chelate-modified resin, as in the case of present invention, the corrosion-preventive effect at anode reaction section owing to the chelate-modified resin and the corrosion-preventive effect at cathode reaction section owing to the ion-exchanged silica are combined to suppress both the anode and the cathode corrosion reactions, which should provide markedly strong corrosion-preventive effect. Furthermore, that kind of combined corrosion-preventive effect is effective in suppressing corrosion at flaws and defects on coatings, and is able to give excellent self-repair work to the coating.

According to the organic coating steel sheet of the present invention, the corrosion resistance can also be increased by blending an adequate amount of silica fine particles (b) with an organic coating consisting of a specific reaction product as described above. That is, by blending silica fine particles such as fumed silica and .colloidal silica (having average primary particle sizes of from 5 to 50 nm, preferably from 5 to 20 nm, more preferably from 5 to 15 nm) having large specific surface area into a specific organic coating, the generation of dense and stable corrosion products such as basic zinc chloride is enhanced, thus suppressing the generation of zinc oxide (white-rust).

Furthermore, according to the organic coating steel sheet of the present invention, the corrosion resistance can further be increased by blending an ion-exchanged silica (a) and silica fine particles (b) together into the organic coating consisting of a specific reaction product as described above. The ion-exchanged silica consists mainly of porous silica, and generally has a relatively large particle size, 1 μm or more. Accordingly, after releasing Ca ion, the rust-preventive effect as silica is not much expectable. Consequently, by accompanying fine particle silica having a relatively large specific surface area, such as fumed silica and colloidal silica, (with primary particle sizes of from 5 to 50 nm, preferably from 5 to 20 nm, more preferably from 5 to 15 nm), the generation of dense and stable corrosion products such as basic zinc chloride may be enhanced, thus suppressing the generation of zinc oxide (white rust). Through the combined rust-preventive mechanisms of ion exchanged silica and fine particle silica, particularly strong corrosion-preventive effect would appear.

Examples of the zinc base plated steel sheet as the base of the organic coating steel sheet according to the present invention are, galvanized steel sheet, Zn—Ni alloy plated steel sheet, Zn—Fe alloy plated steel sheet (electroplated steel sheet and alloyed hot dip galvanized steel sheet), Zn—Cr alloy plated steel sheet, Zn—Mn alloy plated steel sheet, Zn—Co alloy plated steel sheet, Zn—Co—Cr alloy plated steel sheet, Zn—Cr—Ni alloy plated steel sheet, Zn—Cr—Fe alloy plated steel sheet, Zn—Al alloy plated steel sheet (for example, Zn-5%Al alloy plated steel sheet and Zn-55%Al alloy plated steel sheet), Zn—Mg alloy plated steel sheet, Zn—Al—Mg plated steel sheet, zinc base composite plated steel sheet (for example, Zn—SiO 2 dispersion plated steel sheet) which is prepared by dispersing a metallic oxide, a polymer, or the like in the plating film of these plated steel sheets.

Among the platings described above, the same kind or different kinds of them may be plated into two or more layers to form a multi-layered plated steel sheet.

The aluminum base plated steel sheet which is a base of the organic coating steel sheet of the present invention may be an aluminum plated steel sheet, an Al—Si alloy plated steel sheet, or the like.

The plated steel sheet may be prepared from a steel sheet is applied on the surface of which a plating of Ni or the like at a small coating weight in advance, followed by the above-described various kinds of platings.

The plating method may be either applicable one of electrolytic method (electrolysis in an aqueous solution or in a non-aqueous solvent) and vapor phase method.

To prevent occurrence of coating defects and nonuniformity during the step for forming the dual layer coating on the surface of the plating film, there may be applied alkaline degreasing, solvent degreasing, surface-adjustment treatment (alkaline surface-adjustment treatment or acidic surface-adjustment treatment) and the like to the surface of plating film in advance.

To prevent blackening (a kind of oxidization on the plating surface) of organic coating steel sheet under the use conditions, the surface of plating film may be subjected to surface-adjustment treatment using acidic or alkaline aqueous solution containing iron group metal ion(s) (Ni ion, Co ion, Fe ion) in advance. When an electrolytically galvanized steel sheet is used as the base steel sheet, the electroplating bath may contain 1 ppm or more of iron group metal ion(s) (Ni ion, Co ion, Fe ion), thus letting these metals in the plating film prevent blackening. In that case, there is no specific limitation on the upper limit of iron group metal concentration in the plating film.

The following is the description of the composite oxide coating as the primary layer coating which is formed on the surface of zinc base plated steel sheet or aluminum base plated steel sheet.

Quite different from conventional alkali silicate treatment coating which is represented by the coating composition consisting of lithium oxide and silicon oxide, the composite oxide coating according to the present invention comprises:

(α) fine particles of oxide (preferably SiO 2 fine particles);

(β) one or more of metal selected from the group consisting of Mg, Ca, Sr, and Ba (including the case that the metal is in a form of compound and/or composite compound); and

(γ) phosphoric acid and/or phosphoric acid compound.

Particularly preferable oxide fine particles as the above-described component (α) are those of silicon oxide (fine particles of SiO 2 ), and most preferable one among the silicon oxides is colloidal silica.

Examples of the colloidal silica are: SNOWTEX O, SNOWTEX OS, SNOWTEX OXS, SNOWTEX OUP, SNOWTEX AK, SNOWTEX O40, SNOWTEX OL, SNOWTEX OL40, SNOWTEX OZL, SNOWTEX XS, SNOWTEX S, SNOWTEX NXS, SNOWTEX NS, SNOWTEX N, SNOWTEX QAS-25, (these are trade names) manufactured by Nissan Chemical Industries, Ltd.; CATALOID S, CATALOID SI-350, CATALOID SI-40, CATALOID SA, CATALOID SN, (trade names) manufactured by Catalysts & Industries Co., Ltd.; ADERITE AT-20-50, ADERITE AT-20N, ADERITE AT-300, ADERITE AT-300S, ADERITE AT20Q, (trade names) manufactured by Asahi Denka Kogyo, K.K.

Among these silica oxides (SiO 2 fine particles), the ones having particle sizes of 14 nm or less, more preferably 8 nm or less are preferred from the viewpoint of corrosion resistance.

The silica oxide may be used by dispersing dry silica fine particles in a coating composition solution. Examples of the dry silica are AEROSIL 200, AEROSIL 3000, AEROSIL 300CF, AEROSIL 380, (these are trade names) manufactured by Japan Aerosil Co., and particularly the ones having particle sizes of 12 nm or less, more preferably 7 nm or less are preferred.

Other than above-described silica oxides, the oxide fine particles may be colloidal liquid and fine particles of aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, and antimony oxide.

From the viewpoint of corrosion resistance and weldability, a preferred range of coating weight of the above-described component (α) is from 0.01 to 3,000 mg/m 2 , more preferably from 0.1 to 1,000 mg/m 2 , and most preferably from 1 to 500 mg/m 2 .

As for the specific alkali earth metal components (Mg, Ca, Sr, Ba), which are the above-described component (β), one or more of these alkali earth metals are necessary to be contained in the coating. The form of these alkali earth metals existing in the coating is not specifically limited, and they may exist in a form of metal, or compound or composite compound of their oxide, hydroxide, hydrated oxide, phosphoric acid compound, coordination compound, or the like. The ionicity and solubility of these compound, hydroxide, hydrated oxide, phosphoric acid compound, coordination compound, or the like are not specifically limited.

Among those alkali earth metals, it is most preferable to use Mg to obtain particularly superior corrosion resistance. The presumable reason of significant increase in corrosion resistance by the addition of Mg is that Mg shows lower solubility of its hydroxide than other alkali earth metals, thus likely forming slightly soluble salt.

The method to introduce the component (β) into coating may be the addition of phosphate, sulfate, nitrate, chloride, or the like of Mg, Ca, Sr, Ba to the coating composition.

From the standpoint of prevention of degradation in corrosion resistance and in coating appearance, a preferred range of coating weight of the above-described (β) is from 0.01 to 1,000 Mg/m 2 as metal, more preferably from 0.1 to 500 mg/m 2 , and most preferably from 1 to 100 mg/m 2 .

The phosphoric acid and/or phosphoric acid compound as the above-described component (γ) may be blended by adding orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, or metallic salt or compound of them to the coating composition.

There is no specific limitation on the form of existing phosphoric acid and phosphoric acid compound in the coating, and they may be crystals or non-crystals. Also there is no specific limitation on the ionicity and solubility of phosphoric acid and phosphoric acid compound in the coating.

From the viewpoint of corrosion resistance and weldability, a preferred range of coating weight of the above-described component (γ) is from 0.01 to 3,000 mg/m 2 as P 2 O 5 , more preferably from 0.1 to 1,000 mg/m 2 , and most preferably from 1 to 500 mg/m 2 .

The composite oxide coating may further contain an organic resin for improving workability and corrosion resistance of the coating. Examples of the organic resin are epoxy resin, polyurethane resin, polyacrylic resin, acrylic-ethylene copolymer, acrylic-styrene copolymer, alkyd resin, polyester resin, polyethylene resin. These resins may be introduced into the coating in a form of water-soluble resin or water-dispersible resin.

Adding to these water type resins, it is effective to use water-soluble epoxy resin, water-soluble phenol resin, water-soluble polybutadiene rubber (SBR, NBR, MBR), melamine resin, block-polyisocyanate compound, oxazolane compound, and the like as the cross-linking agent.

For further improving the corrosion resistance, the composite oxide coating may further contain polyphosphate, phosphate (for example, zinc phosphate, aluminum dihydrogen phosphate, and zinc phosphate), molybdate, phospo molybdate (for example, aluminum phosphomolybdate), organic phosphate and its salt (for example, phytic acid, phytiate, phosphonic acid, phosphonate, their metal salt and alkali metal salt), organic inhibitor (for example, hydrazine derivative, thiol compound, dithiocarbamate), organic compound (polyethyleneglycol), and the like.

Other applicable additives include organic coloring pigments (for example, condensing polycyclic organic pigments, phthalocyanine base organic pigments), coloring dyes (for example, azo dye soluble inorganic solvent, azo metal dye soluble in water), inorganic pigments (titaniumoxide), chelating agents (for example, thiol), conductive pigments (for example, metallic powder of zinc, aluminum, nickel, or the like, iron phosphide, antimony-dope type tin oxide), coupling agents (for example, silane coupling agent and titanium coupling agent), melamine-cyanuric acid additives.

The composite oxide coating may contain one or more of iron group metallic ions (Ni ion, Co ion, Fe ion) to prevent blackening (an oxidizing phenomenon appeared on plating surface) under a use environment of organic coating steel sheets. As of these ions, addition of Ni ion is most preferable. In that case, concentration of the iron base metallic ion of 1/10,000 mole per 1 mole of the component (β), converted to the metal amount in the target composition, gives satisfactory effect. Although the upper limit of the iron group ion is not specifically limited, it is preferable to select a concentration level thereof not to give influence to the corrosion resistance.

A preferable range of the thickness of the composite oxide coating is from 0.005 to 3 μm, more preferably from 0.01 to 2 μm, further preferably from 0.1 to 1 μm, and most preferably from 0.2 to 0.5 μm. If the thickness of the composite oxide coating is less than 0.005 μm, the corrosion resistance degrades. If the thickness of the composite oxide coating exceeds 3 μm, conductive performance such as weldability degrades. When the composite oxide coating is specified in terms of coating weight, it is adequate to specify the sum of coating weight of the above-described component (α), the above-described component (β) converted to metal amount, and the above-described component (γ) converted to P 2 O 5 , to a range of from 6 to 3,600 mg/m 2 , more preferably from 10 to 1,000 mg/m 2 , and most preferably from 50 to 500 mg/m 2 . If the total coating weight is less than 6 mg/m 2 , the corrosion resistance degrades. If the total coating weight exceeds 3,600 mg/m , the conductive performance such as weldability degrades.

To attain particularly superior performance of the present invention, it is preferable that the above-described oxide coating comprises: SiO 2 fine particles as the component (α) at a specific coating weight; one or more of magnesium components selected from the group consisting of Mg, a compound containing Mg, and a composite compound containing Mg, as the component (β) at a specific coating weight; and phosphoric acid and/or phosphoric acid compound as the component (γ) at a specific coating weight.

The preferred condition for SiO 2 fine particles as the above-described component (α) was described before.

A preferred range of the coating weight of the SiO 2 fine particles in the coating is from 0.01 to 3,000 mg/m 2 as SiO 2 , more preferably from 0.1 to 1,000 mg/m 2 , further preferably from 1 to 500 mg/m 2 , and most preferably from 5 to 100 mg/m 2 .

If the coating weight of SiO 2 fine particles is less than 0.01 mg/m 2 as SiO 2 , the contribution of the silicon component emitted from silicon oxide to the corrosion resistance becomes small to fail in attaining sufficient corrosion resistance. If the coating weight of SiO 2 fine particles exceeds 3,000 mg/m 2 as SiO 2 , the conductive performance such as weldability degrades.

Introduction of the above-described component (α) into the coating may be done by adding a silicic acid sol such as colloidal silica to the film-forming composition. Examples of preferred colloidal silica are described before.

The form of magnesium component as the above-described component (β) existing in the coating is not specifically limited, and it may be metal, or compound or composite compound such as oxide, hydroxide, hydrated oxide, phosphoric acid compound, coordination compound. The ionicity and solubility of these compound, hydroxide, hydrated oxide, phosphoric acid compound, coordination compound, or the like are not specifically limited.

A preferable range of the coating weight of the magnesium component in the coating is from 0.01 to 1,000 mg/m 2 as Mg, more preferably from 0.1 to 500 mg/m 2 , and most preferably from 1 to 100 mg/m 2 .

If the coating weight of magnesium component is less than 0.01 mg/m 2 as Mg, the contribution of the magnesium component to the corrosion resistance becomes small to fail in attaining sufficient corrosion resistance. If the coating weight of magnesium component exceeds 1,000 mg/m 2 as Mg, the excess amount of magnesium exists as a soluble component, which degrades the appearance of the coating.

Introduction of the above-described component (β) into the coating may be done by adding phosphate, sulfate, nitrate, chloride of magnesium, or magnesium oxide fine particles, to the film-forming composition.

In particular, the composite oxide according to the present invention contains phosphoric acid as a constitution component, it is preferable to add a phosphate such as magnesium phosphate to the target composition. In that case, the form of magnesium phosphate is not specifically limited, and it may be orthophosphate, pyrophosphate, tripolyphosphate, phosphate, hypophosphate.

For the methods and the forms in the coating of phosphoric acid and/or phosphoric acid compound as the above-described component (γ), there is no specific limitation as described before.

In the composite oxide coating, since the phosphoric acid component coexists with a magnesium component, the form of phosphoric acid compound in the coating may be phosphate or condensing phosphate of magnesium phosphate. Methods to introduce those phosphoric acid compounds into the coating may be the addition of phosphate or organic phosphoric acid or its salt (for example, phytic acid, phytiate, phosphonic acid, phosphonate, their metal salt) to the target composition.

A preferable range of coating weight of phosphoric acid and/or phosphoric acid compound in the coating is from 0.01 to 3,000 mg/m 2 as P 2 O 5 , more preferably from 0.1 to 1,000 mg/m 2 , and most preferably from 1 to 500 mg/m 2 .

If the coating weight of phosphoric acid and/or phosphoric acid compound is less than 0.01 mg/m 2 as P 2 O 5 , the corrosion resistance degrades. If the coating weight of phosphoric acid and/or phosphoric acid compound exceeds 3,000 mg/m 2 as P 2 O 5 , the conductive performance degrades and the weldability degrades.

To attain particularly superior corrosion resistance, it is preferred to select the ratio of the magnesium component as the component (β) to the SiO 2 fine particles as the component (α) in the composite oxide coating to a range of from 1/100 to 100/1 the molar ratio of the component(β)as Mg to the component (α) as SiO 2 , or [Mg/SiO 2 ], more preferably from 1/10 to 10/1, and most preferably from 1/2 to 5/1.

The reason of giving particularly superior corrosion resistance when the ratio of coating weight of magnesium to SiO 2 fine particles is selected to the range given above is not fully analyzed. It is, however, speculated that, when the ratio of the magnesium component to the SiO 2 fine particles falls in the range given above, the synergy effect of the corrosion-suppressing actions of each of the silicon component emitted from the SiO 2 fine particles and the magnesium component markedly appears.

From the similar viewpoint, it is preferred to select the ratio of the phosphoric acid and/or phosphoric acid compound as the component (γ) to the magnesium component as the component (β) in the composite oxide coating to a range of from 1/100 to 100/1 as the molar ratio of the component (α) as P 2 O 5 to the component (β) as Mg, or [P 2 O 5 /Mg], more preferably from 1/10 to 10/1, and most preferably from 1/2 to 2/1.

The reason of giving particularly superior corrosion resistance when the ratio of coating weight of phosphoric acid and/or phosphoric acid compound to magnesium is selected to the range given above is not fully analyzed. It is, however, speculated that, when the ratio of the phosphoric acid and/or phosphoric acid compound to the magnesium component falls in the range given above, the synergy effect of the corrosion-suppressing actions of each of the phosphoric acid and/or phosphoric acid compound and the magnesium component markedly appears.

To obtain most excellent corrosion resistance, it is preferred to select the ratio of the magnesium component as the component (β) and the SiO 2 fine particles as the component (α) in the composite oxide coating to a range of from 1/100 to 100/1 as the molar ratio of the component (β) as Mg to the component (α) as SiO 2 , or [Mg/SiO 2 ], more preferably from 1/10 to 10/1, and most preferably from 1/2 to 5/1, further to select the ratio of the phosphoric acid and/or phosphoric acid compound as the component (γ) to the magnesium component as the component (β) in the composite oxide coating to a range of from 1/100 to 100/1 as the molar ratio of the component (γ) as P 2 O 5 to the component (β) as Mg, or [P 2 O 5 /Mg], more preferably from 1/10 to 10/1, and most preferably from 1/2 to 2/1.

The reason of giving most excellent corrosion resistance when the ratio of magnesium component, SiO 2 fine particles, and phosphoric acid and/or phosphoric acid compound is selected to the range given above is presumably explained by the significant synergy effect of corrosion-suppressing actions of each component, as described above, and by the optimization of coating mode resulted from the reaction with base material for plating during the film-forming period.

A preferred range of the total coating weight in the composite oxide coating, or the sum of the coating weight of the above-described component (α) as SiO 2 , the coating weight of the above-described component (β) as Mg, and the coating weight of the above-described component (γ) as P 2 O 5 , is from 6 to 3,600 mg/m 2 , more preferably from 10 to 1,000 mg/m 2 , and most preferably from 50 to 500 mg/m 2 . If the total coating weight is less than 6 mg/m 2 , the corrosion resistance becomes insufficient. If the total coating weight exceeds 3,600 mg/m 2 , the conductive performance such as weldability degrades.

The following is the description about the organic coating formed as the secondary layer coating on the above-described oxide coating.

According to the present invention, the organic coating formed on the above-described composite oxide coating contains a product of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, and at need, further contains additives such as rust-preventive agent at an adequate amount, which organic coating has a thickness in a range of from 0.1 to 5 μm.

The kinds of film-forming organic resin (A) are not specifically limited if only the resin reacts with the active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, to bind the active-hydrogen-laden compound (B) with the film-forming organic resin by addition or condensation reaction, and adequately form the coating.

Examples of the film-forming organic resin (A) are epoxy resin, modified epoxy resin, polyurethane resin, polyester resin, alkyd resin, acrylic base copolymer resin, polybutadiene resin, phenol resin, and adduct or condensate thereof. These resins may be applied separately or blending two or more of them.

From the standpoint of reactivity, readiness of reaction, and corrosion-prevention, an epoxy-group-laden resin (D) in the resin is particularly preferred as the film-forming organic resin (A). The epoxy-group-laden resin (D) has no specific limitation if only the resin reacts with an active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, to bind with the active hydrogen-laden compound (B) by addition or condensation reaction, and adequately form the coating. Examples of the epoxy-group-laden resin (D) are epoxy resin, modified epoxy resin, acrylic base copolymer resin copolymerized with an epoxy-group-laden monomer, polybutadiene resin containing epoxy group, polyurethane resin containing epoxy group, and adduct or condensate of these resins. These resins may be applied separately or blending two or more of them together.

From the point of adhesiveness with plating surface and of corrosion resistance, epoxy resin and modified epoxy resin are particularly preferred among these epoxy-group-laden resins (D).

Examples of the above-described epoxy resins are: aromatic epoxy resins prepared by reacting a polyphenol such as bisphenol A, bisphenol F, and novorak type phenol with epihalohydrin such as epychlorohydrin followed by introducing glycidyl group thereinto, or further by reacting a polyphenol with thus obtained product containing glycidyl group to increase the molecular weight; aliphatic epoxy resin, and alicyclic epoxy resin. These resins may be applied separately or blending two or more of them together. If film-formation at a low temperature is required, the epoxy resins preferably have number-average molecular weights of 1500 or more.

The above-described modified epoxy resin may be a resin prepared by reacting epoxy group or hydroxyl group in one of the above-given epoxy resins with various kinds of modifying agents. Examples of the modified epoxy resin are epoxy-ester resin prepared by reacting with a drying oil fatty acid, epoxy-acrylate resin prepared by modifying with a polymerizable unsaturated monomer component containing acrylic acid or methacrylic acid, and urethane-modified epoxy resin prepared by reacting with an isocyanate compound.

Examples of the above-described acrylic base copolymer resin which is copolymerized with the above-described epoxy-group-laden monomer are the resins which are prepared by solution polymerization, emulsion polymerization, or suspension polymerization of an unsaturated monomer containing epoxy group with a polymerizable unsaturated monomer component containing acrylic acid ester or methacrylic acid ester as the essential ingredient.

Examples of the above-described unsaturated monomer component are: C1-24 alkylester of acrylic acid or methacrylic acid, such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, n-iso- or tert-butyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, decyl(meth)acrylate, lauryl(meth)acrylate; C1-4 alkylether compound of acrylic acid, methacrylic acid, styrene, vinyltoluene, acrylamide, acrylonitrile, N-methylol(meth)acrylamide; and N,N-diethylaminoethylmethacryiate.

The unsaturated monomer having epoxy group has no special limitation if only the monomer has epoxy group and polymerizable unsaturated group, such as glycidylmethacrylate, glycidylacrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate.

The acrylic base copolymer resin which was copolymerized with the epoxy-group-laden monomer may be a resin which is modified by polyester resin, epoxy resin, or phenol resin.

A particularly preferred epoxy resin described above is a resin having a chemical structure represented by formula (1) given below, which resin is a product of the reaction between bisphenol A and epihalohydrin. The epoxy resin is preferred because of superior corrosion resistance.

Chemical Formula

The method for manufacturing that kind of bisphenol A type epoxy resin is widely known in the industry concerned. In the above-given chemical formula, q value is in a range of from 0 to 50, preferably from 1 to 40, more preferably from 2 to 20.

The film-forming organic resin (A) may be either organic solvent dissolving type, organic solvent dispersing type, water dissolving type, or water dispersing type.

According to the present invention, a hydrazine derivative is introduced into the molecules of the film-forming organic resin (A). To do this, at least a part of the active-hydrogen-laden compound (B), (preferably whole thereof), is necessary to be a hydrazine derivative (C) containing active hydrogen.

When the film-forming organic resin (A) is an epoxy-group-laden resin, examples of the active-hydrogen-laden compound (B) reacting with the epoxy group are listed below. One or more of these compounds (B) may be applied. Also in that case, at least a part of the active-hydrogen-laden compound (B), (preferably whole thereof), is necessary to be a hydrazine derivative (C) containing active hydrogen.

A hydrazine derivative containing active hydrogen

A primary or secondary amine compound containing active hydrogen

An organic acid such as ammonia and carboxylic acid

A halogenated hydrogen such as hydrogen chloride

An alcohol, a thiol

A hydrazine derivative containing no active hydrogen or a quaternary chlorinating agent which is a mixture with a ternary amine.

Examples of the above-described hydrazine derivative (C) containing active hydrogen are the following.

1) hydrazide compound such as carbohydrazide, propionic acid hydrazide, salicylic acid hydrazide, adipic acid hydrazide, sebacic acid hydrazide, dodecanic acid hydrazide, isophtharic acid hydrazide, thiocarbo-hydrazide, 4,4′-oxy-bis-benzenesulfonyl hydrazide, benzophenone hydrazone, amino-polyacrylamide hydrazide;

2) pyrazole compound such as pyrazole, 3,5-dimethylpyrazole, 3-methyl-5-pyrazolone, 3-amino-5-methylpyrazole;

3) triazole compound such as 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 5-amino-3-mercapto-1,2,4-triazole, 2,3-dihydro-3-oxo-1,2,4-triazole, 1H-benzotriazole, 1-hydroxybenzotriazole (mono hydrate), 6-methyl-8-hydroxytriazolopyridazine, 6-phenyl-8-hydroxytriazolopyrydazine, 5-hydroxy-7-methyl-1,3,8-triazaindolizine;

4) tetrazole compound such as 5-phenyl-1,2,3,4-tetrazole, 5-mercapto-1-phenyl-1,2,3,4-tetrazole;

5) thiadiazole compound such as 5-amino-2-merdapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole;

6) pyridazine compound such as maleic acid hydrazide, 6-methyl-3-pyridazone, 4,5-dichloro-3-pyridazone, 4,5-dibromo-3-pyridazone, 6-methyl-4,5-dihydro-3-pyridazone.

Among these compounds, particularly preferred ones are pyrazole compound and triazole compound which have cyclic structure of five- or six-membered ring and which have nitrogen atom in the cyclic structure.

These hydrazine derivatives may be applied separately or blending two or more of them together.

Examples of above-described amine compound having active hydrogen, which can be used as a part of the active-hydrogen-laden compound (B) are the following.

1) a compound prepared by heating to react a primary amino group of an amine compound containing a single secondary amino group of diethylenetriamine, hydroxylaminoethylamine, ethylaminoethylamine, methylaminopropylamine, or the like and one or more of primary amino group, with ketone, aldehyde, or carboxylic acid, at, for example, approximate temperatures of from 100 to 230° C. to modify them to aldimine, ketimine, oxazoline, or imidazoline;

2) a secondary monoamine such as diethylamine, diethanolamine, di-n- or -iso-propanolamine, N-methylethanolamine, N-ethylethanolamine;

3) a secondary-amine-laden compound prepared by Michael addition reaction through the addition of monoalkanolamine such as monoethanolamine to dialkyl(meth)acrylamide;

4) a compound prepared by modifying a primary amino group of alkanolamine such as monoethanolamine, neopentanolamine, 2-aminopropanol, 3-aminopropanol, 2-hydroxy-2′(aminopropoxy)ethylether to ketimine.

As for the above-described quaternary chlorinating agents which are able to be used as a part of the active-hydrogen-laden compound (B), the hydrazine derivative having active hydrogen or ternary amine has no reactivity with epoxy group as it is. Accordingly, they are mixed with an acid to make them reactive with epoxy group. The quaternary chlorinating agent reacts with epoxy group with the presence of water, at need, to form a quaternary salt with the epoxy-group-laden resin.

The acid used to obtain the quaternary chlorinating agent may be organic acid such as acetic acid and lactic acid, or inorganic acid such as hydrochloric acid. The hydrazine derivative containing no active hydrogen, which is used to obtain quaternary chlorinating agent may be 3,6-dichloropyridazine. The ternary amine may be dimethylethanolamine, triethylamine, trimethylamine, tri-isopropylamine, methyldiethanolamine.

The product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen, may be prepared by reacting the film-forming organic resin (A) with the active-hydrogen-laden compound (B) at temperatures of from 10 to 300° C., preferably from 50 to 15° C., for about 1 to about 8 hours.

The reaction may be carried out adding an organic solvent. The kind of adding organic solvent is not specifically limited. Examples of the organic solvent are: ketone such as acetone, methyethylketone, methylisobutylketone, dibutylketone, cyclohexanone; alcohol or ether having hydroxyl group, such as ethanol, butanol, 2-ethylhexylalcohol, benzylalcohol, ethyleneglycol, ethyleneglycol mono-isopropylether, ethyleneglycol monobutylether, ethyleneglycol monohexylether, propyleneglycol, propyleneglycol monomethylether, diethyleneglycol, diethyleneglycol monoethylether, diethyleneglycol monobutylether; ester such as ethylacetate,. butylacetate, ethyleneglycol monobutylether acetate; and aromatic hydrocarbon such as toluene and xylene. These compounds may be applied separately or blending two or more of them together. Among them, from the viewpoint of solubility and coating film-forming performance with epoxy resin, ketone group or ether group solvents are particularly preferred.

The blending ratio of the film-forming organic resin (A) and the active-hydrogen-laden compound (B), a part or whole of which compound consists of a hydrazine derivative (C) containing active hydrogen, is in a range of from 0.5 to 20 part by weight of the active-hydrogen-laden compound (B), more preferably from 1.0 to 10 parts by weight, to 100 parts by weight of the film-forming organic resin (A).

When the film-forming organic resin (A) is an epoxy-group-laden resin (D), the blending ratio of the epoxy-group-laden resin (D) to the active-hydrogen-laden compound (B) is preferably, from the viewpoint of corrosion resistance and other performance, in a range of from 0.01 to 10 as the ratio of the number of active hydrogen groups in the active-hydrogen-laden compound (B) to the number of epoxy groups in the epoxy-group-laden resin (D), or [the number of active hydrogen groups/the number of epoxy groups], more preferably from 0.1 to 8, most preferably from 0.2 to 4.

A preferred range of hydrazine derivative (C) containing active hydrogen in the active-hydrogen-laden compound (B) is from 10 to 100 mole %, more preferably from 30 to 100 mole %, and most preferably from 40 to 100 mole %. If the rate of hydrazine derivative (C) containing active hydrogen is less than 10 mole %, the organic coating fails to have satisfactory rust-preventive function, thus the obtained rust-preventive effect becomes similar with the case of simple blending of a film-forming organic resin with a hydrazine derivative.

To form a dense barrier coating according to the present invention, it is preferable that a curing agent is blended into the resin composition, and that the organic coating is heated to cure.

Suitable methods for curing to form a resin composition coating include (1) a curing method utilizing a urethanation reaction between isocyanate and hydroxide group in the base resin, and (2) a curing method utilizing an ether reaction between hydroxide group in the base resin and an alkyletherified amino resin which is prepared by reacting between a part of or whole of a methylol compound which is prepared by reacting formaldehyde with one or more of melamine, urea, and benzoguanamine, and a C1-5 primary alcohol. As of these methods, particularly preferred one is to adopt a urethanation reaction between isocyanate and hydroxyl group in the base resin as the main reaction.

The polyisocyanate compound used in the curing method (1) described above is a compound prepared by partially reacting an aliphatic, alicyclic (including heterocyclic), or aromatic isocyanate compound, or a compound thereof using a polyhydric alcohol. Examples of that kind of polyisocyanate compound are the following.

1) m- or p-phenylene diisocyanate, 2,4- or 2,6-trilene diisocyanate, o- or p-xylylene diisocyanate, hexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate;

2) a compound of product of reaction between separate or mixture of the compounds given in 1) with a polyhydric alcohol (for example, a dihydric alcohol such as ethyleneglycol and propyleneglycol, a trihydric alcohol such as glycerin and trimethylolpropane, a tetrahydric alcohol such as pentaerythritol, and hexahydric alcohol such as sorbitol and dipentaerythritol) leaving at least two isocyanate within a molecule.

These isocyanate compounds may be used separately or mixing two or more of them together.

Examples of protective agent (blocking agent) of the polyisocyanate compound are the following.

1) Aliphatic monoalcohol such as methanol, ethanol, propanol, butanol, octylalcohol;

2) Monoether of ethyleneglycol and/or diethyleneglycol, for example, monoether of methyl, ethyl, propyl (n-, iso-), butyl (n-, iso-, sec-);

3) Aromatic alcohol such as phenol and cresol;

4) Oxime such as acetoxime and methylethylketone oxime. Through reaction between one or more of these compounds with above-described polyisocyanate compound, a polyisocyanate compound thus obtained is stably protected at least at normal temperature.

It is preferable to blend that kind of polyisocyanate compound (E) with a film-forming organic resin (A) as the curing agent at a range of (A)/(E)=95/5 to 55/45 (weight ratio of non-volatile matter), more preferably (A)/(E)=90/10 to 65/35. Since polyisocyanate compounds have water-absorbing property, blending of the compound at ratios above (A)/(E)=55/45 degrades the adhesiveness of the organic coating. If top coating is given on the organic coating, unreacted polyisocyanate compound migrates into the coating film to induce hindrance of curing or insufficient adhesiveness of the coating film. Accordingly, the blending ratio of the polyisocyanate compound (E) is preferably not more than (A)/(E)=55/45.

The film-forming organic resin (A) is fully cross-linked by the addition of above-described cross-linking agent (curing agent). For further increasing the cross-linking performance at a low temperature, it is preferable to use a known catalyst for enhancing curing. Examples of the curing-enhancing catalyst are N-ethylmorpholine, dibutyltin dilaurate, cobalt naphthenate, tin(II)chloride, zinc naphthenate, and bismuth nitrate.

When an epoxy-group-laden resin is used as the film-forming organic resin (A), the epoxy-group-laden resin may be blended with a known resin such as that of acrylic, alkyd, and polyester to improve the physical properties such as adhesiveness to some extent.

According to the present invention, the organic coating may be blended with ion-exchanged silica (a) and/or fine particle silica (b) as the rust-preventive additive.

The ion-exchanged silica is prepared by fixing metallic ion such as calcium and magnesium ions on the surface of porous silica gel powder. Under a corrosive environment, the metallic ion is released to form a deposit film. Among these ion-exchanged silicas, Ca ion-exchanged silica is most preferable.

Any type of Ca ion-exchanged silica may be applied. A preferred range of average particle size of Ca ion-exchanged silica is 6 μm or less, more preferably 4 μm or less. For example, Ca ion-exchanged silica having average particle sizes of from 2 to 4 μm may be used. If the average particle size of Ca ion-exchanged silica exceeds 6 μm, the corrosion resistance degrades and the dispersion stability in the coating composition degrades.

A preferred range of Ca concentration in the Ca ion-exchanged silica is 1 wt. % or more, more preferably from 2 to 8 wt. %. If the Ca concentration is below 1 wt. %, the rust-preventive effect by the Ca release becomes insufficient.

Surface area, pH, and oil-absorbance of the Ca ion-exchanged silica are not specifically limited.

Examples of the above-described Ca ion-exchanged silica are: SHIELDEX C303 (trade name) (average particle sizes of from 2.5 to 3.5 μm; Ca concentration of 3 wt. %; manufactured by W. R. Grace & Co.), SHIELDEX AC3 (trade name) (average particle sizes of from 2.3 to 3.1 μm; Ca concentration of 6 wt. %), SHIELDEX AC5 (trade name) (average particle sizes of from 3.8 to 5.2 μm; Ca concentration of 6 wt. %); SHIELDEX (trade name) (average particle size of 3 μm; Ca concentrations of from 6 to 8 wt. %), SHIELDEX SY710 (trade name) (average particle sizes of from 2.2 to 2.5 μm; Ca concentrations of from 6.6 to 7.5 wt. %, manufactured by Fuji Silisia Chemical Co., Ltd.)

The rust-preventive mechanism in the case of addition of ion-exchanged silica (α) to organic coating is described above. Particularly according to the present invention, markedly excellent corrosion preventive effect is attained by combining a specific chelate-modified resin which is the film-forming organic resin with an ion-exchanged silica, thus inducing the combined effect of the corrosion-suppression effect of the chelate-modified resin at the anodic reaction section with the corrosion-suppression effect of the ion-exchanged silica at the cathodic reaction section.

A preferred range of blending ratio of the ion-exchanged silica (a) in the organic resin coating is 1 to 100 parts by weight (solid matter) to 100 parts by weight (solid matter) of the reaction product as the resin composition for film-forming (that is, the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen), more preferably from 5 to 80 parts by weight (solid matter), and most preferably from 10 to 50 parts by weight (solid matter). If the blending ratio of the ion-exchanged silica (a) becomes less than 1 part by weight, the effect of improved corrosion resistance after alkaline degreasing becomes small. If the blending ratio of the ion-exchanged silica (a) exceeds 100 parts by weight, the corrosion resistance degrades, which is unfavorable.

The fine particle silica (b) may be either colloidal silica or fumed silica. When a water-type film-forming resin is used as the base resin, examples of applicable colloidal silica are: SNOWTEX O. SNOWTEX N, SNOWTEX 20, SNOWTEX 30, SNOWTEX 40, SNOWTEX C, SNOWTEX S (trade names) manufactured by Nissan Chemical Industries, Ltd.; CATALOID S. CATALOID SI-35, CATALOID SI-40, CATALOID SA, CATALOID SN (trade names) manufactured by Catalysts & Chemicals Industries Co., Ltd.; ADELITE AT-20-50, ADELITE AT-20N, ADELITE AT-300, ADELITE AT-300S, ADELITE AT-20Q (trade names) manufactured by Asahi Denka Kogyo, KK.

When a solvent-type film-forming resin is used as the base resin, examples of applicable colloidal silica are: ORGANOSILICA SOL MA-ST-M, ORGANOSILICA SOL IPA-ST, ORGANOSILICA SOL EG-ST, ORGANOSILICA SOL E-ST-ZL, ORGANOSILICA SOL NPC-ST, ORGANOSILICA SOL DMAC-ST, ORGANOSILICA SOL DMAC-ST-ZL, ORGANOSILICA SOL XBA-ST, ORGANOSILICA SOL MIBK-ST (trade names) manufactured by Nissan Chemical Industries, Ltd.; OSCAL-1132, OSCAL-1232, OSCAL-1332, OSCAL-1432, OSCAL-1532, OSCAL-1632, OSCAL-1722 (trade names) manufactured by Catalysts & Chemicals Industries Co., Ltd.

In particular, organic solvent dispersion silica sol is superior in corrosion resistance to fumed silica.

Examples of applicable fumed silica are: AEROSIL R971, AEROSIL R812, AEROSIL R811, AEROSIL R974, AEROSIL R202, AEROSIL R805, AEROSIL 130, AEROSIL 200, AEROSIL 300, AEROSIL 300CF (trade names) manufactured by Japan Aerosil Co., Ltd.

The fine particle silica contributes to forming dense and stable zinc corrosion products under a corrosive environment. Thus formed corrosion products cover the plating surface in a dense mode, thus presumably suppressing the development of corrosion.

From the viewpoint of corrosion resistance, the fine particle silica preferably has particle sizes of from 5 to 50 nm, more preferably from 5 to 20 nm, and most preferably from 5 to 15 nm.

A preferred range of blending ratio of the fine particle silica (b) in the organic resin coating is 1 to 100 parts by weight (solid matter) to 100 parts by weight (solid matter) of the reaction product as the resin composition for film-forming (that is, the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen), more preferably from 5 to 80 parts by weight (solid matter), and most preferably from 10 to 30 parts by weight (solid matter). If the blending ratio of the fine particle silica (b) becomes less than 1 part by weight, the effect of improved corrosion resistance after alkaline degreasing becomes small. If the blending ratio of the fine particle silica (b) exceeds 100 parts by weight, the corrosion resistance and the workability degrade, which is unfavorable.

According to the present invention, markedly high corrosion resistance is attained by combined addition of an ion-exchanged silica (a) and a fine particle silica (b) to the organic coating. That is, the combined addition of ion-exchanged silica (a) and fine particle silica (b) induces above-described combined rust-preventive mechanism which gives markedly excellent corrosion-preventive effect.

The blending ratio of combined addition of ion-exchanged silica (a) and fine particle silica (b) to the organic coating is in a range of from 1 to 100 parts by weight (solid matter) of the sum of the ion-exchanged silica (a) and the fine particle silica (b), to 100 parts by weight (solid matter) of the reaction product as the resin composition for film-forming (that is, the product of reaction between the film-forming organic resin (A) and an active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen), preferably from 5 to 80 parts b y weight (solid matter). Further the weight ratio of blending amount (solid matter) of the ion-exchanged silica (a) to the fine particle silica (b), (a)/(b), is selected to a range of from 99/1 to 1/99, preferably from 95/5 to 40/60, more preferably from 90/10 to 60/40.

If the weight ratio of the ion-exchanged silica (a) and the fine particle silica (b) is less than 1 part by weight, the effect of improved corrosion resistance after alkaline degreasing becomes small. If the blending ratio of sum of the ion-exchanged silica (a) and the fine particle silica (b) exceeds 100 parts by weight, the coatability and the weldability degrade, which is unfavorable.

If the weight ratio of the ion-exchanged silica (a) to the fine particle silica (b), (a)/(b), is less than 1/99, the corrosion resistance degrades. If the weight ratio of the ion-exchanged silica (a) to the fine particle silica (b), (a)/(b), exceeds 99/1, the effect of combined addition of the ion-exchanged silica (a) and the fine particle silica (b) cannot fully be attained.

Adding to the above-described rust-preventive agents, the organic coating may contain other corrosion-suppressing agent such as polyphosphate (for example, aluminum polyphosphate such as TEIKA K-WHITE 82, TEIKA K-WHITE 105, TEIKA K-WHITE G105, TEIKA K-WHITE Ca650 (trade marks) manufactured by TEIKOKU KAKO CO.), phosphate (for example, zinc phosphate, aluminum dihydrogenphosphate, zinc phosphate), molybdenate, phosphomolybdenate (for example, aluminum phosphomolybdenate), organic phosphoric acid and its salt (for example, phytic acid, phytiate, phosphonic acid, phosphonate, their metal salt and alkali metal salt, alkali earth metal salt), organic inhibitor (for example, hydrazine derivative, thiol compound).

The organic coating may, at need, further include a solid lubricant (c) to improve the workability of the coating.

Examples of applicable solid lubricant according to the present invention are the following.

(1) Polyolefin wax, paraffin wax: for example, polyethylene wax, synthetic paraffin, natural paraffin, microwax, chlorinated hydrocarbon;

(2) Fluororesin fine particles: for example, polyfluoroethylene resin (such as polytetrafluoroethylene resin), polyvinylfluoride resin, polyvinylidenefluoride resin.

In addition, there may be applied fatty acid amide base compound (such as stearic acid amide, palmitic acid amide, methylene bis-stearoamide, ethylene bis-stearoamide, oleic acid amide, ethyl acid amide, alkylene bis-fatty acid amide), metallic soap (such as calcium stearate, lead stearate, calcium laurate, calcium palmate), metallic sulfide (molybdenum disulfide, tungsten disulfide), graphite, graphite fluoride, boron nitride, polyalkyleneglycol, and alkali metal sulfate.

Among those solid lubricants, particularly preferred ones are polyethylene wax, fluororesin fine particles (particularly poly-tetrafluoroethylene resin fine particles).

Applicable polyethylene wax include: SHERIDUST 9615A, SHERIDUST 3715, SHERIDUST 3620, SHERIDUST 3910 (trade names) manufactured by Hoechst Co., Ltd.; SUNWAX 131-P, SUNWAX 161-P (trade names) manufactured by Sanyo Chemical Industries, Ltd.; CHEMIPEARL W-100, CHEMIPEARL W-200, CHEMIPEARL W-500, CHEMIPEARL W-800, CHEMIPEARL W-956 (trade names) manufactured by Mitsui Petrochemical Industries, Ltd.

A most preferred fluororesin fine particle is tetrafluoroethylene fine particle. Examples of the fine particles are LUBRON L-2, LUBRON L-5 (trade names) manufactured by Daikin Industries, Ltd.; MP 1100, MP 1200 (trade names; manufactured by Du Pont-Mitsui Company, Ltd.); FLUON DISPERSION AD1, FLUON DISPERSION AD2, FLUON L141J, FLUON L150J, FLUON L155J (trade names) manufactured by Asahi ICI Fluoropolymers Co., Ltd.

As of these compounds, combined use of polyolefin wax and tetrafluoroethylene fine particles is expected to provide particularly excellent lubrication effect.

A preferred range of blending ratio of the solid lubricant (c) in the organic resin coating is from 1 to 80 parts by weight (solid matter) to 100 parts by weight (solid matter) of the reaction product as the resin composition for film-forming (that is, the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen), more preferably from 3 to 40 parts by weight (solid matter). If the blending ratio of the solid lubricant (c) becomes less than 1 part by weight, the effect of lubrication is small. If the blending ratio of the solid lubricant (c) exceeds 80 parts by weight, the painting performance degrade, which is unfavorable.

The organic coating of the organic coating steel sheet according to the present invention normally consists mainly of a product (resin composition) of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen). And, at need, an ion-exchanged silica (a), a fine particle silica (b), a solid lubricant (c), and a curing agent may further be added to the organic coating. Furthermore, at need, there may be added other additives such as organic coloring pigment (for example, condensing polycyclic organic pigment, phthalocyanine base organic pigment), coloring dye (for example, azo dye soluble in organic solvent, azo metal dye soluble in water), inorganic pigment (for example, titanium oxide), chelating agent (for example, thiol), conductive pigment (for example, metallic powder of zinc, aluminum, nickel, or the like, iron phosphide, antimony-dope type tin oxide), coupling agent (for example, silane coupling agent and titanium coupling agent), melamine-cyanuric acid additive.

The paint composition for film-formation containing above-described main component and additive components normally contains solvent (organic solvent and/or water), and, at need, further a neutralizer or the like is added.

Applicable organic solvent described above has no specific limitation if only it dissolves or disperses the product of reaction between the above-described film-forming organic resin (A) and the active-hydrogen-laden compound (B), and adjusts the product as the painting composition. Examples of the organic solvent are the organic solvents given above as examples.

The above-described neutralizers are blended, at need, to neutralize the film-forming organic resin (A) to bring it to water-type. When the film-forming organic resin (A) is a cationic resin, acid such as acetic acid, lactic acid, and formic acid may be used as the neutralizer.

The organic coatings described above are formed on the above-described composite oxide coating.

The dry thickness of the organic coating is in a range of from 0.1 to 5 μm, preferably from 0.3 to 3 μm, and most preferably from 0.5 to 2 μm. If the thickness of the organic coating is less than 0.1 μm, the corrosion resistance becomes insufficient. If the thickness of the organic coating exceeds 5 μm, the conductivity and the workability degrade.

The following is the description about the method for manufacturing an organic coating steel sheet according to the present invention.

The organic coating steel sheet according to the present invention is manufactured by the steps of: treating the surface (applying a treatment liquid to the surface) of a zinc base plated steel sheet or an aluminum base plated steel sheet using a treatment liquid containing the components of above-described composite oxide coating; heating and drying the plate; applying a paint composition which contains the product of reaction between above-described film-forming organic resin (A) and an active-hydrogen-laden compound (B) a part of or whole of which consists of ahydrazine derivative (C) containing active hydrogen, which product of reaction is preferably the main component, and at need, further contains an ion-exchanged silica (a), a fine particle silica (b), and a solid lubricant (c), and the like; heating to dry the product.

The surface of the plated steel sheet may be, at need, subjected to alkaline degreasing before applying the above-described treatment liquid, and may further be subjected to preliminary treatment such as surface adjustment treatment for further improving the adhesiveness and corrosion resistance.

For treating the surface of the zinc base plated steel sheet or the aluminum base plated steel sheet with a treatment liquid and for forming a composite oxide coating thereon, it is preferred that the plate is treated by an acidic aqueous solution, at pH ranging from 0.5 to 5, containing:

(aa) oxide fine particles ranging from 0.001 to 3.0 mole/liter;

(ab) one or more of the substances selected from the group consisting of either one metallic ion of Mg, Ca, Sr, Ba; a compound containing at least one metal given above; a composite compound containing at least one metal given above; ranging from 0.001 to 3.0 mole/liter as metal given above;

(ac) phosphoric acid and/or phosphoric acid compound ranging from 0.001 to 6.0 mole/liter as P 2 O 5 ; further adding, at need, above-described additive components (organic resin components, iron group metal ions, corrosion-suppression agents, other additives); then heating and drying the product.

The added components (ab) in the treatment liquid is in a range of from 0.001 to 3.0 mole/liter as metal, preferably from 0.01 to 0.5 mole/liter. If the sum of the added amount of these components is less than 0.001 mole/liter, the effect of addition cannot be fully attained. If the sum of the added amount of these components exceeds 3.0 mole/liter, these components interfere the network of coating, thus failing in forming dense coating. Furthermore, excess amount of addition of these components makes the metallic components likely elute from the coating, which results in defects such as discoloration of appearance under some environmental conditions.

As of above-given additive components (ab), Mg most significantly increases the corrosion resistance. The form of Mg in the treatment liquid may be compound or composite compound. To attain particularly excellent corrosion resistance, however, a metallic ion or a water-soluble ion form containing Mg is particularly preferred.

For supplying ion of the additive components (ab) in a form of metallic salt, the treatment liquid may contain anion such as chlorine ion, nitric acid ion, sulfuric acid ion, acetic acid ion, and boric acid ion.

It should be emphasized that the treatment liquid is an acidic aqueous solution. That is, by bringing the treatment liquid to acidic, the plating components such as zinc are readily dissolved. As a result, at the interface between the chemical conversion treatment film and the plating, a phosphoric acid compound layer containing plating components such as zinc is presumably formed, which layer strengthens the interface bonding of both sides to structure a coating having excellent corrosion resistance.

As the oxide fine particles as an additive component (aa) silicon oxide (SiO 2 ) fine particles are most preferred. The silicon oxide may be commercially available silica sol and water-dispersion type silicic acid oligomer or the like if only the silicon oxide is water-dispersion type SiO 2 fine particles which are stable in an acidic aqueous solution. Since, however, fluoride such as hexafluoro silicic acid is strongly corrosive and gives strong effect to human body, that kind of compound should be avoided from the point of influence to work environment.

A preferred range of blending ratio of the fine particle oxide (the blending ratio as SiO 2 in the case of silicon oxide) in the treating liquid is from 0.001 to 3.0 mole/liter, more preferably from 0.05 to 1.0 mole/liter, and most preferably from 0.1 to 0.5 mole/liter. If the blending ratio of the fine particle oxide becomes less than 0.001 mole/liter, the effect of addition is not satisfactory. If the blending ratio of the fine particle oxide exceeds 3.0 mole/liter, the water-resistance of coating degrades, resulting in degradation of corrosion resistance.

The phosphoric acid and/or phosphoric acid compound as the additive component (ac) includes: a mode of aqueous solution in which a compound specific to phosphoric acid, such as polyphosphoric acid such as orthophosphoric acid, pyrophosphoric acid, and tripolyphosphoric acid, methaphosphoric acid, inorganic salt of these acids (for example, primary aluminum phosphate), phosphorous acid, phosphate, phosphinic acid, phosphinate, exists in a form of anion or complex ion combined with a metallic cation which are generated by dissolving the compound in the aqueous solution; and a mode of aqueous solution in which that kind of compound exists in a form of inorganic salt dispersed therein. The amount of phosphoric acid component according to the present invention is specified by the sum of all these modes of acidic aqueous solution thereof as converted to P 2 O 5 amount.

A preferred range of blending ratio of the phosphoric acid and/or phosphoric acid compound as P 2 O 5 is from 0.001 to 6.0 mole/liter, more preferably from 0.02 to 1.0 mole/liter, and most preferably from 0.1 to 0.8 mole/liter. If the blending ratio of the phosphoric acid and/or phosphoric acid compound becomes less than 0.001 mole/liter, the effect of addition is not satisfactory and the corrosion resistance degrades. If the blending ratio of the phosphoric acid and/or phosphoric acid compound exceeds 6.0 mole/liter, excess amount of phosphoric acid ion reacts with the plating film under a humid environment, which enhances the corrosion of plating base material to cause discoloration and stain-rusting under some corrosive environments.

For obtaining a composite oxide coating providing particularly excellent corrosion resistance, or for preparing a composite oxide coating comprising components (α), (β), and (γ) given below, and having the coating weight of the sum of these components (α), (β), and (γ) in a range of from 6 to 3,600 mg/m 2 , it is preferable that the above-described composite oxide coating contains the additive components (aa), (ab), and (ac) in the acidic aqueous solution, further, the composite oxide coating is treated by an acidic aqueous solution of pH of from 0.5 to containing, at need, above-described additive components (organic resin component, iron group metallic ion, corrosion-suppression agent, and other additives), followed by heating and drying. The above-given composite oxide coating components (α), (β), and (γ), and the above-given additive components (a), (b), and (c) are specified below. (α) SiO 2 fine particles in a range of from 0.01 to 3,000 mg/m 2 as SiO 2 ,

(β) One or more of Mg, compound containing Mg, and composite compound containing Mg in a range of from 0.01 to 1,000 mg/m 2 as Mg,

(γ) Phosphoric acid and/or phosphoric acid compound in a range of from 0.01 to 3,000 mg/m 2 as P 2 O 5 ;

(aa) SiO 2 fine particles in a range of from 0.001 to 3.0 mole/liter as SiO 2 , preferably from 0.05 to 1.0 mole/liter, more preferably from 0.1 to 0.5 mole/liter,

(ab) One or more of the substances selected from the group consisting of Mg ion, water-soluble ion containing Mg, compound containing Mg, composite compound containing Mg in a range of from 0.001 to 3.0 mole/liter as Mg, preferably from 0.01 to 0.5 mole/liter,

(ac) phosphoric acid and/or phosphoric acid compound in a range of from 0.001 to 6.0 mole/liter as P 2 O 5 , preferably from 0.02 to 1.0 mole/liter, more preferably from 0.1 to 0.8 mole/liter.

The reason to specify the conditions and amount of the above-given additives (aa), (ab), and (ac) is described before.

To prepare the range of the ratio of the component (β) to the component (α) in the composite oxide coating, molar ratio [Mg/SiO 2 ], or the component (β) as Mg to the component (α) as SiO 2 , from 1/100 to 100/1, the ratio of the additive component (ab) to the additive component (aa) in the acidic aqueous solution for forming the composite oxide coating may be adjusted to a range of from 1/100 to 100/1 as the molar ratio [Mg/SiO 2 ], or the additive component (ab) as Mg to the additive component (aa) as SiO 2 .

To adjust the ratio of the component (β) to the component (α) in the composite oxide coating to a preferred range of from 1/10 to 10/1, more preferably from 1/2 to 5/1, as the molar ratio [Mg/SiO 2 ], or the ratio of the component (β) as Mg to the component (α) as SiO 2 , it is adequate to adjust the ratio of the additive component (ab) to the additive component (aa) in the acidic aqueous solution for forming the composite oxide coating to a range of from 1/10 to 10/1, more preferably from 1/2 to 5/1, as the molar ratio [Mg/SiO 2 ], or the ratio of the additive component (ab) as Mg to the additive component (aa) as SiO 2 .

To adjust the ratio of the component (γ) to the component (β) in the composite oxide coating to a range of from 1/100 to 100/1 as the molar ratio [P 2 O 5 /Mg], or the ratio of the component (γ) as P 2 O 5 to the component (β) as Mg, it is adequate to adjust the ratio of additive component (ac) to the additive component (ab) in the acidic aqueous solution for forming the composite oxide coating to a range of from 1/100 to 100/1 as the molar ratio [P 2 O 5 /Mg] represented by the ratio of the additive component (ac) as P 2 O 5 to the additive component (ab) as Mg.

To adjust the ratio of the component (γ) to the component (β) in the composite oxide coating to a further preferable range of from 1/10 to 10/1 as the molar ratio [P 2 O 5 /Mg], or the ratio of the component (γ) as P 2 O 5 to the component (β) as Mg, more preferably from 1/2 to 2/1, it is adequate to adjust the ratio of additive component (ac) to the additive component (ab) in the acidic aqueous solution for forming the composite oxide coating to a range of from 1/10 to 10/1, more preferably from 1/2 to 2/1, as the molar ratio [P 2 O 5 /Mg], or the ratio of the additive component (ac) as P 2 O 5 to the additive component (ab) as Mg.

For adjusting the ratio of the additive component (ac) to the additive component (ab) in the acidic aqueous solution for forming the composite oxide coating, it is preferable to use an aqueous solution of primary magnesium phosphate or the like which is prepared by limiting the molar ratio of the magnesium component to the phosphoric acid component, in advance, because other anionic components are prevented from existing in the treatment liquid.

On applying the aqueous solution of primary magnesium phosphate, however, lowered molar ratio [P 2 O 5 /Mg] degrades the stability of the compound in the aqueous solution. Accordingly, a suitable molar ratio [P 2 O 5 /Mg] is not less than 1/2.

On the other hand, increased molar ratio [P 2 O 5 /Mg] in the aqueous solution of primary magnesium phosphate decreases the pH of treatment liquid, which increases the reactivity with the plating base material, which then induces irregular coating caused by non-uniform reaction to give an influence to corrosion resistance. Consequently, when an aqueous solution of primary magnesium phosphate which is prepared by limiting the molar ratio of the magnesium component to the phosphoric acid component, the molar ratio [P 2 O 5 /Mg] is preferably set to not more than 2/1.

To attain the most excellent corrosion resistance, it is preferred that the ratio of the component (β) to the component (α) in the composite oxide coating is adjusted to a range of from 1/100 to 100/1 as the molar ratio [Mg/SiO 2 ], or the component (β) as Mg to the component (α) as SiO 2 , more preferably from 1/10 to 10/1, most preferably from 1/2 to 5/1. And, to adjust the ratio of the component (γ) to the component (β) in the composite oxide coating to a range of from 1/100 to 100/1 as the molar ratio [P 2 O 5 /Mg], or the component (γ) as P 2 O 5 to the component (β) as Mg in the composite oxide coating, more preferably from 1/10 to 10/1, and most preferably from 1/2 to 2/1, it is preferred that the ratio of the additive component (ab) to the additive component (aa) in the acidic aqueous solution for forming the composite oxide coating is adjusted to a range of from 1/100 to 100/1 as the molar ratio [Mg/SiO 2 ], or the additive component (ab) as Mg to the additive component (aa) as SiO 2 , more preferably from 1/10 to 10/1, and most preferably from 1/2 to 5/1, and further the ratio of the additive component (ac) to the additive component (ab) is adjusted to a range of from 1/100 to 100/1 as the molar ratio [P 2 O 5 /Mg], or the additive component (ac) as P 2 O 5 to the additive component (ab) as Mg, preferably from 1/10 to 10/1, more preferably from 1/2 to 2/1.

The treatment liquid may further include an adequate amount of an additive component (ad) which is one or more ions selected from the group consisting of: either one metallic ion of Ni, Fe, and Co; and water-soluble ion containing at least one of the above-listed metals. By adding that kind of iron group metal, blackening phenomenon is avoided. The blackening phenomenon occurs in the case of non-addition of iron group metals caused from corrosion on the plating polar surface layer under a humid environment. Among these iron group metals, Ni provides particularly strong effect even with a slight amount thereof. Since, however, excessive addition of iron group metals such as Ni and Co induces degradation of corrosion resistance, the added amount should be kept at an adequate level.

A preferred range of the added amount of the above-described additive component (ad) is from 1/10,000 to 1 mole as metal per one mole of the additive component (ac), more preferably from 1/10,000 to 1/100. If the added amount of the additive component (ad) is less than 1/10,000 mole to one mole of the additive component (ac), the effect of the addition is not satisfactory. If the added amount of the additive component (ad) exceeds 1 mole, the corrosion resistance degrades as described above.

Adding to the above-described additive components (aa) through (ad), the treatment liquid may further contain an adequate amount of additive components to the coating, which are described before.

A preferable range of pH of the treatment liquid is from 0.5 to 5, more preferably from 2 to 4. If the pH of treatment liquid is less than 0.5, the reactivity of the treatment liquid becomes excessively strong so that micro-defects appear on the surface of the coating to degrade the corrosion resistance. If the pH of the treatment liquid exceeds 5, the reactivity of the treatment liquid becomes poor, and the bonding at interface between the plating face and the coating becomes insufficient, as described above, thus degrading the corrosion resistance.

The methods for applying the treatment liquid onto the plated steel sheet may be either one of coating method, dipping method, and spray method. The coating method may adopt any type such as roll coater (three-roll type, two-roll type, etc.), squeeze coater, die coater. After the coating step using squeeze coater and the like, the dipping step, or the spray step, it is possible to adjust the coating weight, the uniformizing appearance, and the uniformizing the film-thickness using air-knife method and roll-squeezing method.

Although there is no specific limitation on the temperature of the treatment liquid, a preferable range thereof is from normal temperature to around 60° C. Below the normal temperature is uneconomical because a cooling unit or other additional facilities are required. On the other hand, temperatures above 60° C. enhances the vaporization of water, which makes the control of the treatment liquid difficult.

After the coating of treatment liquid as described above, generally the plate is heated to dry without rinsing with water. The treatment liquid according to the present invention forms a slightly soluble salt by a reaction with the substrate plated steel sheet, so that rinsing with water may be applied after the treatment.

Method for heating to dry the coated treatment liquid is not limited. For example, dryer, hot air oven, high frequency induction heating furnace, infrared heating furnace may be applied.

The heating and drying treatment is preferably conducted at reaching temperatures of from 50 to 300° C., more preferably from 80 to 200° C., and most preferably from 80 to 160° C. If the heating temperature is less than 50° C., excess amount of water is left in the coating, which results in insufficient corrosion resistance. If the heating temperature exceeds 300° C., the operation becomes uneconomical and defects likely appear in the coating to degrade the corrosion resistance.

After forming the composite oxide coating on the surface of the zinc base plated steel sheet or the aluminum base plated steel sheet, as described above, a paint composition for forming an organic coating is applied on the composite oxide coating. Method for applying the paint composition is not limited, and examples of the method are coating method, dipping method, and spray method. The coating method may adopt any type such as roll coater (three-roll type, two-roll type, etc.), squeeze coater, die coater. After the coating step using squeeze coater and the like, the dipping step, or the spray step, it is possible to adjust the coating weight, the uniformizing appearance, and the uniformizing the film-thickness using air-knife method and roll-squeezing method.

After applying the paint composition, generally the plate is heated to dry without rinsing with water. After applying the paint composition, however, water-rinse step may be given.

Method for heating to dry the paint composition is not limited. For example, dryer, hot air oven, high frequency induction heating furnace, infrared heating furnace may be applied. The heating treatment is preferably conducted at reaching temperatures of from 50 to 350° C., more preferably from 80 to 250° C. If the heating temperature is less than 50° C., excess amount of water is left in the coating, which results in insufficient corrosion resistance. If the heating temperature exceeds 350° C., the operation becomes uneconomical and defects likely appear in the coating to degrade the corrosion resistance.

As described above, the present invention includes a steel sheet having an organic coating on both sides or on side thereof. Accordingly, modes of the steel sheet according to the present invention include, for example, the followings.

(1) “Plating film—Composite oxide coating—Organic coating” on one side of the steel sheet, and “Plating film” on other side of the steel sheet;

(2) “Plating film—Composite oxide coating—Organic coating” on one side of the steel sheet, and “Plating film—Known coating treated by phosphoric acid, or the like” on other side of the steel sheet;

(3) “Plating film—Composite oxide coating—Organic coating” on both sides of the steel sheet;

(4) “Plating film—Composite oxide coating—Organic coating” on one side of the steel sheet, and “Plating film—Composite oxide coating” on other side of the steel sheet;

(5) “Plating film—Composite oxide coating—Organic coating” on one side of the steel sheet, and “Plating film—Organic coating” on other side of the steel sheet.

Embodiments

Treatment liquids (coating compositions) for forming the primary layer coating, which are listed in Tables 2 through 17, were prepared.

Resin compositions (reaction products) for forming the secondary layer coating were synthesized in the following-described procedure.

SYNTHESIS EXAMPLE 1

A 1870 parts of EP828 (epoxy equivalent 187, manufactured by Yuka Shell Epoxy Co., Ltd.), 912 parts of bisphenol A, 2 parts of tetraethylammonium bromide, and 300 parts of methylethylketone were charged in a flask with four necks, which mixture was then heated to 140° C. to let them react for 4 hours. Thus, an epoxy resin having an epoxy equivalent of 1391 and a solid content of 90% was obtained. A 1500 parts of ethyleneglycol monobutylether was added to the epoxy resin, which were then cooled to 100° C. A 96 parts of 3,5-dimethylpyrazole (molecular weight 96) and 129 parts of dibutylamine (molecular weight 129) were added to the cooled resin, and they were reacted for 6 hours to eliminate the epoxy group. Then, a 205 parts of methylisobutylketone was added while the mixture was cooling, to obtain a pyrazole-modified epoxy resin having 60% of solid matter. The epoxy resin is defined as the resin composition (1). The resin composition (1) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound that contains 50 mole % of hydrazine derivative (C) containing active hydrogen.

SYNTHESIS EXAMPLE 2

A 4000 parts of EP1007 (epoxy equivalent 2000, manufactured by Yuka Shell Epoxy Co., Ltd.) and 2239 parts of ethyleneglycol monobutylether were charged into a flask with four necks, which mixture was then heated to 120° C. to let them react for 1 hour to fully dissolve the epoxy resin. The mixture was cooled to 100° C. A 168 parts of 3-amino-1,2,4-triazole (molecular weight 84) was added to the mixture, and they were reacted for 6 hours to eliminate the epoxy group. Then, a 540 parts of methylisobutylketone was added while the mixture was cooling, to obtain a triazole-modified epoxy resin having 60% of solid matter. The epoxy resin is defined as the resin composition (2). The resin composition (2) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound that contains 100 mole % of hydrazine derivative (C) containing active hydrogen.

SYNTHESIS EXAMPLE 3

A 222 parts of isophorone diisocyanate (epoxy equivalent 111) and 34 parts of methylisobutylketone were charged into a flask with four necks. A 87 parts of methylethylketoxime (molecular weight 87) was added to the mixture dropwise for 3 hours while keeping the mixture at temperatures ranging from 30 to 40° C., then the mixture was kept to 40° C. for 2 hours. Thus, a block isocyanate having isocyanate equivalent of 309 and solid content of 90% was obtained.

A 1489 parts of EP828 (epoxy equivalent 187, manufactured by Yuka Shell Epoxy Co., Ltd.), 684 parts of bisphenol A, 1 part of tetraethylammonium bromide, and 241 parts of methylisobutylketone were charged into a flask with four necks, which mixture was then heated to 140° C. to let them react for 4 hours. Thus, an epoxy resin having epoxy equivalent of 1090 and solid content of 90% was obtained. To the epoxy resin, 1000 parts of methylisobutylketone was added, then the mixture was cooled to 100° C., and 202 parts of 3-mercapto-1,2,4-triazole (molecular weight 101) was added to the mixture, and let the mixture react for 6 hours to fully eliminate the epoxy group. After that, the part-block isocyanate of the above-described 90% solid portion was added to the reaction product to let the mixture react at 100° C. for 3 hours, and the vanish of isocyanate group was confirmed. Further, 461 parts of ethyleneglycol monobutylether was added to the product to obtain a triazole-modified epoxy resin having 60% solid content. The product is defined as the resin composition (3). The resin composition (3) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound that contains 100 mole % of hydrazine derivative (C) containing active hydrogen.

SYNTHESIS EXAMPLE 4

A 1870 parts of EP828 (epoxy equivalent 187, manufactured by Yuka Shell Epoxy Co., Ltd.), 912 parts of bisphenol A, 2 parts of tetraethylammonium bromide, and 300 parts of methylisobutylketone were charged into a flask with four necks, which mixture was then heated to 140° C. to let them react for 4 hours. Thus, an epoxy resin having epoxy equivalent of 1391 and solid content of 90% was obtained. To the epoxy resin, 1500 parts of ethyleneglycol monobutylether was added, then the mixture was cooled to 100° C., and 258 parts of dibutylamine (molecular weight 129) was added to the mixture, and let the mixture react for 6 hours to fully eliminate the epoxy group. While cooling the mixture, 225 parts of methylisobutylketone was further added to the mixture to obtain an epoxyamine adduct having 60% solid content. The product is defined as the resin composition (4). The resin composition (4) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound of hydrazine derivative (C) containing no active hydrogen.

A curing agent was blended to each of the synthesized resin compositions (1) through (4) to prepare the resin compositions (paint compositions) listed in Table 18. To each of these paint compositions, ion-exchanged silica, fine particle silica given in Table 19, and solid lubricant given in Table 20 were added at specified amounts, and they were dispersed in the composition using a paint dispersion machine (sand grinder) for a necessary time. For the above-described ion-exchanged silica, SHILDEX C303 (average particle sizes of from 2.5 to 3.5 μm and Ca concentration of 3 wt. %) manufactured by W.R. Grace & Co., which is a Ca-exchanged silica, was used.

To obtain organic coating steel sheets for household electric appliances, building materials, and automobile parts, the plated steel sheets shown in Table 1 were used as the target base plates, which plates were prepared by applying zinc base plating or aluminum base plating on the cold-rolled steel sheets having a plate thickness of 0.8 mm and a surface roughness Ra of 1.0 μm. The surface of the plated steel sheet was treated by alkaline degreasing and water washing, then the treatment liquids (coating compositions) shown in Tables 2 through 17 was applied to the surface using a roll coater, followed by heating to dry to form the first layer coating. The thickness of the first layer coating was adjusted by the solid content in the treatment liquid (heating residue) or applying conditions (roll pressing force, rotational speed, and other variables). Then, the paint composition given in Table 18 was applied using a roll coater, which was then heated to dry to form the secondary layer coating, thus manufactured the organic coating steel sheets as Examples and Comparative Examples. The thickness of the second layer coating was adjusted by the solid content in the treatment liquid (heating residue) or applying conditions (roll pressing force, rotational speed, and other variables).

To each of thus obtained organic coating steel sheets, evaluation was given in terms of quality performance (appearance of coating, white-rust resistance, white-rust resistance after alkaline degreasing, paint adhesiveness, and workability). The results are given in Tables 21 through 87 along with the structure of primary layer coating and of secondary layer coating.

The quality performance evaluation on the organic coating steel sheets was carried out in the following-described manner.

(1) Appearance of Coating

For each sample, visual observation was given on the uniformity of coating appearance (presence/absence of irregular appearance). The criteria for evaluation are the following.

◯: Uniform appearance without no irregularity

Δ: Appearance showing some irregularity

X: Appearance showing significant irregularity

(2) White-rust Resistance

For each sample, the salt spray test (JIS Z2371) was applied, and the evaluation was given by the area percentage of white-rust.

The criteria for evaluation are the following.

⊚  No white-rust appeared
◯+ White-rust area less than 5%
◯  White-rust area not less than 5% and less than 10%
◯− White-rust area not less than 10% and less than 25%
Δ  White-rust area not less than 25% and less than 50%
X  White-rust area not less than 50%

 

(3) White-rust Resistance After Alkaline Degreasing

For each sample, alkaline degreasing was applied using the alkali treatment liquid CLN-364S (60° C., spraying for 2 min) produced by Nihon Parkerizing Co., followed by salt spray test (JIS Z2371). The result was evaluated by the white-rust area percentage after a specified time has past.

The criteria for evaluation are the following.

⊚  No white-rust appeared
◯+ White-rust area less than 5%
◯  White-rust area not less than 5% and less than 10%
◯− White-rust area not less than 10% and less than 25%
Δ  White-rust area not less than 25% and less than 50%
X  White-rust area not less than 50%

 

(4) Paint Adhesiveness

For each sample, a melamine base baking paint (film thickness of 30 μm) was applied, and the sample was dipped in a boiling water for 2 hours. Immediately after 2 hours of dipping, cross-cut (10×10 squares with 10 mm of spacing) was given to the surface of the sample. Then the test of attaching and peeling of adhesive tapes was given to the sample to evaluate the paint adhesiveness by the peeled paint film area percentage.

The criteria for evaluation are the following.

⊚ No peeling occurred
◯ Peeled area less than 5%
Δ Peeled area not less than %% and less than 20%
X Peeled area of less than 20%

 

(5) Workability

For each sample, a deep-drawing test (under oil-free condition) was given using a blank diameter of 120 mm and a die diameter of 50 mm. The drawing height to generate crack on the sample was determined.

The criteria for evaluation are the following.

⊚: Draw-off occurred

◯: Drawn height not less than 30 mm

Δ: Drawn height not less than 20 mm and less than 30 mm

X: Drawn height less than 20 mm

In the following-given Tables 21 through 87, each of *1 through *13 appeared in the tables expresses the following.

*1: Corresponding to No. given in Table 1.

*2: Corresponding to No. given in Tables 2 through 17.

*3: Corresponding to No. given in Table 18.

*4: Coating weight of SiO 2 fine particles (α)=Coating weight of one ore more substances selected from the group consisting of Mg, compound containing Mg, composite compound containing Mg, converted to Mg.

 : Coating weight of P 2 O 5 component (γ)=Coating weight of phosphoric acid and/or phosphoric acid compound, converted to P 2 O 5 .

 : Total coating weight=(α)+(β)+(γ).

*5: Molar ratio of Mg component (β) as Mg to SiO 2 fine particles (α) as SiO 2 .

*6: Molar ratio of P 2 O 5 component (γ) as P 2 O 5 to Mg component (β) as Mg.

*7: Blending ratio (weight parts) of solid portion of ion-exchanged silica to 100 parts by weight of solid portion of resin composition.

*8: Corresponding to No. given in Table 19.

*9: Blending ratio (weight parts) of solid portion of fine particle silica to 100 parts by weight of solid portion of resin composition.

*10: Blending ratio (weight parts) of solid portion of the sum of ion-exchanged silica (a) and fine particle silica (b) to 100 parts by weight of solid portion of resin composition.

*11: Weight ratio of solid portion of ion-exchanged silica (a) to fine particle silica (b).

*12: Corresponding to No. given in Table 20.

*13: Blending ratio (weight parts) of solid portion of solid lubricant to 100 parts by weight of solid portion of resin composition.

As the conventional reaction type chromate steel sheet treatment liquid, a solution containing 30 g/l of anhydrous chromic acid, 10 g/l of phosphoric acid, 0.5 g/l of NaF, and 4 g/l of K 2 TiF 6 was used. After spray treatment at a bath temperature of 40° C., the steel sheet was washed with water and was dried, thus a chromated steel sheet having a chromium coating weight of 20 mg/m 2 as metallic chromium as prepared. Thus obtained steel sheet was subjected to the salt spray test under the same condition that applied to Examples, and the plate generated white-rust within about 24 hours. Consequently, the results of Examples show that the organic coating steel sheets according to the present invention provide remarkably superior corrosion resistance to the conventional type chromate treated steel sheets.

TABLE 1
		Coating
		weight
No.	Kind	(g/m 2 )
1	Electrolytically galvanized steel sheet	20
2	Hot dip galvanized steel sheet	60
3	Alloyed hot dip galvanized steel sheet (Fe: 10 wt. %)	60
4	Zn—Ni alloy plating steel sheet (Ni: 12 wt. %)	20
5	Zn—Co alloy plating steel plat (Co: 0.5 wt. %)	20
6	Zn—Cr alloy plating steel sheet (Cr: 12 wt. %)	20
7	Hot dip Zn—Al alloy plating steel sheet (Al: 55 wt. %)	90
8	Hot dip Zn-5 wt. % Al-0.5 wt. % Mg alloy plating	90
	steel sheet
9	Electrolytically Zn-SiO2 composite plating steel sheet	20
10	Hot dip aluminized steel sheet (Al-6 wt. % Si	60
	alloy plating)
11	Electrolytically Al—Mn alloy plating steel sheet	40
	(Mn: 30 wt. %)
12	Electrolytically aluminized steel sheet	40
13	Hot dip Zn—Mg alloy plating steel sheet	150
	(Mg: 0.5 wt. %)

 

TABLE 2
[Composition for Primary Layer Coating]
	Oxide fine particles (aa)		Phosphoric acid,	Organic resin
	Particle		Alkali earth metal (ab)	phosphoric acid compound (ac)		Concen-
			size	Concentration		Concentration		Concentration		tration
No.	Type	Trade name	(nm)	(M/L)	Type	(M/L)	Type	(M/L) *1	Type	(g/l)
1	Colloidal	Nissan Chemical	12 to 14	0.11	Mg 2−	0.20	Orthophosphoric	0.42	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-O
2	Colloidal	Nissan Chemical	12 to 14	0.18	Mg 2+	0.17	Orthophosphoric	0.36	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-O
3	Colloidal	Nissan Chemical	12 to 14	0.40	Mg 2+	0.40	Orthophosphoric	0.80	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-O
4	Colloidal	Nissan Chemical	8 to 10	0.18	Mg 2+	0.17	Orthophosphoric	0.36	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
5	Colloidal	Nissan Chemical	6 to 8	0.11	Mg 2−	0.20	Orthophosphoric	0.42	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OXS
6	Alumina	Nissan Chemical	&Asteriskpseud;	0.20	Mg 2+	0.30	Orthophosphoric	0.60	—	—
	sol	Industries, Ltd.					acid
		SNOWTEX-OS
7	Zirconia	Nissan Chemical	60 to 70	0.40	Mg 2+	0.40	Orthophosphoric	0.80	—	—
	sol	Industries, Ltd.					acid
		NZS-30A
8	Colloidal	Nissan Chemical	12 to 14	0.30	Mg 2+	0.10	Orthophosphoric	0.20	Acrylic-	180
	silica	Industries, Ltd.					acid		ethylene
		SNOWTEX-O							base water-
									dispersible
									resin
*1 Converted to P 2 O 5
&Asteriskpseud; feather-shape particle (10 nm × 100 nm)

 

TABLE 3
				Adaptability to the
	Molar Ratio	Molar Ratio	pH of	condition of the
No.	(ab)/(aa)	(ac)/(ab)	composition	invention* 2
1	1.82	2.10	3.1	◯
2	0.94	2.12	3.1	◯
3	1.00	2.00	2.7	◯
4	0.94	2.12	3.1	◯
5	1.82	2.10	3.0	◯
6	1.50	2.00	3.5	◯
7	1.00	2.00	3.2	◯
8	0.33	2.00	2.5	◯
* 2 ◯: Satisfies the conditions of the invention
X: Dissatisfies the condition of the invention

 

TABLE 4
[Composition for Primary Layer Coating]
	Oxide fine particles (aa)		Phosphoric acid,	Organic resin
	Particle		Alkali earth metal (ab)	phosphoric acid compound (ac)		Concen-
			size	Concentration		Concentration		Concentration		tration
No.	Type	Trade name	(nm)	(M/L)	Type	(M/L)	Type	(M/L) *1	Type	(g/l)
9	Colloidal	Nissan Chemical	12 to 14	0.20	Ca 2+	0.20	Orthophosphoric	0.40	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-O
10	Colloidal	Nissan Chemical	12 to 14	0.10	Sr 2+	0.10	Orthophosphoric	0.20	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-O
11	Colloidal	Nissan Chemical	12 to 14	0.05	Ba 2+	0.10	Orthophosphoric	0.20	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-O
12	—	—	—	—	Mg 2+	0.30	Orthophosphoric	0.60	—	—
							acid
13	Colloidal	Nissan Chemical	12 to 14	0.40	—	—	Orthophosphoric	0.30	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-O
14	Colloidal	Nissan Chemical	12 to 14	0.40	Mg 2+	0.20	—	—	—	—
	silica	Industries, Ltd.
		SNOWTEX-O
15	Lithium	Nissan Chemical	—	1.00	—	—	—	—	—	—
	silicate	Industries, Ltd.
		LSS-35
*1 Converted to P 2 O 5

 

TABLE 5
				Adaptability to the
	Molar Ratio	Molar Ratio	pH of	condition of the
No.	(ab)/(aa)	(ac)/(ab)	composition	invention* 2
9	1.00	2.00	3.0	◯
10	1.00	2.00	3.1	◯
11	2.00	2.00	3.2	◯
12	—	2.00	2.8	X
13	—	—	3.0	X
14	0.50	—	2.1	X
15	—	—	11	X
* 2 ◯: Satisfies the conditions of the invention
X: Dissatisfies the condition of the invention

 

TABLE 6
[Composition for Primary Layer Coating]
	Oxide fine particles (aa)		Phosphoric acid,	Organic resin
	Particle		Alkali earth metal (ab)	phosphoric acid compound (ac)		Concen-
			size	Concentration		Concentration		Concentration		tration
No.	Type	Trade name	(nm)	(M/L)	Type	(M/L)	Type	(M/L) *1	Type	(g/l)
16	Colloidal	Nissan Chemical	8 to 10	0.2	Mg 2+	0.4	Orthophosphoric	0.46	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
17	Colloidal	Nissan Chemical	8 to 10	0.1	Mg 2−	0.2	Orthophosphoric	0.23	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
18	Colloidal	Nissan Chemical	8 to 10	0.3	Mg 2+	0.3	Orthophosphoric	0.31	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
19	Colloidal	Nissan Chemical	8 to 10	0.15	Mg 2+	0.2	Orthophosphoric	0.4	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
20	Colloidal	Nissan Chemical	8 to 10	0.3	Mg 2+	0.35	Orthophosphoric	0.4	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
21	Alumina	Nissan Chemical	8 to 10	0.1	Mg 2−	0.5	Orthophosphoric	0.5	—	—
	sol	Industries, Ltd.					acid
		SNOWTEX-OS
22	Zirconia	Nissan Chemical	8 to 10	0.3	Mg 2−	0.15	Orthophosphoric	0.16	—	—
	sol	Industries, Ltd.					acid
		SNOWTEX-OS
23	Colloidal	Nissan Chemical	8 to 10	0.3	Mg 2+	0.4	Orthophosphoric	0.2	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
*1 Converted to P 2 O 5

 

TABLE 7
				Adaptability to the
	Molar Ratio	Molar Ratio	pH of	condition of the
No.	(ab)/(aa)	(ac)/(ab)	composition	invention* 2
16	2.00	1.2	2.7	◯
17	2.00	1.2	2.8	◯
18	1.00	1.0	3.0	◯
19	1.33	2.0	1.9	◯
20	1.17	1.1	2.8	◯
21	5.00	1.0	3.1	◯
22	0.50	1.1	3.3	◯
23	1.33	0.5	3.0	◯
* 2 ◯: Satisfies the conditions of the invention
X: Dissatisfies the condition of the invention

 

TABLE 8
[Composition for Primary Layer Coating]
	Oxide fine particles (aa)		Phosphoric acid,	Organic resin
	Particle		Alkali earth metal (ab)	phosphoric acid compound (ac)		Concen-
			size	Concentration		Concentration		Concentration		tration
No.	Type	Trade name	(nm)	(M/L)	Type	(M/L)	Type	(M/L) *1	Type	(g/l)
24	Colloidal	Nissan Chemical	6 to 8	0.2	Mg 2+	0.4	Orthophosphoric	0.4	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OXS
25	Colloidal	Nissan Chemical	6 to 8	0.2	Mg 2−	0.4	Orthophosphoric	0.4	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OXS
26	Colloidal	Nissan Chemical	12 to 14	0.2	Mg 2+	0.4	Orthophosphoric	0.4	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-O
27	Colloidal	Nissan Chemical	8 to 10	0.5	Mg 2+	0.05	Orthophosphoric	0.1	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
28	Colloidal	Nissan Chemical	8 to 10	0.05	Mg 2−	0.5	Orthophosphoric	0.6	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
29	Colloidal	Nissan Chemical	8 to 10	0.2	Mg 2+	0.3	Orthophosphoric	0.03	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
30	Colloidal	Nissan Chemical	8 to 10	0.1	Mg 2+	0.1	Orthophosphoric	1.0	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
31	Colloidal	Nissan Chemical	8 to 10	0.04	Mg 2−	0.3	Orthophosphoric	0.32	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
*1 Converted to P 2 O 5

 

TABLE 9
				Adaptability to the
	Molar Ratio	Molar Ratio	pH of	condition of the
No.	(ab)/(aa)	(ac)/(ab)	composition	invention* 2
24	2.00	1.0	2.9	◯
24	2.00	1.0	2.9	◯
25	2.00	1.0	2.9	◯
26	2.00	1.0	2.9	◯
27	0.10	2.0	2.5	◯
28	10.00	1.2	1.8	◯
29	1.50	0.1	3.0	◯
30	1.00	10.0	1.5	◯
31	7.50	1.1	2.6	◯
* 2 ◯: Satisfies the conditions of the invention
X: Dissatisfies the condition of the invention

 

TABLE 10
[Composition for Primary Layer Coating]
	Oxide fine particles (aa)		Phosphoric acid,	Organic resin
	Particle		Alkali earth metal (ab)	phosphoric acid compound (ac)		Concen-
			size	Concentration		Concentration		Concentration		tration
No.	Type	Trade name	(nm)	(M/L)	Type	(M/L)	Type	(M/L) *1	Type	(g/l)
32	Colloidal	Nissan Chemical	8 to 10	0.01	Mg 2+	0.5	Orthophosphoric	0.51	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
33	Colloidal	Nissan Chemical	8 to 10	0.5	Mg 2+	0.01	Orthophosphoric	0.3	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
34	Colloidal	Nissan Chemical	8 to 10	1.0	Mg 2+	0.01	Orthophosphoric	0.5	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
35	Colloidal	Nissan Chemical	8 to 10	0.02	Mg 2−	2.0	Orthophosphoric	0.5	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
36	Colloidal	Nissan Chemical	8 to 10	0.01	Mg 2+	2.0	Orthophosphoric	0.5	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
37	Colloidal	Nissan Chemical	8 to 10	2.0	Mg 2+	0.01	Orthophosphoric	0.5	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
38	Colloidal	Nissan Chemical	8 to 10	2.0	Mg 2+	0.01	Orthophosphoric	2.5	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
39	Colloidal	Nissan Chemical	8 to 10	0.02	Mg 2+	2.5	Orthophosphoric	0.01	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
*1 Converted to P 2 O 5

 

TABLE 11
				Adaptability to the
	Molar Ratio	Molar Ratio	pH of	condition of the
No.	(ab)/(aa)	(ac)/(ab)	composition	invention* 2
32	50	1.0	2.0	◯
33	0.02	30.0	2.5	◯
34	0.01	50.0	2.2	◯
35	100	0.3	2.0	◯
36	200	0.3	1.9	◯
37	0.005	50.0	2.1	◯
38	0.005	250.0	1.6	◯
39	125	0.004	2.5	◯
* 2 ◯: Satisfies the conditions of the invention
X: Dissatisfies the condition of the invention

 

TABLE 12
[Composition for Primary Layer Coating]
	Oxide fine particles (aa)		Phosphoric acid,	Organic resin
	Particle		Alkali earth metal (ab)	phosphoric acid compound (ac)		Concen-
			size	Concentration		Concentration		Concentration		tration
No.	Type	Trade name	(nm)	(M/L)	Type	(M/L)	Type	(M/L) *1	Type	(g/l)
40	Colloidal	Nissan Chemical	8 to 10	0.001	Mg 2+	2.0	Orthophosphoric	0.5	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
41	Colloidal	Nissan Chemical	8 to 10	0.002	Mg 2+	3.0	Orthophosphoric	0.5	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
42	Colloidal	Nissan Chemical	8 to 10	2.5	Mg 2+	0.02	Orthophosphoric	0.5	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
43	Colloidal	Nissan Chemical	8 to 10	3.0	Mg 2+	0.05	Orthophosphoric	0.3	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
44	Colloidal	Nissan Chemical	8 to 10	0.5	Mg 2+	0.001	Orthophosphoric	0.6	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
45	Colloidal	Nissan Chemical	8 to 10	0.2	Mg 2+	0.6	Orthophosphoric	0.001	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
46	Colloidal	Nissan Chemical	8 to 10	0.5	Mg 2+	2.0	Orthophosphoric	4.0	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
47	Colloidal	Nissan Chemical	8 to 10	0.001	Mg 2+	3.0	Orthophosphoric	6.0	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
*1 Converted to P 2 O 5

 

TABLE 13
				Adaptability to the
	Molar Ratio	Molar Ratio	pH of	condition of the
No.	(ab)/(aa)	(ac)/(ab)	composition	invention* 2
40	2000	0.3	1.9	◯
41	1500	0.2	1.9	◯
42	0.008	25.0	2.0	◯
43	0.017	6.0	2.2	◯
44	0.002	600.0	1.9	◯
45	3	0.002	3.2	◯
46	4	2.0	0.51	◯
47	3000	2.0	0.5	◯
* 2 ◯: Satisfies the conditions of the invention
X: Dissatisfies the condition of the invention

 

TABLE 14
[Composition for Primary Layer Coating]
	Oxide fine particles (aa)		Phosphoric acid,	Organic resin
	Particle		Alkali earth metal (ab)	phosphoric acid compound (ac)		Concen-
			size	Concentration		Concentration		Concentration		tration
No.	Type	Trade name	(nm)	(M/L)	Type	(M/L)	Type	(M/L) *1	Type	(g/l)
48	Colloidal	Nissan Chemical	8 to 10	0.001	Mg 2+	0.02	Orthophosphoric	0.02	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
49	Colloidal	Nissan Chemical	8 to 10	0.05	Mg 2+	0.1	Orthophosphoric	0.1	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
50	Colloidal	Nissan Chemical	8 to 10	2.0	Mg 2−	3.0	Orthophosphoric	4.2	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
51	Colloidal	Nissan Chemical	8 to 10	0.3	Mg 2+	0.001	Orthophosphoric	0.2	Acrylic-	180
	silica	Industries, Ltd.					acid		ethylene
		SNOWTEX-OS							base water-
									dispersible
									resin
52	Colloidal	Nissan Chemical	8 to 10	0.3	Mg 2+	0.4	Orthophosphoric	0.42	Acrylic-	180
	silica	Industries, Ltd.					acid		ethylene
		SNOWTEX-OS							base water-
									dispersible
									resin
53	Colloidal	Nissan Chemical	8 to 10	0.3	Mg 2−	0.02	Orthophosphoric	0.2	Acrylic-	180
	silica	Industries, Ltd.					acid		ethylene
		SNOWTEX-OS							base water-
									dispersible
									resin
*1 Converted to P 2 O 5

 

TABLE 15
				Adaptability to the
	Molar Ratio	Molar Ratio	pH of	condition of the
No.	(ab)/(aa)	(ac)/(ab)	composition	invention* 2
48	2	1.0	4.0	◯
49	2	1.0	3.3	◯
50	1.5	1.4	0.8	◯
51	0.003	200	2.5	◯
52	1.3	1.1	2.2	◯
53	0.1	10	2.5	◯
* 2 ◯: Satisfies the conditions of the invention
X: Dissatisfies the condition of the invention

 

TABLE 16
[Composition for Primary Layer Coating]
	Oxide fine particles (aa)		Phosphoric acid,	Organic resin
	Particle		Alkali earth metal (ab)	phosphoric acid compound (ac)		Concen-
			size	Concentration		Concentration		Concentration		tration
No.	Type	Trade name	(nm)	(M/L)	Type	(M/L)	Type	(M/L) *1	Type	(g/l)
54	Colloidal	Nissan Chemical	8 to 10	3.2	Mg 2−	0.1	Orthophosphoric	0.3	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
55	—	—	—	—	Mg 2+	0.5	Orthophosphoric	2.0	—	—
							acid
56	Colloidal	Nissan Chemical	8 to 10	0.2	Mg 2+	4.0	Orthophosphoric	0.5	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
57	Colloidal	Nissan Chemical	8 to 10	3.0	Mg 2+	—	Orthophosphoric	0.5	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
58	Colloidal	Nissan Chemical	8 to 10	0.02	Mg 2+	3.0	Orthophosphoric	6.5	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
59	Colloidal	Nissan Chemical	8 to 10	0.5	Mg 2+	0.2	Orthophosphoric	—	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
60	Colloidal	Nissan Chemical	8 to 10	0.001	Mg 2+	0.02	Orthophosphoric	0.001	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
61	Colloidal	Nissan Chemical	8 to 10	0.5	Mg 2+	3.0	Orthophosphoric	6.0	—	—
	silica	Industries, Ltd.					acid
		SNOWTEX-OS
*1 Converted to P 2 O 5

 

TABLE 17
				Adaptability to the
	Molar Ratio	Molar Ratio	pH of	condition of the
No.	(ab)/(aa)	(ac)/(ab)	composition	invention* 2
54	0.03	3.0	3.5	X
55	—	4.0	1.5	X
56	20	0.1	2.0	X
57	—	—	2.2	X
58	150	2.2	0.4	X
59	0.4	—	2.2	X
60	20	0.1	5.2	X
61	6	2.0	0.4	X
* 2 ◯: Satisfies the conditions of the invention
X: Dissatisfies the condition of the invention

 

TABLE 18
[Resin Composition of Secondary Layer Coating]
	Base resin	Curing agent		Adaptability to the
No.	Type *1	Blending rate	Type *2	Blending rate	Catalyst	conditions of the invention
1	(1)	100 parts	A	5 parts	Dibutyltin dilaurate (0.2 part)	Satisfies
2	(1)	100 parts	B	25 parts	Dibutyltin dilaurate (1.0 part)	Satisfies
3	(1)	100 parts	C	25 parts	—	Satisfies
4	(2)	100 parts	A	50 parts	Dibutyltin dilaurate (2.0 part)	Satisfies
5	(2)	100 parts	B	50 parts	Dibutyltin dilaurate (3.0 part)	Satisfies
6	(2)	100 parts	C	80 parts	Dibutyltin dilaurate (4.0 part)	Satisfies
7	(3)	100 parts	A	25 parts	Cobalt naphthenate (1.0 part)	Satisfies
8	(3)	100 parts	B	10 parts	Tin (II) chloride (1.0 part)	Satisfies
9	(3)	100 parts	C	50 parts	N-ethylmorpholine (1.0 part)	Satisfies
10	(1)	100 parts	D	25 parts	—	Satisfies
11	(3)	100 parts	D	30 parts	—	Satisfies
12	(4)	100 parts	B	25 parts	Dibutyltin dilaurate (0.2 part)	Dissatisfies
13	Aqueous solution of a hydrazine derivative (aqueous solution of 5 wt. %	Dissatisfies
	3,5-dimethylpyrazole)
14	Mixture of an epoxyamine additive and a hydrazine derivative (3 parts by weight	Dissatisfies
	of 3,5-dimethylpyrazole is added to 100 parts by weight of base resin in the
	composition No. 12, followed by agitating the mixture.)
*1 The resin compositions (1) through (4) which were synthesized in Synthesis Examples 1 through 4 described in the body of this specification.
*2 A An MEK oxime block body of IPDI, “TAKENATE B-870N” produced by Takeda Chemical Industries, Ltd.
B Isocyanurate type: “DESMODUR BL-3175” produced by Bayer A. G.
C An MEK oxime block body of HMDI, “DURANATE MF-B80M” produced by Asahi Chemical Industry Co., Ltd.
D A melamine resin of imino-base: “CYMEL 325” produced by Mitsui Cytech Co., Ltd.

 

TABLE 19
No.	Type	Trade name
1	Dry silica	“AEROSIL R972” produced by Japan Aerosil
		Co., Ltd.
2	Dry silica	“AEROSIL R812” produced by Japan Aerosil
		Co., Ltd.
3	Dry silica	“AEROSIL R805” produced by Japan Aerosil
		Co., Ltd.
4	Dry silica	“AEROSIL R974” produced by Japan Aerosil
		Co., Ltd.
5	Dry silica	“AEROSIL R811” produced by Japan Aerosil
		Co., Ltd.
6	Dry silica	“AEROSIL RX200” produced by Japan Aerosil
		Co., Ltd.
7	Dry silica	“AEROSIL 130” produced by Japan Aerosil
		Co., Ltd.
8	Dry silica	“AEROSIL 200” produced by Japan Aerosil
		Co., Ltd.
9	Dry silica	“AEROSIL 300” produced by Japan Aerosil
		Co., Ltd.
10	Colloidal silica	“ORGANOSILCASOL EG-ST” (containing 20%
		solid matter), produced by Nissan Chemical
		Industries, Ltd.
11	Colloidal silica	“OSCAL 1632” (containing 30% solid matter),
		produced by Catalysts & Chemicals Industries
		Co., Ltd.

 

TABLE 20
No.	Type	Trade name
1	Polyethylene wax	“LUVAX1151” produced by
		Nippon Seiro Co., Ltd.
2	Polyethylene wax	“3620” produced by Sheridust Co.,
		Ltd.
3	Polyethylene wax	“CHEMIPEARL W-100” produced
		by Mitsui Petrochemical Industries,
		Ltd.
4	Polytetrafluoroethylene	“MP1100”, produced by
	resin	Du Pont-Mitsui Company, Ltd.
5	Polytetrafluoroethylene	“L-2”, produced by Daikin
	resin	Industries, Ltd.
6	Mixture of No. 1 and No. 4
	(blend ratio of 1:1)	—

 

	TABLE 21
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5
		Coating	Drying	Coating	coating	particles	component	component
	Plating steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )
1	1	1	140	0.3	366	34	25	307
2	1	1	140	0.3	366	34	25	307
3	1	1	140	0.3	366	34	25	307
4	1	1	140	0.3	366	34	25	307
5	1	1	140	0.3	366	34	25	307
6	1	1	140	0.3	366	34	25	307
7	1	1	140	0.3	366	34	25	307
8	1	1	140	0.3	366	34	25	307
9	1	1	140	0.3	366	34	25	307
10	1	1	140	0.3	366	34	25	307
11	1	1	140	0.3	366	34	25	307
12	1	1	140	0.3	366	34	25	307
13	1	1	140	0.3	366	34	25	307
14	1	1	140	0.3	366	34	25	307
	Primary layer coating
	Molar ratio of	Secondary layer coating
	coating components	Resin	Drying	Coating
		Mg/SiO 2	P 2 O 5 /Mg	composition	temperature	thickness
	No.	*5	*6	*3	(° C.)	(μm)	Classification
	1	1.82	2.1	1	230	1	Example
	2	1.82	2.1	2	230	1	Example
	3	1.82	2.1	3	230	1	Example
	4	1.82	2.1	4	230	1	Example
	5	1.82	2.1	5	230	1	Example
	6	1.82	2.1	6	230	1	Example
	7	1.82	2.1	7	230	1	Example
	8	1.82	2.1	8	230	1	Example
	9	1.82	2.1	9	230	1	Example
	10	1.82	2.1	10	230	1	Example
	11	1.82	2.1	11	230	1	Example
	12	1.82	2.1	12	230	1	Comparative
							example
	13	1.82	2.1	13	230	1	Comparative
							example
	14	1.82	2.1	14	230	1	Comparative
							example

 

	TABLE 22
	Performance
			White-rust
			resistance after
		White-rust resistance:	alkaline degreasing:	Paint
No.	Appearance	SST 96 hrs	SST 96 hrs	adhesiveness	Classification
1	◯	⊚	⊚	⊚	Example
2	◯	⊚	⊚	⊚	Example
3	◯	⊚	⊚	⊚	Example
4	◯	⊚	⊚	⊚	Example
5	◯	⊚	⊚	⊚	Example
6	◯	⊚	⊚	⊚	Example
7	◯	⊚	⊚	⊚	Example
8	◯	⊚	⊚	⊚	Example
9	◯	⊚	⊚	⊚	Example
10	◯	⊚	⊚	⊚	Example
11	◯	⊚	⊚	⊚	Example
12	◯	◯−	Δ	⊚	Comparative
					example
13	◯	X	X	X	Comparative
					example
14	◯	◯−	Δ	⊚	Comparative
					example

 

	TABLE 23
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5
		Coating	Drying	Coating	coating	particles	component	component
	Plating steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )
15	1	2	140	0.3	400	66	25	310
16	1	3	140	0.3	303	49	20	234
17	1	4	140	0.3	320	53	20	248
18	1	5	140	0.3	293	27	20	245
19	1	6	140	0.3	317	(Al 2 O 3 )	25	292
20	1	7	140	0.3	317	(ZrO 2 )	25	292
21	1	8	140	0.3	403	150	20	234
22	1	9	140	0.3	320	95	(Ca)	225
23	1	10	140	0.3	320	90	(Sr)	230
24	1	11	140	0.3	329	89	(Ba)	240
25	1	12	140	0.3	320	—	40	280
26	1	13	140	0.3	300	50	—	250
27	1	14	140	0.3	416	346	70	0
28	1	15	140	0.3	500	—	—	0
	Primary layer coating
	Molar ratio of	Secondary layer coating
	coating components	Resin	Drying	Coating
		Mg/SiO 2	P 2 O 5 /Mg	composition	temperature	thickness
	No.	*5	*6	*3	(° C.)	(μm)	Classification
	15	0.94	2.12	1	230	1	Example
	16	1	2	1	230	1	Example
	17	0.94	2.12	1	230	1	Example
	18	1.82	2.1	1	230	1	Example
	19	1.5	2	1	230	1	Example
	20	1	2	1	230	1	Example
	21	0.33	2	1	230	1	Example
	22	—	—	1	230	1	Example
	23	—	—	1	230	1	Example
	24	2	8	1	230	1	Example
	25	—	1.2	1	230	1	Comparative
							example
	26	—	—	1	230	1	Comparative
							example
	27	0.5	—	1	230	1	Comparative
							example
	28	—	—	1	230	1	Comparative
							example

 

	TABLE 24
	Performance
			White-rust	Paint
	Ap-	White-rust	resistance after	adhe-
	pear-	resistance:	alkaline degreasing:	sive-
No.	ance	SST 96 hrs	SST 96 hrs	ness	Classification
15	◯	⊚	⊚	⊚	Example
16	◯	⊚	⊚	⊚	Example
17	◯	⊚	⊚	⊚	Example
18	◯	⊚	⊚	⊚	Example
19	◯	◯	◯	⊚	Example
20	◯	◯	◯	⊚	Example
21	◯	⊚	⊚	⊚	Example
22	◯	◯+	◯+	⊚	Example
23	◯	◯	◯	⊚	Example
24	◯	◯	◯	⊚	Example
25	◯	Δ	Δ	⊚	Comparative
					example
26	◯	Δ	Δ	⊚	Comparative
					example
27	◯	Δ	Δ	⊚	Comparative
					example
28	◯	X	Δ	⊚	Comparative
					example

 

	TABLE 25
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5
		Coating	Drying	Coating	coating	particles	component	component
	Plating steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )
29	1	1	140	0.3	366	34	25	307
30	1	1	140	0.3	366	34	25	307
31	1	1	140	0.3	366	34	25	307
32	1	1	140	0.3	366	34	25	307
33	1	1	140	0.3	366	34	25	307
34	1	1	140	0.3	366	34	25	307
35	1	1	140	0.3	366	34	25	307
36	1	1	140	0.3	366	34	25	307
37	1	1	140	0.3	366	34	25	307
38	1	1	140	0.3	366	34	25	307
39	1	1	140	0.3	366	34	25	307
	Secondary layer coating
	Primary layer coating		Fine particles
	Molar ratio of		silica (b)
	coating components	Resin		Blending	Drying	Coating
		Mg/SiO 2	P 2 O 5 /Mg	composition	Type	rate	temperature	thickness
	No.	*5	*6	*3	*8	*9	(° C.)	(μm)	Classification
	29	1.82	2.1	1	1	10	230	1	Example
	30	1.82	2.1	1	2	10	230	1	Example
	31	1.82	2.1	1	3	10	230	1	Example
	32	1.82	2.1	1	4	10	230	1	Example
	33	1.82	2.1	1	5	10	230	1	Example
	34	1.82	2.1	1	6	10	230	1	Example
	35	1.82	2.1	1	7	10	230	1	Example
	36	1.82	2.1	1	8	10	230	1	Example
	37	1.82	2.1	1	9	10	230	1	Example
	38	1.82	2.1	1	10	10	230	1	Example
	39	1.82	2.1	1	11	10	230	1	Example

 

	TABLE 26
	Performance
			White-rust	Paint
	Ap-	White-rust	resistance after	adhe-
	pear-	resistance:	alkaline degreasing:	sive-
No.	ance	SST 96 hrs	SST 96 hrs	ness	Classification
29	◯	⊚	⊚	⊚	Example
30	◯	⊚	⊚	⊚	Example
31	◯	⊚	⊚	⊚	Example
32	◯	⊚	⊚	⊚	Example
33	◯	⊚	⊚	⊚	Example
34	◯	⊚	⊚	⊚	Example
35	◯	⊚	⊚	⊚	Example
36	◯	⊚	⊚	⊚	Example
37	◯	⊚	⊚	⊚	Example
38	◯	⊚	⊚	⊚	Example
39	◯	⊚	⊚	⊚	Example

 

	TABLE 27
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5
		Coating	Drying	Coating	coating	particles	component	component
	Plating steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )
40	1	1	140	0.3	366	34	25	307
41	1	1	140	0.3	366	34	25	307
42	1	1	140	0.3	366	34	25	307
43	1	1	140	0.3	366	34	25	307
44	1	1	140	0.3	366	34	25	307
45	1	1	140	0.3	366	34	25	307
46	1	1	140	0.3	366	34	25	307
47	1	1	140	0.3	366	34	25	307
48	1	1	140	0.3	366	34	25	307
49	1	1	140	0.3	366	34	25	307
50	1	1	140	0.3	366	34	25	307
	Secondary layer coating
	Primary layer coating		Fine particles
	Molar ratio of		silica (b)
	coating components	Resin		Blending	Drying	Coating
		Mg/SiO 2	P 2 O 5 /Mg	composition	Type	rate	temperature	thickness
	No.	*5	*6	*3	*8	*9	(° C.)	(μm)	Classification
	40	1.82	2.1	1	—	—	230	1	Example
	41	1.82	2.1	1	1	1	230	1	Example
	42	1.82	2.1	1	1	5	230	1	Example
	43	1.82	2.1	1	1	10	230	1	Example
	44	1.82	2.1	1	1	20	230	1	Example
	45	1.82	2.1	1	1	30	230	1	Example
	46	1.82	2.1	1	1	40	230	1	Example
	47	1.82	2.1	1	1	50	230	1	Example
	48	1.82	2.1	1	1	80	230	1	Example
	49	1.82	2.1	1	1	100	230	1	Example
	50	1.82	2.1	1	1	150	230	1	Comparative
									example

 

	TABLE 28
	Performance
			White-rust	Paint
	Ap-	White-rust	resistance after	adhe-
	pear-	resistance:	alkaline degreasing:	sive-
No.	ance	SST 96 hrs	SST 96 hrs	ness	Classification
40	◯	◯−	◯−	⊚	Example
41	◯	◯	◯	⊚	Example
42	◯	◯+	◯+	⊚	Example
43	◯	⊚	⊚	⊚	Example
44	◯	⊚	⊚	⊚	Example
45	◯	⊚	⊚	⊚	Example
46	◯	⊚	⊚	⊚	Example
47	◯	◯+	◯+	⊚	Example
48	◯	◯	◯	⊚	Example
49	◯	◯−	◯−	⊚	Example
50	◯	Δ	Δ	⊚	Comparative
					example

 

	TABLE 29
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5
		Coating	Drying	Coating	coating	particles	component	component
	Plating steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )
51	2	1	140	0.3	366	34	25	307
52	3	1	140	0.3	366	34	25	307
53	4	1	140	0.3	366	34	25	307
54	5	1	140	0.3	366	34	25	307
55	6	1	140	0.3	366	34	25	307
56	7	1	140	0.3	366	34	25	307
57	8	1	140	0.3	366	34	25	307
58	9	1	140	0.3	366	34	25	307
59	10	1	140	0.3	366	34	25	307
60	11	1	140	0.3	366	34	25	307
61	12	1	140	0.3	366	34	25	307
62	13	1	140	0.3	366	34	25	307
	Secondary layer coating
	Primary layer coating		Fine particles
	Molar ratio of		silica (b)
	coating components	Resin		Blending	Drying	Coating
		Mg/SiO 2	P 2 O 5 /Mg	composition	Type	rate	temperature	thickness
	No.	*5	*6	*3	*8	*9	(° C.)	(μm)	Classification
	51	1.82	2.1	1	1	10	230	1	Example
	52	1.82	2.1	1	1	10	230	1	Example
	53	1.82	2.1	1	1	10	230	1	Example
	54	1.82	2.1	1	1	10	230	1	Example
	55	1.82	2.1	1	1	10	230	1	Example
	56	1.82	2.1	1	1	10	230	1	Example
	57	1.82	2.1	1	1	10	230	1	Example
	58	1.82	2.1	1	1	10	230	1	Example
	59	1.82	2.1	1	1	10	230	1	Example
	60	1.82	2.1	1	1	10	230	1	Example
	61	1.82	2.1	1	1	10	230	1	Example
	62	1.82	2.1	1	1	10	230	1	Example

 

	TABLE 30
	Performance
			White-rust
			resistance after
		White-rust resistance:	alkaline degreasing:	Paint
No.	Appearance	SST 120 hrs	SST 120 hrs	adhesiveness	Workability	Classification
51	◯	⊚	⊚	⊚	⊚	Example
52	◯	⊚	⊚	⊚	⊚	Example
53	◯	⊚	⊚	⊚	⊚	Example
54	◯	⊚	⊚	⊚	⊚	Example
55	◯	⊚	⊚	⊚	⊚	Example
56	◯	⊚	⊚	⊚	⊚	Example
57	◯	⊚	⊚	⊚	⊚	Example
58	◯	⊚	⊚	⊚	⊚	Example
59	◯	⊚	⊚	⊚	⊚	Example
60	◯	⊚	⊚	⊚	⊚	Example
61	◯	⊚	⊚	⊚	⊚	Example
62	◯	⊚	⊚	⊚	⊚	Example

 

	TABLE 31
	Primary layer coating
	Coating weight *4
	Plating				Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	steel	Coating	Drying	Coating	coating	particles	component	component	components
	plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6
63	1	1	140	0.3	366	34	25	307	1.82	2.1
64	1	1	140	0.3	366	34	25	307	1.82	2.1
65	1	1	140	0.3	366	34	25	307	1.82	2.1
66	1	1	140	0.3	366	34	25	307	1.82	2.1
67	1	1	140	0.3	366	34	25	307	l.82	2.1
68	1	1	140	0.3	366	34	25	307	1.82	2.1
69	1	1	140	0.3	366	34	25	307	1.82	2.1
70	1	1	140	0.3	366	34	25	307	1.82	2.1
71	1	1	140	0.3	366	34	25	307	1.82	2.1
72	1	1	140	0.3	366	34	25	307	1.82	2.1
	Secondary layer coating
		Fine particles
	Resin	silica (b)	Drying	Coating
		composition	Type	Blending	temperature	thickness
	No.	*3	*8	rate *9	(° C.)	(μm)	Classification
	63	1	1	10	230	0.01	Comparative
							example
	64	1	1	10	230	0.1	Example
	65	1	1	10	230	0.5	Example
	66	1	1	10	230	1	Example
	67	1	1	10	230	2	Example
	68	1	1	10	230	2.5	Example
	69	1	1	10	230	3	Example
	70	1	1	10	230	4	Example
	71	1	1	10	230	5	Example
	72	1	1	10	230	20	Comparative
							example

 

	TABLE 32
	Performance
			White-rust
			resistance	Paint
		White-rust	after alkaline	ad-
	Appear-	resistance:	degreasing:	hesive-
No.	ance	SST 120 hrs	SST 120 hrs	ness	Classification
63	∘	x	x	⊚	Comparative
					example
64	∘	∘−	∘−	⊚	Example
65	∘	∘	∘	⊚	Example
66	∘	⊚	⊚	⊚	Example
67	∘	⊚	⊚	⊚	Example
68	∘	⊚	⊚	⊚	Example
69	∘	⊚	⊚	⊚	Example
70	∘	⊚	⊚	⊚	Example
71	∘	⊚	⊚	⊚	Example
72	∘	⊚	⊚	⊚	Comparative&Asteriskpseud;1
					example
&Asteriskpseud;1 Unable to weld

 

	TABLE 33
	Primary layer coating
	Coating weight *4
	Plating				Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	steel	Coating	Drying	Coating	coating	particles	component	component	components
	plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6
73	1	1	140	0.3	366	34	25	307	1.82	2.1
74	1	1	140	0.3	366	34	25	307	1.82	2.1
75	1	1	140	0.3	366	34	25	307	1.82	2.1
76	1	1	140	0.3	366	34	25	307	1.82	2.1
77	1	1	140	0.3	366	34	25	307	1.82	2.1
78	1	1	140	0.3	366	34	25	307	1.82	2.1
79	1	1	140	0.3	366	34	25	307	1.82	2.1
80	1	1	140	0.3	366	34	25	307	1.82	2.1
81	1	1	140	0.3	366	34	25	307	1.82	2.1
82	1	1	140	0.3	366	34	25	307	1.82	2.1
	Secondary layer coating
		Fine particles
	Resin	silica (b)	Drying	Coating
		composition	Type	Blending	temperature	thickness
	No.	*3	*8	rate *9	(° C.)	(μm)	Classification
	73	1	1	10	40	1	Comparative
							example
	74	1	1	10	50	1	Example
	75	1	1	10	80	1	Example
	76	1	1	10	120	1	Example
	77	1	1	10	180	1	Example
	78	1	1	10	200	1	Example
	79	1	1	10	230	1	Example
	80	1	1	10	250	1	Example
	81	1	1	10	350	1	Example
	82	1	1	10	380	1	Comparative
							example

 

	TABLE 34
	Performance
		White-rust	White-rust	Paint
		resistance:	resistance after	adhe-
	Appear-	SST	alkaline degreasing:	sive-	Classi-
No.	ance	120 hrs	SST 120 hrs	ness	fication
73	◯	X	X	X	Comparative
					example
74	◯	◯−	◯−	◯	Example
75	◯	◯	◯−	◯+	Example
76	◯	⊚	◯	⊚	Example
77	◯	⊚	⊚	⊚	Example
78	◯	⊚	⊚	⊚	Example
79	◯	⊚	⊚	⊚	Example
80	◯	⊚	⊚	⊚	Example
81	◯	◯	◯	⊚	Example
82	◯	Δ	Δ	⊚	Comparative
					example

 

TABLE 35
		Primary layer coating
					Coating weight *4
	Plating				Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	steel	Coating	Drying	Coating	coating	particles	component	component	components
	plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	Classification
83	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
84	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
85	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
86	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
87	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
88	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
89	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
90	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
91	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
92	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
93	1	1	140	0.3	366	34	25	307	1.82	2.1	Comparative
											example
94	1	1	140	0.001	1.46	0.14	0.10	1.23	1.82	2.1	Comparative
											example
95	1	1	140	0.005	5.85	0.54	0.40	4.91	1.82	2.1	Example
96	1	1	140	0.01	14.63	1.36	1.00	12.27	1.82	2.1	Example

 

	TABLE 36
	Secondary layer coating
	Resin	Fine particles silica (b)	Solid lubricant (c)	Drying	Coating
	composition	Type	Blending rate	Type	Blending rate	temperature	thickness
No.	*3	*8	*9	*12	*13	(° C.)	(μm)	Classification
83	1	1	10	1	5	230	1	Example
84	1	1	10	2	5	230	1	Example
85	1	1	10	3	5	230	1	Example
86	1	1	10	4	5	230	1	Example
87	1	1	10	5	5	230	1	Example
88	1	1	10	6	5	230	1	Example
89	1	1	10	1	1	230	1	Example
90	1	1	10	1	10	230	1	Example
91	1	1	10	1	30	230	1	Example
92	1	1	10	1	80	230	1	Example
93	1	1	10	1	100	230	1	Comparative
								example
94	1	1	10	1	5	230	1	Comparative
								example
95	1	1	10	1	5	230	1	Example
96	1	1	10	1	5	230	1	Example

 

	TABLE 37
	Performance
			White-rust
			resistance after
		White-rust resistance:	alkaline degreasing:	Paint
No.	Appearance	SST 120 hrs	SST 120 hrs	adhesiveness	Workability	Classification
83	◯	◯+	◯+	⊚	⊚	Example
84	◯	⊚	⊚	⊚	⊚	Example
85	◯	⊚	⊚	⊚	⊚	Example
86	◯	⊚	⊚	⊚	⊚	Example
87	◯	⊚	⊚	⊚	⊚	Example
88	◯	⊚	⊚	⊚	⊚	Example
89	◯	⊚	⊚	⊚	◯	Example
90	◯	⊚	⊚	⊚	⊚	Example
91	◯	⊚	⊚	⊚	⊚	Example
92	◯	⊚	⊚	◯	⊚	Example
93	◯	⊚	⊚	X	⊚	Comparative
						example
94	◯	X	X	⊚	⊚	Comparative
						example
95	◯	◯−	◯−	⊚	⊚	Example
96	◯	◯	◯	⊚	⊚	Example
&Asteriskpseud;1: Unable to weld

 

	TABLE 38
	Primary layer coating
	Coating weight *4
	Plating				Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	steel	Coating	Drying	Coating	coating	particles	component	component	components
	plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	Classification
97	1	1	140	0.1	146	14	10	123	1.82	2.1	Example
98	1	1	140	0.5	585	54	40	491	1.82	2.1	Example
99	1	1	140	1	1170	109	80	982	1.82	2.1	Example
100	1	1	140	2	2341	217	160	1963	1.82	2.1	Example
101	1	1	140	3	3511	326	240	2945	1.82	2.1	Example
102	1	1	140	5	5851	543	400	4909	1.82	2.1	Comparative
											example
103	1	1	30	0.3	366	34	25	307	1.82	2.1	Comparative
											example
104	1	1	50	0.3	366	34	25	307	1.82	2.1	Example
105	1	1	80	0.3	366	34	25	307	1.82	2.1	Example
106	1	1	120	0.3	366	34	25	307	1.82	2.1	Example
107	1	1	180	0.3	366	34	25	307	1.82	2.1	Example
108	1	1	200	0.3	366	34	25	307	1.82	2.1	Example
109	1	1	300	0.3	366	34	25	307	1.82	2.1	Example
110	1	1	350	0.3	366	34	25	307	1.82	2.1	Comparative
											example

 

	TABLE 39
	Secondary layer coating
	Resin	Fine particles silica (b)	Solid lubricant (c)	Drying	Coating
	composition	Type	Blending rate	Type	Blending rate	temperature	thickness
No.	*3	*8	*9	*12	*13	(° C.)	(μm)	Classification
97	1	1	10	1	5	230	1	Example
98	1	1	10	1	5	230	1	Example
99	1	1	10	1	5	230	1	Example
100	1	1	10	1	5	230	1	Example
101	1	1	10	1	5	230	1	Example
102	1	1	10	1	5	230	1	Comparative
								example
103	1	1	10	1	5	230	1	Comparative
								example
104	1	1	10	1	5	230	1	Example
105	1	1	10	1	5	230	1	Example
106	1	1	10	1	5	230	1	Example
107	1	1	10	1	5	230	1	Example
108	1	1	10	1	5	230	1	Example
109	1	1	10	1	5	230	1	Example
110	1	1	10	1	5	230	1	Comparative
								example

 

	TABLE 40
	Performance
			White-rust
			resistance after
		White-rust resistance:	alkaline degreasing:	Paint
No.	Appearance	SST 120 hrs	SST 120 hrs	adhesiveness	Workability	Classification
97	◯	◯+	◯+	⊚	⊚	Example
98	◯	⊚	⊚	⊚	⊚	Example
99	◯	⊚	⊚	⊚	⊚	Example
100	◯	⊚	⊚	⊚	⊚	Example
101	◯	⊚	⊚	⊚	⊚	Example
102	◯	⊚	⊚	⊚	⊚	Comparative
						example &Asteriskpseud;1
103	◯	X	X	X	⊚	Comparative
						example
104	◯	◯−	◯−	◯	⊚	Example
105	◯	⊚	⊚	⊚	⊚	Example
106	◯	⊚	⊚	⊚	⊚	Example
107	◯	⊚	⊚	⊚	⊚	Example
108	◯	⊚	⊚	⊚	⊚	Example
109	◯	⊚	⊚	⊚	⊚	Example
110	◯	X	X	⊚	⊚	Comparative
						example
&Asteriskpseud;1: Unable to weld

 

TABLE 41
		Primary layer coating
					Coating weight *4
	Plating				Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	steel	Coating	Drying	Coating	coating	particles	component	component	components
	plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6
111	1	1	140	0.3	366	34	25	307	1.82	2.1
112	1	1	140	0.3	366	34	25	307	1.82	2.1
113	1	1	140	0.3	366	34	25	307	1.82	2.1
114	1	1	140	0.3	366	34	25	307	1.82	2.1
115	1	1	140	0.3	366	34	25	307	1.82	2.1
116	1	1	140	0.3	366	34	25	307	1.82	2.1
117	1	1	140	0.3	366	34	25	307	1.82	2.1
118	1	1	140	0.3	366	34	25	307	1.82	2.1
119	1	1	140	0.3	366	34	25	307	1.82	2.1
120	1	1	140	0.3	366	34	25	307	1.82	2.1
121	1	1	140	0.3	366	34	25	307	1.82	2.1
122	1	1	140	0.3	366	34	25	307	1.82	2.1
123	1	1	140	0.3	366	34	25	307	1.82	2.1
124	1	1	140	0.3	366	34	25	307	1.82	2.1
	Secondary layer coating
		Resin	Ion-exchanged	Drying	Coating
		composition	silica (a)	temperature	thickness
	No.	*3	content *7	(° C.)	(μm)	Classification
	111	1	30	230	1	Example
	112	2	30	230	1	Example
	113	3	30	230	1	Example
	114	4	30	230	1	Example
	115	5	30	230	1	Example
	116	6	30	230	1	Example
	117	7	30	230	1	Example
	118	8	30	230	1	Example
	119	9	30	230	1	Example
	120	10	30	230	1	Example
	121	11	30	230	1	Example
	122	12	30	230	1	Comparative
						example
	123	13	30	230	1	Comparative
						example
	124	14	30	230	1	Comparative
						example

 

	TABLE 42
	Performance
			White-rust	Paint
	Ap-	White-rust	resistance after	adhe-
	pear-	resistance:	alkaline degreasing:	sive-
No.	ance	SST 150 hrs	SST 150 hrs	ness	Classification
111	◯	⊚	⊚	⊚	Example
112	◯	⊚	⊚	⊚	Example
113	◯	⊚	⊚	⊚	Example
114	◯	⊚	⊚	⊚	Example
115	◯	⊚	⊚	⊚	Example
116	◯	⊚	⊚	⊚	Example
117	◯	⊚	⊚	⊚	Example
118	◯	⊚	⊚	⊚	Example
119	◯	⊚	⊚	⊚	Example
120	◯	⊚	⊚	⊚	Example
121	◯	⊚	⊚	⊚	Example
122	◯	Δ	X	⊚	Comparative
					example
123	◯	X	X	X	Comparative
					example
124	◯	Δ	X	⊚	Comparative
					example

 

	TABLE 43
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5
		Coating	Drying	Coating	coating	particles	component	component
	Plating steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )
125	1	2	140	0.3	400	66	25	310
126	1	3	140	0.3	303	49	20	234
127	1	4	140	0.3	320	53	20	248
128	1	5	140	0.3	293	27	20	245
129	1	6	140	0.3	317	(Al 2 O 3 )	25	292
130	1	7	140	0.3	317	(ZrO 2 )	25	292
131	1	8	140	0.3	403	150	20	234
132	1	9	140	0.3	320	95	(Ca)	225
133	1	10	140	0.3	320	90	(Sr)	230
134	1	11	140	0.3	329	89	(Ba)	240
135	1	12	140	0.3	320	—	40	280
136	1	13	140	0.3	300	50	—	250
137	1	14	140	0.3	416	346	70	0
138	1	15	140	0.3	500	—	—	0
	Secondary layer coating
	Primary layer coating		Ion-
	Molar ratio of coating		exchanged
	components	Resin	silica (a)	Drying	Coating
		Mg/SiO 2	P 2 O 5 /Mg	composition	content	temperature	thickness
	No.	*5	*6	*3	*7	(° C.)	(μm)	Classification
	125	0.94	2.12	1	30	230	1	Example
	126	1	2	1	30	230	1	Example
	127	0.94	2.12	1	30	230	1	Example
	128	1.82	2.1	1	30	230	1	Example
	129	1.5	2	1	30	230	1	Example
	130	1	2	1	30	230	1	Example
	131	0.33	2	1	30	230	1	Example
	132	—	—	1	30	230	1	Example
	133	—	—	1	30	230	1	Example
	134	2	8	1	30	230	1	Example
	135	—	1.2	1	30	230	1	Comparative
								example
	136	—	—	1	30	230	1	Comparative
								example
	137	0.5	—	1	30	230	1	Comparative
								example
	138	—	—	1	30	230	1	Comparative
								example

 

	TABLE 44
	Performance
			White-rust	Paint
	Ap-	White-rust	resistance after	adhe-
	pear-	resistance:	alkaline degreasing:	sive-
No.	ance	SST 150 hrs	SST 150 hrs	ness	Classification
125	◯	⊚	⊚	⊚	Example
126	◯	⊚	⊚	⊚	Example
127	◯	⊚	⊚	⊚	Example
128	◯	⊚	⊚	⊚	Example
129	◯	◯	◯	⊚	Example
130	◯	◯	◯	⊚	Example
131	◯	⊚	⊚	⊚	Example
132	◯	◯+	◯+	⊚	Example
133	◯	◯	◯	⊚	Example
134	◯	◯	◯	⊚	Example
135	◯	Δ	Δ	⊚	Comparative
					example
136	◯	Δ	Δ	⊚	Comparative
					example
137	◯	Δ	Δ	⊚	Comparative
					example
138	◯	X	Δ	⊚	Comparative
					example

 

	TABLE 45
	Primary layer coating
	Coating weight *4
				Total	SiO 2 fine	Mg	P 2 O 5
	Coating	Drying	Coating	coating	particles	component	component
	Plating steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )
139	1	1	140	0.3	366	34	25	307
140	1	1	140	0.3	366	34	25	307
141	1	1	140	0.3	366	34	25	307
142	1	1	140	0.3	366	34	25	307
143	1	1	140	0.3	366	34	25	307
144	1	1	140	0.3	366	34	25	307
145	1	1	140	0.3	366	34	25	307
146	1	1	140	0.3	366	34	25	307
147	1	1	140	0.3	366	34	25	307
148	1	1	140	0.3	366	34	25	307
	Secondary layer coating
	Primary layer coating		Ion-
	Molar ratio of		exchanged
	coating components	Resin	silica (a)	Drying	Coating
		Mg/SiO 2	P 2 O 5 /Mg	composition	content	temperature	thickness
	No.	*5	*6	*3	*7	(° C.)	(μm)	Classification
	139	1.82	2.1	1	—	230	1	Example
	140	1.82	2.1	1	1	230	1	Example
	141	1.82	2.1	1	5	230	1	Example
	142	1.82	2.1	1	10	230	1	Example
	143	1.82	2.1	1	30	230	1	Example
	144	1.82	2.1	1	40	230	1	Example
	145	1.82	2.1	1	50	230	1	Example
	146	1.82	2.1	1	80	230	1	Example
	147	1.82	2.1	1	100	230	1	Example
	148	1.82	2.1	1	150	230	1	Comparative
								example

 

	TABLE 46
	Performance
			White-rust	Paint
	Ap-	White-rust	resistance after	adhe-
	pear-	resistance:	alkaline degreasing:	sive-
No.	ance	SST 150 hrs	SST 150 hrs	ness	Classification
139	◯	Δ	Δ	⊚	Example
140	◯	◯	◯	⊚	Example
141	◯	◯+	◯+	⊚	Example
142	◯	⊚	⊚	⊚	Example
143	◯	⊚	⊚	⊚	Example
144	◯	⊚	⊚	⊚	Example
145	◯	⊚	⊚	⊚	Example
146	◯	◯+	◯+	⊚	Example
147	◯	◯	◯	⊚	Example
148	◯	Δ	Δ	⊚	Comparative
					example

 

	TABLE 47
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5
		Coating	Drying	Coating	coating	particles	component	component
	Plating steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )
149	2	1	140	0.3	366	34	25	307
150	3	1	140	0.3	366	34	25	307
151	4	1	140	0.3	366	34	25	307
152	5	1	140	0.3	366	34	25	307
153	6	1	140	0.3	366	34	25	307
154	7	1	140	0.3	366	34	25	307
155	8	1	140	0.3	366	34	25	307
156	9	1	140	0.3	366	34	25	307
157	10	1	140	0.3	366	34	25	307
158	11	1	140	0.3	366	34	25	307
159	12	1	140	0.3	366	34	25	307
160	13	1	140	0.3	366	34	25	307
	Secondary layer coating
	Primary layer coating		Ion-
	Molar ratio of		exchanged
	coating components	Resin	silica (a)	Drying	Coating
		Mg/SiO 2	P 2 O 5 /Mg	composition	content	temperature	thickness
	No.	*5	*6	*3	*7	(° C.)	(μm)	Classification
	149	1.82	2.1	1	30	230	1	Example
	150	1.82	2.1	1	30	230	1	Example
	151	1.82	2.1	I	30	230	1	Example
	152	1.82	2.1	1	30	230	1	Example
	153	1.82	2.1	1	30	230	1	Example
	154	1.82	2.1	1	30	230	1	Example
	155	1.82	2.1	1	30	230	1	Example
	156	1.82	2.1	1	30	230	1	Example
	157	1.82	2.1	1	30	230	1	Example
	158	1.82	2.1	1	30	230	1	Example
	159	1.82	2.1	1	30	230	1	Example
	160	1.82	2.1	1	30	230	1	Example

 

	TABLE 48
	Performance
			White-rust
			resistance after
		White-rust resistance:	alkaline degreasing:	Paint
No.	Appearance	SST 150 hrs	SST 150 hrs	adhesiveness	Workability	Classification
149	◯	⊚	◯	⊚	⊚	Example
150	◯	⊚	⊚	⊚	⊚	Example
151	◯	⊚	⊚	⊚	⊚	Example
152	◯	⊚	⊚	⊚	⊚	Example
153	◯	⊚	⊚	⊚	⊚	Example
154	◯	⊚	⊚	⊚	⊚	Example
155	◯	⊚	⊚	⊚	⊚	Example
156	◯	⊚	⊚	⊚	⊚	Example
157	◯	⊚	⊚	⊚	⊚	Example
158	◯	⊚	⊚	⊚	⊚	Example
159	◯	⊚	⊚	⊚	⊚	Example
160	◯	⊚	⊚	⊚	⊚	Example

 

	TABLE 49
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5
		Coating	Drying	Coating	coating	particles	component	component
	Plating steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )
161	1	1	140	0.3	366	34	25	307
162	1	1	140	0.3	366	34	25	307
163	1	1	140	0.3	366	34	25	307
164	1	1	140	0.3	366	34	25	307
165	1	1	140	0.3	366	34	25	307
166	1	1	140	0.3	366	34	25	307
167	1	1	140	0.3	366	34	25	307
168	1	1	140	0.3	366	34	25	307
169	1	1	140	0.3	366	34	25	307
170	1	1	140	0.3	366	34	25	307
	Secondary layer coating
	Primary layer coating		Ion-
	Molar ratio of		exchanged
	coating components	Resin	silica (a)	Drying	Coating
		Mg/SiO 2	P 2 O 5 /Mg	composition	content	temperature	thickness
	No.	*5	*6	*3	*7	(° C.)	(μm)	Classification
	161	1.82	2.1	1	30	230	0.01	Comparative
								example
	162	1.82	2.1	1	30	230	0.1	Example
	163	1.82	2.1	1	30	230	0.5	Example
	164	1.82	2.1	1	30	230	1	Example
	165	1.82	2.1	1	30	230	2	Example
	166	1.82	2.1	1	30	230	2.5	Example
	167	1.82	2.1	1	30	230	3	Example
	168	1.82	2.1	1	30	230	4	Example
	169	1.82	2.1	1	30	230	5	Example
	170	1.82	2.1	1	30	230	20	Comparative
								example

 

	TABLE 50
	Performance
			White-rust
			resistance	Paint
		White-rust	after alkaline	ad-
	Appear-	resistance:	degreasing:	hesive-
No.	ance	SST 150 hrs	SST 150 hrs	ness	Classification
161	∘	x	x	⊚	Comparative
					example
162	∘	∘−	∘−	⊚	Example
163	∘	◯+	∘+	⊚	Example
164	∘	⊚	⊚	⊚	Example
165	∘	⊚	⊚	⊚	Example
166	∘	⊚	⊚	⊚	Example
167	∘	⊚	⊚	⊚	Example
168	∘	⊚	⊚	⊚	Example
169	∘	⊚	⊚	⊚	Example
170	∘	⊚	⊚	⊚	Comparative&Asteriskpseud;1
					example
&Asteriskpseud;1 Unable to weld

 

	TABLE 51
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5
		Coating	Drying	Coating	coating	particles	component	component
	Plating steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )
171	1	1	140	0.3	366	34	25	307
172	1	1	140	0.3	366	34	25	307
173	1	1	140	0.3	366	34	25	307
174	1	1	140	0.3	366	34	25	307
175	1	1	140	0.3	366	34	25	307
176	1	1	140	0.3	366	34	25	307
177	1	1	140	0.3	366	34	25	307
178	1	1	140	0.3	366	34	25	307
179	1	1	140	0.3	366	34	25	307
180	1	1	140	0.3	366	34	25	307
	Secondary layer coating
	Primary layer coating		Ion-
	Molar ratio of		exchanged
	coating components	Resin	silica (a)	Drying	Coating
		Mg/SiO 2	P 2 O 5 /Mg	composition	content	temperature	thickness
	No.	*5	*6	*3	*7	(° C.)	(μm)	Classification
	171	1.82	2.1	1	30	40	1	Comparative
								example
	172	1.82	2.1	1	30	50	1	Example
	173	1.82	2.1	1	30	80	1	Example
	174	1.82	2.1	1	30	120	1	Example
	175	1.82	2.1	1	30	180	1	Example
	176	1.82	2.1	1	30	200	1	Example
	177	1.82	2.1	1	30	230	1	Example
	178	1.82	2.1	1	30	250	1	Example
	179	1.82	2.1	1	30	350	1	Example
	180	1.82	2.1	1	30	380	1	Comparative
								example

 

	TABLE 52
	Performance
			White-rust
			resistance	Paint
		White-rust	after alkaline	ad-
	Appear-	resistance:	degreasing:	hesive-
No.	ance	SST 150 hrs	SST 150 hrs	ness	Classification
171	∘	x	x	x	Comparative
					example
172	∘	∘−	∘−	∘	Example
173	∘	∘	∘−	∘+	Example
174	∘	⊚	∘	⊚	Example
175	∘	⊚	⊚	⊚	Example
176	∘	⊚	⊚	⊚	Example
177	∘	⊚	⊚	⊚	Example
178	∘	⊚	⊚	⊚	Example
179	∘	∘	∘	⊚	Example
180	∘	Δ	Δ	⊚	Comparative
					example

 

	TABLE 53
	Primary layer coating
	Coating weight *4
	Plating	Coating	Drying	Coating		SiO 2 fine	Mg		Molar ratio of coating
	steel	com-	tempera-	thick-	Total coating	particles	component	P 2 O 5 component	components
	plate	position	ture	ness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	Classification
181	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
182	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
183	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
184	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
185	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
186	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
187	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
188	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
189	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
190	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
191	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
192	1	1	140	0.3	366	34	25	307	1.82	2.1	Comparative
											example
193	1	1	140	0.3	366	34	25	307	1.82	2.1	Comparative
											example
194	1	1	140	0.3	366	34	25	307	1.82	2.1	Comparative
											example
195	1	1	140	0.3	366	34	25	307	1.82	2.1	Example

 

	TABLE 54
	Secondary layer coating
	Resin	Ion-exchanged	Fine particles silica (b)	(a) + (b)	(a)/(b)	Drying	Coating
	composition	silica (a)	Type	Blending	Blending	Weight	temperature	thickness
No.	*3	content *7	*8	rate *9	rate *10	ratio *11	(° C.)	(μm)	Classification
181	1	30	5	5	35	6/1	230	1	Example
182	2	30	5	5	35	6/1	230	1	Example
183	3	30	5	5	35	6/1	230	1	Example
184	4	30	5	5	35	6/1	230	1	Example
185	5	30	5	5	35	6/1	230	1	Example
186	6	30	5	5	35	6/1	230	1	Example
187	7	30	5	5	35	6/1	230	1	Example
188	8	30	5	5	35	6/1	230	1	Example
189	9	30	5	5	35	6/1	230	1	Example
190	10	30	5	5	35	6/1	230	1	Example
191	11	30	5	5	35	6/1	230	1	Example
192	12	30	5	5	35	6/1	230	1	Comparative
									example
193	13	30	5	5	35	6/1	230	1	Comparative
									example
194	14	30	5	5	35	6/1	230	1	Comparative
									example
195	1	30	—	—	30	30/0	230	1	Example

 

	TABLE 55
	Performance
			White-rust	Paint
	Ap-	White-rust	resistance after	adhe-
	pear-	resistance:	alkaline degreasing:	sive-
No.	ance	SST 180 hrs	SST 180 hrs	ness	Classification
181	◯	⊚	⊚	⊚	Example
182	◯	⊚	⊚	⊚	Example
183	◯	⊚	⊚	⊚	Example
184	◯	⊚	⊚	⊚	Example
185	◯	⊚	⊚	⊚	Example
186	◯	⊚	⊚	⊚	Example
187	◯	⊚	⊚	⊚	Example
188	◯	⊚	⊚	⊚	Example
189	◯	⊚	⊚	⊚	Example
190	◯	⊚	⊚	⊚	Example
191	◯	⊚	⊚	⊚	Example
192	◯	Δ	X	⊚	Comparative
					example
193	◯	X	X	X	Comparative
					example
194	◯	Δ	X	⊚	Comparative
					example
195	◯	◯	◯	⊚	Example

 

	TABLE 56
	Primary layer coating
	Coating weight *4
	Plating				Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	steel	Coating	Drying	Coating	coating	particles	component	component	components
	plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	Classification
196	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
197	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
198	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
199	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
200	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
201	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
202	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
203	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
204	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
205	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
206	1	I	140	0.3	366	34	25	307	1.82	2.1	Example
207	1	1	140	0.3	366	34	25	307	I.82	2.1	Example
208	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
209	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
210	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
211	1	1	140	0.3	366	34	25	307	1.82	2.1	Example

 

	TABLE 57
	Secondary layer coating
	Resin	Ion-exchanged	Fine particles silica (b)	(a) + (b)	(a)/(b)	Drying	Coating
	composition	silica (a)	Type	Blending	Content	Weight	temperature	thickness
No.	*3	content *7	*8	rate *9	*10	ratio *11	(° C.)	(μm)	Classification
196	1	29.9	5	0.1	30	299/1	230	1	Example
197	1	29	5	1	30	29/1	230	1	Example
198	1	20	5	10	30	2/1	230	1	Example
199	1	15	5	15	30	1/1	230	1	Example
200	1	10	5	20	30	1/2	230	1	Example
201	1	1	5	29	30	1/29	230	1	Example
202	1	0.1	5	29.9	30	1/299	230	1	Example
203	1	50	—	—	50	50/0	230	1	Example
204	1	49	5	1	50	49/1	230	1	Example
205	1	45	5	5	50	9/1	230	1	Example
206	1	40	5	10	50	4/1	230	1	Example
207	1	30	5	20	50	3/2	230	1	Example
208	1	25	5	25	50	1/1	230	1	Example
209	1	10	5	40	50	1/4	230	1	Example
210	1	1	5	49	50	1/50	230	1	Example
211	1	0.45	5	0.05	0.5	9/1	230	1	Example

 

	TABLE 58
	Performance
			White-rust	Paint
	Ap-	White-rust	resistance after	adhe-
	pear-	resistance:	alkaline degreasing:	sive-
No.	ance	SST 180 hrs	SST 180 hrs	ness	Classification
196	◯	◯	◯	⊚	Example
197	◯	◯+	◯+	⊚	Example
198	◯	⊚	⊚	⊚	Example
199	◯	⊚	⊚	⊚	Example
200	◯	◯	◯	⊚	Example
201	◯	◯	◯	⊚	Example
202	◯	◯−	◯−	⊚	Example
203	◯	◯	◯	⊚	Example
204	◯	◯+	◯+	⊚	Example
205	◯	⊚	⊚	⊚	Example
206	◯	⊚	⊚	⊚	Example
207	◯	⊚	⊚	⊚	Example
208	◯	⊚	⊚	⊚	Example
209	◯	◯	◯	⊚	Example
210	◯	◯	◯	⊚	Example
211	◯	X	X	⊚	Example

 

	TABLE 59
	Primary layer coating
	Coating weight *4
	Plating				Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	steel	Coating	Drying	Coating	coating	particles	component	component	components
	plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	Classification
212	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
213	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
214	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
215	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
216	1	1	140	0.3	366	34	25	307	1.82	2.1	Comparative
											example
217	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
218	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
219	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
220	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
221	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
222	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
223	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
224	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
225	1	1	140	0.3	366	34	25	307	1.82	2.1	Example

 

	TABLE 60
	Secondary layer coating
	Resin	Ion-exchanged	Fine particles silica (b)	(a) + (b)	(a)/(b)	Drying	Coating
	composition	silica (a)	Type	Blending	Blending	Weight	temperature	thickness
No.	*3	content *7	*8	rate *9	rate *10	ratio *11	(° C.)	(μm)	Classification
212	1	9	5	1	10	9/1	230	1	Example
213	1	27	5	3	30	9/1	230	1	Example
214	1	72	5	8	80	9/1	230	1	Example
215	1	90	5	10	100	9/1	230	1	Example
216	1	135	5	15	150	9/1	230	1	Comparative
									example
217	1	30	1	5	35	6/1	230	1	Example
218	1	30	2	5	35	6/1	230	1	Example
219	1	30	3	5	35	6/1	230	1	Example
220	1	30	4	5	35	6/1	230	1	Example
221	1	30	6	5	35	6/1	230	1	Example
222	1	30	7	5	35	6/1	230	1	Example
223	1	30	8	5	35	6/1	230	1	Example
224	1	30	9	5	35	6/1	230	1	Example
225	1	30	11	5	35	6/1	230	1	Example

 

	TABLE 61
	Performance
			White-rust	Paint
	Ap-	White-rust	resistance after	adhe-
	pear-	resistance:	alkaline degreasing:	sive-
No.	ance	SST 180 hrs	SST 180 hrs	ness	Classification
212	◯	◯+	◯+	⊚	Example
213	◯	⊚	⊚	⊚	Example
214	◯	⊚	⊚	⊚	Example
215	◯	◯+	◯+	⊚	Example
216	◯	X	X	⊚	Comparative
					example
217	◯	⊚	⊚	⊚	Example
218	◯	⊚	⊚	⊚	Example
219	◯	⊚	⊚	⊚	Example
220	◯	⊚	⊚	⊚	Example
221	◯	⊚	⊚	⊚	Example
222	◯	⊚	⊚	⊚	Example
223	◯	⊚	⊚	⊚	Example
224	◯	⊚	⊚	⊚	Example
225	◯	⊚	⊚	⊚	Example

 

	TABLE 62
	Primary layer coating
	Coating weight *4
	Plating				Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	steel	Coating	Drying	Coating	coating	particles	component	component	components
	plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	Classification
226	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
227	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
228	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
229	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
230	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
231	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
232	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
233	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
234	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
235	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
236	1	1	140	0.3	366	34	25	307	1.82	2.1	Comparative
											example

 

	TABLE 63
	Secondary layer coating
	Resin	Ion-exchanged	Solid lubricant (c)	Drying	Coating
	composition	silica (a)	Type	Blending	temperature	thickness
No.	*3	content *7	*12	rate *13	(° C.)	(μm)	Classification
226	1	30	1	10	230	1	Example
227	1	30	2	10	230	1	Example
228	1	30	3	10	230	1	Example
229	1	30	4	10	230	1	Example
230	1	30	5	10	230	1	Example
231	1	30	6	10	230	1	Example
232	1	30	1	1	230	1	Example
233	1	30	1	3	230	1	Example
234	1	30	1	40	230	1	Example
235	1	30	1	80	230	1	Example
236	1	30	1	100	230	1	Comparative
							example

 

	TABLE 64
	Performance
			White-rust
			resistance after
		White-rust resistance:	alkaline degreasing:	Paint
No.	Appearance	SST 150 hrs	SST 150 hrs	adhesiveness	Workability	Classification
226	◯	⊚	⊚	⊚	⊚	Example
227	◯	⊚	⊚	⊚	⊚	Example
228	◯	⊚	⊚	⊚	⊚	Example
229	◯	⊚	⊚	⊚	⊚	Example
230	◯	⊚	⊚	⊚	⊚	Example
231	◯	⊚	⊚	⊚	⊚	Example
232	◯	⊚	⊚	⊚	◯	Example
233	◯	⊚	⊚	⊚	⊚	Example
234	◯	⊚	⊚	⊚	⊚	Example
235	◯	⊚	⊚	◯	⊚	Example
236	◯	⊚	⊚	X	⊚	Comparative
						example

 

	TABLE 65
	Primary layer coating
	Coating weight *4
	Plating				Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	steel	Coating	Drying	Coating	coating	particles	component	component	components
	plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	Classification
237	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
238	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
239	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
240	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
241	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
242	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
243	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
244	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
245	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
246	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
247	1	1	140	0.3	366	34	25	307	1.82	2.1	Comparative
											example

 

	TABLE 66
	Secondary layer coating
		Ion-	Fine particles silica (b)			Solid lubricant (c)
	Resin	exchanged		Blending	(a) + (b)	(a)/(b)		Blending	Drying	Coating
	composition	silica (a)	Type	rate	Blending	Weight	Type	rate	temperature	thickness
No.	*3	content *7	*8	*9	rate *10	ratio *11	*12	*13	(° C.)	(μm)	Classification
237	1	30	1	5	35	6/1	1	10	230	1	Example
238	1	30	2	5	35	6/1	2	10	230	1	Example
239	1	30	3	5	35	6/1	3	10	230	1	Example
240	1	30	4	5	35	6/1	4	10	230	1	Example
241	1	30	6	5	35	6/1	5	10	230	1	Example
242	1	30	7	5	35	6/1	6	10	230	1	Example
243	1	30	8	5	35	6/1	1	1	230	1	Example
244	1	30	9	5	35	6/1	1	3	230	1	Example
245	1	30	11	5	35	6/1	1	40	230	1	Example
246	1	30	11	5	35	6/1	1	80	230	1	Example
247	1	30	11	5	35	6/1	1	100	230	1	Comparative
											example

 

	TABLE 67
	Performance
			White-rust
			resistance after
		White-rust resistance:	alkaline degreasing:	Paint
No.	Appearance	SST 180 hrs	SST 180 hrs	adhesiveness	Workability	Classification
237	◯	⊚	⊚	⊚	⊚	Example
238	◯	⊚	⊚	⊚	⊚	Example
239	◯	⊚	⊚	⊚	⊚	Example
240	◯	⊚	⊚	⊚	⊚	Example
241	◯	⊚	⊚	⊚	⊚	Example
242	◯	⊚	⊚	⊚	⊚	Example
243	◯	⊚	⊚	⊚	◯	Example
244	◯	⊚	⊚	⊚	⊚	Example
245	◯	⊚	⊚	⊚	⊚	Example
246	◯	⊚	⊚	◯	⊚	Example
247	◯	⊚	⊚	X	⊚	Comparative
						example

 

	TABLE 68
	Primary layer coating
	Coating weight *4
	Plating				Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	steel	Coating	Drying	Coating	coating	particles	component	component	components
	plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6
248	1	1	140	0.001	1	0.14	0.1	1	1.82	2.1
249	1	1	140	0.005	5.9	0.54	0.4	5	1.82	2.1
250	1	1	140	0.01	15	1.4	1	12	1.82	2.1
251	1	1	140	0.1	146	14	10	123	1.82	2.1
252	1	1	140	0.5	585	54	40	491	1.82	2.1
253	1	1	140	1	1170	109	80	982	1.82	2.1
254	1	1	140	2	2341	217	160	1963	1.82	2.1
255	1	1	140	3	3511	326	240	2945	1.82	2.1
256	1	1	140	5	5851	543	400	4909	1.82	2.1
	Secondary layer coating
		Resin	Ion-exchanged	Drying	Coating
		composition	silica (a)	temperature	thickness
	No.	*3	content *7	(° C.)	(μm)	Classification
	248	1	30	230	1	Comparative
						example
	249	1	30	230	1	Example
	250	1	30	230	1	Example
	251	1	30	230	1	Example
	252	1	30	230	1	Example
	253	1	30	230	1	Example
	254	1	30	230	1	Example
	255	1	30	230	1	Example
	256	1	30	230	1	Comparative
						example

 

	TABLE 69
	Performance
			White-rust
			resistance	Paint
		White-rust	after alkaline	ad-
	Appear-	resistance:	degreasing:	hesive-
No.	ance	SST 150 hrs	SST 150 hrs	ness	Classification
248	∘	x	x	⊚	Comparative
					example
249	∘	∘−	∘−	⊚	Example
250	∘	∘	∘	⊚	Example
251	∘	∘+	∘+	⊚	Example
252	∘	⊚	⊚	⊚	Example
253	∘	⊚	⊚	⊚	Example
254	∘	⊚	⊚	⊚	Example
255	∘	⊚	⊚	⊚	Example
256	∘	⊚	⊚	⊚	Comparative&Asteriskpseud;1
					example
&Asteriskpseud;1 Unable to weld

 

	TABLE 70
	Primary layer coating
	Coating weight *4
	Plating				Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	steel	Coating	Drying	Coating	coating	particles	component	component	components
	plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6
257	1	1	30	0.3	366	34	25	307	1.82	2.1
258	1	1	50	0.3	366	34	25	307	1.82	2.1
259	1	1	80	0.3	366	34	25	307	1.82	2.1
260	1	1	120	0.3	366	34	25	307	1.82	2.1
261	1	1	180	0.3	366	34	25	307	1.82	2.1
262	1	1	200	0.3	366	34	25	307	1.82	2.1
263	1	1	300	0.3	366	34	25	307	1.82	2.1
264	1	1	350	0.3	366	34	25	307	1.82	2.1
	Secondary layer coating
		Resin	Ion-exchanged	Drying	Coating
		composition	silica (a)	temperature	thickness
	No.	*3	content *7	(° C.)	(μm)	Classification
	257	1	30	230	1	Comparative
						example
	258	1	30	230	1	Example
	259	1	30	230	1	Example
	260	1	30	230	1	Example
	261	1	30	230	1	Example
	262	1	30	230	1	Example
	263	1	30	230	1	Example
	264	1	30	230	1	Comparative
						example

 

	TABLE 71
	Performance
			White-rust
			resistance after
		White-rust resistance:	alkaline degreasing:	Paint
No.	Appearance	SST 150 hrs	SST 150 hrs	adhesiveness	Classification
257	◯	X	X	X	Comparative
					example
258	◯	◯−	◯−	◯	Example
259	◯	⊚	⊚	⊚	Example
260	◯	⊚	⊚	⊚	Example
261	◯	⊚	⊚	⊚	Example
262	◯	⊚	⊚	⊚	Example
263	◯	⊚	⊚	⊚	Example
264	◯	X	X	⊚	Comparative
					example

 

	TABLE 72
	Primary layer coating
	Coating weight *4
	Plating				Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	steel	Coating	Drying	Coating	coating	particles	component	component	components
	plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6
265	1	16	140	0.3	324	43.2	35	245.4	2	1.2
266	1	17	140	0.3	324	43.2	35	245.4	2	1.2
267	1	18	140	0.3	335	88.9	36	210.4	1	1
268	1	19	140	0.3	292	38.0	20	233.7	1.3	2
269	1	20	140	0.3	332	72.0	35	225.0	1.2	1.1
270	1	21	140	0.3	330	22.2	45	263.0	5	1
271	1	22	140	0.3	371	148.1	30	192.8	0.5	1.1
272	1	23	140	0.3	349	114.0	60	175.3	1.3	0.5
273	1	24	140	0.3	323	49.4	40	233.7	2.0	1.0
274	1	25	140	0.3	323	49.4	40	233.7	2.0	1.0
275	1	26	140	0.3	323	49.4	40	233.7	2.0	1.0
276	1	27	140	0.3	374	246.9	10	116.9	0.1	2.0
	Secondary coating layer
		Resin	Drying
		composition	temperature	Coating thickness
	No.	*3	(° C.)	(μm)	Classification
	265	1	230	1	Example
	266	1	230	1	Example
	267	1	230	1	Example
	268	1	230	1	Example
	269	1	230	1	Example
	270	1	230	1	Example
	271	1	230	1	Example
	272	1	230	1	Example
	273	1	230	1	Example
	274	1	230	1	Example
	275	1	230	1	Example
	276	1	230	1	Example

 

	TABLE 73
	Performance
			White-rust	Paint
	Ap-	White-rust	resistance after	adhe-
	pear-	resistance:	alkaline degreasing:	sive-
No.	ance	SST 96 hrs	SST 96 hrs	ness	Classification
265	◯	⊚	⊚	⊚	Example
266	◯	⊚	⊚	⊚	Example
267	◯	⊚	⊚	⊚	Example
268	◯	⊚	⊚	⊚	Example
269	◯	⊚	⊚	⊚	Example
270	◯	⊚	⊚	⊚	Example
271	◯	⊚	⊚	⊚	Example
272	◯	⊚	⊚	⊚	Example
273	◯	⊚	⊚	⊚	Example
274	◯	⊚	⊚	⊚	Example
275	◯	⊚	◯+	⊚	Example
276	◯	⊚	◯+	⊚	Example

 

	TABLE 74
	Primary layer coating
	Coating weight *4
	Plating				Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	steel	Coating	Drying	Coating	coating	particles	component	component	components
	plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6
277	1	28	140	0.3	330	9.9	40	280.5	10.0	1.2
278	1	29	140	0.3	323	164.6	100	58.4	1.5	0.1
279	1	30	140	0.3	310	12.3	5	292.2	1.0	10.0
280	1	31	140	0.3	310	13.2	40	257.1	7.5	1.1
281	1	32	140	0.3	310	2.2	45	263.0	50.0	1.0
282	1	33	140	0.3	300	123.5	1	175.3	0.02	30
283	1	34	140	0.3	324	148.1	0.6	175.3	0.01	50
284	1	35	140	0.3	389	3.5	140	245.4	100	0.3
285	1	36	140	0.3	401	1.8	145	254.2	200	0.3
286	1	37	140	0.3	394	246.9	0.5	146.1	0.005	50
287	1	38	140	0.3	293	74.1	0.15	219.1	0.005	250
288	1	39	140	0.3	365	6.9	350	8.2	125	0.004
	Secondary coating layer
		Resin	Drying
		composition	temperature	Coating thickness
	No.	*3	(° C.)	(μm)	Classification
	277	1	230	1	Example
	278	1	230	1	Example
	279	1	230	1	Example
	280	1	230	1	Example
	281	1	230	1	Example
	282	1	230	1	Example
	283	1	230	1	Example
	284	1	230	1	Example
	285	1	230	1	Example
	286	1	230	1	Example
	287	1	230	1	Example
	288	1	230	1	Example

 

	TABLE 75
	Performance
			White-rust	Paint
	Ap-	White-rust	resistance after	adhe-
	pear-	resistance:	alkaline degreasing:	sive-
No.	ance	SST 96 hrs	SST 96 hrs	ness	Classification
277	◯	⊚	◯+	⊚	Example
278	◯	⊚	◯+	⊚	Example
279	◯	⊚	◯+	⊚	Example
280	◯	⊚	◯+	⊚	Example
281	◯	⊚	◯	⊚	Example
282	◯	⊚	◯	⊚	Example
283	◯	⊚	◯	⊚	Example
284	◯	⊚	◯	⊚	Example
285	◯	⊚	◯−	⊚	Example
286	◯	⊚	◯−	⊚	Example
287	◯	◯+	◯+	⊚	Example
288	◯	◯+	◯+	⊚	Example

 

	TABLE 76
	Primary layer coating	Secondary
	Coat-			Coating weight *4	Molar ratio	layer coating
		ing	Drying			SiO 2	Mg	P 2 O 5	of coating	Resin	Drying	Coat-
	Plating	com-	tem-	Coating	Total	fine	com-	com-	components	com-	tem-	ing
	steel	posi-	pera-	thick-	coating	particles	ponent	ponent	Mg/	P 2 O 5 /	posi-	pera-	thick-	Class-
	plate	tion	ture	ness	weight	(α)	(β)	(γ)	SiO 2	Mg	tion	ture	ness	ifica-
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	*3	(° C.)	(μm)	tion
289	1	40	140	0.3	394	0.2	160	233.7	2000	0.25	1	230	1	Example
290	1	41	140	0.3	391	0.3	180	210.4	1500	0.2	1	230	1	Example
291	1	42	140	0.3	365	246.9	0.8	116.9	0.008	25	1	230	1	Example
292	1	43	140	0.3	399	319.5	2.2	77.1	0.017	6	1	230	1	Example
293	1	44	140	0.3	379	98.8	0.08	280.5	0.002	600	1	230	1	Example
294	1	45	140	0.3	404	181.1	220	2.6	3	0.002	1	230	1	Example
295	1	46	140	0.3	399	18.5	30	350.6	4	2	1	230	1	Example
296	1	47	140	0.3	321	0.03	40	280.5	3000	1.2	1	230	1	Example
297	1	48	140	0.3	323	49.4	40	233.7	2	1	1	230	1	Example
298	1	49	140	0.3	323	49.4	40	233.7	2	1	1	230	1	Example
299	1	50	140	0.3	379	57.6	35	286.3	1.5	1.4	1	230	1	Example

 

	TABLE 77
	Performance
		White-rust	White-rust
		resistance:	resistance after	Paint
	Appear-	SST	alkaline degreasing:	adhesive-	Classi-
No.	ance	96 hrs	SST 96 hrs	ness	fication
289	◯	◯+	◯+	⊚	Example
290	◯	◯+	◯+	⊚	Example
291	◯	◯+	◯+	⊚	Example
292	◯	◯+	◯+	⊚	Example
293	◯	◯+	◯+	⊚	Example
294	◯	◯+	◯+	⊚	Example
295	◯	◯+	◯+	⊚	Example
296	◯	◯+	◯+	⊚	Example
297	◯	⊚	◯+	⊚	Example
298	◯	⊚	◯+	⊚	Example
299	◯	⊚	⊚	⊚	Example

 

	TABLE 78
	Primary layer coating	Secondary
	Coat-			Coating weight *4	Molar ratio	layer coating
		ing	Drying			SiO 2	Mg	P 2 O 5	of coating	Resin	Drying	Coat-
	Plating	com-	tem-	Coating	Total	fine	com-	com-	components	com-	tem-	ing
	steel	posi-	pera-	thick-	coating	particles	ponent	ponent	Mg/	P 2 O 5 /	posi-	pera-	thick-	Class-
	plate	tion	ture	ness	weight	(α)	(β)	(γ)	SiO 2	Mg	tion	ture	ness	ifica-
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	*3	(° C.)	(μm)	tion
300	1	51	140	0.3	399	164.6	0.2	233.7	0.003	200	1	230	1	Example
301	1	52	140	0.3	326	66.5	35	225.0	1.3	1.1	1	230	1	Example
302	1	53	140	0.3	337	98.8	4	233.7	0.1	10	1	230	1	Example
303	1	54	140	0.3	393	318.6	4	70.1	0.031	3	1	230	1	Comparative
														example
304	1	55	140	0.3	366	0.0	15	350.6	—	4	1	230	1	Comparative
														example
305	1	56	140	0.3	359	25.9	210	122.7	20	0.1	1	230	1	Comparative
														example
306	1	57	140	0.3	400	280.0	0	120.0	—	—	1	230	1	Comparative
														example
307	1	58	140	0.3	347	0.4	25	321.4	150	2.2	1	230	1	Comparative
														example
308	1	59	140	0.3	359	308.6	50	0.0	0.4	—	1	230	1	Comparative
														example
309	1	60	140	0.3	297	25.9	210	61.4	20	0.05	1	230	1	Comparative
														example
310	1	61	140	0.3	327	10.3	25	292.2	6	2	1	230	1	Comparative
														example

 

	TABLE 79
	Performance
		White-rust	White-rust	Paint
		resistance:	resistance after	ad-
	Appear-	SST	alkaline degreasing:	hesive-	Classi-
No.	ance	96 hrs	SST 96 hrs	ness	fication
300	◯	⊚	⊚	⊚	Example
301	◯	⊚	⊚	⊚	Example
302	◯	⊚	⊚	⊚	Example
303	◯	◯	Δ	Δ	Comparative
					example
304	◯	X	X	⊚	Comparative
					example
305	X	Δ	◯	⊚	Comparative
					example
306	◯	Δ	X	⊚	Comparative
					example
307	X	Δ	Δ	⊚	Comparative
					example
308	◯	Δ	Δ	⊚	Comparative
					example
309	◯	X	Δ	⊚	Comparative
					example
310	◯	◯	◯	X	Comparative
					example

 

	TABLE 80
	Primary layer coating	Secondary layer coating
	Coat-			Coating weight *4	Molar ratio		Ion-
		ing	Drying			SiO 2	Mg	P 2 O 5	of coating	Resin	exchanged	Drying	Coat-
	Plating	com-	tem-	Coating	Total	fine	com-	com-	components	com-	silica	tem-	ing
	steel	posi-	pera-	thick-	coating	particles	ponent	ponent	Mg/	P 2 O 5 /	posi-	(a)	pera-	thick-	Class-
	plate	tion	ture	ness	weight	(α)	(β)	(γ)	SiO 2	Mg	tion	content	ture	ness	ifica-
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	*3	*7	(° C.)	(μm)	tion
311	1	16	140	0.3	324	43.2	35	245.4	2	1.2	1	30	230	1	Example
312	1	17	140	0.3	324	43.2	35	245.4	2	1.2	1	30	230	1	Example
313	1	18	140	0.3	335	88.9	36	210.4	1	1	1	30	230	1	Example
314	1	19	140	0.3	292	38.0	20	233.7	1.3	2	1	30	230	1	Example
315	1	20	140	0.3	332	72.0	35	225.0	1.2	1.1	1	30	230	1	Example
316	1	21	140	0.3	330	22.2	45	263.0	5	1	1	30	230	1	Example
317	1	22	140	0.3	371	148.1	30	192.8	0.5	1.1	1	30	230	1	Example
318	1	23	140	0.3	349	114.0	60	175.3	1.3	0.5	1	30	230	1	Example
319	1	24	140	0.3	323	49.4	40	233.7	2.0	1.0	1	30	230	1	Example
320	1	25	140	0.3	323	49.4	40	233.7	2.0	1.0	1	30	230	1	Example
321	1	26	140	0.3	323	49.4	40	233.7	2.0	1.0	1	30	230	1	Example
322	1	27	140	0.3	374	246.9	10	116.9	0.1	2.0	1	30	230	1	Example

 

	TABLE 81
	Performance
		White-rust	White-rust
		resistance:	resistance after	Paint
	Appear-	SST	alkaline degreasing:	adhesive-	Classi-
No.	ance	150 hrs	SST 150 hrs	ness	fication
311	◯	⊚	⊚	⊚	Example
312	◯	⊚	⊚	⊚	Example
313	◯	⊚	⊚	⊚	Example
314	◯	⊚	⊚	⊚	Example
315	◯	⊚	⊚	⊚	Example
316	◯	⊚	⊚	⊚	Example
317	◯	⊚	⊚	⊚	Example
318	◯	⊚	⊚	⊚	Example
319	◯	⊚	⊚	⊚	Example
320	◯	⊚	⊚	⊚	Example
321	◯	⊚	◯+	⊚	Example
322	◯	⊚	◯+	⊚	Example

 

	TABLE 82
	Primary layer coating	Secondary layer coating
	Coat-			Coating weight *4	Molar ratio		Ion-
		ing	Drying			SiO 2	Mg	P 2 O 5	of coating	Resin	ex-	Drying	Coat-
	Plating	com-	tem-	Coating	Total	fine	com-	com-	components	com-	changed	tem-	ing
	steel	posi-	pera-	thick-	coating	particles	ponent	ponent	Mg/	P 2 O 5 /	posi-	silica	pera-	thick-	Class-
	plate	tion	ture	ness	weight	(α)	(β)	(γ)	SiO 2	Mg	tion	(a) con-	ture	ness	ifica-
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	*3	tent *7	(° C.)	(μm)	tion
323	1	28	140	0.3	330	9.9	40	280.5	10.0	1.2	1	30	230	1	Example
324	1	29	140	0.3	323	164.6	100	58.4	1.5	0.1	1	30	230	1	Example
325	1	30	140	0.3	310	12.3	5	292.2	1.0	10.0	1	30	230	1	Example
326	1	31	140	0.3	310	13.2	40	257.1	7.5	1.1	1	30	230	1	Example
327	1	32	140	0.3	310	2.2	45	263.0	50.0	1.0	1	30	230	1	Example
328	1	33	140	0.3	300	123.5	1	175.3	0.02	30	1	30	230	1	Example
329	1	34	140	0.3	324	148.1	0.6	175.3	0.01	50	1	30	230	1	Example
330	1	35	140	0.3	389	3.5	140	245.4	100	0.3	1	30	230	1	Example
331	1	36	140	0.3	401	1.8	145	254.2	200	0.3	1	30	230	1	Example
332	1	37	140	0.3	394	246.9	0.5	146.1	0.005	50	1	30	230	1	Example
333	1	38	140	0.3	293	74.1	0.15	219.1	0.005	250	1	30	230	1	Example
334	1	39	140	0.3	365	6.9	350	8.2	125	0.004	1	30	230	1	Example

 

	TABLE 83
	Performance
		White-rust	White-rust
		resistance:	resistance after	Paint
	Appear-	SST	alkaline degreasing:	adhesive-	Classi-
No.	ance	150 hrs	SST 150 hrs	ness	fication
323	◯	⊚	◯+	⊚	Example
324	◯	⊚	◯+	⊚	Example
325	◯	⊚	◯+	⊚	Example
326	◯	⊚	◯+	⊚	Example
327	◯	⊚	◯	⊚	Example
328	◯	⊚	◯	⊚	Example
329	◯	⊚	◯	⊚	Example
330	◯	⊚	◯	⊚	Example
331	◯	⊚	◯−	⊚	Example
332	◯	⊚	◯−	⊚	Example
333	◯	◯+	◯+	⊚	Example
334	◯	◯+	◯+	⊚	Example

 

	TABLE 84
	Primary layer coating	Secondary layer coating
	Coat-			Coating weight *4	Molar ratio		Ion-
	Plat-	ing	Drying	Coat-		SiO 2	Mg	P 2 O 5	of coating	Resin	ex-	Drying	Coat-
	ing	com-	tem-	ing	Total	fine	com-	com-	components	com-	changed	tem-	ing
	steel	posi-	pera-	thick-	coating	particles	ponent	ponent	Mg/	P 2 O 5 /	posi-	silica	pera-	thick-	Class-
	plate	tion	ture	ness	weight	(α)	(β)	(γ)	SiO 2	Mg	tion	(a) con-	ture	ness	ifica-
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	*3	tent *7	(° C.)	(μm)	tion
335	1	40	140	0.3	394	0.2	160	233.7	2000	0.25	1	30	230	1	Example
336	1	41	140	0.3	391	0.3	180	210.4	1500	0.2	1	30	230	1	Example
337	1	42	140	0.3	365	246.9	0.8	116.9	0.008	25	1	30	230	1	Example
338	1	43	140	0.3	399	319.5	2.2	77.1	0.017	6	1	30	230	1	Example
339	1	44	140	0.3	379	98.8	0.08	280.5	0.002	600	1	30	230	1	Example
340	1	45	140	0.3	404	181.1	220	2.6	3	0.002	1	30	230	1	Example
341	1	46	140	0.3	399	18.5	30	350.6	4	2	1	30	230	1	Example
342	1	47	140	0.3	321	0.03	40	280.5	3000	1.2	1	30	230	1	Example
343	1	48	140	0.3	323	49.4	40	233.7	2	1	1	30	230	1	Example
344	1	49	140	0.3	323	49.4	40	233.7	2	1	1	30	230	1	Example
345	1	50	140	0.3	379	57.6	35	286.3	1.5	1.4	1	30	230	1	Example

 

	TABLE 85
	Performance
		White-rust	White-rust
		resistance:	resistance after	Paint
	Appear-	SST	alkaline degreasing:	adhesive-	Classi-
No.	ance	150 hrs	SST 150 hrs	ness	fication
335	◯	◯+	◯+	⊚	Example
336	◯	◯+	◯+	⊚	Example
337	◯	◯+	◯+	⊚	Example
338	◯	◯+	◯+	⊚	Example
339	◯	◯+	◯+	⊚	Example
340	◯	◯+	◯+	⊚	Example
341	◯	◯+	◯+	⊚	Example
342	◯	◯+	◯+	⊚	Example
343	◯	⊚	◯+	⊚	Example
344	◯	⊚	◯+	⊚	Example
345	◯	⊚	⊚	⊚	Example

 

	TABLE 86
	Primary layer coating	Secondary layer coating
	Coat-			Coating weight *4	Molar ratio		Ion-	Dry-
	Plat-	ing	Drying	Coat-		SiO 2	Mg	P 2 O 5	of coating	Resin	ex-	ing	Coat-
	ing	com-	tem-	ing	Total	fine	com-	com-	components	com-	changed	tem-	ing
	steel	posi-	pera-	thick-	coating	particles	ponent	ponent	Mg/	P 2 O 5 /	posi-	silica	pera-	thick-	Class-
	plate	tion	ture	ness	weight	(α)	(β)	(γ)	SiO 2	Mg	tion	(a) con-	ture	ness	ifica-
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	*3	tent *7	(° C.)	(μm)	tion
346	1	51	140	0.3	399	164.6	0.2	233.7	0.003	200	1	30	230	1	Example
347	1	52	140	0.3	326	66.5	35	225.0	1.3	1.1	1	30	230	1	Example
348	1	53	140	0.3	337	98.8	4	233.7	0.1	10	1	30	230	1	Example
349	1	54	140	0.3	393	318.6	4	70.1	0.031	3	1	30	230	1	Comparative
															example
350	1	55	140	0.3	366	0.0	15	350.6	—	4	1	30	230	1	Comparative
															example
351	1	56	140	0.3	359	25.9	210	122.7	20	0.1	1	30	230	1	Comparative
															example
352	1	57	140	0.3	400	280.0	0	120.0	—	—	1	30	230	1	Comparative
															example
353	1	58	140	0.3	347	0.4	25	321.4	150	2.2	1	30	230	1	Comparative
															example
354	1	59	140	0.3	359	308.6	50	0.0	0.4	—	1	30	230	1	Comparative
															example
355	1	60	140	0.3	297	25.9	210	61.4	20	0.05	1	30	230	1	Comparative
															example
356	1	61	140	0.3	327	10.3	25	292.2	6	2	1	30	230	1	Comparative
															example

 

	TABLE 87
	Performance
		White-rust	White-rust
		resistance:	resistance after	Paint
	Appear-	SST	alkaline degreasing:	adhesive-	Classi-
No.	ance	150 hrs	SST 150 hrs	ness	fication
346	◯	⊚	⊚	⊚	Example
347	◯	⊚	⊚	⊚	Example
348	◯	⊚	⊚	⊚	Example
349	◯	◯	Δ	Δ	Compar-
					ative
					Example
350	◯	X	X	⊚	Compar-
					ative
					Example
351	X	Δ	◯	⊚	Compar-
					ative
					Example
352	◯	Δ	X	⊚	Compar-
					ative
					Example
353	X	Δ	Δ	⊚	Compar-
					ative
					Example
354	◯	Δ	Δ	⊚	Compar-
					ative
					Example
355	◯	X	Δ	⊚	Compar-
					ative
					Example
356	◯	◯	◯	X	Compar-
					ative
					Example

 

Best Mode 2

A basic feature of the present invention is the following.

On the surface of a zinc base plated steel sheet or an aluminum base plated steel sheet, a composite oxide coating as the primary layer coating is formed, which composite oxide coating comprises (α) oxide fine particles and (β) phosphoric acid and/or phosphoric acid compound, and at need, (γ) at least one substance selected from the group consisting of Li, Mn, Fe, Co, Ni, Zn, Al, La, and Ce. Furthermore, on the composite oxide coating, an organic coating is formed as the secondary layer coating, which organic coating comprises a chelate-forming resin which is a product of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, thus applying the hydrazine derivative (C) as a chelating group to the film-forming resin (A).

The present invention adopts a dual layer coating structure consisting of the above-described primary layer as the lower layer and the secondary layer as the upper layer. The synergy effect of the dual layer coating structure achieved to obtain corrosion resistance equivalent to that of chromate coating even with a thin coating film. Although the mechanism of corrosion resistance in the dual layer coating structure consisting of a specific composite oxide coating and a specific organic coating is not fully analyzed, the corrosion-preventive effect of the dual layer coating structure presumably comes from the combination of corrosion-suppression actions of individual coatings.

The corrosion preventive mechanism of the composite oxide coating as the primary layer coating is not fully understood. The excellent corrosion-preventive performance, supposedly, owes to the features described below.

(a) The dense and slightly soluble composite oxide coating acts as a barrier coating to shut off corrosion causes;

(b) The fine particles of oxide such as silicon oxide form a stable and dense barrier coating along with a metal and phosphoric acid and/or phosphoric acid compound; and

(c) When the fine particles of oxide are those of silicon oxide, the silicic acid ion emitted from the silicon oxide forms basic zinc chloride under a corrosive environment to improve the barrier performance.

In addition, phosphoric acid and/or phosphoric acid compound contributes to the improved denseness of the composite oxide coating, and the phosphoric acid component catches the zinc ion which is eluted during an anodic reaction as a corrosion reaction in the coating-defect section, then the phosphoric acid component is converted to a slightly soluble zinc phosphate compound to form a precipitate at that place.

If at least one element selected from the group consisting of Li, Mn, Fe, Co, Ni, Zn, Al, La, and Ce is further added to the composite oxide coating, the corrosion resistance further improves. Although the reason of further improving corrosion resistance by these elements is not fully understood, any one of these elements likely forms slightly soluble salt with a phosphate in alkaline region, so that a cathodic reaction of oxygen in the corrosion reaction yields OH ion, which seals the corrosion site under an alkaline environment to provide high barrier effect.

Among these metallic elements, Mn and Ni particularly gave favorable corrosion resistance. The reason is, however, not fully analyzed, and the presumable reason is that these phosphates are difficult to dissolve under an alkaline environment.

The corrosion-preventive mechanism of the organic coating as the above-described secondary layer coating is also not fully analyzed. The mechanism is, however, presumably the following.

The rust-preventive effect of the chelate-forming resin as the secondary layer according to the present invention is not fully understood. And it is known that hydrazine derivatives provide light rust-preventive effect to metals. However, those derivatives cannot give high grade rust-preventive effect necessary to the steel sheets for household electric appliances and other products. According to the present invention, addition of a hydrazine derivative, not a simple low molecular weight chelating agent, to the film-forming organic resin provides the following-described work effects, and suppresses efficiently the progress of corrosion, thus assuring excellent corrosion resistance.

(1) The dense organic polymer coating gives an effect to shut-off corrosion causes such as oxygen and chlorine ions.

(2) The hydrazine derivative is able to form a stable passive layer by strongly bonding with the surface of the primary layer coating.

(3) The free hydrazine derivative in the coating traps the zinc ion which is eluted by a corrosion reaction, thus forming a stable insoluble chelated compound layer, which suppresses the formation of an ion conduction layer at interface to suppress the progress of corrosion.

When a resin containing epoxy group is used as the film-forming organic resin (A), a dense barrier coating is formed by the reaction between the epoxy-group-laden resin and a cross-linking agent. Thus, the formed barrier coating has excellent penetration-suppression performance against the corrosion causes such as oxygen, and gains excellent bonding force with the base material owing to the hydroxyl group in the molecule, which results in particularly superior corrosion resistance.

Further excellent corrosion resistance is obtained by using an active-hydrogen-laden pyrazole compound and/or an active-hydrogen-laden triazole compound as the hydrazine derivative (C) containing active hydrogen.

As in the case of prior art, blending simply a hydrazine derivative with the film-forming organic resin gives very little improvement in corrosion-suppression. The reason is presumably that the hydrazine derivative which does not enter the molecules of the film-forming organic resin forms a chelate compound with zinc which is eluted under a corrosive environment, and the chelate compound cannot form a dense barrier layer because of low molecular weight. To the contrary, introduction of a hydrazine derivative into the molecules of film-forming organic resin, as in the case of present invention, provides markedly high corrosion-suppression effect.

As described above, the plurality of corrosion-preventive effects of the primary layer and the plurality of corrosion preventive effects of the secondary layer work as the total in combination and synergy mode, thus providing excellent corrosion resistance with a thin coating film for the first time without using chromium.

As the plated steel sheet as the base of the organic coating steel sheet according to the present invention, a zinc base plated steel sheet or an aluminum base plated steel sheet which are described in the best mode 1 is used.

The following is the description about the composite oxide coating as the primary layer coating formed on the surface of the zinc base plated steel sheet or the aluminum base plated steel sheet.

Quite different from conventional alkali silicate treatment coating which is represented by the coating composition consisting of lithium oxide and silicon oxide, the composite oxide coating according to the present invention comprises: (α) fine particles of oxide; and (β) phosphoric acid and/or phosphoric acid compound. If necessary, (γ) one or more of metal selected from the group consisting of Li, Mn, Fe, Co, Ni, Zn, Al, La, and Ce are contained.

From the viewpoint of corrosion resistance, particularly preferable oxide fine particles as the above-described component (α) are those of silicon oxide (fine particles of SiO 2 ), and most preferable one among the silicon oxides is colloidal silica.

Among these silicon oxides (SiO 2 fine particles), the ones having particle sizes of 14 nm or less, more preferably 8 nm or less are preferred from the viewpoint of corrosion resistance.

The silicon oxide may be used by dispersing dry silica fine particles in a coating composition solution. Examples of the dry silica are AEROSIL 200, AEROSIL 3000, AEROSIL 300CF, AEROSIL 380, (these are trade names) manufactured by Japan Aerosil Co., Ltd., and particularly the ones having particle sizes of 12 nm or less, more preferably 7 nm or less are preferred.

Other than above-described silicon oxides, the oxide fine particles may be colloidal liquid and fine particles of aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, and antimony oxide.

The phosphoric acid and/or phosphoric acid compound as the above-described component (β) may be blended by adding orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, methaphosphoric acid, or metallic salt or compound of them to the coating composition. The target composition may include organic phosphoric acid and salt thereof (for example, phytic acid, phytiate, phosphonic acid, phosphonate, their metal salt). Among them, primary phosphonic acid is preferable from the point of stability of the coating composition. When primary ammonium phosphate, secondary ammonium phosphate, or ternary ammonium phosphate was added as the phosphate to the coating composition solution, the corrosion resistance was improved. Although the reason is not fully analyzed, the presumable reason is that, since generally metallic salts become insoluble in alkaline region, when the metallic salts are formed from a composition solution of high pH, compounds of further difficult to dissolve are generated during the drying step.

There is no specific limitation on the form of existing phosphoric acid and phosphoric acid compound in the coating, and they may be crystals or non-crystals. Also there is no specific limitation on the ionicity and solubility of phosphoric acid and phosphoric acid compound in the coating.

The form of the above-described component (γ) existing in the coating is not specifically limited, and it may be metal, or compound or composite compound such as oxide, hydroxide, hydrated oxide, phosphoric acid compound, or composite compound or metal. The ionicity and solubility of these compound, hydroxide, hydrated oxide, phosphoric acid compound, coordination compound, or the like are not specifically limited.

There is no specific limitation on introducing the component (γ) into the coating, and the component (γ) may be added to the coating composition in a form of phosphate, sulfate, nitrate, and chloride of Li, Mn, Fe, Co, Ni, Zn, Al, La, and Ce.

A preferable range of coating weight of the composite oxide is, when the oxide fine particles (α) and the above-described composition (α) as P 2 O 5 , and further the component (γ) exist, from 5 to 4,000 mg/m 2 as the sum of (α), (β), and (γ) as metal, more preferably from 50 to 1,000 mg/m 2 , further preferably from 100 to 500 mg/m 2 , and most preferably from 200 to 400 mg/m 2 . If the coating weight is less than 5 mg/m 2 , the corrosion resistance degrades. If the coating weight exceeds 4,000 mg/m 2 , the conductive performance degrades and the weldability degrades.

To attain particularly superior corrosion resistance, it is preferred to select the ratio of silicon oxide as the component (α), converted to SiO 2 , to the total composite oxide coating to a range of from 5 to 95 wt. %, more preferably from 10 to 60 wt. %.

The reason of giving particularly superior corrosion resistance when the ratio of the silicon oxide is selected to the range given above is not fully analyzed. It is, however, speculated that the phosphoric acid component supports the barrier effect which cannot be attained solely by silicon oxide, thus contributing to forming a dense film, further that the synergy effect of corrosion-suppression actions of each of phosphoric acid component and silicon oxide component, resulting in obtaining the excellent corrosion resistance.

From the similar viewpoint, it is preferred to select the ratio of the phosphoric acid and/or phosphoric acid compound as the component (β) to the metallic component as the component (γ) (if there are two or more metals, the sum of each of them converted to respective metals) in the composite oxide coating to a range of from 1/2 to 2/1 as the molar ratio of the component (β) as P 2 O 5 to the component (γ) as metal, or [P 2 O 5 /Me] for attaining further excellent corrosion resistance.

The reason of giving particularly superior corrosion resistance when the ratio of phosphoric acid component to metallic component is selected to the range given above is not fully analyzed. It is, however, speculated that, since the solubility of phosphoric component varies with the ratio of phosphoric acid to metal, the corrosion resistance becomes particularly high when the coating non-soluble property stays within the range given above, so that the barrier performance of the coating increases.

For further improving the workability and the corrosion resistance of the coating, the composite oxide coating may further contain organic resins. Examples of the organic resin are epoxy resin, polyurethane resin, polyacrylic resin, acrylic-ethylene copolymer resin, acrylic-styrene copolymer resin, alkyd resin, polyester resin, polyethylene resin. These resins may be introduced into the coating in a form of water-soluble resin or water-dispersible resin.

Adding to these water-dispersible resins, it is effective to use water-soluble epoxy resin, water-soluble phenol resin, water-soluble polybutadiene rubber (SBR, NBR, MBR), melamine resin, block-polyisocyanate compound, oxazolane compound, and the like as the cross-linking agent.

For further improving the corrosion resistance, the composite oxide coating may further contain polyphosphate, phosphate (for example, zinc phosphate, aluminum dihydrogen phosphate, and zinc phosphate), molybdate, phospho molybdate (for example, aluminum phosphomolybdate), organic phosphate and its salt (for example, phytic acid, phytiate, phosphonic acid, phosphonate, their metal salt and alkali metal salt), organic inhibitor (for example, hydrazine derivative, thiol compound, dithiocarbamate), organic compound (polyethyleneglycol), and the like.

Other applicable additives include organic coloring pigments (for example, condensing polycyclic organic pigments, phthalocyanine base organic pigments), coloring dyes (for example, azo dye soluble in organic solvent, azo metal dye soluble in water), inorganic pigments (titanium oxide), chelating agents (for example, thiol), conductive pigments (for example, metallic powder of zinc, aluminum, nickel, or the like, iron phosphide, antimony-dope type tin oxide), coupling agents (for example, silane coupling agent and titanium coupling agent), melamine-cyanuric acid additives.

As for the organic coating formed as the secondary layer coating on the above-described oxide coating, similar ones described in the best mode 1 may be applied.

According to the best mode 2, an inorganic rust-preventive pigment (a) is further added to the organic coating.

Examples of the inorganic rust-preventive pigment are: silica compound such as ion-exchanged silica and fine particle silica; celium oxide; aluminum oxide; zirconium oxide; antimonium oxide; polyphosphoric acid (for example, aluminum polyphosphate, TAICA K-WHITE 80, 84, 105, G105, 90, 90, (produced by TAYCA CORPORATION); molybdenate; phospho-molybdenate (such as aluminum-phosphomolybdenate). Particularly improved corrosion resistance is obtained when the system includes at least one of silica compound such as ion-exchanged silica (c), fine particle silica (d), phosphate such as zinc phosphate (e) and aluminum phosphate (f), and calcium compound.

The adding amount of inorganic rust-preventive pigment is in a range of from 1 to 100 parts by weight (solid matter) as the total inorganic rust-preventive pigment to 100 parts by weight of the reaction product as the resin composition for forming coating (the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen), preferably from 5 to 80 parts by weight (solid matter).

The ion-exchanged silica is prepared by fixing metallic ion such as calcium and magnesium ions on the surface of porous silica gel powder. Under a corrosive environment, the metallic ion is released to form a deposit film. Among these ion-exchanged silicas, Ca ion-exchanged silica is most preferable.

The corrosion-preventive mechanism obtained by blending ion-exchanged silica (a) in the organic coating is presumably the following. That is, when cation such as Na ion enters under the corrosion environment, the iron exchange action emits Ca ion and Mg ion from the surface of silica. Furthermore, when OH ion is generated by the cathode reaction under the corrosive environment to increase pH value near the plating interface, the Ca ion (or Mg ion) emitted from the ion-exchanged silica precipitates in the vicinity of the plating interface in a form of Ca(OH) 2 or Mg(OH) 2 , respectively. The precipitate seals defects as a dense and slightly soluble product to suppress the corrosion reactions. Furthermore, the eluted Zn ion exchanges Ca ion (or Mg ion) to be fixed onto the surface of silica.

Any type of Ca-exchanged silica may be used, and a preferred one has an average particle size not more than 6 μm, more preferably not more than 4 μm. For example, Ca-exchanged silica having average particle sizes of from 2 to 4 μm may be used. If the average particle size of the Ca-exchanged silica exceeds 6 μm, the corrosion resistance degrades, and the dispersion stability in a paint composition degrades.

A preferred range of the Ca concentration in the Ca-exchanged silica is 1 wt. % or more, more preferably from 2 to 8 wt. %. Ca content of less than 1 wt. % fails to obtain satisfactory rust-preventive effect under the Ca emission.

There is no specific limitation on the surface area, pH, and oil absorbing capacity of Ca-exchanged silica.

The corrosion-preventive mechanism in the case that ion-exchanged silica (c) is added to the organic coating is described before. In particular, according to the present invention, when an ion-exchanged silica is blended with an organic coating consisting of a specific chelate-modified resin, the corrosion-preventive effect at anode reaction section owing to the chelate-modified resin and the corrosion-preventive effect at cathode reaction section owing to the ion-exchanged silica are combined to suppress both the anode and the cathode corrosion reactions, which should provide markedly strong corrosion-preventive effect.

The adding amount of ion-exchanged silica (c) in the organic resin coating is in a range of from 1 to 100 parts by weight (solid matter) to 100 parts by weight of the reaction product as the resin composition for forming coating (the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen), preferably from 5 to 80 parts by weight (solid matter), more preferably from 10 to 50 parts by weight (solid matter). When the amount of ion-exchanged silica (c) is less than 1 part by weight, the effect to improve the corrosion resistance after alkaline degreasing becomes small. If the amount of ion-exchanged silica (c) exceeds 100 parts by weight, the corrosion resistance degrades, which is unfavorable.

The fine particle silica (d) may be either colloidal silica or fumed silica.

Particularly an organic solvent dispersible silica sol has superior dispersibility, and shows superior corrosion resistance to fumed silica.

Fine particle silica is supposed to contribute to forming dense and stable zinc corrosion products under a corrosive environment. Thus formed corrosion products cover the plating surface in a dense mode, thus presumably suppressing the development of corrosion.

From the viewpoint of corrosion resistance, the fine particle silica preferably has particle sizes of from 5 to 50 nm, more preferably from 5 to 20 nm, and most preferably from 5 to 15 nm.

The adding amount of fine particle silica (d) in the organic resin coating is in a range of from 1 to 100 parts by weight (solid matter) to 100 parts by weight of the reaction product as the resin composition for forming coating (the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen), preferably from 5 to 80 parts by weight (solid matter), more preferably from 10 to 30 parts by weight (solid matter). When the amount of fine particle silica (d) is less than 1 part by weight, the effect to improve the corrosion resistance after alkaline degreasing becomes small. If the amount of fine particle silica (d) exceeds 100 parts by weight, the corrosion resistance degrades, which is unfavorable.

According to the present invention, combined addition of ion-exchanged silica (c) and fine particle silica (d) to the organic coating provides particularly excellent corrosion resistance. That is, the combined addition of ion-exchanged silica (c) and fine particle silica (d) induces combined rust-preventive mechanism of both components as described before to give particularly excellent corrosion-preventive effect.

A preferred range of ratio of combined blend of ion-exchanged silica (c) and fine particle silica (d) in the organic resin coating is 1 to 100 parts by weight (solid matter) of the sum of the ion-exchanged silica (c) and the fine particle silica (d) to 100 parts by weight (solid matter) of the reaction product as the resin composition for film-forming (that is, the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen), and a preferred range of blending ratio of the ion-exchanged silica (c) to the fine particle silica (d), (solid matter), or (c)/(d), is from 99/1 to 1/99, more preferably from 95/5 to 40/60, and most preferably from 90/10 to 16/40.

If the blending ratio of the sum of the ion-exchanged silica (c) and the fine particle silica (d) becomes less than 1 part by weight, the effect of improved corrosion resistance after alkaline degreasing becomes small. If the blending ratio of the sum of the ion-exchanged silica (c) and the fine particle silica (d) exceeds 100 parts by weight, the paintability and the work ability degrade, which is unfavorable.

If the weight ratio of the ion-exchanged silica (c) to the fine particle silica (d), (c)/(d), is less than 1/99, the corrosion resistance degrades. If the weight ratio of the ion-exchanged silica (c) to the fine particle silica (d), (c)/(d), exceeds 99/1, the effect of combined addition of the ion-exchanged silica (c) and the fine particle silica (d) cannot fully be attained.

There is no specific limitation on the skeleton and degree of condensation of phosphoric acid ions for the zinc phosphate (e) and the aluminum phosphate (f) blended in the organic coating. They may be normal salt, dihydrogen salt, monohydrogen salt, or phosphite. The normal salt includes orthophosphoric acid and all the condensed phosphates such as polyphosphate. For example, zinc phosphate may be LF-BOSEI ZP-DL produced by Kikuchi Color Co., and aluminum phosphate may be K-WHITE produced by TAYCA CORPORATION.

These zinc phosphates and aluminum phosphates dissociate to phosphoric acid ion by hydrolysis under a corrosive environment, and form a protective coating through the complex-forming reaction with the eluted metals.

A preferred range of blending amount of zinc phosphate and/or aluminum phosphate (e, f) in the organic resin coating is from 1 to 100 parts by weight (solid matter) to 100 parts by weight (solid matter) of the film-forming organic resin (A), more preferably from 5 to 80 parts by weight (solid matter), and most preferably from 10 to 50 parts by weight (solid matter). If the blending amount of the zinc phosphate and/or aluminum phosphate (e, f) is less than 1 part by weight, the improved effect of corrosion resistance after alkaline degreasing becomes small. If the blending amount of the zinc phosphate and/or aluminum phosphate (e, f) exceeds 100 parts by weight, the corrosion resistance degrades, which is unfavorable.

According to the present invention, combined addition of zinc phosphate and/or aluminum phosphate (e, f) and calcium compound (g) to the organic coating provides particularly excellent corrosion resistance. That is, the combined addition of zinc phosphate and/or aluminum phosphate (e, f) and calcium compound (g) to the organic coating provides particularly excellent corrosion resistance which induces combined rust-preventive mechanism of both components as described before to give particularly excellent corrosion-preventive effect.

Calcium compound (g) may be either one of calcium oxide, calcium hydroxide, and calcium salt, and at least one of them is adopted. There is no specific limitation on the kind of calcium salt, and the salt may be a single salt containing only calcium as cation, for example, calcium silicate, calcium carbonate, and calcium phosphate, and may be complex salt containing cation other than calcium cation, for example, zinc calcium phosphate, magnesium calcium phosphate.

Since calcium compounds elute preferentially to metals under a corrosive environment, it presumably induces a complex-forming reaction with phosphoric acid ion without triggering the elution of plating metal, thus forming a dense and slightly-soluble protective coating to suppress the corrosion reactions.

A preferred blending ratio of combined addition of zinc phosphate and/or aluminum phosphate (e, f) and calcium compound (g) to the organic resin coating is from 1 to 100 parts by weight (solid matter) to 100 parts by weight (solid matter) of the film-forming organic resin (A), more preferably from 5 to 80 parts by weight, and a preferred blending weight ratio (solid matter) of the zinc phosphate and/or aluminum phosphate (e, f) and the calcium compound (g), (e, f)/(g), is from 99/1 to 1/99, more preferably from 95/5 to 40/60, and most preferably from 90/10 to 60/40.

If the blending amount of the sum of zinc phosphate and/or aluminum phosphate (e, f) and calcium compound (g) is less than 1 part by weight, the improved effect of corrosion resistance after alkaline degreasing becomes small. If the blending amount of the sum of zinc phosphate and/or aluminum phosphate (e, f) and calcium compound (g) exceeds 100 parts by weight, the corrosion resistance degrades, which is unfavorable.

If the blending ratio (solid matter) of zinc phosphate and/or aluminum phosphate (e, f) to calcium compound (g) is less than 1/99, the corrosion resistance is inferior. If the blending ratio (solid matter) of zinc phosphate and/or aluminum phosphate (e, f) to calcium compound (g) exceeds 99/1, the effect of combined addition of zinc phosphate and/or aluminum phosphate (e, f) and calcium compound (g) cannot be fully attained.

The organic coating may further contain, adding to the above-described inorganic rust-preventive pigments, corrosion-suppression agents such as organic inhibitors including organic phosphate and its salt (for example, phytic acid, phytiate, phosphonic acid, phosphonate, their metal salt, alkali metal salt, and alkali earth metal salt), hydrazine derivative, thiol compound, dithiocarbamate.

The organic coating may, at need, further include a solid lubricant (b) to improve the workability of the coating.

Examples of applicable solid lubricant according to the present invention are the following.

(1) Polyolefin wax, paraffin wax: for example, polyethylene wax, synthetic paraffin, natural paraffin, microwax, chlorinated hydrocarbon;

(2) Fluororesin fine particles: for example, polyfluoroethylene resin (such as poly-tetrafluoroethylene resin), polyvinylfluoride resin, polyvinylidenefluoride resin.

In addition, there may be applied fatty acid amide base compound (such as stearic acid amide, palmitic acid amide, methylene bis-stearoamide, ethylene bis-stearoamide, oleic acid amide, ethyl acid amide, alkylene bis-fatty acid amide), metallic soap (such as calcium stearate, lead stearate, calcium laurate, calcium palmate), metallic sulfide (molybdenum disulfide, tungsten disulfide), graphite, graphite fluoride, boron nitride, polyalkyleneglycol, and alkali metal sulfate.

Among those solid lubricants, particularly preferred ones are polyethylene wax, fluororesin fine particles (particularly poly-tetrafluoroethylene resin fine particles).

Applicable polyethylene wax include: Sheridust 9615A, CELIDUST 3715, CELIDUST 3620, CELIDUST 3910 (trade names) manufactured by Hoechst Co., Ltd.; SUNWAX 131-P, SUNWAX 161-P (trade names) manufactured by Sanyo Chemical Industries, Ltd.; CHEMIPEARL W-100, CHEMIPEARL W-200, CHEMIPEARL W-500, CHEMIPEARL W-800, CHEMIPEARL W-950 (trade names) manufactured by Mitsui Petrochemical Industries, Ltd.

A most preferred fluororesin fine particle is tetrafluoroethylene fine particle. Examples of the fine particles are LUBRON L-2, LUBRON L-5 (trade names) manufactured by Daikin Industries, Ltd.; MP 1100, MP 1200 (trade names; manufactured by Du Pont-Mitsui Company, Ltd.); FLUON DISPERSION AD1, FLUONDISPERSION AD2, FLUON L141J, FLUON L150J, FLUON L155J (trade names) manufactured by Asahi ICI Fluoropolymers Co., Ltd.

As of these compounds, combined use o f polyolefin in wax and tetrafluoroethylene fine particles is expected to provide particularly excellent lubrication effect.

A preferred range of blending ratio of the solid lubricant (b) in the organic resin coating is from 1 to 80 parts by weight (solid matter) to 100 parts by weight (solid matter) of the reaction product as the resin composition for film-forming (that is, the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen), more preferably from 3 to 40 parts by weight (solid matter). If the blending ratio of the solid lubricant (b) becomes less than 1 part by weight, the effect of lubrication is small. If the blending ratio of the solid lubricant (b) exceeds 80 parts by weight, the pain ting performance degrade, which is unfavorable.

The organic coating of the organic coating steel sheet according to the present invention normally consists mainly of a product (resin composition) of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen). And, at need, an inorganic rust-preventive pigment (a), a solid lubricant (b), a curing agent, or the like may further be added to the organic coating. Furthermore, at need, there may be added other additives such as organic coloring pigment (for example, condensing polycyclic organic pigment, phthalocyanine base organic pigment), coloring dye (for example, azo dye soluble in organic solvent, azo metal dye soluble in water), inorganic pigment (for example, titanium oxide), chelating agent (for example, thiol), conductive pigment (for example, metallic powder of zinc, aluminum, nickel, or the like, iron phosphide, antimony-dope type tin oxide), coupling agent (for example, silane coupling agent and titanium coupling agent), melamine-cyanuric acid additive.

The paint composition for film-formation containing above-described main component and additive components normally contains solvent (organic solvent and/or water), and, at need, further a neutralizer or the like is added.

Applicable organic solvent described above has no specific limitation if only it dissolves or disperses the product of reaction between the above-described film-forming organic resin (A) and the active-hydrogen-laden compound (B), and adjusts the product as the painting composition. Examples of the organic solvent are the organic solvents given above as examples.

The above-described neutralizers are blended, at need, to neutralize the film-forming organic resin (A) to bring it to water-type. When the film-forming organic resin (A) is a cationic resin, acid such as acetic acid, lactic acid, and formic acid may be used as the neutralizer.

The organic coatings described above are formed on the above-described composite oxide coating.

The dry thickness of the organic coating is in a range of from 0.1 to 5 μm, preferably from 0.3 to 3 μm, and most preferably from 0.5 to 2 μm. If the thickness of the organic coating is less than 0.1 μm, the corrosion resistance becomes insufficient. If the thickness of the organic coating exceeds 5 μm, the conductivity and the workability degrade.

The following is the description about the method for manufacturing an organic coating steel sheet according to the present invention.

The organic coating steel sheet according to the present invention is manufactured by the steps of: treating the surface (applying a treatment liquid to the surface) of a zinc base plated steel sheet or an aluminum base plated steel sheet using a treatment liquid containing the components of above-described composite oxide coating; heating and drying the plate; applying a paint composition which contains the product of reaction between above-described film-forming organic resin (A) and an active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen, which product of reaction is preferably the main component, and at need, further contains an inorganic rust-preventive pigment (a), a solid lubricant (b), and the like; heating to dry the product.

The surface of the plated steel sheet may be, at need, subjected to alkaline degreasing before applying the above-described treatment liquid, and may further be subjected to preliminary treatment such as surface adjustment treatment for further improving the adhesiveness and corrosion resistance.

For treating the surface of the zinc base plated steel sheet or the aluminum base plated steel sheet with a treatment liquid and for forming a composite oxide coating thereon, it is preferred that the plate is treated by an aqueous solution containing:

(aa) oxide fine particles ranging from 0.001 to 3.0 mole/liter; and

(ab) phosphoric acid and/or phosphoric acid compound ranging from 0.001 to 6.0 mole/liter as P 2 O 5 ; followed by heating to dry.

The aqueous solution may further contain: (ac) one or more of the substances selected from the group consisting of either one metallic ion of Li, Mn, Fe, Co, Ni, Zn, Al, La, and Ce; a compound containing at least one metal given above; a composite compound containing at least one metal given above; ranging from 0.001 to 3.0 mole/liter as metal given above.

As the oxide fine particles as an additive component (ab), silicon oxide (SiO 2 ) fine particles are most preferred. The silicon oxide may be commercially available silica sol and water-dispersion type silicic acid oligomer or the like if only the silicon oxide is water-dispersion type SiO 2 fine particles which are stable in an acidic aqueous solution. Since, however, fluoride such as hexafluoro silicic acid is strongly corrosive and gives strong effect to human body, that kind of compound should be avoided from the point of influence to work environment.

A preferred range of blending ratio of the fine particle oxide (the blending ratio as SiO 2 in the case of silicon oxide) in the treating liquid is from 0.001 to 3.0 mole/liter, more preferably from 0.05 to 1.0 mole/liter, and most preferably from 0.1 to 0.5 mole/liter. If the blending ratio of the fine particle oxide becomes less than 0.001 mole/liter, the effect of addition is not satisfactory. If the blending ratio of the fine particle oxide exceeds 3.0 mole/liter, the water-resistance of coating degrades, resulting in degradation of corrosion resistance.

The phosphoric acid and/or phosphoric acid compound as the additive component (ab) includes: a mode of aqueous solution in which a compound specific to phosphoric acid, such as polyphosphoric acid such as orthophosphoric acid, pyrophosphoric acid, and tripolyphosphoric acid, methaphosphoric acid, inorganic salt of these acids (for example, primary aluminum phosphate), phosphorous acid, phosphite, phosphinic acid, phosphinate, exists in a form of anion or complex ion combined with a metallic cation which are generated by dissolving the compound in the aqueous solution; and a mode of aqueous solution in which that kind of compound exists in a form of inorganic salt dispersed therein. The amount of phosphoric acid component according to the present invention is specified by the sum of all these modes of acidic aqueous solution thereof as converted to P 2 O 5 amount.

A preferred range of blending ratio of the phosphoric acid and/or phosphoric acid compound as P 2 O 5 is from 0.001 to 6.0 mole/liter, more preferably from 0.02 to 1.0 mole/liter, and most preferably from 0.1 to 0.8 mole/liter. If the blending ratio of the phosphoric acid and/or phosphoric acid compound becomes less than 0.001 mole/liter, the effect of addition is not satisfactory and the corrosion resistance degrades. If the blending ratio of the phosphoric acid and/or phosphoric acid compound exceeds 6.0 mole/liter, excess amount of phosphoric acid ion reacts with the plating film under a humid environment, which enhances the corrosion of plating base material to cause discoloration and stain-rusting under some corrosive environments.

As the component (ab), use of ammonium phosphate is also effective because the compound provides a highly anti-corrosive composite oxide. As for the ammonium phosphate, primary ammonium phosphate and secondary ammonium phosphate are preferred.

The added components (ac) in the treatment liquid is in a range of from 0.001 to 3.0 mole/liter as metal, preferably from 0.01 to 0.5 mole/liter. If the sum of the added amount of these components is less than 0.001 mole/liter, the effect of addition cannot be fully attained. If the sum of the added amount of these components exceeds 3.0 mole/liter, these components become soluble cations to interfere the network of coating.

For supplying ion of the additive components (ac) in a form of metallic salt, the treatment liquid may contain anion such as chlorine ion, nitric acid ion, sulfuric acid ion, acetic acid ion, and boric acid ion.

The treatment liquid may further contain an organic resin (ad) for improving workability and corrosion resistance of the composite oxide coating. Examples of the organic resin are water-soluble resins and/or water-dispersible resins such as epoxy resin, polyurethane resin, polyacrylic resin, acrylic-ethylene copolymer, acrylic-styrene copolymer, alkyd resin, polyester resin, polyethylene resin.

Adding to these water-dispersible resins, it is also possible to use water-soluble epoxy resin, water-soluble phenol resin, water-soluble polybutadiene rubber (SBR, NBR, MBR), melamine resin, block-polyisocyanate compound, oxazolane compound, and the like as the cross-linking agent.

Adding to the above-described additive components (ab) through (ad), the treatment liquid may further contain an adequate amount of additive components to the coating, which are described before.

The methods for applying the treatment liquid onto the plated steel sheet may be either one of coating method, dipping method, and spray method. The coating method may adopt any type such as roll coater (three-roll type, two-roll type, etc.), squeeze coater, die coater. After the coating step using squeeze coater and the like, the dipping step, or the spray step, it is possible to adjust the coating weight, the uniformizing appearance, and the uniformizing the film-thickness using air-knife method and roll-squeezing method.

Although there is no specific limitation on the temperature of the treatment liquid, a preferable range thereof is from normal temperature to around 60° C. Below the normal temperature is uneconomical because a cooling unit or other additional facilities are required. On the other hand, temperatures above 60° C. enhances the vaporization of water, which makes the control of the treatment liquid difficult.

After the coating of treatment liquid as described above, generally the plate is heated to dry without rinsing with water.

The treatment liquid according to the present invention forms a slightly soluble salt by a reaction with the substrate plated steel sheet, so that, rinsing with water may be applied after the treatment.

Method for heating to dry the coated treatment liquid is not limited. For example, dryer, hot air oven, high frequency induction heating furnace, infrared heating furnace may be applied.

The heating and drying treatment is preferably conducted at reaching temperatures of from 50 to 30° C., more preferably from 80 to 200° C., and most preferably from 80 to 160° C. If the heating temperature is less than 50° C., excess amount of water is left in the coating, which results in insufficient corrosion resistance. If the heating temperature exceeds 300° C., the operation becomes uneconomical and defects likely appear in the coating to degrade the corrosion resistance.

After forming the composite oxide coating on the surface of the zinc base plated steel sheet or the aluminum base plated steel sheet, as described above, a paint composition for forming an organic coating is applied on the composite oxide coating. Method for applying the paint composition is not limited, and examples of the method are coating method, dipping method, and spray method. The coating method may adopt any type such as roll coater (three-roll type, two-roll type, etc.), squeeze coater, die coater. After the coating step using squeeze coater and the like, the dipping step, or the spray step, it is possible to adjust the coating weight, the uniformizing appearance, and the uniformizing the film-thickness using air-knife method and roll-squeezing method.

After applying the paint composition, generally the plate is heated to dry without rinsing with water. After applying the paint composition, however, water-rinse step may be given.

Method for heating to dry the paint composition is not limited. For example, dryer, hot air oven, high frequency induction heating furnace, infrared heating furnace may be applied. The heating treatment is preferably conducted at reaching temperatures of from 50 to 350° C., more preferably from 80 to 250° C. If the heating temperature is less than 50° C., excess amount of water is left in the coating, which results in insufficient corrosion resistance. If the heating temperature exceeds 350° C., the operation becomes uneconomical and defects likely appear in the coating to degrade the corrosion resistance.

As described above, the present invention includes a steel sheet having an organic coating on both sides or on side thereof. Accordingly, modes of the steel sheet according to the present invention include, for example, the followings.

(1) Plating film—Composite oxide coating—Organic coatings on one side of the steel sheet, and “Plating film” on other side of the steel sheet;

(2) “Plating film—Composite oxide coating—Organic coating” on one side of the steel sheet, and “Plating film—Known coating treated by phosphoric acid, or the like” on other side of the steel sheet;

(3) “Plating film—Composite oxide coating—Organic coating” on both sides of the steel sheet;

(4) “Plating film—Composite oxide coating—Organic coating” on one side of the steel sheet, and “Plating film—Composite oxide coating” on other side of the steel sheet;

(5) “Plating film—Composite oxide coating—Organic coating” on one side of the steel sheet, and “Plating film—Organic coating” on other side of the steel sheet.

Embodiments

Treatment liquids (coating compositions) for forming the primary layer coating, which are listed in Tables 88 through 90, were prepared.

In Tables 88 through 90, the concentration of oxide fine particles, (mole/liter), is converted to SiO 2 , and the concentration of phosphoric acid and/or phosphoric acid compound, (mole/liter), is converted to P 2 O 5 . In the column “Adaptability to the conditions of the Invention”, the symbol “◯” signifies “Satisfies”, and the symbol “x” signifies “Dissatisfies”.

Resin compositions (reaction products) for forming the secondary layer coating were synthesized in the following-described procedure.

SYNTHESIS EXAMPLE 1

A 1870 parts of EP828 (epoxy equivalent 187, manufactured by Yuka Shell-Epoxy Co., Ltd.), 912 parts of bisphenol A, 2 parts of tetraethylammonium bromide, and 300 parts of methylethylketone were charged into a flask with four necks, which mixture was then heated to 140° C. to let them react for 4 hours. Thus, an epoxy resin having an epoxy equivalent of 1391 and a solid content of 90% was obtained. A 1500 parts of ethyleneglycol monobutylether was added to the epoxy resin, which were then cooled to 100° C. A 96 parts of 3,5-dimethylpyrazole (molecular weight 96) and 129 parts of dibutylamine (molecular weight 129) were added to the cooled resin, and they were reacted for 6 hours to eliminate the epoxy group. Then, a 205 parts of methylisobutylketone was added while the mixture was cooling, to obtain a pyrazole-modified epoxy resin having 60% of solid matter. The epoxy resin is defined as the resin composition (1). The resin composition (1) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound that contains 50 mole % of hydrazine derivative (C) containing active hydrogen.

To the resin composition (1) thus synthesized, a curing agent was blended to prepare a resin composition (a paint composition).

Resin composition
Base resin   Resin composition (1), 100 parts
Curing agent IPDI MEK oxime block, 5 parts
Catalyst     Dibutyl laurate, 0.2 part

 

To the resin composition, the inorganic rust-preventive pigment shown in Table 91, and polyethylene wax as the solid lubricant were blended at respective adequate amounts, which resin composition was then treated in a paint dispersion machine (sand grinder) for a necessary time to obtain designed paint compositions. For the above-described ion-exchanged silica, SHILDEX C303 (average particle sizes of from 2.5 to 3.5 μm and Ca concentration of 3 wt. %) manufactured by W.R. Grace & Co., which is a Ca-exchanged silica, was used.

To obtain organic coating steel sheets for household electric appliances, building materials, and automobile parts, the plated steel sheets processed by electrolytic galvanizing at a coating weight of 20 mg/m2 were used as the target base plates which were the cold-rolled steel sheets having a plate thickness of 0.8 mm and a surface roughness Ra of 1.0 μm. The surface of the plated steel sheet was treated by alkaline degreasing and water washing, then the treatment liquids (coating compositions) shown in Tables 88 through 90 were applied to the surface using a roll coater, followed by heating to dry to form the first layer coating. The thickness of the first layer coating was adjusted by the solid content in the treatment liquid (heating residue) or applying conditions (roll pressing force, rotational speed, and other variables). Then, the paint composition was applied using a roll coater, which was then heated to dry to form the secondary layer coating, thus manufactured the organic coating steel sheets as Examples and Comparative Examples. The thickness of the second layer coating was adjusted by the solid content in the treatment liquid (heating residue) or applying conditions (roll pressing force, rotational speed, and other variables).

To each of thus obtained organic coating steel sheets, evaluation was given in terms of quality performance (appearance of coating, white-rust resistance, white-rust resistance after alkaline degreasing, paint adhesiveness, and workability). The results are given in Tables 92 through 96 along with the structure of primary layer coating and of secondary layer coating.

The quality performance evaluation on the organic coating steel sheets was carried out similar to the procedure of the best mode 1.

In Tables 92 through 96, each of *1 through *11 appeared in the tables expresses the following.

*1: Numeral “1” in Column 1 of the plated steel sheet signifies “Electrolytically galvanized steel sheets”.

*2: Each “No.” of coating composition corresponds to the “No.” given in Tables 88 through 90.

*3: Ratio (wt. %) converted to SiO 2 is a weight ratio to the sum of the weight of the first layer (composite oxide).

*4: “(β)/(γ)” signifies the ratio of the moles of phosphoric acid and/or phosphoric acid compound (β) converted to P 2 O 5 to the total moles of component (γ) converted to metal.

*5: Total coating weight=(α)+(β)+(γ).

*6: Numeral “1” signifies the resin composition described in this specification.

*7: The inorganic rust-preventive pigment given in Table 91.

*8: The blending ratio of solid matter (parts by weight) to 100 parts by weight of the solid matter in the resin compound.

*9: Total blending amount of the inorganic rust-preventive pigment 1 and the inorganic rust-preventive pigment 2.

*10: Solid weight ratio of the sum of the inorganic rust-preventive pigment 1 and the inorganic rust-preventive pigment 2.

*11: Solid blending rate (parts by weight) of the solid lubricant to 100 parts by weight of the solid matter in the resin composition.

TABLE 91
No.	Kind of inorganic rust-preventive pigment
1	Ion-exchanged silica	Ca-exchanged silica	SHIELDEX C 303, produced by W. R. Grace & Co.
			average particle size 2.5-3.5 μm, Ca conc. 3 wt. %
13	Zinc phosphate	Zinc orthophosphate
28	Calcium compound	Calcium carbonate 60 wt. %
		+ Calcium silicate 40 wt. %

 

	TABLE 92
	Secondary layer coating
	Primary layer coating		Inorganic rust-prevention pigment
						Molar					(Pigment
				Blending		ratio of					1) +	(Pigment
	Plat-			ratio		phosphoric	Total				(Pigment	1)/
	ing	Coating	Drying	converted	(γ)	acid	coating	Resin	(Pigment 1)	(Pigment 2)	2)	(Pigment
	steel	compo-	temper-	to SiO 2	Com-	component	weight	compo-		Blending		Blending	Total	2)
	plate	sition	ature	(wt %)	po-	(β)/(γ)	(mg/m 2 )	sition	Type	ratio	Type	ratio	amount	Ratio
No.	*1	*2	(° C.)	*3	nent	*4	*5	*6	*7	*8	*7	*8	*9	*10
1	1	5	120	40	Ni	1.2	300	1	1	30
15	1	1	120	40	Li	1	320	1	1	30
16	1	2	120	40	Mn	1.47	290	1	1	30
17	1	3	120	40	Fe	1.3	320	1	1	30
18	1	4	120	40	Co	1.21	315	1	1	30
19	1	6	120	40	Zn	1.1	280	1	1	30
20	1	7	120	40	Al	1.5	350	1	1	30
21	1	8	120	40	La	1.8	350	1	1	30
22	1	9	120	40	Ce	1.8	350	1	1	30
23	1	10	120	60	Mn	1.47	360	1	1	30
24	1	11	120	60	Ni	1.2	290	1	1	30
25	1	12	120	40	Co	1.2	290	1	1	30
26	1	13	120	40	Al	1.5	280	1	1	30
27	1	14	120	20	Ni	1.2	320	1	1	30
28	1	15	120	20	Al	1.2	330	1	1	30
	Performance
	Secondary layer coating			White-rust
	Solid					resistance
	lubricant				White-rust	after alkaline				Classification
		Blending	Drying	Coating		resistance:	degreasing:				Example/
	Type	ratio	temperature	thickness	Appear-	SST	SST	Paint			Comparative
No.	*11	*12	(° C.)	(μm)	ance	120 hrs	120 hrs	adhesiveness	Workability	Remark	Example
1			230	1	◯	⊚	⊚	⊚			Example
15			230	1	◯	◯	◯	⊚			Example
16			230	1	◯	⊚	⊚	⊚			Example
17			230	1	◯	⊚	◯	⊚			Example
18			230	1	◯	⊚	◯+	⊚			Example
19			230	1	◯	⊚	◯	⊚			Example
20			230	1	◯	⊚	◯+	⊚			Example
21			230	1	◯	⊚	◯	⊚			Example
22			230	1	◯	⊚	◯	⊚			Example
23			230	1	◯	⊚	⊚	⊚			Example
24			230	1	◯	⊚	⊚	⊚			Example
25			230	1	◯	⊚	◯+	⊚			Example
26			230	1	◯	⊚	◯+	⊚			Example
27			230	1	◯	⊚	⊚	⊚			Example
28			230	1	◯	⊚	◯+	⊚			Example

 

	TABLE 93
	Secondary layer coating
	Primary layer coating		Inorganic rust-prevention pigment
						Molar					(Pigment
				Blending		ratio of					1) +	(Pigment
	Plat-			ratio		phosphoric	Total				(Pigment	1)/
	ing	Coating	Drying	converted	(γ)	acid	coating	Resin	(Pigment 1)	(Pigment 2)	2)	(Pigment
	steel	compo-	temper-	to SiO 2	Com-	component	weight	compo-		Blending		Blending	Total	2)
	plate	sition	ature	(wt %)	po-	(β)/(γ)	(mg/m 2 )	sition	Type	ratio	Type	ratio	amount	Ratio
No.	*1	*2	(° C.)	*3	nent	*4	*5	*6	*7	*8	*7	*8	*9	*10
29	1	16	120		Mn	1.03	290	1	1	30
30	1	17	120		Mn	1.47	320	1	1	30
31	1	18	120	40			320	1	1	30
32	1	19	120	40	Ni,	1.2	290	1	1	30
					Mn
33	1	20	120	40	Al,	1.05	300	1	1	30
					Mg
34	1	21	120	40	Ni	2.5	320	1	1	30
35	1	22	120	98	Ni	1.03	280	1	1	30
36	1	23	120	4	Ni	1.2	320	1	1	30
37	1	24	120	40	Ni	1.33	350	1	1	30
38	1	25	120	40	Li	1	280	1	1	30
39	1	26	120	40			500	1	1	30
40	1	27	120	40	Ni	1.2	4200	1	1	30
41	1	28	120	0	Ni	1.1	360	1	1	30
42	1	29	120	60			290	1	1	30
43	1	30	120	60	Ni	0	290	1	1	30
	Performance
	Secondary layer coating			White-rust
	Solid					resistance
	lubricant				White-rust	after alkaline				Classification
		Blending	Drying	Coating		resistance:	degreasing:				Example/
	Type	ratio	temperature	thickness	Appear-	SST	SST	Paint			Comparative
No.	*11	*12	(° C.)	(μm)	ance	120 hrs	120 hrs	adhesiveness	Workability	Remark	Example
29			230	1	◯	⊚	⊚	⊚			Example
30			230	1	◯	⊚	⊚	⊚			Example
31			230	1	◯	⊚	◯	⊚			Example
32			230	1	◯	⊚	⊚	⊚			Example
33			230	1	◯	⊚	◯+	⊚			Example
34			230	1	◯	⊚	⊚	⊚			Example
35			230	1	◯	⊚	◯−	⊚			Example
36			230	1	◯	⊚	◯−	⊚			Example
37			230	1	◯	⊚	⊚	⊚			Example
38			230	1	◯	⊚	◯+	⊚			Example
39			230	1	◯	⊚	◯+	⊚			Example
40			230	1	X	⊚	⊚	X			Comparative
											Example
41			230	1	◯	Δ	Δ	Δ			Comparative
											Example
42			230	1	◯	⊚	◯+	⊚			Example
43			230	1	◯	X	X	X			Comparative
											Example

 

TABLE 94

Secondary layer coating

Primary layer coating

Inorganic rust-prevention pigment

Molar

(Pigment

Blending

ratio of

1) +

(Pigment

Plat-

ratio

phosphoric

Total

(Pigment

1)/

ing

Coating

Drying

converted

(γ)

acid

coating

Resin

(Pigment 1)

(Pigment 2)

2)

(Pigment

steel

compo-

temper-

to SiO 2

Com-

component

weight

compo-

Blending

Blending

Total

2)

plate

sition

ature

(wt %)

po-

(β)/(γ)

(mg/m 2 )

sition

Type

ratio

Type

ratio

amount

Ratio

No.

*1

*2

(° C.)

*3

nent

*4

*5

*6

*7

*8

*7

*8

*9

*10

73

1

5

120

40

Ni

1.2

300

1

13

30

Performance

Secondary layer coating

White-rust

Solid

resistance

lubricant

White-rust

after alkaline

Classification

Blending

Drying

Coating

resistance:

degreasing:

Example/

Type

ratio

temperature

thickness

Appear-

SST

SST

Paint

Comparative

No.

*11

*12

(° C.)

(μm)

ance

120 hrs

120 hrs

adhesiveness

Workability

Remark

Example

73

230

1

◯

⊚

⊚

⊚

Example

 

TABLE 95

Secondary layer coating

Primary layer coating

Inorganic rust-prevention pigment

Molar

(Pigment

Blending

ratio of

1) +

(Pigment

Plat-

ratio

phosphoric

Total

(Pigment

1)/

ing

Coating

Drying

converted

(γ)

acid

coating

Resin

(Pigment 1)

(Pigment 2)

2)

(Pigment

steel

compo-

temper-

to SiO 2

Com-

component

weight

compo-

Blending

Blending

Total

2)

plate

sition

ature

(wt %)

po-

(β)/(γ)

(mg/m 2 )

sition

Type

ratio

Type

ratio

amount

Ratio

No.

*1

*2

(° C.)

*3

nent

*4

*5

*6

*7

*8

*7

*8

*9

*10

81

1

5

120

40

Ni

1.2

300

1

13

30

28

20

50

3/2

Performance

Secondary layer coating

White-rust

Solid

resistance

lubricant

White-rust

after alkaline

Classification

Blending

Drying

Coating

resistance:

degreasing:

Example/

Type

ratio

temperature

thickness

Appear-

SST

SST

Paint

Comparative

No.

*11

*12

(° C.)

(μm)

ance

120 hrs

120 hrs

adhesiveness

Workability

Remark

Example

81

230

1

◯

⊚

⊚

⊚

Example

 

TABLE 96

Secondary layer coating

Primary layer coating

Inorganic rust-prevention pigment

Molar

(Pigment

Blending

ratio of

1) +

(Pigment

Plat-

ratio

phosphoric

Total

(Pigment

1)/

ing

Coating

Drying

converted

(γ)

acid

coating

Resin

(Pigment 1)

(Pigment 2)

2)

(Pigment

steel

compo-

temper-

to SiO 2

Com-

component

weight

compo-

Blending

Blending

Total

2)

plate

sition

ature

(wt %)

po-

(β)/(γ)

(mg/m 2 )

sition

Type

ratio

Type

ratio

amount

Ratio

No.

*1

*2

(° C.)

*3

nent

*4

*5

*6

*7

*8

*7

*8

*9

*10

140

1

5

120

40

Ni

1.2

300

1

13

30

28

20

50

3/2

Performance

Secondary layer coating

White-rust

Solid

resistance

lubricant

White-rust

after alkaline

Classification

Blending

Drying

Coating

resistance:

degreasing:

Example/

Type

ratio

temperature

thickness

Appear-

SST

SST

Paint

Comparative

No.

*11

*12

(° C.)

(μm)

ance

120 hrs

120 hrs

adhesiveness

Workability

Remark

Example

140

1

10

230

1

◯

⊚

⊚

⊚

⊚

Example

 

Best Mode 3

The inventors of the present invention found that, through the formation of a specific chelating resin coating on the chemical conversion treatment coating which is formed on the surface of a zinc base plated steel sheet or an aluminum base plated steel sheet, further preferably blending an adequate amount of a specific rust-preventive agent in the chelating resin coating, excellent corrosion resistance is obtained without applying chromate treatment as the chemical conversion treatment.

The organic coating steel sheet according to the present invention is basically characterized in that a chemical conversion treatment coating is formed on the surface of a zinc base plated steel sheet or an aluminum base plated steel sheet, and that, further on the chemical conversion treatment coating, an organic coating containing a chelating resin is formed as the product of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, thus applying the hydrazine derivative (C) as a chelating group to the film-forming resin (A).

The corrosion-preventive mechanism of the organic coating comprising above-described specific reaction product is not fully analyzed. The mechanism is, however, presumably the following. By adding a hydrazine derivative, not applying a simple low molecular weight chelating agent, to the film-forming organic resin, (1) the dense organic polymer coating gives an effect to shut-off corrosion causes such as oxygen and chlorine ions, (2) the hydrazine derivative is able to form a stable passive layer by strongly bonding with the surface of the primary layer coating, and (3) the free hydrazine derivative in the coating traps the zinc ion which is eluted by a corrosion reaction, thus forming a stable insoluble chelated compound layer, which suppresses the formation of an ion conduction layer at interface to suppress the progress of corrosion. These work effects should effectively suppress the development of corrosion, thus giving excellent corrosion resistance.

As a result, even when a chemical conversion treatment coating (such as phosphate treatment coating) which contains no hexavalent chromium is used as the chemical conversion treatment coating on the base material, the obtained corrosion resistance is equivalent to that of chromate coating. When a chromate coating as the chemical conversion treatment coating, the obtained corrosion-preventive effect is combined with the corrosion-preventive effect of the organic coating, so that the attained corrosion resistance is markedly higher than that of conventional chromated steel sheets, while attaining superior chromium elution resistance.

Particularly when a resin containing epoxy group is used as the film-forming organic resin (A), a dense barrier coating is formed by the reaction between the epoxy-group-laden resin and a cross-linking agent. Thus, the formed barrier coating has excellent penetration-suppression performance against the corrosion causes such as oxygen, and gains excellent bonding force with the base material owing to the hydroxyl group in the molecule, which results in particularly superior corrosion resistance.

Further excellent corrosion resistance is obtained by using an active-hydrogen-laden pyrazole compound and/or an active-hydrogen-laden triazole compound as the hydrazine derivative (C) containing active hydrogen.

As in the case of prior art, blending simply a hydrazine derivative with the film-forming organic resin gives very little improvement in corrosion-suppression. The reason is presumably that the hydrazine derivative which does not enter the molecules of the film-forming organic resin forms a chelate compound with zinc which is eluted under a corrosive environment, and the chelate compound cannot form a dense barrier layer because of low molecular weight. To the contrary, introduction of a hydrazine derivative into the molecules of film-forming organic resin, as in the case of present invention, provides markedly high corrosion-suppression effect.

According to the organic coating steel sheet of the present invention, further high anti-corrosive performance (self-repair work at coating-defect section) is attained by blending adequate amount of ion-exchanged silica (a) with an organic coating consisting of above-described specific reaction products. The corrosion-preventive mechanism which is obtained by blending the ion-exchanged silica (a) with the specific organic coating is speculated as follows. First, under a corrosion environment, the zinc ion which is eluted from the plating coating is trapped by the above-described hydrazine derivative, thus suppressing the anode reaction. On the other hand, when cation such as Na ion enters under the corrosion environment, the iron exchange action emits Ca ion and Mg ion from the surface of silica. Furthermore, when OH ion is generated by the cathode reaction under the corrosive environment to increase pH value near the plating interface, the Ca ion (or Mg ion) emitted from the ion-exchanged silica precipitates in the vicinity of the plating interface in a form of Ca(OH) 2 or Mg(OH) 2 , respectively. The precipitate seals defects as a dense and slightly soluble product to suppress the corrosion reactions.

There may given an effect that the eluted zinc ion is exchanged with Ca ion (or Mg ion) and is fixed onto the surface of silica. By combining both the anti-corrosive actions of hydrazine derivative and ion-exchanged silica, particularly strong corrosion-preventive effect would appear.

Also in the case that an ion-exchanged silica is blended with a general organic coating, corrosion-preventive effect is obtained to some extent. Nevertheless, when an ion-exchanged silica is blended with an organic coating consisting of a specific chelate-modified resin, as in the case of present invention, the corrosion-preventive effect at anode reaction section owing to the chelate-modified resin and the corrosion-preventive effect at cathode reaction section owing to the ion-exchanged silica are combined to suppress both the anode and the cathode corrosion reactions, which should provide markedly strong corrosion-preventive effect. Furthermore, that kind of combined corrosion-preventive effect is effective in suppressing corrosion at flaws and defects on coatings, and is able to give excellent self-repair work to the coating.

According to the organic coating steel sheet of the present invention, the corrosion resistance can also be increased by blending an adequate amount of silica fine particles (b) with an organic coating consisting of a specific reaction product as described above. That is, by blending silica fine particles such as fumed silica and colloidal silica (having average primary particle sizes of from 5 to 50 nm, preferably from 5 to 20 nm, more preferably from 5 to 15 nm) having large specific surface area into a specific organic coating, the generation of dense and stable corrosion products such as basic zinc chloride is enhanced, thus suppressing the generation of zinc oxide (white-rust).

Furthermore, according to the organic coating steel sheet of the present invention, the corrosion resistance can further be increased by blending an ion-exchanged silica (a) and silica fine particles (b) together into the organic coating consisting of a specific reaction product as described above. The ion-exchanged silica consists mainly of porous silica, and generally has a relatively large particle size, 1 μm or more. Accordingly, after releasing Ca ion, the rust-preventive effect as silica is not much expectable. Consequently, by accompanying fine particle silica having a relatively large specific surface area, such as fumed silica and colloidal silica, (with primary particle sizes of from 5 to 50 nm, preferably from 5 to 20 nm, more preferably from 5 to 15 nm), the generation of dense and stable corrosion products such as basic zinc chloride may be enhanced, thus suppressing the generation of zinc oxide (white-rust). Through the combined rust-preventive mechanisms of ion-exchanged silica and fine particle silica, particularly strong corrosion-preventive effect would appear.

The following is the detail description of the present invention and the reasons to specify the conditions of the present invention.

First, the description is given about the chemical conversion treatment coating formed on the surface of a zinc base plated steel sheet or an aluminum base plated steel sheet.

The chemical conversion treatment coating is formed to suppress the activity of the plated steel sheet and to improve the corrosion resistance and the adhesiveness of the coating. The kind of chemical conversion treatment coating is not specifically limited, and it may be a chemical conversion treatment coating having no hexavalent chromium or a chromate coating.

Examples of the chemical conversion treatment coating having no hexavalent chromium are inorganic coating including:

(1) Phosphate treatment coating;

(2) Passive coating such as coating treated by molybdate or tungstate, coating treated by phosphoric acid/molybdic acid;

(3) Alkali silicate treatment coating comprising silicon oxide and alkali metal oxide such as lithium oxide;

(4) Composite oxide coating comprising trivalent chromium; and

(5) Oxide coating comprising titanium oxide and zirconium oxide.

Other than the above-described inorganic coatings, the following may, for example, be applied:

(6) Thin film organic resin coating (0.1 to 2 μm of thicknesses), or organic composite silicate coating;

(7) Chelating organic coating such as that of tannic acid, phitic acid, and phosphonic acid; and

(8) Composite coating comprising an inorganic coating of either one of (1) through (3) given above and an organic resin.

Among them, it is most preferable to use a slightly soluble coating containing silicon oxide (such as alkali silicate coating) from the viewpoint of suppression of white-rust on zinc.

The above-described chemical conversion treatment coating may further contain organic resin to improve the workability and the corrosion resistance. Examples of the organic resin are epoxy resin, polyurethane resin, polyacrylic resin, acrylic-ethylene copolymer, acrylic-styrene copolymer, alkyd resin, polyester resin, polyethylene resin. These resins may be supplied as water-soluble resin and/or water-dispersible resin. Adding to these water-dispersible resins, it is effective to use water-soluble epoxy resin, water-soluble phenol resin, water-soluble polybutadiene rubber (SBR, NBR, MBR), melamine resin, block-polyisocyanate compound, oxazolane compound, and the like as the cross-linking agent.

For further improving the corrosion resistance, the composite oxide coating may further contain polyphosphate, phosphate (for example, zinc phosphate, aluminum dihydrogen phosphate, and zinc phosphate), molybdate, phospho molybdate (for example, aluminum phosphomolybdate), organic phosphate and its salt (for example, phytic acid, phytiate, phosphonic acid, phosphonate, their metal salt and alkali metal salt), organic inhibitor (for example, hydrazine derivative, thiol compound, dithiocarbamate), organic compound (polyethyleneglycol), and the like.

Other applicable additives include organic coloring pigments (for example, condensing polycyclic organic pigments, phthalocyanine base organic pigments), coloring dyes (for example, azo dye soluble in organic solvent, azo metal dye soluble in water), inorganic pigments (titanium oxide), chelating agents (for example, thiol), conductive pigments (for example, metallic powder of zinc, aluminum, nickel, or the like, iron phosphide, antimony-dope type tin oxide), coupling agents (for example, silane coupling agent and titanium coupling agent), melamine-cyanuric acid additives.

The composite oxide coating may contain one or more of iron group metallic ions (Ni ion, Co ion, Fe ion), preferably Ni ion, to prevent blackening (an oxidizing phenomenon appeared on plating surface) under a use environment of organic coating steel sheets. In that case, concentration of the iron base metallic ion of 1/10,000 mole per 1 mole of the component (β), converted to the metal amount in the target composition, gives satisfactory effect. Although the upper limit of the iron group ion is not specifically limited, it is preferable to select a concentration level thereof not to give influence to the corrosion resistance.

The thickness of these chemical conversion treatment coating is specified.to 3 μm or less. If the coating thickness exceeds 3 μm, workability and conductivity degrade. The lower limit of the thickness of these chemical conversion treatment coatings is not specifically limited, and the coating thickness may be selected to a level that gives improvement of corrosion resistance.

Next, the description is given about the organic coating which is formed on the above-described chemical conversion treatment coating. An organic coating similar with that is described in the best mode 1 is formed.

According to the present invention, the organic coating formed on the chemical conversion treatment coating is an organic coating having thicknesses of from 0.1 to 5 μm, containing a product of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, and, at need, containing additives such as rust-preventive agent.

The kinds of film-forming organic resin (A) are not specifically limited if only the resin reacts with the active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, to bind the active-hydrogen-laden compound (B) with the film-forming organic resin by addition or condensation reaction, and adequately form the coating.

Examples of the film-forming organic resin (A) are epoxy resin, modified epoxy resin, polyurethane resin, polyester resin, alkyd resin, acrylic base copolymer resin, polybutadiene resin, phenol resin, and adduct or condensate thereof. These resins may be applied separately or blending two or more of them.

From the standpoint of reactivity, readiness of reaction, and corrosion-prevention, an epoxy-group-laden resin (D) in the resin is particularly preferred as the film-forming organic resin (A). The epoxy-group-laden resin (D) has no specific limitation if only the resin reacts with an active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, to bind with the active hydrogen-laden compound (B) by addition or condensation reaction, and adequately form the coating. Examples of the epoxy-group-laden resin (D) are epoxy resin, modified epoxy resin, acrylic base copolymer resin copolymerized with an epoxy-group-laden monomer, polybutadiene resin containing epoxy group, polyurethane resin containing epoxy group, and adduct or condensate of these resins. These resins may be applied separately or blending two or more of them together.

From the point of adhesiveness with plating surface and of corrosion resistance, epoxy resin and modified epoxy resin are particularly preferred among these epoxy-group-laden resins (D).

The acrylic base copolymer resin which was copolymerized with the epoxy-group-laden monomer may be a resin which is modified by polyester resin, epoxy resin, or phenol resin.

A particularly preferred epoxy resin described above is a resin is the product of the reaction between bisphenol A and epihalohydrin. The epoxy resin is preferred because of superior corrosion resistance.

The film-forming organic resin (A) may be either organic solvent dissolving type, organic solvent dispersing type, water dissolving type, or water dispersing type.

According to the present invention, a hydrazine derivative is introduced into the molecules of the film-forming organic resin (A). To do this, at least a part of the active-hydrogen-laden compound (B), (preferably whole thereof), is necessary to be a hydrazine derivative (C) containing active hydrogen.

When the film-forming organic resin (A) is an epoxy-group-laden resin, examples of the active-hydrogen-laden compound (B) reacting with the epoxy group are listed below. One or more of these compounds (B) may be applied. Also in that case, at least a part of the active-hydrogen-laden compound (B), (preferably whole thereof), is necessary to be a hydrazine derivative (C) containing active hydrogen.

A hydrazine derivative containing active hydrogen

A primary or secondary amine compound containing active hydrogen

An organic acid such as ammonia and carboxylic acid

A halogenated hydrogen such as hydrogen chloride

An alcohol, a thiol

A hydrazine derivative containing no active hydrogen or a quaternary chlorinating agent which is a mixture with a ternary amine.

Examples of the above-described hydrazine derivative (C) containing active hydrogen are the following.

Hydrazide compound such as carbohydrazide, propionic acid hydrazide, salicylic acid hydrazide, adipic acid hydrazide, sebacic acid hydrazide, dodecanic acid hydrazide, isophtharic acid hydrazide, thiocarbo-hydrazide, 4,4′-oxy-bis-benzenesulfonyl hydrazide, benzophenone hydrazone, amino-polyacrylamide hydrazide;

Pyrazole compound such as pyrazole, 3,5-dimethylpyrazole, 3-methyl-5-pyrazolone, 3-amino-5-methylpyrazole;

Triazole compound such as 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 5-amino-3-mercapto-1,2,4-triazole, 2,3-dihydro-3-oxo-1,2,4-triazole, 1H-benzotriazole, 1-hydroxybenzotriazole (mono hydrate), 6-methyl-8-hydroxytriazolopyridazine, 6-phenyl-8-hydroxytriazolopyrydazine, 5-hydroxy-7-methyl-1,3,8-triazaindolizine;

Tetrazole compound such as 5-phenyl-1,2,3,4-tetrazole, 5-mercapto-1-phenyl-1,2,3,4-tetrazole;

Thiadiazole compound such as 5-amino-2-mercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole;

Pyridazine compound such as maleic acid hydrazide, 6-methyl-3-pyridazone, 4,5-dichloro-3-pyridazone, 4,5-dibromo-3-pyridazone, 6-methyl-4,5-dihydro-3-pyridazone.

Among these compounds, particularly preferred ones are pyrazole compound and triazole compound which have cyclic structure of five- or six-membered ring and which have nitrogen atom in the cyclic structure.

These hydrazine derivatives may be applied separately or blending two or more of them together.

Examples of above-described amine compound having active hydrogen, which can be used as a part of the active-hydrogen-laden compound (B) are the following.

A compound prepared by heating to react a primary amino group of an amine compound containing a single secondary amino group of diethylenetriamine, hydroxylaminoethylamine, ethylaminoethylamine, methylaminopropylamine, or the like and one or more of primary amino group, with ketone, aldehyde, or carboxylic acid, at, for example, approximate temperatures of from 100 to 230° C. to modify them to aldimine, ketimine, oxazoline, or imidazoline;

A secondary monoamine such as diethylamine, diethanolamine, di-n- or -iso-propanolamine, N-methylethanolamine, N-ethylethanolamine;

A secondary-amine-laden compound prepared by Michael addition reaction through the addition of monoalkanolamine such as monoethanolamine to dialkyl(meth)acrylamide;

A compound prepared by modifying a primary amino group of alkanolamine such as monoethanolamine, neopentanolamine, 2-aminopropanol, 3-aminopropanol, 2-hydroxy-2′ (aminopropoxy)ethylether to ketimine.

As for the above-described quaternary chlorinating agents which are able to be used as a part of the active-hydrogen-laden compound (B), the hydrazine derivative having active hydrogen or ternary amine has no reactivity with epoxy group as it is. Accordingly, they are mixed with an acid to make them reactive with epoxy group. The quaternary chlorinating agent reacts with epoxy group with the presence of water, at need, to form a quaternary salt with the epoxy-group-laden resin.

The acid used to obtain the quaternary chlorinating agent may be organic acid such as acetic acid and lactic acid, or inorganic acid such as hydrochloric acid. The hydrazine derivative containing no active hydrogen, which is used to obtain quaternary chlorinating agent may be 3,6-dichloropyridazine. The ternary amine may be dimethylethanolamine, triethylamine, trimethylamine, tri-isopropylamine, methyldiethanolamine.

The product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen, may be prepared by reacting the film-forming organic resin (A) with the active-hydrogen-laden compound (B) at temperatures of from 10 to 300° C., preferably from 50 to 150° C., for about 1 to about 8 hours.

The reaction may be carried out adding an organic solvent. The kind of adding organic solvent is not specifically limited. From the viewpoint of solubility and coating film-forming performance with epoxy resin, ketone group or ether group solvents are particularly preferred.

The blending ratio of the film-forming organic resin (A) and the active-hydrogen-laden compound (B), a part or whole of which compound consists of a hydrazine derivative (C) containing active hydrogen, is in a range of from 0.5 to 20 parts by weight of the active-hydrogen-laden compound (B), more preferably from 1.0 to 10 parts by weight, to 100 parts by weight of the film-forming organic resin (A).

When the film-forming organic resin (A) is an epoxy-group-laden resin (D), the blending ratio of the epoxy-group-laden resin (D) to the active-hydrogen-laden compound (B) is preferably, from the viewpoint of corrosion resistance and other performance, in a range of from 0.01 to 10 as the ratio of the number of active hydrogen groups in the active-hydrogen-laden compound (B) to the number of epoxy groups in the epoxy-group-laden resin (D), or [the number of active hydrogen groups/the number of epoxy groups], more preferably from 0.1 to 8, most preferably from 0.2 to 4.

A preferred range of hydrazine derivative (C) containing active hydrogen in the active-hydrogen-laden compound (B) is from 10 to 100 mole %, more preferably from 30 to 100 mole %, and most preferably from 40 to 100 mole %. If the rate of hydrazine derivative (C) containing active hydrogen is less than 10 mole %, the organic coating fails to have satisfactory rust-preventive function, thus the obtained rust-preventive effect becomes similar with the case of simple blending of a film-forming organic resin with a hydrazine derivative.

To form a dense barrier coating according to the present invention, it is preferable that a curing agent is blended into the resin composition, and that the organic coating is heated to cure.

Suitable methods for curing to form a resin composition coating include (1) a curing method utilizing a urethanation reaction between isocyanate and hydroxide group in the base resin, and (2) a curing method utilizing an ether reaction between hydroxide group in the base resin and an alkyletherified amino resin which is prepared by reacting between a part of or whole of a methylol compound which is prepared by reacting formaldehyde with one or more of melamine, urea, and benzoguanamine, and a C1-5 primary alcohol. As of these methods, particularly preferred one is to adopt a urethanation reaction between isocyanate and hydroxyl group in the base resin as the main reaction.

The polyisocyanate compound used in the curing method (1) described above is a compound prepared by partially reacting an aliphatic, alicyclic (including heterocyclic), or aromatic isocyanate compound, or a compound thereof using a polyhydric alcohol. Examples of that kind of polyisocyanate compound are the following.

These polyisocyanate compounds may be used separately or mixing two or more of them together.

Examples of protective agent (blocking agent) of the polyisocyanate compound are the following.

Aliphatic monoalcohol such as methanol, ethanol, propanol, butanol, octylalcohol;

Monoether of ethyleneglycol and/or diethyleneglycol, for example, monoether of methyl, ethyl, propyl (n-, iso-), butyl (n-, iso-, sec-);

Aromatic alcohol such as phenol and cresol;

Oxime such as acetoxime and methylethylketone oxime.

Through reaction between one or more of these compounds with above-described polyisocyanate compound, a polyisocyanate compound thus obtained is stably protected at least at normal temperature.

It is preferable to blend that kind of polyisocyanate compound (E) with a film-forming organic resin (A) as the curing agent at a range of (A)/(E)=95/5 to 55/45 (weight ratio of non-volatile matter), more preferably (A)/(E)=90/10 to 65/35. Since polyisocyanate compounds have water-absorbing property, blending of the compound at ratios above (A)/(E)=55/45 degrades the adhesiveness of the organic coating. If top coating is given on the organic coating, unreacted polyisocyanate compound migrates into the coating film to induce hindrance of curing or insufficient adhesiveness of the coating film. Accordingly, the blending ratio of the polyisocyanate compound (E) is preferably not more than (A)/(E)=55/45.

The film-forming organic resin (A) is fully cross-linked by the addition of above-described cross-linking agent (curing agent). For further increasing the cross-linking performance at a low temperature, it is preferable to use a known catalyst for enhancing curing. Examples of the curing-enhancing catalyst are N-ethylmorpholine, dibutyltin dilaurate, cobalt naphthenate, tin(II)chloride, zinc naphthenate, and bismuth nitrate.

When an epoxy-group-laden resin is used as the film-forming organic resin (A), the epoxy-group-laden resin may be blended with a known resin such as that of acrylic, alkyd, and polyester to improve the physical properties such as adhesiveness to some extent.

According to the present invention, the organic coating may be blended with ion-exchanged silica (a) and/or fine particle silica (b) as the rust-preventive additive.

The ion-exchanged silica is prepared by fixing metallic ion such as calcium and magnesium ions on the surface of porous silica gel powder. Under a corrosive environment, the metallic ion is released to form a deposit film. Among these ion-exchanged silicas, Ca ion-exchanged silica is most preferable.

Any type of Ca ion-exchanged silica may be applied. A preferred range of average particle size of Ca ion-exchanged silica is 6 μm or less, more preferably 4 μm or less. For example, Ca ion-exchanged silica having average particle sizes of from 2 to 4 μm may be used. If the average particle size of Ca ion-exchanged silica exceeds 6 μm, the corrosion resistance degrades and the dispersion stability in the coating composition degrades.

A preferred range of Ca concentration in the Ca ion-exchanged silica is 1 wt. % or more, more preferably from 2 to 8 wt. %. If the Ca concentration is below 1 wt. %, the rust-preventive effect by the Ca release becomes insufficient.

Surface area, pH, and oil-absorbance of the Ca ion-exchanged silica are not specifically limited.

The rust-preventive mechanism in the case of addition of ion-exchanged silica (a) to organic coating is described above. Particularly according to the present invention, markedly excellent corrosion preventive effect is attained by combining a specific chelate-modified resin which is the film-forming organic resin with an ion-exchanged silica, thus inducing the combined effect of the corrosion-suppression effect of the chelate-modified resin at the anodic reaction section with the corrosion-suppression effect of the ion-exchanged silica at the cathodic reaction section.

A preferred range of blending ratio of the ion-exchanged silica (a) in the organic resin coating is 1 to 100 parts by weight (solid matter) to 100 parts by weight (solid matter) of the reaction product as the resin composition for film-forming (that is, the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen), more preferably from 5 to 80 parts by weight (solid matter), and most preferably from 10 to 50 parts by weight (solid matter). If the blending ratio of the ion-exchanged silica (a) becomes less than 1 part by weight, the effect of improved corrosion resistance after alkaline degreasing becomes small. If the blending ratio of the ion-exchanged silica (a) exceeds 100 parts by weight, the corrosion resistance degrades, which is unfavorable.

The fine particle silica (b) may be either colloidal silica or fumed silica.

In particular, organic solvent dispersion silica sol is superior in corrosion resistance to fumed silica.

The fine particle silica contributes to forming dense and stable zinc corrosion products under a corrosive environment. Thus formed corrosion products cover the plating surface in a dense mode, thus presumably suppressing the development of corrosion.

From the viewpoint of corrosion resistance, the fine particle silica preferably has particle sizes of from 5 to 50 nm, more preferably from 5 to 20 nm, and most preferably from 5 to 15 nm.

A preferred range of blending ratio of the fine particle silica (b) in the organic resin coating is 1 to 100 parts by weight (solid matter) to 100 parts by weight (solid matter) of the reaction product as the resin composition for film-forming (that is, the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen), more preferably from 5 to 80 parts by weight (solid matter), and most preferably from 10 to 30 parts by weight (solid matter). If the blending ratio of the fine particle silica (b) becomes less than 1 part by weight, the effect of improved corrosion resistance after alkaline degreasing becomes small. If the blending ratio of the fine particle silica (b) exceeds 100 parts by weight, the corrosion resistance and the workability degrade, which is unfavorable.

According to the present invention, markedly high corrosion resistance is attained by combined addition of an ion-exchanged silica (a) and a fine particle silica (b) to the organic coating. That is, the combined addition of ion-exchanged silica (a) and fine particle silica (b) induces above-described combined rust-preventive mechanism which gives markedly excellent corrosion-preventive effect.

The blending ratio of combined addition of ion-exchanged silica (a) and fine particle silica (b) to the organic coating is in a range of from 1 to 100 parts by weight (solid matter) of the sum of the ion-exchanged silica (a) and the fine particle silica (b), to 100 parts by weight (solid matter) of the reaction product as the resin composition for film-forming (that is, the product of reaction between the film-forming organic resin (A) and an active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen), preferably from 5 to 80 parts by weight (solid matter). Further the weight ratio of blending amount (solid matter) of the ion-exchanged silica (a) to the fine particle silica (b), (a)/(b), is selected to a range of from 99/1 to 1/99, preferably from 95/5 to 40/60, more preferably from 90/10 to 60/40.

If the blending ratio of sum of the ion-exchanged silica (a) and the fine particle silica (b) is less than 1 part by weight, the effect of improved corrosion resistance after alkaline degreasing becomes small. If the blending ratio of sum of the ion-exchanged silica (a) and the fine particle silica (b) exceeds 100 parts by weight, the coatability and the weldability degrade, which is unfavorable.

If the weight ratio of the ion-exchanged silica (a) to the fine particle silica (b), (a)/(b), is less than 1/99, the corrosion resistance degrades. If the weight ratio of the ion-exchanged silica (a) to the fine particle silica (b), (a)/(b), exceeds 99/1, the effect of combined addition of the ion-exchanged silica (a) and the fine particle silica (b) cannot fully be attained.

Adding to the above-described rust-preventive agents, the organic coating may contain other corrosion-suppressing agent such as polyphosphate (for example, aluminum polyphosphate such as TAICA K-WHITE 82, TAICA K-WHITE 105, TAICA K-WHITE G105, TAICA K-WHITE Ca650 (trade marks) manufactured by TAYCA CORPORATION), phosphate (for example, zinc phosphate, aluminum dihydrogenphosphate, zinc phosphite), molybdenate, phosphomolybdenate (for example, aluminum phosphomolybdenate), organic phosphoric acid and its salt (for example, phytic acid, phytiate, phosphonic acid, phosphonate, their metal salt and alkali metal salt, alkali earth metal salt), organic inhibitor (for example, hydrazine derivative, thiol compound).

The organic coating may, at need, further include a solid lubricant (c) to improve the workability of the coating.

Examples of applicable solid lubricant according to the present invention are the following.

(1) Polyolefin wax, paraffin wax; and

(2) Fluororesin fine particles.

Among those solid lubricants, particularly preferred ones are polyethylene wax, fluororesin fine particles (particularly poly-tetrafluoroethylene resin fine particles).

As of these compounds, combined use of polyolefin wax and tetrafluoroethylene fine particles is expected to provide particularly excellent lubrication effect.

A preferred range of blending ratio of the solid lubricant (c) in the organic resin coating is from 1 to 80 parts by weight (solid matter) to 100 parts by weight (solid matter) of the reaction product as the resin composition for film-forming (that is, the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen), more preferably from 3 to 40 parts by weight (solid matter). If the blending ratio of the solid lubricant (c) becomes less than 1 part by weight, the effect of lubrication is small. If the blending ratio of the solid lubricant (c) exceeds 80 parts by weight, the painting performance degrade, which is unfavorable.

The organic coating of the organic coating steel sheet according to the present invention normally consists mainly of a product (resin composition) of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen). And, at need, an ion-exchanged silica (a), a fine particle silica (b), a solid lubricant (c), and a curing agent may further be added to the organic coating. Furthermore, at need, there may be added other additives such as organic coloring pigment (for example, condensing polycyclic organic pigment, phthalocyanine base organic pigment), coloring dye (for example, azo dye soluble in organic solvent, azo metal dye soluble in water), inorganic pigment (for example, titanium oxide), chelating agent (for example, thiol), conductive pigment (for example, metallic powder of zinc, aluminum, nickel, or the like, iron phosphide, antimony-dope type tin oxide), coupling agent (for example, silane coupling agent and titanium coupling agent), melamine-cyanuric acid additive.

The paint composition for film-formation containing above-described main component and additive components normally contains solvent (organic solvent and/or water), and, at need, further a neutralizer or the like is added.

Applicable organic solvent described above has no specific limitation if only it dissolves or disperses the product of reaction between the above-described film-forming organic resin (A) and the active-hydrogen-laden compound (B), and adjusts the product as the painting composition. Examples of the organic solvent are the organic solvents given above as examples.

The above-described neutralizers are blended, at need, to neutralize the film-forming organic resin (A) to bring it to water-type. When the film-forming organic resin (A) is a cationic resin, acid such as acetic acid, lactic acid, and formic acid may be used as the neutralizer.

The organic coatings described above are formed on the above-described composite oxide coating.

The dry thickness of the organic coating is in a range of from 0.1 to 5 μm, preferably from 0.3 to 3 μm, and most preferably from 0.5 to 2 μm. If the thickness of the organic coating is less than 0.1 μμm, the corrosion resistance becomes insufficient. If the thickness of the organic coating exceeds 5 μm, the conductivity and the workability degrade.

The following is the description about the method for manufacturing an organic coating steel sheet according to the present invention.

The organic coating steel sheet according to the present invention is manufactured by the steps of: treating the surface of a zinc base plated steel sheet or an aluminum base plated steel sheet by chemical conversion treatment; applying a paint composition which contains the product of reaction between above-described film-forming organic resin (A) and an active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen, which product of reaction is preferably the main component, and at need, further contains an ion-exchanged silica (a), a fine particle silica (b), and a solid lubricant (c), and the like; heating to dry the product.

The surface of the plated steel sheet may be, at need, subjected to alkaline degreasing before applying the above-described treatment liquid, and may further be subjected to preliminary treatment such as surface adjustment treatment for further improving the adhesiveness and corrosion resistance.

In the case that a chemical conversion treatment coating containing no hexavalent chromium is formed as the chemical conversion treatment coating, the methods for applying the treatment liquid onto the plated steel sheet may be either one of coating method, dipping method, and spray method. The coating method may adopt any type such as roll coater (three-roll type, two-roll type, etc.), squeeze coater, die coater. After the coating step using squeeze coater and the like, the dipping step, or the spray step, it is possible to adjust the coating weight, the uniformizing appearance, and the uniformizing the film-thickness using air-knife method and roll-squeezing method.

After the coating of treatment liquid as described above, there may applied, at need, rinsing with water, followed by heating to dry.

Method for heating to dry the coated treatment liquid is not limited. For example, dryer, hot air oven, high frequency induction heating furnace, infrared heating furnace may be applied.

The heating and drying treatment is preferably conducted at reaching temperatures of from 40 to 350°C., more preferably from 80 to 20° C., and most preferably from 80 to 160° C. If the heating temperature is less than 50° C., excess amount of water is left in the coating, which results in insufficient corrosion resistance. If the heating temperature exceeds 350° C., the operation becomes uneconomical and defects likely appear in the coating to degrade the corrosion resistance.

After forming the chemical conversion treatment coating on the surface of the zinc base plated steel sheet or the aluminum base plated steel sheet, as described above, a paint composition for forming an organic coating is applied on the composite oxide coating. Method for applying the paint composition is not limited, and examples of the method are coating method, dipping method, and spray method. The coating method may adopt any type such as roll coater (three-roll type, two-roll type, etc.), squeeze coater, die coater. After the coating step using squeeze coater and the like, the dipping step, or the spray step, it is possible to adjust the coating weight, the uniformizing appearance, and the uniformizing the film-thickness using air-knife method and roll-squeezing method.

After applying the paint composition, generally the plate is heated to dry without rinsing with water. After applying the paint composition, however, water-rinse step may be given.

Method for heating to dry the paint composition is not limited. For example, dryer, hot air oven, high frequency induction heating furnace, infrared heating furnace may be applied. The heating treatment is preferably conducted at reaching temperatures of from 50 to 350° C., more preferably from 80 to 250° C. If the heating temperature is less than 50° C., excess amount of water is left in the coating, which results in insufficient corrosion resistance. If the heating temperature exceeds 350° C., the operation becomes uneconomical and defects likely appear in the coating to degrade the corrosion resistance.

As described above, the present invention includes a steel sheet having an organic coating on both sides or on side thereof. Accordingly, modes of the steel sheet according to the present invention include, for example, the followings.

(1) “Plating film—Chemical conversion treatment coating—Organic coating” on one side of the steel sheet, and “Plating film” on other side of the steel sheet;

(2) “Plating film—Chemical conversion treatment coating—Organic coating” on one side of the steel sheet, and “Plating film—Chemical conversion treatment coating” on other side of the steel sheet;

(3) “Plating film—Chemical conversion treatment coating—Organic coating” on both sides of the steel sheet;

(4) “Plating film—Chemical conversion treatment coating—Organic coating” on one side of the steel sheet, and “Plating film—Organic coating” on other side of the steel sheet;

Embodiments

Resin compositions (reaction products) for forming the organic coating were synthesized in the following-described procedure.

SYNTHESIS EXAMPLE 1

A 1870 parts of EP828 (epoxy equivalent 187, manufactured by Yuka Shell Epoxy Co., Ltd.), 912 parts of bisphenol A, 2 parts of tetraethylammonium bromide, and 300 parts of methylethylketone were charged in a flask with four necks, which mixture was then heated to 14° C. to let them react for 4 hours. Thus, an epoxy resin having an epoxy equivalent of 1391 and a solid content of 90% was obtained. A 1500 parts of ethyleneglycol monobutylether was added to the epoxy resin, which were then cooled to 100° C. A 96 parts of 3,5-dimethylpyrazole (molecular weight 96) and 129 parts of dibutylamine (molecular weight 129) were added to the cooled resin, and they were reacted for 6 hours to eliminate the epoxy group. Then, a 205 parts of methylisobutylketone was added while the mixture was cooling, to obtain a pyrazole-modified epoxy resin having 60% of solid matter. The epoxy resin is defined as the resin composition (1). The resin composition (1) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound that contains 50 mole % of hydrazine derivative (C) containing active hydrogen.

SYNTHESIS EXAMPLE 2

A 4000 parts of EP1007 (epoxy equivalent 2000, manufactured by Yuka Shell Epoxy Co., Ltd.) and 2239 parts of ethyleneglycol monobutylether were charged into a flask with four necks, which mixture was then heated to 120° C. to let them react for 1 hour to fully dissolve the epoxy resin. The mixture was cooled to 100° C. A 168 parts of 3-amino-1,2,4-triazole (molecular weight 84) was added to the mixture, and they were reacted for 6 hours to eliminate the epoxy group. Then, a 540 parts of methylisobutylketone was added while the mixture was cooling, to obtain a triazole-modified epoxy resin having 60% of solid matter. The epoxy resin is defined as the resin composition (2). The resin composition (2) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound that contains 100 mole % of hydrazine derivative (C) containing active hydrogen.

SYNTHESIS EXAMPLE 3

A 222 parts of isophorone diisocyanate (epoxy equivalent 111) and 34 parts of methylisobutylketone were charged into a flask with four necks. A 87 parts of methylethylketoxime (molecular weight 87) was added to the mixture dropwise for 3 hours while keeping the mixture at temperatures ranging from 30 to 40° C., then the mixture was kept to 40° C. for 2 hours. Thus, a block isocyanate having isocyanate equivalent of 309 and solid content of 90% was obtained.

A 1489 parts of EP828 (epoxy equivalent 187, manufactured by Yuka Shell Epoxy Co., Ltd.) 684 parts of bisphenol A, 1 part of tetraethylammonium bromide, and 241 parts of methylisobutylketone were charged into a flask with four necks, which mixture was then heated to 140° C. to let them react for 4 hours. Thus, an epoxy resin having epoxy equivalent of 1090 and solid content of 90% was obtained. To the epoxy resin, 1000 parts of methylisobutylketone was added, then the mixture was cooled to 1000° C., and 202 parts of 3-mercapto-1,2,4-triazole (molecular weight 101) was added to the mixture, and let the mixture react for 6 hours to fully eliminate the epoxy group. After that, the part-block isocyanate of the above-described 90% solid portion was added to the reaction product to let the mixture react at 1000° C. for 3 hours, and the vanish of isocyanate group was confirmed. Further, 461 parts of ethyleneglycol monobutylether was added to the product to obtain a triazole-modified epoxy resin having 60% solid content. The product is defined as the resin composition (3). The resin composition (3) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound that contains 100 mole % of hydrazine derivative (C) containing active hydrogen.

SYNTHESIS EXAMPLE 4

A 1870 parts of EP828 (epoxy equivalent 187, manufactured by Yuka Shell Epoxy Co., Ltd.), 912 parts of bisphenol A, 2 parts of tetraethylammonium bromide, and 300 parts of methylisobutylketone were charged into a flask with four necks, which mixture was then heated to 140° C. to let them react for 4 hours. Thus, an epoxy resin having epoxy equivalent of 1391 and solid content of 90% was obtained. To the epoxy resin, 1500 parts of ethyleneglycol monobutylether was added, then the mixture was cooled to 100° C., and 258 parts of dibutylamine (molecular weight 129) was added to the mixture, and let the mixture react for 6 hours to fully eliminate the epoxy group. While cooling the mixture, 225 parts of methylisobutylketone was further added to the mixture to obtain an epoxyamine adduct having 60% solid content. The product is defined as the resin composition (4). The resin composition (4) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound of hydrazine derivative (C) containing no active hydrogen.

A curing agent was blended to each of the synthesized resin compositions (1) through (4) to prepare the resin compositions (paint compositions) listed in Table 101. The Nos. allotted to the kinds of the base resins in Table 101 correspond to respective Nos. of the resin composition which were synthesized in Synthesis Examples (1) through (4).

The kinds of curing agents (A) through (D) in Table 101 are the following.

A: IPDI MEK oxime block body.

B: isocyanurate type.

C: HMDI MEK oxime block body.

D: imino group type melamine resin.

To each of these paint compositions, ion-exchanged silica, fine particle silica given in Table 98, and solid lubricant given in Table 99 were added at specified amounts, and they were dispersed in the composition using a paint dispersion machine (sand grinder) for a necessary time. For the above-described ion-exchanged silica, SHIELDEX C303 (average particle sizes of from 2.5 to 3.5 μm and Ca concentration of 3 wt. %) manufactured by W.R. Grace & Co., which is a Ca-exchanged silica, was used.

EXAMPLE 1

To obtain organic coating steel sheets for household electric appliances, building materials, and automobile parts, the plated steel sheets shown in Table 97 were used as the target base plates, which plates were prepared by applying zinc base plating or aluminum base plating on the cold-rolled steel sheets having a plate thickness of 0.8 mm and a surface roughness Ra of 1.0 μm. The surface of the plated steel sheet was treated by alkaline degreasing and water washing, followed by drying, then the chemical conversion treatment was applied using the treatment liquid under the treatment condition shown in Table 100 to form the chemical conversion coating. Then, the paint composition given in Table 101 was applied using a roll coater, which was then heated to dry to form the secondary layer coating (the organic coating), thus manufactured the organic coating steel sheets as Examples and Comparative Examples. The thickness of the secondary layer coating was adjusted by the solid content in the treatment liquid (heating residue) or applying conditions (roll pressing force, rotational speed, and other variables).

To each of thus obtained organic coating steel sheets, evaluation was given in terms of quality performance (appearance of coating, white-rust resistance, white-rust resistance after alkaline degreasing, paint adhesiveness, and workability). The results are given in Tables 102 through 114 along with the structure of chemical conversion treatment layer coating and of organic coating.

The quality performance evaluation on the organic coating steel sheets was carried out by the same procedure as in the best mode 1.

TABLE 97
No.	Type	Coating weight (g/m 2 )
1	Electrolytically galvanized steel	20
	plate

 

TABLE 98
[Fine particle silica]
No.	Type	Trade name
5	Dry silica	“AEROSIL R811” produced by Japan Aerosil Co.

 

TABLE 99
[Solid lubricant]
No.	Type	Trade name
1	Polyethylene wax	“LUVAX 1151” produced by Nippon Seiro Co.

 

	TABLE 100
				Adaptability to the
	Target composition		Coating	conditions of
No.	Type	Trade name	Remark	Treatment method	thickness	the invention
1	Lithium silicate	Nissan Kagaku Kogyo Co.	SiO 2 /LiO 2 = 3.5	Coating→drying at 150° C.	0.5 μm	Satisfies
		LSS-35
2	Lithium silicate	Nissan Kagaku Kogyo Co.	SiO 2 /LiO 2 = 4.5	Coating→drying at 150° C.	0.5 μm	Satisfies
		LSS-45
3	Lithium silicate	Nissan Kagaku Kogyo Co.	SiO 2 /LiO 2 = 7.5	Coating→drying at 150° C.	0.5 μm	Satisfies
		LSS-75
4	Lithium silicate	DuPont	SiO 2 /LiO 2 = 4.6-5.0	Coating→drying at 150° C.	0.5 μm	Satisfies
		Polysilicate 48
5	Phosphate	Nihon Parkerizing Co.	—	Spray→drying	2 μm	Satisfies
	treatment	PB3312
6	Organic resin	Acrylic-ethylene copolymer	Organic resin: Colloidal	Coating→drying at 150° C.	1 μm	Satisfies
	coating		silica = 100:10
7	Phitinic acid	Mitsui Chemicals Inc.	—	Coating→drying at 150° C.	0.5 μm	Satisfies
	treatment	Phytinic acid 10 g/L aqueous solution
8	Tannic acid	Fuji Chemical Co., Ltd.	—	Coating→drying at 150° C.	0.5 μm	Satisfies
	treatment	Tannin AL 10 g/L aqueous solution
9	Polymer	Miyoshi Oil & Fat Co.	—	Coating→drying at 150° C.	0.5 μm	Satisfies
	chelating agent	Dithiocarbamic acid Antimonate

 

TABLE 101
[Resin composition of secondary layer coating]
	Base resin	Curing agent		Adaptability to the
No.	Type *1	Blending rate	Type *2	Blending rate	Catalyst	conditions of the invention
1	(1)	100 parts	A	5 parts	Dibutyltin dilaurate (0.2 part)	Satisfies
2	(1)	100 parts	B	25 parts	Dibutyltin dilaurate (1.0 part)	Satisfies
3	(1)	100 parts	C	25 parts	—	Satisfies
4	(2)	100 parts	A	50 parts	Dibutyltin dilaurate (2.0 part)	Satisfies
5	(2)	100 parts	B	50 parts	Dibutyltin dilaurate (3.0 part)	Satisfies
6	(2)	100 parts	C	80 parts	Dibutyltin dilaurate (4.0 part)	Satisfies
7	(3)	100 parts	A	25 parts	Cobalt naphthenate (1.0 part)	Satisfies
8	(3)	100 parts	B	10 parts	Tin (II) chloride (1.0 part)	Satisfies
9	(3)	100 parts	C	50 parts	N-ethylmorpholine (1.0 part)	Satisfies
10	(1)	100 parts	D	25 parts	—	Satisfies
11	(3)	100 parts	D	30 parts	—	Satisfies
12	(4)	100 parts	B	25 parts	Dibutyltin dilaurate (1.0 part)	Dissatisfies
13	Aqueous solution of a hydrazine derivative	Dissatisfies
	(aqueous solution of 5 wt. % 3,5-dimethylpyrazole)
14	Mixture of an epoxyamine adduct and a hydrazine derivative (3 parts by weight of	Dissatisfies
	3,5-dimethylpyrazole per 100 parts by weight of base resin is added
	to the composition No. 12, followed by agitating the mixture.)

 

	TABLE 102
		Primary		Performance
	Plating	layer coating	Secondary layer coating			White-rust
	steel	Coating	Resin	Drying	Coating		White-rust	resistance after
	plate	composition	composition	temperature	thickness		resistance:	alkaline degreasing:	Paint	Classifi-
No.	*1	*2	*3	(° C.)	(μm)	Appearance	SST 72 hrs	SST 72 hrs	adhesiveness	cation
1	1	1	1	230	1.5	◯	⊚	⊚	⊚	Example
2	1	1	2	230	1.5	◯	⊚	⊚	⊚	Example
3	1	1	3	230	1.5	◯	⊚	⊚	⊚	Example
4	1	1	4	230	1.5	◯	⊚	⊚	⊚	Example
5	1	1	5	230	1.5	◯	⊚	⊚	⊚	Example
6	1	1	6	230	1.5	◯	⊚	⊚	⊚	Example
7	1	1	7	230	1.5	◯	⊚	⊚	⊚	Example
8	1	1	8	230	1.5	◯	⊚	⊚	⊚	Example
9	1	1	9	230	1.5	◯	⊚	⊚	⊚	Example
10	1	1	10	230	1.5	◯	⊚	⊚	⊚	Example
11	1	1	11	230	1.5	◯	⊚	⊚	⊚	Example
12	1	1	12	230	1.5	◯	Δ	Δ	⊚	Comparative
										example
*1: Corresponding to No. given in Table 97
*2: Corresponding to No. given in Table 100
*3: Corresponding to No. given in Table 101

 

	TABLE 103
		Primary		Performance
	Plating	layer coating	Secondary layer coating			White-rust
	steel	Coating	Resin	Drying	Coating		White-rust	resistance after
	plate	composition	composition	temperature	thickness		resistance:	alkaline degreasing:	Paint	Classifi-
No.	*1	*2	*3	(° C.)	(μm)	Appearance	SST 72 hrs	SST 72 hrs	adhesiveness	cation
13	1	1	13	230	1.5	◯	X	X	X	Comparative
										example
14	1	1	14	230	1.5	◯	Δ	Δ	⊚	Comparative
										example
15	1	2	1	230	1.5	◯	⊚	⊚	⊚	Example
16	1	3	1	230	1.5	◯	⊚	⊚	⊚	Example
17	1	4	1	230	1.5	◯	⊚	⊚	⊚	Example
18	1	5	1	230	1.5	◯	⊚	⊚	⊚	Example
19	1	6	1	230	1.5	◯	⊚	⊚	⊚	Example
20	1	7	1	230	1.5	◯	⊚	⊚	⊚	Example
21	1	8	1	230	1.5	◯	⊚	⊚	⊚	Example
22	1	9	1	230	1.5	◯	⊚	⊚	⊚	Example
23	1	2	2	230	1.5	◯	⊚	⊚	⊚	Example
*1: Corresponding to No. given in Table 97
*2: Corresponding to No. given in Table 100
*3: Corresponding to No. given in Table 101

 

	TABLE 104
	Primary
	layer	Secondary layer coating	Performance
	Plat-	coating		Fine particles		White-		White-rust	White-rust
	ing	Coating	Resin	silica (b)	Drying	rust		resis-	resistance after
	steel	compo-	compo-		Blending	temper-	resis-		tance:	alkaline degreasing:	Paint
	plate	sition	sition	Type	rate	ature	tance:	Appear-	SST	SST	adhe-	Classifi-
No.	*1	*2	*3	*5	*6	(° C.)	(μm)	ance	96 hrs	96 hrs	siveness	cation
24	1	1	1	1	10	230	1.5	◯	⊚	⊚	⊚	Example
36	1	1	1	1	1	230	1.5	◯	◯	◯	⊚	Example
37	1	1	1	1	5	230	1.5	◯	◯+	◯+	⊚	Example
38	1	1	1	1	10	230	1.5	◯	⊚	⊚	⊚	Example
39	1	1	1	1	20	230	1.5	◯	⊚	⊚	⊚	Example
40	1	1	1	1	30	230	1.5	◯	⊚	⊚	⊚	Example
41	1	1	1	1	40	230	1.5	◯	◯+	◯+	⊚	Example
42	1	1	1	1	50	230	1.5	◯	◯+	◯+	⊚	Example
43	1	1	1	1	80	230	1.5	◯	◯	◯	⊚	Example
44	1	1	1	1	100	230	1.5	◯	◯−	◯−	⊚	Example
45	1	1	1	1	150	230	1.5	◯	Δ	Δ	⊚	Comparative
												example
*1: Corresponding to No. given in Table 97
*2: Corresponding to No. given in Table 100
*3: Corresponding to No. given in Table 101
*5: Corresponding to No. given in Table 98
*6: Blending rate (parts by weight) of fine particles silica to 100 parts by weight of solid matter of resin

 

	TABLE 105
	Primary
	layer	Secondary layer coating	Performance
	Plat-	coating		Fine particles		White-		White-rust	White-rust
	ing	Coating	Resin	silica (b)	Drying	rust		resis-	resistance after
	steel	compo-	compo-		Blending	temper-	resis-		tance:	alkaline degreasing:	Paint
	plate	sition	sition	Type	rate	ature	tance:	Appear-	SST	SST	adhe-	Classifi-
No.	*1	*2	*3	*5	*6	(° C.)	(μm)	ance	96 hrs	96 hrs	siveness	cation
59	1	1	1	1	10	230	0.01	◯	X	X	⊚	Comparative
												example
60	1	1	1	1	10	230	0.1	◯	◯−	◯−	⊚	Example
61	1	1	1	1	10	230	0.5	◯	◯−	◯−	⊚	Example
62	1	1	1	I	10	230	1	◯	◯	◯	⊚	Example
63	1	1	I	1	10	230	2	◯	⊚	⊚	⊚	Example
64	1	1	1	1	10	230	2.5	◯	⊚	⊚	⊚	Example
65	1	1	1	1	10	230	3	◯	⊚	⊚	⊚	Example
66	1	1	1	1	10	230	4	◯	⊚	⊚	⊚	Example
67	1	1	1	1	10	230	5	◯	⊚	⊚	⊚	Example
68	1	1	1	1	10	230	20	◯	⊚	⊚	⊚	Comparative
												example
												&Asteriskpseud;1
*1: Corresponding to No. given in Table 97
*2: Corresponding to No. given in Table 100
*3: Corresponding to No. given in Table 101
*5: Corresponding to No. given in Table 98
*6: Blending rate (parts by weight) of fine particles silica to 100 parts by weight of solid matter of resin
&Asteriskpseud;1: Unable to weld

 

TABLE 106

Primary

Secondary layer coating

Performance

layer

Fine particles

Solid lub-

White-rust

Plat-

coating

silica(b)

ricant(c)

resistance

ing

Coating

Resin

Blend-

Blend-

Drying

Coating

White-rust

after alkaline

Paint

steel

compo-

compo-

ing

ing

temper-

thick-

resistance:

degreasing:

adhe-

Classifi-

plate

sition

sition

Type

rate

Type

rate

ature

ness

Appear-

SST

SST

sive-

Work-

cation

No.

*1

*2

*3

*5

*6

*9

*10

(° C.)

(μm)

ance

96 hrs

96 hrs

ness

ability

&Asteriskpseud;1

79

1

1

1

1

10

1

5

230

1.5

◯

⊚

⊚

⊚

⊚

Example

85

1

1

1

1

10

1

1

230

1.5

◯

⊚

⊚

⊚

◯

Example

86

1

1

1

1

10

1

10

230

1.5

◯

⊚

⊚

⊚

⊚

Example

87

1

1

1

1

10

1

30

230

1.5

◯

⊚

⊚

⊚

⊚

Example

88

1

1

1

1

10

1

80

230

1.5

◯

⊚

⊚

◯

⊚

Example

89

1

1

1

1

10

1

100

230

1.5

◯

⊚

⊚

X

⊚

Compara-

tive

example

*1: Corresponding to No. given in Table 97

*2: Corresponding to No. given in Table 100

*3: Corresponding to No. given in Table 101

*5: Corresponding to No. given in Table 98

*6: Blending rate (parts by weight) of fine particles silica to 100 parts by weight of solid matter of resin

*9: Corresponding to No. given in Table 99

*10: Blending rate (parts by weight) of solid lubricant to 100 parts by weight of solid matter of resin

 

	TABLE 107
	Primary
	layer	Secondary layer coating	Performance
	Plat-	coating		Ion-					White-rust
	ing	Coating	Resin	exchanged	Drying	Coating			resistance
	steel	compo-	compo-	silica (a)	temper-	thick-		White-rust	after alkaline	Paint
	plate	sition	sition	blending rate	ature	ness	Appear-	resistance:	degreasing:	adhe-	Classifi-
No.	*1	*2	*3	*4	(° C.)	(μm)	ance	SST 120 hrs	SST 120 hrs	siveness	cation
1	1	1	1	30	230	1.5	◯	⊚	⊚	⊚	Example
2	1	1	2	30	230	1.5	◯	⊚	⊚	⊚	Example
3	1	1	3	30	230	1.5	◯	⊚	⊚	⊚	Example
4	1	1	4	30	230	1.5	◯	⊚	⊚	⊚	Example
5	1	1	5	30	230	1.5	◯	⊚	⊚	⊚	Example
6	1	1	6	30	230	1.5	◯	⊚	⊚	⊚	Example
7	1	1	7	30	230	1.5	◯	⊚	⊚	⊚	Example
8	1	1	8	30	230	1.5	◯	⊚	⊚	⊚	Example
9	1	1	9	30	230	1.5	◯	⊚	⊚	⊚	Example
10	1	1	10	30	230	1.5	◯	⊚	⊚	⊚	Example
11	1	1	11	30	230	1.5	◯	⊚	⊚	⊚	Example
12	1	1	12	30	230	1.5	◯	Δ	X	⊚	Compara-
											tive
											example
*1: Corresponding to No. given in Table 97
*2: Corresponding to No. given in Table 100
*3: Corresponding to No. given in Table 101
*4: Blending rate (parts by weight) of ion-exchanged silica to 100 parts by weight of solid matter of resin

 

	TABLE 108
	Primary
	layer	Secondary layer coating	Performance
	Plat-	coating		Ion-					White-rust
	ing	Coating	Resin	exchanged	Drying	Coating			resistance
	steel	compo-	compo-	silica (a)	temper-	thick-		White-rust	after alkaline	Paint
	plate	sition	sition	blending rate	ature	ness	Appear-	resistance:	degreasing:	adhe-	Classifi-
No.	*1	*2	*3	*4	(° C.)	(μm)	ance	SST 120 hrs	SST 120 hrs	siveness	cation
13	1	1	13	30	230	1.5	◯	X	X	X	Compara-
											tive
											example
14	1	1	14	30	230	1.5	◯	Δ	X	⊚	Compara-
											tive
											example
15	1	2	1	30	230	1.5	◯	⊚	⊚	⊚	Example
16	1	3	1	30	230	1.5	◯	⊚	⊚	⊚	Example
17	1	4	1	30	230	1.5	◯	⊚	⊚	⊚	Example
18	1	5	1	30	230	1.5	◯	⊚	⊚	⊚	Example
19	1	6	1	30	230	1.5	◯	⊚	⊚	⊚	Example
20	1	7	1	30	230	1.5	◯	⊚	⊚	⊚	Example
21	1	8	1	30	230	1.5	◯	⊚	⊚	⊚	Example
22	1	9	1	30	230	1.5	◯	⊚	⊚	⊚	Example
*1: Corresponding to No. given in Table 97
*2: Corresponding to No. given in Table 100
*3: Corresponding to No. given in Table 101
*4: Blending rate (parts by weight) of ion-exchanged silica to 100 parts by weight of solid matter of resin

 

	TABLE 109
	Primary
	layer	Secondary layer coating	Performance
	Plat-	coating		Ion-					White-rust
	ing	Coating	Resin	exchanged	Drying	Coating			resistance
	steel	compo-	compo-	silica (a)	temper-	thick-		White-rust	after alkaline	Paint
	plate	sition	sition	blending rate	ature	ness	Appear-	resistance:	degreasing:	adhe-	Classifi-
No.	*1	*2	*3	*4	(° C.)	(μm)	ance	SST 120 hrs	SST 120 hrs	siveness	cation
24	1	1	13	—	230	1.5	◯	Δ	Δ	⊚	Example
25	1	1	14	1	230	1.5	◯	◯	◯	⊚	Example
26	1	1	1	5	230	1.5	◯	◯+	◯+	⊚	Example
27	1	1	1	10	230	1.5	◯	⊚	⊚	⊚	Example
28	1	1	1	30	230	1.5	◯	⊚	⊚	⊚	Example
29	1	1	1	40	230	1.5	◯	⊚	⊚	⊚	Example
30	1	1	1	50	230	1.5	◯	⊚	⊚	⊚	Example
31	1	1	1	80	230	1.5	◯	◯+	◯+	⊚	Example
32	1	1	1	100	230	1.5	◯	◯	◯	⊚	Example
33	1	1	1	150	230	1.5	◯	Δ	Δ	⊚	Compara-
											tive
											example
*1: Corresponding to No. given in Table 97
*2: Corresponding to No. given in Table 100
*3: Corresponding to No. given in Table 101
*4: Blending rate (parts by weight) of ion-exchanged silica to 100 parts by weight of solid matter of resin

 

	TABLE 110
	Secondary layer coating
		Primary			Fine particles
	Plating	layer coating		Ion-exchanged	silica (b)	(a) + (b)	(a)/(b)	Drying	Coating
	steel	Coating	Resin	silica (a)		Blending	Blending	Weight	temperature	thickness	Classi-
No.	plate*1	composition*2	composition*3	blending rate*4	Type*5	rate*6	rate*7	ratio*8	(° C.)	(μm)	fication
66	1	1	1	30	5	5	35	6/1	230	1.5	Example
81	1	1	1	30	—	—	30	30/0	230	1.5	Example
82	1	1	1	29.9	5	0.1	30	299/1	230	1.5	Example
83	1	1	1	29	5	1	30	29/1	230	1.5	Example
84	1	1	1	20	5	10	30	2/1	230	1.5	Example
85	1	1	1	15	5	15	30	1/1	230	1.5	Example
86	1	1	1	10	5	20	30	1/2	230	1.5	Example
87	1	1	1	1	5	29	30	1/29	230	1.5	Example
88	1	1	1	0.1	5	29.9	30	1/299	230	1.5	Example
*1 Corresponding to No. given in Table 97
*2 Corresponding to No. given in Table 100
*3 Corresponding to No. given in Table 101
*4 Blending rate (parts by weight) of ion-exchanged silica (a) to 100 parts by weight of solid matter of resin
*5 Corresponding to No. given in Table 98
*6 Blending rate (parts by weight) of fine particles silica (b) to 100 parts by weight of solid matter of resin
*7 Total blending rate (parts by weight) of ion-exchanged silica (a) and fine particles silica (b) to 100 parts by weight of solid matter of resin
*8 Weight ratio of ion-exchanged silica (a) and fine particles silica (b) of solid matter of resin

 

	TABLE 111
	Performance
			White-rust
			resistance	Paint
		White-rust	after alkaline	ad-
	Appear-	resistance:	degreasing:	hesive-
No.	ance	SST 150 hrs	SST 150 hrs	ness	Classification
66	∘	⊚	⊚	⊚	Example
81	∘	∘	∘	⊚	Example
82	∘	∘	∘	⊚	Example
83	∘	∘+	∘+	⊚	Example
84	∘	⊚	⊚	⊚	Example
85	∘	⊚	⊚	⊚	Example
86	∘	∘	∘	⊚	Example
87	∘	∘	∘	⊚	Example
88	∘	∘−	∘−	⊚	Example

 

	TABLE 112
	Performance
			White-rust resistance after
		White-rust resistance:	alkaline degreasing:	Paint
No.	Appearance	SST 120 hrs	SST 120 hrs	adhesiveness	Workability	Classification
112	∘	⊚	⊚	⊚	⊚	Example
114	∘	⊚	⊚	⊚	⊚	Example
115	∘	⊚	⊚	⊚	⊚	Example
116	∘	⊚	⊚	⊚	⊚	Example
117	∘	⊚	⊚	⊚	⊚	Example
118	∘	⊚	⊚	⊚	∘	Example
119	∘	⊚	⊚	⊚	⊚	Example
120	∘	⊚	⊚	⊚	⊚	Example
121	∘	⊚	⊚	∘	⊚	Example
122	∘	⊚	⊚	x	⊚	Comparative
						example
123	∘	⊚	⊚	⊚	⊚	Example

 

	TABLE 113
	Secondary layer coating
				Ion-exchanged
	Plating	Primary layer coating	Resin	silica (a)	Solid lubricant (c)	Drying	Coating
	steel plate	Coating composition	composition	blending rate	Type	Blending rate	temperature	thickness
No.	*1	*2	*3	*4	*5	*6	(° C.)	(μm)	Classification
112	1	1	1	30	1	10	230	1.5	Example
114	1	1	1	30	3	10	230	1.5	Example
115	1	1	1	30	4	10	230	1.5	Example
116	1	1	1	30	5	10	230	1.5	Example
117	1	1	1	30	6	10	230	1.5	Example
118	I	1	1	30	1	1	230	1.5	Example
119	1	1	1	30	1	3	230	1.5	Example
120	1	1	1	30	1	40	230	1.5	Example
121	1	1	1	30	1	80	230	1.5	Example
122	1	1	1	30	1	100	230	1.5	Comparative
									example
*1: Corresponding to No. given in Table 97
*2: Corresponding to No. given in Table 100
*3: Corresponding to No. given in Table 101
*4: Blending rate (parts by weight) of ion-exchanged silica to 100 parts by weight of solid matter of resin
*9: Corresponding to No. given in Table 99
*10: Blending rate (parts by weight) of solid lubricant to 100 parts by weight of solid matter of resin

 

	TABLE 114
	Secondary layer coating
	Plating			Ion-exchanged
	steel	Primary layer coating	Resin	silica (a)	Fine particles silica (b)	(a) + (b)
	plate	Coating composition	composition	blending rate	Type	Blending rate	Blending rate
No.	*1	*2	*3	*4	*5	*6	*7
123	1	1	1	30	1	5	35
	Secondary layer coating
	(a)/(b)	Solid lubricant (c)	Drying	Coating
		Weight ratio	Type	Blending rate	temperature	thickness
	No.	*8	*9	*10	(° C.)	(μm)	Classification
	123	6/1	1	10	230	1.5	Example
	*1: Corresponding to No. given in Table 97
	*2: Corresponding to No. given in Table 100
	*3: Corresponding to No. given in Table 101
	*5: Corresponding to No. given in Table 4
	*6: Blending rate (parts by weight) of fine particles silica to 100 parts by weight of solid matter of resin
	*7: Blending rate (parts by weight) of ion-exchanged silica to 100 parts by weight of solid matter of resin
	*8: Weight ratio of ion-exchanged silica (a) and fine particles silica (b) of solid matter of resin
	*9: Corresponding to No. given in Table 99
	*10: Blending rate (parts by weight) of solid lubricant to 100 parts by weight of solid matter of resin

 

Best Mode 4

The organic coating steel sheet according to the present invention is basically characterized in that a chemical conversion treatment coating is formed on the surface of a zinc base plating steel sheet or an aluminum base plating steel sheet, and that, further on the chemical conversion treatment coating, a reaction is given between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, thus applying the hydrazine derivative (C) which is the reaction product as the base resin as a chelating group to the film-forming resin (A), and that zinc phosphate and/or aluminum phosphate (a) is blended to the base resin as a rust-preventive additive, and that, at need, further a calcium compound (b) is blended to the base resin.

The corrosion-preventive mechanism of the organic coating comprising above-described specific reaction product is not fully analyzed. The mechanism is, however, presumably the following. By adding a hydrazine derivative, not applying a simple low molecular weight chelating agent, to the film-forming organic resin, (1) the dense organic polymer coating gives an effect to shut-off corrosion causes such as oxygen and chlorine ions, (2) the hydrazine derivative is able to form a stable passive layer by strongly bonding with the surface of the primary layer coating, and (3) the free hydrazine derivative in the coating traps the zinc ion which is eluted by a corrosion reaction, thus forming a stable insoluble chelated compound layer, which suppresses the formation of an ion conduction layer at interface to suppress the progress of corrosion. These work effects should effectively suppress the development of corrosion, thus giving excellent corrosion resistance.

As a result, even when a chemical conversion treatment coating (such as phosphate treatment coating) which contains no hexavalent chromium is used as the chemical conversion treatment coating on the base material, the obtained corrosion resistance is equivalent to that in the case of using a chromate coating as the chemical conversion treatment coating. Furthermore, the obtained corrosion-preventive effect is combined with the corrosion-preventive effect of the organic coating, so that the attained corrosion resistance is markedly higher than that of conventional chromated steel sheets, while attaining superior chromium elution resistance.

Particularly when a resin containing epoxy group is used as the film-forming organic resin (A), a dense barrier coating is formed by the reaction between the epoxy-group-laden resin and a cross-linking agent. Thus, the formed barrier coating has excellent penetration-suppression performance against the corrosion causes such as oxygen, and gains excellent bonding force with the base material owing to the hydroxyl group in the molecule, which results in particularly superior corrosion resistance.

Further excellent corrosion resistance is obtained by using an active-hydrogen-laden pyrazole compound and/or an active-hydrogen-laden triazole compound as the hydrazine derivative (C) containing active hydrogen.

As in the case of prior art, blending simply a hydrazine derivative with the film-forming organic resin gives very little improvement in corrosion-suppression. The reason is presumably that the hydrazine derivative which does not enter the molecules of the film-forming organic resin forms a chelate compound with zinc which is eluted under a corrosive environment, and the chelate compound cannot form a dense barrier layer because of low molecular weight. To the contrary, introduction of a hydrazine derivative into the molecules of film-forming organic resin, as in the case of present invention, provides markedly high corrosion-suppression effect.

According to the organic coating steel sheet of the present invention, further high anti-corrosive performance (self-repair work at coating-defect section) is attained by blending adequate amount of zinc phosphate and/or aluminum phosphate (a) with an organic coating consisting of above-described specific reaction products. The corrosion-preventive mechanism which is obtained by blending the zinc phosphate and/or aluminum phosphate (a) with the specific organic coating is speculated to proceed conforming to the reaction steps given below.

[The first step]:  under a corrosive environment, zinc,
                   aluminum, and the like which are the plating
                   metals are eluted.
[The second step]: Zinc phosphate and/or aluminum phosphate is
                   hydrolyzed to dissociate to phosphoric acid
                   ion.
[The third step]:  The eluted zinc ion and aluminum ion initiate
                   complex-forming reactions with phosphoric
                   acid ion to form a dense and slightly soluble
                   protective coating, which coating then seals
                   the defects on the coating to suppress the
                   corrosion reactions.

 

Also in the case that zinc phosphate and/or aluminum phosphate is blended with a general organic coating, corrosion-preventive effect is obtained to some extent. Nevertheless, when zinc phosphate and/or aluminum phosphate is blended with an organic coating consisting of a specific chelate-modified resin, as in the case of present invention, the combined corrosion-preventive effect of both compounds appears, which should provide markedly strong corrosion-preventive effect.

Furthermore, according to the organic coating steel sheet of the present invention, the corrosion resistance can further be increased by blending a zinc phosphate and/or aluminum phosphate (a) and calcium compound (b) together into the organic coating consisting of a specific reaction product as described above. The reason of the superior corrosion resistance is speculated as follows. The self-repair action by zinc phosphate and/or aluminum phosphate cannot fully suppress the corrosion reactions, though the action suppresses the corrosion reactions during very early period of the corrosion, because the action triggers the elution of plating metals as described in the first step given above. By applying a calcium compound which is less noble metal than zinc and aluminum, the calcium is preferentially eluted rather than zinc and aluminum which are noble than calcium, thus the corrosion reactions are suppressed without depending on the elution of plating metals. Through the mechanism, the combined rust-preventive effect resulted from combined use of zinc phosphate and/or aluminum phosphate with calcium compound would appear.

The chemical conversion treatment coating formed on the surface of a zinc plating steel sheet or an aluminum plating steel sheet is the same as the chemical conversion treatment coating described in the best mode 3.

The following is the description of the organic coating formed on the above-described chemical conversion treatment coating.

According to the present invention, the organic coating formed on the above-described chemical conversion treatment coating contains a product of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, and a zinc phosphate and/or aluminum phosphate (a), and at need, further contains a calcium compound (b) and a solid lubricant (c), which organic coating has a thickness in a range of from 0.1 to 5 μm.

The kinds of film-forming organic resin (A) are not specifically limited if only the resin reacts with the active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, to bind the active-hydrogen-laden compound (B) with the film-forming organic resin by addition or condensation reaction, and adequately form the coating.

Examples of the film-forming organic resin (A) are epoxy resin, modified epoxy resin, polyurethane resin, polyester resin, alkyd resin, acrylic base copolymer resin, polybutadiene resin, phenol resin, and adduct or condensate thereof. These resins may be applied separately or blending two or more of them.

From the standpoint of reactivity, readiness of reaction, and corrosion-prevention, an epoxy-group-laden resin (D) in the resin is particularly preferred as the film-forming organic resin (A). The epoxy-group-laden resin (D) has no specific limitation if only the resin reacts with an active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, to bind with the active hydrogen-laden compound (B) by addition or condensation reaction, and adequately form the coating. Examples of the epoxy-group-laden resin (D) are epoxy resin, modified epoxy resin, acrylic base copolymer resin copolymerized with an epoxy-group-laden monomer, polybutadiene resin containing epoxy group, polyurethane resin containing epoxy group, and adduct or condensate of these resins. These resins may be applied separately or blending two or more of them together.

From the point of adhesiveness with plating surface and of corrosion resistance, epoxy resin and modified epoxy resin are particularly preferred among these epoxy-group-laden resins (D).

Examples of the above-described epoxy resins are: aromatic epoxy resins prepared by reacting a polyphenol such as bisphenol A, bisphenol F, and novorak type phenol with epihalohydrin such as epychlorohydrin followed by introducing glycidyl group thereinto, or further by reacting a polyphenol with thus obtained product containing glycidyl group to increase the molecular weight; aliphatic epoxy resin, and alicyclic epoxy resin. These resins may be applied separately or blending two or more of them together. If film-formation at a low temperature is required, the epoxy resins preferably have number-average molecular weights of 1500 or more.

The above-described modified epoxy resin may be a resin prepared by reacting epoxy group or hydroxyl group in one of the above-given epoxy resins with various kinds of modifying agents. Examples of the modified epoxy resin are epoxy-ester resin prepared by reacting with a drying oil fatty acid, epoxy-acrylate resin prepared by modifying with a polymerizable unsaturated monomer component containing acrylic acid or methacrylic acid, and urethane-modified epoxy resin prepared by reacting with an isocyanate compound.

Examples of the above-described acrylic base copolymer resin which is copolymerized with the above-described epoxy-group-laden monomer are the resins which are prepared by solution polymerization, emulsion polymerization, or suspension polymerization of an unsaturated monomer containing epoxy group with a polymerizable unsaturated monomer component containing acrylic acid ester or methacrylic acid ester as the essential ingredient.

Examples of the above-described unsaturated monomer component are: C1-24 alkylester of acrylic acid or methacrylic acid, such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, n-iso- or tert-butyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, decyl(meth)acrylate, lauryl(meth)acrylate; C1-4 alkylether compound of acrylic acid, methacrylic acid, styrene, vinyltoluene, acrylamide, acrylonitrile, N-methylol(meth)acrylamide, N-methylol(meth)acrylamide; and N,N-diethylaminoethylmethacrylate.

The unsaturated monomer having epoxy group has no special limitation if only the monomer has epoxy group and polymerizable unsaturated group, such as glycidylmethacrylate, glycidylacrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate.

The acrylic base copolymer resin which was copolymerized with the epoxy-group-laden monomer may be a resin which is modified by polyester resin, epoxy resin, or phenol resin.

A particularly preferred epoxy resin described above is an epoxy resin as a product of the reaction between bisphenol A and epihalohydrin because of superior corrosion resistance.

The method for manufacturing that kind of bisphenol A type epoxy resin is widely known in the industry concerned. In the above-given chemical formula, q value is in a range of from 0 to 50, preferably from 1 to 40, more preferably from 2 to 20.

The film-forming organic resin (A) may be either organic solvent dissolving type, organic solvent dispersing type, water dissolving type, or water dispersing type.

According to the present invention, a hydrazine derivative is introduced into the molecules of the film-forming organic resin (A). To do this, at least a part of the active-hydrogen-laden compound (B), (preferably whole thereof), is necessary to be a hydrazine derivative (C) containing active hydrogen.

When the film-forming organic resin (A) is an epoxy-group-laden resin, examples of the active-hydrogen-laden compound (B) reacting with the epoxy group are listed below. One or more of these compounds (B) may be applied. Also in that case, at least a part of the active-hydrogen-laden compound (B), (preferably whole thereof), is necessary to be a hydrazine derivative (C) containing active hydrogen.

A hydrazine derivative containing active hydrogen

A primary or secondary amine compound containing active hydrogen

An organic acid such as ammonia and carboxylic acid

A halogenated hydrogen such as hydrogen chloride

An alcohol, a thiol

A hydrazine derivative containing no active hydrogen or a quaternary chlorinating agent which is a mixture with a ternary amine.

Examples of the above-described hydrazine derivative (C) containing active hydrogen are the following.

Hydrazide compound such as carbohydrazide, propionic acid hydrazide, salicylic acid hydrazide, adipic acid hydrazide, sebacic acid hydrazide, dodecanic acid hydrazide, isophtharic acid hydrazide, thiocarbo-hydrazide, 4,4′-oxy-bis-benzenesulfonyl hydrazide, benzophenone hydrazone, amino-polyacrylamide hydrazide;

Pyrazole compound such as pyrazole, 3,5-dimethylpyrazole, 3-methyl-5-pyrazolone, 3-amino-5-methylpyrazole;

Triazole compound such as 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 5-amino-3-mercapto-1,2,4-triazole, 2,3-dihydro-3-oxo-1,2,4-triazole, 1H-benzotriazole, 1-hydroxybenzotriazole (mono hydrate), 6-methyl-8-hydroxytriazolopyridazine, 6-phenyl-8-hydroxytriazolopyrydazine, 5-hydroxy-7-methyl-1,3,8-triazaindolizine;

Tetrazole compound such as 5-phenyl-1,2,3,4-tetrazole, 5-mercapto-1-phenyl-1,2,3,4-tetrazole;

Thiadiazole compound such as 5-amino-2-mercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole;

Pyridazine compound such as maleic acid hydrazide, 6-methyl-3-pyridazone, 4,5-dichloro-3-pyridazone, 4,5-dibromo-3-pyridazone, 6-methyl-4,5-dihydro-3-pyridazone. Among these compounds, particularly preferred ones are pyrazole compound and triazole compound which have cyclic structure of five- or six-membered ring and which have nitrogen atom in the cyclic structure.

These hydrazine derivatives may be applied separately or blending two or more of them together.

Examples of above-described amine compound having active hydrogen, which can be used as a part of the active-hydrogen-laden compound (B), are the following.

A compound prepared by heating to react a primary amino group of an amine compound containing a single secondary amino group of diethylenetriamine, hydroxylaminoethylamine, ethylaminoethylamine, methylaminopropylamine, or the like and one or more of primary amino group, with ketone, aldehyde, or carboxylic acid, at, for example, approximate temperatures of from 100 to 230° C. to modify them to aldimine, ketimine, oxazoline, or imidazoline;

A secondary monoamine such as diethylamine, diethanolamine, di-n- or -iso-propanolamine, N-methylethanolamine, N-ethylethanolamine;

A secondary-amine-laden compound prepared by Michael addition reaction through the addition of monoalkanolamine such as monoethanolamine to dialkyl(meth)acrylamide;

A compound prepared by modifying a primary amino group of alkanolamine such as monoethanolamine, neopentanolamine, 2-aminopropanol, 3-aminopropanol, 2-hydroxy-2′(aminopropoxy)ethylether to ketimine.

As for the above-described quaternary chlorinating agents which are able to be used as a part of the active-hydrogen-laden compound (B), the hydrazine derivative having active hydrogen or ternary amine has no reactivity with epoxy group as it is. Accordingly, they are mixed with an acid to make them reactive with epoxy group. The quaternary chlorinating agent reacts with epoxy group with the presence of water, at need, to form a quaternary salt with the epoxy-group-laden resin.

The acid used to obtain the quaternary chlorinating agent may be organic acid such as acetic acid and lactic acid, or inorganic acid such as hydrochloric acid. The hydrazine derivative containing no active hydrogen, which is used to obtain quaternary chlorinating agent may be 3,6-dichloropyridazine. The ternary amine may be dimethylethanolamine, triethylamine, trimethylamine, tri-isopropylamine, methyldiethanolamine.

The product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen, may be prepared by reacting the film-forming organic resin (A) with the active-hydrogen-laden compound (B) at temperatures of from 10 to 300° C., preferably from 50 to 150° C., for about 1 to about 8 hours.

The reaction may be carried out adding an organic solvent. The kind of adding organic solvent is not specifically limited. Examples of the organic solvent are: ketone such as acetone, methyethylketone, methylisobutylketone, dibutylketone, cyclohexanone; alcohol or ether having hydroxyl group, such as ethanol, butanol, 2-ethylhexylalcohol, benzylalcohol, ethyleneglycol, ethyleneglycol mono-isopropylether, ethyleneglycol monobutylether, ethyleneglycol monohexylether, propyleneglycol, propyleneglycol monomethylether, diethyleneglycol, diethyleneglycol monoethylether, diethyleneglycol monobutylether; ester such as ethylacetate, butylacetate, ethyleneglycol monobutylether acetate; and aromatic hydrocarbon such as toluene and xylene. These compounds may be applied separately or blending two or more of them together.

From the viewpoint of solubility and coating film-forming performance with epoxy resin, ketone group or ether group solvents are particularly preferred.

The blending ratio of the film-forming organic resin (A) and the active-hydrogen-laden compound (B), a part or whole of which compound consists of a hydrazine derivative (C) containing active hydrogen, is in a range of from 0.5 to 20 parts by weight of the active-hydrogen-laden compound (B), more preferably from 1.0 to 10 parts by weight, to 100 parts by weight of the film-forming organic resin (A).

When the film-forming organic resin (A) is an epoxy-group-laden resin (D), the blending ratio of the epoxy-group-laden resin (D) to the active-hydrogen-laden compound (B) is preferably, from the viewpoint of corrosion resistance and other performance, in a range of from 0.01 to 10 as the ratio of the number of active hydrogen groups in the active-hydrogen-laden compound (B) to the number of epoxy groups in the epoxy-group-laden resin (D), or [the number of active hydrogen groups/the number of epoxy groups], more preferably from 0.1 to 8, most preferably from 0.2 to 4.

A preferred range of hydrazine derivative (C) containing active hydrogen in the active-hydrogen-laden compound (B) is from 10 to 100 mole %, more preferably from 30 to 100 mole %, and most preferably from 40 to 100 mole %. If the rate of hydrazine derivative (C) containing active hydrogen is less than 10 mole %, the organic coating fails to have satisfactory rust-preventive function, thus the obtained rust-preventive effect becomes similar with the case of simple blending of a film-forming organic resin with a hydrazine derivative.

To form a dense barrier coating according to the present invention, it is preferable that a curing agent is blended into the resin composition, and that the organic coating is heated to cure.

Suitable methods for curing to form a resin composition coating include (1) a curing method utilizing a urethanation reaction between isocyanate and hydroxide group in the base resin, and (2) a curing method utilizing an ether reaction between hydroxide group in the base resin and an alkyletherified amino resin which is prepared by reacting between a part of or whole of a methylol compound which is prepared by reacting formaldehyde with one or more of melamine, urea, and benzoguanamine, and a C1-5 primary alcohol. As of these methods, particularly preferred one is to adopt a urethanation reaction between isocyanate and hydroxyl group in the base resin as the main reaction.

The polyisocyanate compound used in the curing method (1) described above is a compound prepared by partially reacting an aliphatic, alicyclic (including heterocyclic), or aromatic isocyanate compound, or a compound thereof using a polyhydric alcohol. Examples of that kind of polyisocyanate compound are the following. m- or p-Phenylene diisocyanate, 2,4- or 2,6-trilene diisocyanate, o- or p-xylylene diisocyanate, hexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate;

A compound of product of reaction between separate or mixture of the compounds given in (1) with a polyhydric alcohol (for example, a dihydric alcohol such as ethyleneglycol and propyleneglycol, a trihydric alcohol such as glycerin and trimethylolpropane, a tetrahydric alcohol such as pentaerythritol, and hexahydric alcohol such as sorbitol and dipentaerythritol) leaving at least two isocyanate within a molecule.

These polyisocyanate compounds may be used separately or mixing two or more of them together.

Examples of protective agent (blocking agent) of the polyisocyanate compound are the following.

Aliphatic monoalcohol such as methanol, ethanol, propanol, butanol, octylalcohol;

Monoether of ethyleneglycol and/or diethyleneglycol, for example, monoether of methyl, ethyl, propyl (n-, iso-), butyl (n-, iso-, sec-);

Aromatic alcohol such as phenol and cresol;

Oxime such as acetoxime and methylethylketone oxime.

Through reaction between one or more of these compounds with above-described polyisocyanate compound, a polyisocyanate compound thus obtained is stably protected at least at normal temperature.

It is preferable to blend that kind of polyisocyanate compound (E) with a film-forming organic resin (A) as the curing agent at a range of (A)/(E)=95/5 to 55/45 (weight ratio of non-volatile matter), more preferably (A)/(E)=90/10 to 65/35. Since polyisocyanate compounds have water-absorbing property, blending of the compound at ratios above (A)/(E)=55/45 degrades the adhesiveness of the organic coating. If top coating is given on the organic coating, unreacted polyisocyanate compound migrates into the coating film to induce hindrance of curing or insufficient adhesiveness of the coating film. Accordingly, the blending ratio of the polyisocyanate compound (E) is preferably not more than (A)/(E)=55/45.

The film-forming organic resin (A) is fully cross-linked by the addition of above-described cross-linking agent (curing agent). For further increasing the cross-linking performance at a low temperature, it is preferable to use a known catalyst for enhancing curing. Examples of the curing-enhancing catalyst are N-ethylmorpholine, dibutyltin dilaurate, cobalt naphthenate, tin(II)chloride, zinc naphthenate, and bismuth nitrate.

When an epoxy-group-laden resin is used as the film-forming organic resin (A), the epoxy-group-laden resin may be blended with a known resin such as that of acrylic, alkyd, and polyester to improve the physical properties such as adhesiveness to some extent.

According to the present invention, the organic coating is blended with zinc phosphate and/or aluminum phosphate (a) as the rust-preventive additive.

There is no specific limitation on the skeleton and degree of condensation of phosphoric acid ions for the zinc phosphate and the aluminum phosphate blended in the organic coating. They may be normal salt, dihydrogen salt, monohydrogen salt, or phosphate. The normal salt includes orthophosphoric acid and all the condensed phosphates such as polyphosphate. For example, zinc phosphate may be LF-BOSEI ZP-DL produced by Kikuchi Color Co., and aluminum phosphate ma y be K-WHITE produced by TAYCA CORPORATION.

These zinc phosphates and aluminum phosphates dissociate to phosphoric acid ion by hydrolysis under a corrosive environment, and form a protective coating through the complex-forming reaction with the eluted metals.

The rust-preventive mechanism in the case of addition of zinc phosphate and/or aluminum phosphate (a) to organic coating is described above. Particularly according to the present invention, markedly excellent corrosion preventive effect is attained by combining a specific chelate-modified resin which is the film-forming organic resin with zinc phosphate and/or aluminum phosphate (a), thus inducing the combined effect of the corrosion-suppression effect of the chelate-modified resin at the anodic reaction section with the corrosion-suppression effect of the zinc phosphate and/or aluminum phosphate (a).

A preferred range of blending ratio of the zinc phosphate and/or aluminum phosphate (a) in the organic resin coating is 1 to 100 parts by weight (solid matter) to 100 parts by weight (solid matter) of the reaction product as the resin composition for film-forming (that is, the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen), more preferably from 5 to 80 parts by weight (solid matter), and most preferably from 10 to 50 parts by weight (solid matter). If the blending ratio of the zinc phosphate and/or aluminum phosphate (a) becomes less than 1 part by weight, the effect of improved corrosion resistance after alkaline degreasing becomes small. If the blending ratio of the zinc phosphate and/or aluminum phosphate (a) exceeds 100 parts by weight, the corrosion resistance degrades, which is unfavorable.

According to the present invention, markedly high corrosion resistance is attained by combined addition of zinc phosphate and/or aluminum phosphate (a) and a calcium compound (b) to the organic coating. That is, the combined addition of zinc phosphate and/or aluminum phosphate (a) and calcium compound (b) induces above-described combined rust-preventive mechanism which gives markedly excellent corrosion-preventive effect.

Calcium compound (b) may be either one of calcium oxide, calcium hydroxide, and calcium salt, and at least one of them may be adopted. There is no specific limitation on the kind of calcium salt, and the salt may be a single salt containing only calcium as cation, for example, calcium silicate, calcium carbonate, and calcium phosphate, and may he complex salt containing cation other than calcium cation, for example, zinc calcium phosphate, magnesium calcium phosphate.

Since calcium compounds elute preferentially to metals under a corrosive environment, it presumably induces a complex-forming reaction with phosphoric acid ion without triggering the elution of plating metal, thus forming a dense and slightly-soluble protective coating to suppress the corrosion reactions.

A preferred blending ratio of combined addition of zinc phosphate and/or aluminum phosphate (a) and calcium compound (b) to the organic resin coating is from 1 to 100 parts by weight as the sum of them (solid matter) to 100 parts by weight (solid matter) of the reaction product as the resin composition for film-forming (that is, the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen), more preferably from 5 to 80 parts by weight, and a preferred blending weight ratio (solid matter) of the zinc phosphate and/or aluminum phosphate (a) and the calcium compound (b), (a)/(b), is from 99/1 to 1/99, more preferably from 95/5 to 40/60, and most preferably from 90/10 to 60/40.

If the blending amount of the sum of zinc phosphate and/or aluminum phosphate (a) and calcium compound (b) is less than 1 part by weight, the improved effect of corrosion resistance after alkaline degreasing becomes small. If the blending amount of the sum of zinc phosphate and/or aluminum phosphate (a) and calcium compound (b) exceeds 100 parts by weight, the corrosion resistance degrades, which is unfavorable. If the blending ratio (solid matter) of zinc phosphate and/or aluminum phosphate (a) to calcium compound (b) is less than 1/99, the corrosion resistance is inferior. If the blending ratio (solid matter) of zinc phosphate and/or aluminum phosphate (a) to calcium compound (b) exceeds 99/1, the effect of combined addition of zinc phosphate and/or aluminum phosphate (a) and calcium compound (b) cannot be fully attained.

The organic coating may further contain, adding to the above-described inorganic rust-preventive pigments, corrosion-suppression agents such as oxide fine particles (for example, fine particles of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, antimonium oxide), molybdate, phosphomolybdate (for example, aluminum phosphomolybdate), organic phosphoric acid and its salt (for example, phytic acid, phytiate, -phosphonic acid, phosphonate, their metal salt, alkali metal salt, and alkali earth metal salt), organic inhibitor (for example, hydrazine derivative, thiol compound, dithiocarbamate).

The organic coating may, at need, further include a solid lubricant (c) to improve the workability of the coating.

Examples of applicable solid lubricant according to the present invention are the following.

(1) Polyolefin wax, paraffin wax: for example, polyethylene wax, synthetic paraffin, natural paraffin, microwax, chlorinated hydrocarbon;

(2) Fluororesin fine particles: for example, polyfluoroethylene resin (such as poly-tetrafluoroethylene resin), polyvinylfluoride resin, polyvinylidenefluoride resin.

In addition, there may be applied fatty acid amide base compound (such as stearic acid amide, palmitic acid amide, methylene bis-stearoamide, ethylene bis-stearoamide, oleic acid amide, ethyl acid amide, alkylene bis-fatty acid amide), metallic soap (such as calcium stearate, lead stearate, calcium laurate, calcium palmate), metallic sulfide (molybdenum disulfide, tungsten disulfide), graphite, graphite fluoride, boron nitride, polyalkyleneglycol, and alkali metal sulfate.

Among those solid lubricants, particularly preferred ones are polyethylene wax, fluororesin fine particles (particularly poly-tetrafluoroethylene resin fine particles).

Applicable polyethylene wax include: Sheridust 9615A, Sheridust 3715, Sheridust 3620, Sheridust 3910 (trade names) manufactured by Hoechst Co., Ltd.; SUNWAX 131-P, SUNWAX 161-P (trade names) manufactured by Sanyo Chemical Industries, Ltd.; CHEMIPEARL W-100, CHEMIPEARL W-200, CHEMIPEARL W-500, CHEMIPEARL W-800, CHEMIPEARL W-950 (trade names) manufactured by Mitsui Petrochemical Industries, Ltd.

A most preferred fluororesin fine particle is tetrafluoroethylene fine particle. Examples of the fine particles are LUBRON L-2, LUBRON L-5 (trade names) manufactured by Daikin Industries, Ltd.; MP 1100, MP 1200 (trade names; manufactured by Du Pont-Mitsui Company, Ltd.); FLUON DISPERSION AD1, FLUON DISPERSION AD2, FLUON L141J, FLUON L150J, FLUON L155J (trade names) manufactured by Asahi ICI Fluoropolymers Co., Ltd.

As of these compounds, combined use of polyolefin wax and tetrafluoroethylene fine particles is expected to provide particularly excellent lubrication effect.

A preferred range of blending ratio of the solid lubricant (c) in the organic resin coating is from 1 to 80 parts by weight (solid matter) to 100 parts by weight (solid matter) of the reaction product as the resin composition for film-forming (that is, the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen), more preferably from 3 to 40 parts by weight (solid matter). If the blending ratio of the solid lubricant (c) becomes less than 1 part by weight, the effect of lubrication is small. If the blending ratio of the solid lubricant (b) exceeds 80 parts by weight, the painting performance degrade, which is unfavorable.

The organic coating of the organic coating steel sheet according to the present invention normally consists mainly of a product (resin composition) of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen). And, a zinc phosphate and/or aluminum phosphate (a) is added, further at need, a calcium compound (b), a solid lubricant (c), and a curing agent may further be added to the organic coating. Furthermore, at need, there may be added other additives such as organic coloring pigment (for example, condensing polycyclic organic pigment, phthalocyanine base organic pigment), coloring dye (for example, azo dye soluble in organic solvent, azo metal dye soluble in water), inorganic pigment (for example, titanium oxide), chelating agent (for example, thiol), conductive pigment (for example, metallic powder of zinc, aluminum, nickel, or the like, iron phosphide, antimony-dope type tin oxide), coupling agent (for example, silane coupling agent and titanium coupling agent), melamine-cyanuric acid additive.

The paint composition for film-formation containing above-described main component and additive components normally contains solvent (organic solvent and/or water), and, at need, further a neutralizer or the like is added.

Applicable organic solvent described above has no specific limitation if only it dissolves or disperses the product of reaction between the above-described film-forming organic resin (A) and the active-hydrogen-laden compound (B), and adjusts the product as the painting composition. Examples of the organic solvent are the organic solvents given above as examples.

The above-described neutralizers are blended, at need, to neutralize the film-forming organic resin (A) to bring it to water-type. When the film-forming organic resin (A) is a cationic resin, acid such as acetic acid, lactic acid, and formic acid may be used as the neutralizer.

The organic coatings described above are formed on the above-described composite oxide coating.

The dry thickness of the organic coating is in a range of from 0.1 to 5 μm, preferably from 0.3 to 3 μm, and most preferably from 0.5 to 2 μm. If the thickness of the organic coating is less than 0.1 μm, the corrosion resistance becomes insufficient. If the thickness of the organic coating exceeds 5 μm, the conductivity and the workability degrade.

The following is the description about the method for manufacturing an organic coating steel sheet according to the present invention.

The organic coating steel sheet according to the present invention is manufactured by the steps of: treating the surface of a zinc base plating steel sheet or an aluminum base plating steel sheet by chemical conversion treatment; applying a paint composition which contains the product of reaction between above-described film-forming organic resin (A) and an active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen, which product of reaction is preferably the main component, further contains a zinc phosphate and/or aluminum phosphate (a), and at need, a calcium compound (b), a solid lubricant (c), and the like; heating to dry the product.

The surface of the plating steel sheet may be, at need, subjected to alkaline degreasing before applying the above-described treatment liquid, and may further be subjected to preliminary treatment such as surface adjustment treatment for further improving the adhesiveness and corrosion resistance.

In the case that a chemical conversion treatment coating containing no hexavalent chromium is formed as the chemical conversion treatment coating, the methods for applying the treatment liquid onto the plating steel sheet may be either one of coating method, dipping method, and spray method. The coating method may adopt any type such as roll coater (three-roll type, two-roll type, etc.), squeeze coater, die coater. After the coating step using squeeze coater and the like, the dipping step, or the spray step, it is possible to adjust the coating weight. the uniformizing appearance, and the uniformizing the film-thickness using air-knife method and roll-squeezing method.

After the coating of treatment liquid as described above, there may applied, at need, rinsing with water, followed by heating to dry.

Method for heating to dry the coated treatment liquid is not limited. For example, dryer, hot air oven, high frequency induction heating furnace, infrared heating furnace may be applied.

The heating and drying treatment is preferably conducted at reaching temperatures of from 40 to 350° C., more preferably from 80 to 200° C., and most preferably from 80 to 160° C. If the heating temperature is less than 40° C., excess amount of water is left in the coating, which results in insufficient corrosion resistance. If the heating temperature exceeds 350° C., the operation becomes uneconomical and defects likely appear in the coating to degrade the corrosion resistance.

After forming the chemical conversion treatment coating on the surface of the zinc base plating steel sheet or the aluminum base plating steel sheet, as described above, a paint composition for forming an organic coating is applied on the composite oxide coating. Method for applying the paint composition is not limited, and examples of the method are coating method, dipping method, and spray method. The coating method may adopt any type such as roll coater (three-roll type, two-roll type, etc.), squeeze coater, die coater. After the coating step using squeeze coater and the like, the dipping step, or the spray step, it is possible to adjust the coating weight, the uniformizing appearance, and the uniformizing the film-thickness using air-knife method and roll-squeezing method.

After applying the paint composition, generally the plate is heated to dry without rinsing with water. After applying the paint composition, however, water-rinse step may be given.

Method for heating to dry the paint composition is not limited. For example, dryer, hot air oven, high frequency induction heating furnace, infrared heating furnace may be applied. The heating treatment is preferably conducted at reaching temperatures of from 50 to 350° C., more preferably from 80 to 250° C. If the heating temperature is less than 50° C., excess amount of water is left in the coating, which results in insufficient corrosion resistance. If the heating temperature exceeds 350° C., the operation becomes uneconomical and defects likely appear in the coating to degrade the corrosion resistance.

As described above, the present invention includes a steel sheet having an organic coating on both sides or on side thereof. Accordingly, modes of the steel sheet according to the present invention include, for example, the followings.

(1) “Plating film—Chemical conversion treatment coating—Organic coating” on one side of the steel sheet, and “Plating film” on other side of the steel sheet;

(2) “Plating film—Chemical conversion treatment coating—Organic coating” on one side of the steel sheet, and “Plating film—Chemical conversion treatment coating” on other side of the steel sheet;

(3) “Plating film—Chemical conversion treatment coating—Organic coating” on both sides of the steel sheet;

(4) “Plating film—Chemical conversion treatment coating—Organic coating” on one side of the steel sheet, and “Plating film—Organic coating” on other side of the steel sheet;

Embodiments

Resin compositions (reaction products) for forming the organic coating were synthesized in the following-described procedure.

SYNTHESIS EXAMPLE 1

A 1870 parts of EP828 (epoxy equivalent 187, manufactured by Yuka Shell Epoxy Co., Ltd.), 912 parts of bisphenol A, 2 parts of tetraethylammonium bromide, and 300 parts of methylethylketone were charged in a flask with four necks, which mixture was then heated to 14° C. to let them react for 4 hours. Thus, an epoxy resin having an epoxy equivalent of 1391 and a solid content of 90% was obtained. A 1500 parts of ethyleneglycol monobutylether was added to the epoxy resin, which were then cooled to 100° C. A 96 parts of 3,5-dimethylpyrazole (molecular weight 96) and 129 parts of dibutylamine (molecular weight 129) were added to the cooled resin, and they were reacted for 6 hours to eliminate the epoxy group. Then, a 205 parts of methylisobutylketone was added while the mixture was cooling, to obtain a pyrazole-modified epoxy resin having 60% of solid matter. The epoxy resin is defined as the resin composition (1). The resin composition (1) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound that contains 50 mole % of hydrazine derivative (C) containing active hydrogen.

SYNTHESIS EXAMPLE 2

A 4000 parts of EP1007 (epoxy equivalent 2000, manufactured by Yuka Shell Epoxy Co., Ltd.) and 2239 parts of ethyleneglycol monobutylether were charged into a flask with four necks, which mixture was then heated to 120° C. to let them react for 1 hour to fully dissolve the epoxy resin. The mixture was cooled to 100° C. A 168 parts of 3-amino-1,2,4-triazole (molecular weight 84) was added to the mixture, and they were reacted for 6 hours to eliminate the epoxy group. Then, a 540 parts of methylisobutylketone was added while the mixture was cooling, to obtain a triazole-modified epoxy resin having 60% of solid matter. The epoxy resin is defined as the resin composition (2). The resin composition (2) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound that contains 100 mole % of hydrazine derivative (C) containing active hydrogen.

SYNTHESIS EXAMPLE 3

A 222 parts of isophorone diisocyanate (epoxy equivalent 111) and 34 parts of methylisobutylketone were charged into a flask with four necks. A 87 parts of methylethylketoxime (molecular weight 87) was added to the mixture dropwise for 3 hours while keeping the mixture at temperatures ranging from 30 to 40° C., then the mixture was kept to 40° C. for 2 hours. Thus, a block isocyanate having isocyanate equivalent of 309 and solid content of 90% was obtained.

A 1489 parts of EP828 (epoxy equivalent 187, manufactured by Yuka Shell Epoxy Co., Ltd.), 684 parts of bisphenol A, 1 part of tetraethylammonium bromide, and 241 parts of methylisobutylketone were charged into a flask with four necks, which mixture was then heated to 140° C. to let them react for 4 hours. Thus, an epoxy resin having epoxy equivalent of 1090 and solid content of 90% was obtained. To the epoxy resin, 1000 parts of methylisobutylketone was added, then the mixture was cooled to 100° C., and 202 parts of 3-mercapto-1,2,4-triazole (molecular weight 101) was added to the mixture, and let the mixture react for 6 hours to fully eliminate the epoxy group. After that, the part-block isocyanate of the above-described 90% solid portion was added to the reaction product to let the mixture react at 100° C. for 3 hours, and the vanish of isocyanate group was confirmed. Further, 461 parts of ethyleneglycol monobutylether was added to the product to obtain a triazole-modified epoxy resin having 60% solid content. The product is defined as the resin composition (3). The resin composition (3) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound that contains 100 mole % of hydrazine derivative (C) containing active hydrogen.

SYNTHESIS EXAMPLE 4

A 1870 parts of EP828 (epoxy equivalent 187, manufactured by Yuka Shell Epoxy Co., Ltd.), 912 parts of bisphenol A, 2 parts of tetraethylammonium bromide, and 300 parts of methylisobutylketone were charged into a flask with four necks, which mixture was then heated to 140° C. to let them react for 4 hours. Thus, an epoxy resin having epoxy equivalent of 1391 and solid content of 90% was obtained. To the epoxy resin, 1500 parts of ethyleneglycol monobutylether was added, then the mixture was cooled to 100° C., and 258 parts of dibutylamine (molecular weight 129) was added to the mixture, and let the mixture react for 6 hours to fully eliminate the epoxy group. While cooling the mixture, 225 parts of methylisobutylketone was further added to the mixture to obtain an epoxyamine adduct having 60% solid content. The product is defined as the resin composition (4). The resin composition (4) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound of hydrazine derivative (C) containing no active hydrogen.

A curing agent was blended to each of the synthesized resin compositions (1) through (4) to prepare the resin compositions (paint compositions) listed in Table 119. To these paint compositions, zinc phosphate and/or aluminum phosphate shown in Table 120, calcium compound shown in Table 116, and solid lubricant shown in Table 117 were added at respective adequate amounts, then the mixture was dispersed to each other using a paint dispersion apparatus (a sand grinder) to prepare desired plating compositions.

EXAMPLE 1

To obtain organic coating steel sheets for household electric appliances, building materials, and automobile parts, the plating steel sheets shown in Table 115 were used as the target base plates, which plates were prepared by applying zinc base plating or aluminum base plating on the cold-rolled steel sheets having a plate thickness of 0.8 mm and a surface roughness Ra of 1.0 μm. The surface of the plating steel sheet was treated by alkaline degreasing and water washing, followed by drying, then the chemical conversion treatment was applied using the treatment liquid under the treatment condition shown in Table 118 to form the chemical conversion coating. Then, the paint composition given in Table 119 was applied using a roll coater, which was then heated to dry to form the secondary layer coating (the organic coating), thus manufactured the organic coating steel sheets as Examples and Comparative Examples. The thickness of the secondary layer coating was adjusted by the solid content in the treatment liquid (heating residue) or applying conditions (roll pressing force, rotational speed, and other variables).

To each of thus obtained organic coating steel sheets, evaluation was given in terms of quality performance (appearance of coating, white-rust resistance, white-rust resistance after alkaline degreasing, paint adhesiveness, and workability). The results are given in Tables 121 through 134 along with the structure of chemical conversion treatment layer coating and of organic coating.

The quality performance evaluation on the organic coating steel sheets was carried out by the same procedure as in the best mode 1.

As the conventional reaction type chromate steel sheet treatment liquid, a solution containing 30 g/l of anhydrous chromic acid, 10 g/l of phosphoric acid, 0.5 g/l of NaF, and 4 g/l of K 2 TiF 6 was used. After spray treatment at a bath temperature of 40° C., the steel sheet was washed with water and was dried, thus a chromated steel sheet having a chromium coating weight of 20 mg/m 2 as metallic chromium as prepared. Thus obtained steel sheet was subjected to the salt spray test under the same condition that applied to Examples, and the plate generated white-rust within about 24 hours. Consequently, the results of Examples show that the organic coating steel sheets according to the present invention provide remarkably superior corrosion resistance to the conventional type chromate treated steel sheets.

TABLE 115
[Plating steel plate]
No.	Type	Coating weight (g/m 2 )
1	Electrolytically galvanized steel plate	20

 

TABLE 116
[Calcium compound]
No. Type and compound
1   Calcium carbonate
2   Calcium silicate
3   Calcium phosphate
4   Calcium phosphate, zinc
5   Calcium carbonate (60 wt. %) + calcium silicate (40 wt. %)
6   Calcium carbonate (12 wt. %) + calcium silicate (6 wt. %)
    + calcium phosphate, zinc (82 wt. %)

 

TABLE 117
[Solid lubricant]
No.	Type	Trade name
1	Polyethylene wax	LUVAX 1151 Produced by Nippon Seiro
		Co.

 

	TABLE 118
				Adaptability to the
	Target composition		Coating	conditions of
No.	Type	Trade name	Remark	Treatment method	thickness	the invention
1	Lithium silicate	Nissan Kagaku Kogyo Co.	SiO 2 /LiO 2 = 3.5	Coating → drying at 150° C.	0.5 μm	Satisfies
		LSS-35
2	Lithium silicate	Nissan Kagaku Kogyo Co.	SiO 2 /LiO 2 = 4.5	Coating → drying at 150° C.	0.5 μm	Satisfies
		LSS-45
3	Lithium silicate	Nissan Kagaku Kogyo Co.	SiO 2 /LiO 2 = 7.5	Coating → drying at 150° C.	0.5 μm	Satisfies
		LSS-75
4	Lithium silicate	DuPont	SiO 2 /LiO 2 = 4.6-5.0	Coating → drying at 150° C.	0.5 μm	Satisfies
		Polysilicate 48
5	Phosphate	Nihon Parkerizing Co.	—	Spray → drying	2 μm	Satisfies
	treatment	PB3312
6	Organic resin	Acrylic-ethylene copolymer	Organic	Coating → drying at 150° C.	1 μm	Satisfies
	coating		resin:Colloidal
			silica = 100:10
7	Phitinic acid	Mitsui Chemicals Inc. Phytinic acid	—	Coating → drying at 150° C.	0.5 μm	Satisfies
	treatment	10 g/L aqueous solution
8	Tannic acid	Fuji Chemicals Inc. Tannin AL 10 g/L	—	Coating → drying at 150° C.	0.5 μm	Satisfies
	treatment	aqueous solution
9	Polymer	Miyoshi Oil & Fat Co.	—	Coating → drying at 150° C.	0.5 μm	Satisfies
	chelating agent	Dithiocarbamic acid Antimonate

 

TABLE 119
[Resin composition of secondary layer coating]
	Base resin	Curing agent		Adaptability to the
No.	Type *1	Blending rate	Type	Blending rate	Catalyst	conditions of the invention
1	(1)	100 parts	A	5 parts	Dibutyltin dilaurate (0.2 part)	Satisfies
2	(1)	100 parts	B	25 parts	Dibutyltin dilaurate (1.0 part)	Satisfies
3	(1)	100 parts	C	25 parts	—	Satisfies
4	(2)	100 parts	A	50 parts	Dibutyltin dilaurate (2.0 part)	Satisfies
5	(2)	100 parts	B	50 parts	Dibutyltin dilaurate (3.0 part)	Satisfies
6	(2)	100 parts	C	80 parts	Dibutyltin dilaurate (4.0 part)	Satisfies
7	(3)	100 parts	A	25 parts	Cobalt naphthenate (1.0 part)	Satisfies
8	(3)	100 parts	B	10 parts	Tin (II) chloride (1.0 part)	Satisfies
9	(3)	100 parts	C	50 parts	N-ethylmorpholine (1.0 part)	Satisfies
10	(1)	100 parts	D	25 parts	—	Satisfies
11	(3)	100 parts	D	30 parts	—	Satisfies
12	(4)	100 parts	B	25 parts	Dibutyltin dilaurate (1.0 part)	Dissatisfies
13	Aqueous solution of a hydrazine derivative (aqueous solution of 5 wt. % 3,5-dimethylpyrazole)	Dissatisfies
14	Mixture of an epoxyamine adduct and a hydrazine derivative (3 parts by weight of 3,5-dimethylpyrazole per 100	Dissatisfies
	parts by weight of base resin is added to the composition No. 12, followed by agitating the mixture.)
*1 The resin compositions (1) through (4) which were synthesized in Synthesis Examples 1 through 4 described in the body of this specification.

 

TABLE 120
[Zinc phosphate/aluminum phosphate]
No. Kind and composition
1   Zinc orthophosphate
2   Zinc polyphosphate
3   Zinc monohydrogenphosphate
4   Zinc dihydrogenphosphate
5   Zinc phosphite
6   Aluminum orthophosphate
7   Aluminum polyphosphate
8   Aluminum monohydrogenphosphate
9   Aluminum dihydrogenphosphate
10  Zinc polyphosphate (50 wt. %) + Aluminum
    monohydrogenphosphate (50 wt. %)
11  Zinc orthophosphate (50 wt. %) + Aluminum
    dihydrogenphosphate (50 wt. %)

 

	TABLE 121
	Primary layer	Secondary layer coating
		coating		Zinc phosphate and/or
	Plating steel	Coating	Resin	aluminum phosphate (a)	Drying	Coating
	plate	composition	composition	Type	Blending ratio	temperature	thickness
No.	*1	*2	*3	*4	*5	(° C.)	(μm)
1	1	1	1	1	30	230	1.5
2	1	1	1	2	30	230	1.5
3	1	1	1	3	30	230	1.5
4	1	1	1	4	30	230	1.5
5	1	1	1	5	30	230	1.5
6	1	1	1	6	30	230	1.5
7	1	1	1	7	30	230	1.5
8	1	1	1	8	30	230	1.5
9	1	1	1	9	30	230	1.5
10	1	1	1	10	30	230	1.5
11	1	1	1	11	30	230	1.5
12	1	1	1	—	—	230	1.5
	Performance
				White-rust
			White-rust	resistance after
			resistance:	alkaline degreasing:	Paint	Classification
	No.	Appearance	SST 96 hrs	SST 96 hrs	adhesiveness	&Asteriskpseud;1
	1	◯	⊚	⊚	⊚	Example
	2	◯	⊚	⊚	⊚	Example
	3	◯	⊚	⊚	⊚	Example
	4	◯	⊚	⊚	⊚	Example
	5	◯	⊚	⊚	⊚	Example
	6	◯	⊚	⊚	⊚	Example
	7	◯	⊚	⊚	⊚	Example
	8	◯	⊚	⊚	⊚	Example
	9	◯	⊚	⊚	⊚	Example
	10	◯	⊚	⊚	⊚	Example
	11	◯	⊚	⊚	⊚	Example
	12	◯	X	X	⊚	Comparative
						example
	*1: Corresponding to No. given in Table 115
	*2: Corresponding to No. given in Table 118
	*3: Corresponding to No. given in Table 119
	*4: Corresponding to No. given in Table 120
	*5: Blending rate (parts by weight) of solid matter of zinc phosphate and/or aluminum phosphate (a) to 100 parts by weight of solid matter of resin composition
	&Asteriskpseud;1: Example/Comparative example

 

	TABLE 122
	Primary layer	Secondary layer coating
		coating		Zinc phosphate and/or
	Plating steel	Coating	Resin	aluminum phosphate (a)	Drying	Coating
	plate	composition	composition	Type	Blending ratio	temperature	thickness
No.	*1	*2	*3	*4	*5	(° C.)	(μm)
13	1	1	1	1	1	230	1.5
14	1	1	1	1	5	230	1.5
15	1	1	1	1	10	230	1.5
16	1	1	1	1	20	230	1.5
17	1	1	1	1	25	230	1.5
18	1	1	1	1	40	230	1.5
19	1	1	1	1	50	230	1.5
20	1	1	1	1	80	230	l.5
21	1	1	1	1	100	230	1.5
22	1	1	1	1	150	230	1.5
	Performance
				White-rust
			White-rust	resistance after
			resistance:	alkaline degreasing:	Paint
	No.	Appearance	SST 96 hrs	SST 96 hrs	adhesiveness	Classification
	13	◯	◯	◯	⊚	Example
	14	◯	◯+	◯+	⊚	Example
	15	◯	⊚	⊚	⊚	Example
	16	◯	⊚	⊚	⊚	Example
	17	◯	⊚	⊚	⊚	Example
	18	◯	◯+	◯+	⊚	Example
	19	◯	◯+	◯+	⊚	Example
	20	◯	◯	◯	⊚	Example
	21	◯	◯−	◯−	⊚	Example
	22	◯	Δ	Δ	⊚	Comparative
						example
	*1: Corresponding to No. given in Table 115
	*2: Corresponding to No. given in Table 118
	*3: Corresponding to No. given in Table 119
	*4: Corresponding to No. given in Table 120
	*5: Blending rate (parts by weight) of solid matter of zinc phosphate and/or aluminum phosphate (a) to 100 parts by weight of solid matter of resin composition

 

	TABLE 123
	Primary layer	Secondary layer coating
		coating		Zinc phosphate and/or
	Plating steel	Coating	Resin	aluminum phosphate (a)	Drying	Coating
	plate	composition	composition	Type	Blending ratio	temperature	thickness
No.	*1	*2	*3	*4	*5	(° C.)	(μm)
35	1	1	1	1	30	230	0.01
36	1	1	1	1	30	230	0.1
37	1	1	1	1	30	230	0.5
38	1	1	1	1	30	230	1
39	1	1	1	1	30	230	2
40	1	1	1	1	30	230	2.5
41	1	1	1	1	30	230	3
42	1	1	1	1	30	230	4
43	1	1	1	1	30	230	5
44	1	1	1	1	30	230	20
	Performance
				White-rust
			White-rust	resistance after
			resistance:	alkaline degreasing:	Paint
	No.	Appearance	SST 96 hrs	SST 96 hrs	adhesiveness	Classification
	35	◯	X	X	⊚	Comparative
						example
	36	◯	◯−	◯−	⊚	Example
	37	◯	◯−	◯−	⊚	Example
	38	◯	◯	◯	⊚	Example
	39	◯	⊚	⊚	⊚	Example
	40	◯	⊚	⊚	⊚	Example
	41	◯	⊚	⊚	⊚	Example
	42	◯	⊚	⊚	⊚	Example
	43	◯	⊚	⊚	⊚	Example
	44	◯	⊚	⊚	⊚	Comparative
						example &Asteriskpseud;2
	*1: Corresponding to No. given in Table 115
	*2: Corresponding to No. given in Table 118
	*3: Corresponding to No. given in Table 119
	*4: Corresponding to No. given in Table 120
	*5: Blending rate (parts by weight) of solid matter of zinc phosphate and/or aluminum phosphate (a) to 100 parts by weight of solid matter of resin composition
	&Asteriskpseud;2: Unable to weld

 

	TABLE 124
	Primary layer	Secondary layer coating
	Plating	coating		Zinc phosphate and/or
	steel	Coating	Resin	aluminum phosphate (a)	Solid lubricant (c)	Drying	Coating
	plate	composition	composition	Type	Blending ratio	Type	Blending ratio	temperature	thickness
No.	*1	*2	*3	*4	*5	*10	*11	(° C.)	(μm)
54	1	1	1	1	10	1	5	230	1.5
60	1	1	1	1	10	1	1	230	1.5
61	1	1	1	1	10	1	10	230	1.5
62	1	1	1	1	10	1	30	230	1.5
63	1	1	1	1	10	1	80	230	1.5
64	1	1	1	1	10	1	100	230	1.5
	Performance
				White-rust
			White-rust	resistance after
			resistance:	alkaline degreasing:	Paint
	No.	Appearance	SST 96 hrs	SST 96 hrs	adhesiveness	Workability	Classification
	54	◯	⊚	⊚	⊚	⊚	Example
	60	◯	⊚	⊚	⊚	◯	Example
	61	◯	⊚	⊚	⊚	⊚	Example
	62	◯	⊚	⊚	⊚	⊚	Example
	63	◯	⊚	⊚	◯	⊚	Example
	64	◯	⊚	⊚	X	⊚	Comparative
							example
	*1: Corresponding to No. given in Table 115
	*2: Corresponding to No. given in Table 118
	*3: Corresponding to No. given in Table 119
	*4: Corresponding to No. given in Table 120
	*5: Blending rate (parts by weight) of solid matter of zinc phosphate and/or aluminum phosphate (a) to 100 parts by weight of solid matter of resin composition
	*10: Corresponding to No. given in Table 6
	*11: Blending rate (parts by weight) of solid lubricant (c) to 100 parts by weight of solid matter of resin

 

	TABLE 125
	Primary layer	Secondary layer coating
		coating		Zinc phosphate and/or
	Plating steel	Coating	Resin	aluminum phosphate (a)	Drying	Coating
	plate	composition	composition	Type	Blending ratio	temperature	thickness
No.	*1	*2	*3	*4	*5	(° C.)	(μm)
65	1	1	2	1	30	230	1.5
66	1	1	3	1	30	230	1.5
67	1	1	4	1	30	230	1.5
68	1	1	5	1	30	230	1.5
69	1	1	6	1	30	230	1.5
70	1	1	7	1	30	230	1.5
71	1	1	8	1	30	230	1.5
72	1	1	9	1	30	230	1.5
73	1	1	10	1	30	230	1.5
74	1	1	11	1	30	230	1.5
75	1	1	12	1	30	230	1.5
76	1	1	13	1	30	230	1.5
77	1	1	14	1	30	230	1.5
	Performance
				White-rust
			White-rust	resistance after
			resistance:	alkaline degreasing:	Paint
	No.	Appearance	SST 96 hrs	SST 96 hrs	adhesiveness	Classification
	65	◯	⊚	⊚	⊚	Comparative
						example
	66	◯	◯+	◯	⊚	Example
	67	◯	◯+	◯	⊚	Example
	68	◯	◯	◯−	⊚	Example
	69	◯	◯	◯−	⊚	Example
	70	◯	◯	◯−	⊚	Example
	71	◯	◯	◯−	⊚	Example
	72	◯	⊚	⊚	⊚	Example
	73	◯	⊚	⊚	⊚	Example
	74	◯	⊚	⊚	⊚	Example
	75	◯	Δ	Δ	⊚	Comparative
						example
	76	X	X	X	X	Comparative
						example
	77	◯	Δ	Δ	⊚	Comparative
						example
	*1: Corresponding to No. given in Table 115
	*2: Corresponding to No. given in Table 118
	*3: Corresponding to No. given in Table 119
	*4: Corresponding to No. given in Table 120
	*5: Blending rate (parts by weight) of solid matter of zinc phosphate and/or aluminum phosphate (a) to 100 parts by weight of solid matter of resin composition

 

	TABLE 126
	Primary layer	Secondary layer coating
		coating		Zinc phosphate and/or
	Plating steel	Coating	Resin	aluminum phosphate (a)	Drying	Coating
	plate	composition	composition	Type	Blending ratio	temperature	thickness
No.	*1	*2	*3	*4	*5	(° C.)	(μm)
78	1	2	1	1	30	230	1.5
79	1	3	1	1	30	230	1.5
80	1	4	1	1	30	230	l.5
81	1	5	1	1	30	230	1.5
82	1	6	1	1	30	230	1.5
83	1	7	1	1	30	230	l.5
84	1	8	1	1	30	230	1.5
85	1	9	1	1	30	230	1.5
	Performance
				White-rust
			White-rust	resistance after
			resistance:	alkaline degreasing:	Paint
	No.	Appearance	SST 96 hrs	SST 96 hrs	adhesiveness	Classification
	78	◯	⊚	⊚	⊚	Example
	79	◯	⊚	⊚	⊚	Example
	80	◯	⊚	⊚	⊚	Example
	81	◯	⊚	⊚	⊚	Example
	82	◯	⊚	⊚	⊚	Example
	83	◯	⊚	⊚	⊚	Example
	84	◯	⊚	⊚	⊚	Example
	85	◯	⊚	⊚	⊚	Example
	*1: Corresponding to No. given in Table 115
	*2: Corresponding to No. given in Table 118
	*3: Corresponding to No. given in Table 119
	*4: Corresponding to No. given in Table 120
	*5: Blending rate (parts by weight) of solid matter of zinc phosphate and/or aluminum phosphate (a) to 100 parts by weight of solid matter of resin composition

 

	TABLE 127
	Primary layer	Secondary layer coating
		coating		Zinc phosphate and/or
	Plating steel	Coating	Resin	aluminum phosphate (a)	Fine particles silica (b)
	plate	composition	composition	Type	Blending ratio	Type	Blending ratio
No.	*1	*2	*3	*4	*5	*6	*7
86	1	1	1	1	30	1	20
87	1	1	2	1	30	2	20
88	1	1	3	1	30	3	20
89	1	1	4	1	30	4	20
90	1	1	5	1	30	5	20
91	1	1	6	1	30	6	20
92	1	1	7	1	30	6	20
93	1	1	8	1	30	6	20
94	1	1	9	1	30	6	20
95	1	1	10	1	30	6	20
96	1	1	11	1	30	6	20
97	1	1	12	1	30	6	20
	Secondary layer coating
		(a) + (b)	(a)/(b)	Drying	Coating
		Blending rate	Weight ratio	temperature	thickness
	No.	*8	*9	(° C.)	(μm)	Classification
	86	50	3/2	230	1.5	Example
	87	50	3/2	230	1.5	Example
	88	50	3/2	230	1.5	Example
	89	50	3/2	230	1.5	Example
	90	50	3/2	230	1.5	Example
	91	50	3/2	230	1.5	Example
	92	50	3/2	230	1.5	Example
	93	50	3/2	230	1.5	Example
	94	50	3/2	230	1.5	Example
	95	50	3/2	230	1.5	Example
	96	50	3/2	230	1.5	Example
	97	50	3/2	230	1.5	Comparative
						example
	*1: Corresponding to No. given in Table 115
	*2: Corresponding to No. given in Table 118
	*3: Corresponding to No. given in Table 119
	*4: Corresponding to No. given in Table 120
	*5: Blending rate (parts by weight) of solid matter of zinc phosphate and/or aluminum phosphate (a) to 100 parts by weight of solid matter of resin composition
	*6: Given in Table 116
	*7: Blending rate (parts by weight) of calcium compound (b) to 100 parts by weight of solid matter of resin composition
	*8: Blending rate (parts by weight) of the sum of zinc phosphate and/or aluminum phosphate (a) and calcium compound (b) to 100 parts by weight of solid matter of resin composition
	*9: Weight ratio of zinc phosphate and/or aluminum phosphate (a) to calcium compound (b)

 

	TABLE 128
	Performance
			White-rust resistance after
		White-rust resistance:	alkaline degreasing:	Paint
No.	Appearance	SST 120 hrs	SST 120 hrs	adhesiveness	Classification
86	◯	⊚	⊚	⊚	Example
87	◯	⊚	⊚	⊚	Example
88	◯	⊚	⊚	⊚	Example
89	◯	⊚	⊚	⊚	Example
90	◯	⊚	⊚	⊚	Example
91	◯	⊚	⊚	⊚	Example
92	◯	⊚	⊚	⊚	Example
93	◯	⊚	⊚	⊚	Example
94	◯	⊚	⊚	⊚	Example
95	◯	⊚	⊚	⊚	Example
96	◯	⊚	⊚	⊚	Example
97	◯	Δ	X	⊚	Comparative
					example

 

	TABLE 129
	Secondary layer coating
				Zinc phosphate
		Primary layer		and/or aluminum	Fine particles			Drying
	Plating	coating		phosphate (a)	silica (b)	(a) + (b)	(a)/(b)	temper-	Coating
	steel	Coating	Resin		Blending		Blending	Blending	Weight	ature	thickness	Classi-
No.	plate*1	composition*2	composition*3	Type*4	ratio*5	Type*6	ratio*7	rate*8	ratio*9	(° C.)	(μm)	fication
98	1	1	13	1	30	6	20	50	3/2	230	1.5	Comparative
												example
99	1	1	14	1	30	6	20	50	3/2	230	1.5	Comparative
												example
100	1	1	1	1	30	—	—	30	30/0	230	1.5	Example
101	1	1	1	1	29.9	6	0.1	30	299/1	230	1.5	Example
102	1	1	1	1	29	6	1	30	29/1	230	1.5	Example
103	1	1	1	1	20	6	10	30	2/1	230	1.5	Example
104	1	1	1	1	15	6	15	30	1/1	230	1.5	Example
105	1	1	1	1	10	6	20	30	1/2	230	1.5	Example
106	1	1	1	1	1	6	29	30	1/29	230	1.5	Example
107	1	1	1	1	0.1	6	29.9	30	1/299	230	1.5	Comparative
												example
108	1	1	1	1	50	—	—	30	50/0	230	1.5	Example
*1 Corresponding to No. given in Table 115
*2 Corresponding to No. given in Table 118
*3 Corresponding to No. given in Table 119
*4 Corresponding to No. given in Table 120
*5 Blending rate (parts by weight) of solid matter of zinc phosphate and/or aluminum phosphate (a) to 100 parts by weight of solid matter of resin composition
*6 Given in Table 116
*7 Blending rate (parts by weight) of calcium compound (b) to 100 parts by weight of solid matter of resin composition
*8 Blending rate (parts by weight) of the sum of zinc phosphate and/or aluminum phosphate (a) and calcium compound (b) to 100 parts by weight of solid matter of resin composition
*9 Weight ratio of zinc phosphate and/or aluminum phosphate (a) to calcium compound (b)

 

	TABLE 130
	Performance
			White-rust resistance after
		White-rust resistance:	alkaline degreasing:	Paint
No.	Appearance	SST 120 hrs	SST 120 hrs	adhesiveness	Classification
98	◯	X	X	X	Comparative
					example
99	◯	Δ	X	⊚	Comparative
					example
100	◯	◯	◯	⊚	Example
101	◯	◯	◯	⊚	Example
102	◯	◯+	◯+	⊚	Example
103	◯	⊚	⊚	⊚	Example
104	◯	⊚	⊚	⊚	Example
105	◯	◯	◯	⊚	Example
106	◯	◯	◯	⊚	Example
107	◯	Δ	Δ	⊚	Comparative
					example
108	◯	◯	◯	⊚	Example

 

	TABLE 131
	Secondary layer coating
				Zinc phosphate
		Primary layer		and/or aluminum	Fine particles			Drying
	Plating	coating		phosphate (a)	silica (b)	(a) + (b)	(a)/(b)	temper-	Coating
	steel	Coating	Resin		Blending		Blending	Blending	Weight	ature	thickness	Classi-
No.	plate*1	composition*2	composition*3	Type*4	ratio*5	Type*6	ratio*7	rate*8	ratio*9	(° C.)	(μm)	fication
109	1	1	1	1	49	6	1	50	49/1	230	1	Example
110	1	1	1	1	45	6	5	50	9/1	230	1	Example
111	1	1	1	1	40	6	10	50	4/1	230	1	Example
112	1	1	1	1	30	6	20	50	3/2	230	1	Example
113	1	1	1	1	25	6	25	50	1/1	230	1	Example
114	1	1	1	1	10	6	40	50	1/4	230	1	Example
115	1	1	1	1	1	6	49	50	1/49	230	1	Example
*1 Corresponding to No. given in Table 115
*2 Corresponding to No. given in Table 118
*3 Corresponding to No. given in Table 119
*4 Corresponding to No. given in Table 120
*5 Blending rate (parts by weight) of solid matter of zinc phosphate and/or aluminum phosphate (a) to 100 parts by weight of solid matter of resin composition
*6 Given in Table 116
*7 Blending rate (parts by weight) of calcium compound (b) to 100 parts by weight of solid matter of resin composition
*8 Blending rate (parts by weight) of the sum of zinc phosphate and/or aluminum phosphate (a) and calcium compound (b) to 100 parts by weight of solid matter of resin composition
*9 Weight ratio of zinc phosphate and/or aluminum phosphate (a) to calcium compound (b)

 

	TABLE 132
	Performance
			White-rust resistance after
		White-rust resistance:	alkaline degreasing:	Paint
No.	Appearance	SST 120 hrs	SST 120 hrs	adhesiveness	Classification
109	◯	◯+	◯+	⊚	Example
110	◯	⊚	⊚	⊚	Example
111	◯	⊚	⊚	⊚	Example
112	◯	⊚	⊚	⊚	Example
113	◯	⊚	⊚	⊚	Example
114	◯	◯	◯	⊚	Example
115	◯	◯	◯	⊚	Example

 

	TABLE 133
		Secondary layer coating
		Primary		Zinc phosphate
		layer		and/or aluminum	Calcium			Solid
		coating		phosphate (a)	compound (b)		(a)/(b)	lubricant (c)	Drying	Coating
	Plating	Coating	Resin		Blend-		Blend-	(a) + (b)	Blending		Blend-	temper-	thick-
	steel	compo-	compo-		ing		ing	Blending	ratio by		ing	ature	ness	Classi-
No.	plate*1	sition*2	sition*3	Type*4	ratio*5	Type*6	ratio*7	ratio*8	weight*9	Type*10	rate*11	(° C.)	(μm)	fication
116	1	1	1	1	30	6	20	50	3/2	1	10	230	1.5	Example
117	1	1	1	2	30	6	20	50	3/2	2	10	230	1.5	Example
118	1	1	1	3	30	6	20	50	3/2	3	10	230	1.5	Example
119	1	1	1	4	30	6	20	50	3/2	4	10	230	1.5	Example
120	1	1	1	5	30	6	20	50	3/2	5	10	230	1.5	Example
121	1	1	1	6	30	6	20	50	3/2	6	10	230	1.5	Example
122	1	1	1	7	30	6	20	50	3/2	1	10	230	1.5	Example
123	1	1	1	8	30	6	20	50	3/2	1	1	230	1.5	Example
124	1	1	1	9	30	6	20	50	3/2	1	3	230	1.5	Example
125	1	1	1	10	30	6	20	50	3/2	1	10	230	1.5	Example
126	1	1	1	11	30	6	20	50	3/2	1	40	230	1.5	Example
127	1	1	1	11	30	6	20	50	3/2	1	80	230	1.5	Example
128	1	1	1	11	30	6	20	50	3/2	1	100	230	1.5	Com-
														parative
														example
*1 Corresponding to No. given in Table 115
*2 Corresponding to No. given in Table 118
*3 Corresponding to No. given in Table 119
*4 Corresponding to No. given in Table 120
*5 Blending rate (parts by weight) of solid matter of zinc phosphate and/or aluminum phosphate (a) to 100 parts by weight of solid matter of resin composition
*6 Given in Table 116
*7 Blending rate (parts by weight) of calcium compound (b) to 100 parts by weight of solid matter of resin composition
*8 Blending rate (parts by weight) of the sum of zinc phosphate and/or aluminum phosphate (a) and calcium compound (b) to 100 parts by weight of solid matter of resin composition
*9 Weight ratio of zinc phosphate and/or aluminum phosphate (a) to calcium compound (b)
*10 Corresponding to No. given in Table 117
*11 Blending rate (parts by weight) of solid lubricant (c) to 100 parts by weight of solid matter of resin composition

 

	TABLE 134
	Performance
			White-rust resistance after
		White-rust resistance:	alkaline degreasing:	Paint
No.	Appearance	SST 120 hrs	SST 120 hrs	adhesiveness	Workability	Classification
116	∘	⊚	⊚	⊚	⊚	Example
117	∘	⊚	⊚	⊚	⊚	Example
118	∘	⊚	⊚	⊚	⊚	Example
119	∘	⊚	⊚	⊚	⊚	Example
120	∘	⊚	⊚	⊚	⊚	Example
121	∘	⊚	⊚	⊚	⊚	Example
122	∘	⊚	⊚	⊚	∘	Example
123	∘	⊚	⊚	⊚	⊚	Example
124	∘	⊚	⊚	⊚	⊚	Example
125	∘	⊚	⊚	⊚	⊚	Example
126	∘	⊚	⊚	⊚	⊚	Example
127	∘	⊚	⊚	∘	⊚	Example
128	∘	⊚	⊚	x	⊚	Comparative
						example

 

Best Mode 5

According to a finding of the inventors of the present invention, an organic coating steel sheet inducing no pollution problem and providing excellent corrosion resistance is obtained without applying chromate treatment which may give bad influence to environment and human body, by forming a specific chelating resin coating on the surface of a zinc base plating steel sheet or an aluminum base plating steel sheet.

The organic coating steel sheet according to the present invention is basically characterized in that a chelating resin is formed as the rust-preventive coating as the product of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, thus applying the hydrazine derivative (C) as a chelating group to the film-forming resin (A), and that the chelating resin is formed on the surface of a zinc base plating steel sheet or an aluminum base plating steel sheet.

The corrosion-preventive mechanism of the organic coating as the above-described organic coating is not fully analyzed. The mechanism is, however, presumably the following. By adding a hydrazine derivative, not applying a simple low molecular weight chelating agent, to the film-forming organic resin, (1) the dense organic polymer coating gives an effect to shut-off corrosion causes such as oxygen and chlorine ions, (2) the hydrazine derivative is able to form a stable passive layer by strongly adsorbing to the surface of the plating film or reacting with the surface of the plating film, (3) the hydrazine derivative traps the zinc ion which is eluted during the film-forming stage to form an electrically neutral insoluble chelate compound layer (a dense barrier layer having a complex structure), which suppresses the formation of an ion conduction layer at interface between the plating film and the organic resin layer to suppress the progress of corrosion, and (4) further in a corrosive environment, free hydrazine derivative in the coating traps the zinc ion which is generated by corrosion to form a stable metallic complex structure, thus suppressing the progress of corrosion. These work effects should effectively suppress the development of corrosion, thus giving excellent corrosion resistance.

Particularly when a resin containing epoxy group is used as the film-forming organic resin (A), a dense barrier coating is formed by the reaction between the epoxy-group-laden resin and a cross-linking agent. Thus, the formed barrier coating has excellent penetration-suppression performance against the corrosion causes such as oxygen, and gains excellent bonding force with the base material owing to the hydroxyl group in the molecule, which results in particularly superior corrosion resistance.

Further excellent corrosion resistance is obtained by using an active-hydrogen-laden pyrazole compound and/or an active-hydrogen-laden triazole compound as the hydrazine derivative (C) containing active hydrogen.

As in the case of prior art, blending simply a hydrazine derivative (C) with the film-forming organic resin (A) gives very little improvement in corrosion-suppression. The reason is presumably that the hydrazine derivative which does not enter the molecules of the film-forming organic resin cannot form a dense barrier layer because of low molecular weight, though the hydrazine derivative is adsorbed onto the metal surface. To the contrary, introduction of a hydrazine derivative into the molecules of film-forming organic resin (A), as in the case of present invention, provides markedly high corrosion-suppression effect.

The following is the description about a specific organic coating formed on the above-described zinc base plating steel sheet or aluminum base plating steel sheet.

According to the present invention, the organic coating formed on the zinc base plating steel sheet or aluminum base plating steel sheet contains a product of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, which organic coating has a thickness in a range of from 0.1 to 5 μm.

The kinds of film-forming organic resin (A) are not specifically limited if only the resin reacts with the active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, to bind the active-hydrogen-laden compound (B) with the film-forming organic resin by addition or condensation reaction, and adequately form the coating.

Examples of the film-forming organic resin (A) are epoxy resin, modified epoxy resin, polyurethane resin, polyester resin, alkyd resin, acrylic base copolymer resin, polybutadiene resin, phenol resin, and adduct or condensate thereof. These resins may be applied separately or blending two or more of them.

From the standpoint of reactivity, readiness of reaction, and corrosion-prevention, an epoxy-group-laden resin (D) in the resin is particularly preferred as the film-forming organic resin (A).

The epoxy-group-laden resin (D) has no specific limitation if only the resin reacts with an active-hydrogen-laden compound (B), a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen, to bind with the active hydrogen-laden compound (B) by addition or condensation reaction, and adequately form the coating. Examples of the epoxy-group-laden resin (D) are epoxy resin, modified epoxy resin, acrylic base copolymer resin copolymerized with an epoxy-group-laden monomer, polybutadiene resin containing epoxy group, polyurethane resin containing epoxy group, and adduct or condensate of these resins. These resins may be applied separately or blending two or more of them together.

From the point of adhesiveness with plating surface and of corrosion resistance, epoxy resin and modified epoxy resin are particularly preferred among these epoxy-group-laden resins Examples of the above-described epoxy resins are: aromatic epoxy resins prepared by reacting a polyphenol such as bisphenol A, bisphenol F, and novorak type phenol with epihalohydrin such as epychlorohydrin followed by introducing glycidyl group thereinto, or further by reacting a polyphenol with thus obtained product containing glycidyl group to increase the molecular weight; aliphatic epoxy resin, and alicyclic epoxy resin. These resins may be applied separately or blending two or more of them together. If film-formation at a low temperature is required, the epoxy resins preferably have number-average molecular weights of 1500 or more.

The above-described modified epoxy resin may be a resin prepared by reacting epoxy group or hydroxyl group in one of the above-given epoxy resins with various kinds of modifying agents. Examples of the modified epoxy resin are epoxy-ester resin prepared by reacting with a drying oil fatty acid, epoxy-acrylate resin prepared by modifying with a polymerizable unsaturated monomer component containing acrylic acid or methacrylic acid, and urethane-modified epoxy resin prepared by reacting with an isocyanate compound.

Examples of the above-described acrylic base copolymer resin which is copolymerized with the above-described epoxy-group-laden monomer are the resins which are prepared by solution polymerization, emulsion polymerization, or suspension polymerization of an unsaturated monomer containing epoxy group with a polymerizable unsaturated monomer component containing acrylic acid ester or methacrylic acid ester as the essential ingredient.

Examples of the above-described unsaturated monomer component are: C1-24 alkylester of acrylic acid or methacrylic acid, such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, n-iso- or tert-butyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, decyl(meth)acrylate, lauryl(meth)acrylate; C1-4 alkylether compound of acrylic acid, methacrylic acid, styrene, vinyltoluene, acrylamide, acrylonitrile, N-methylol(meth)acrylamide, N-methylol(meth)acrylamide; and N,N-diethylaminoethylmethacrylate.

The unsaturated monomer having epoxy group has no special limitation if only the monomer has epoxy group and polymerizable unsaturated group, such as glycidylmethacrylate, glycidylacrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate.

The acrylic base copolymer resin which was copolymerized with the epoxy-group-laden monomer may be a resin which is modified by polyester resin, epoxy resin, or phenol resin.

A particularly preferred epoxy resin described above is a resin, which is a product of the reaction between bisphenol A and epihalohydrin. The epoxy resin is preferred because of superior corrosion resistance.

The method for manufacturing that kind of bisphenol A type epoxy resin is widely known in the industry concerned.

The film-forming organic resin (A) may be either organic solvent dissolving type, organic solvent dispersing type, water dissolving type, or water dispersing type.

According to the present invention, a hydrazine derivative is introduced into the molecules of the film-forming organic resin (A). To do this, at least a part of the active-hydrogen-laden compound (B), (preferably whole thereof), is necessary to be a hydrazine derivative (C) containing active hydrogen.

When the film-forming organic resin (A) is an expoxy-group group-laden resin, examples of the active-hydrogen-laden compound (B) reacting with the epoxy group are listed below. One or more of these compounds (B) may be applied. Also in that case, at least a part of the active-hydrogen-laden compound (B), (preferably whole thereof), is necessary to be a hydrazine derivative (C) containing active hydrogen.

A hydrazine derivative containing active hydrogen

A primary or secondary amine compound containing active hydrogen

An organic acid such as ammonia and carboxylic acid

A halogenated hydrogen such as hydrogen chloride

An alcohol, a thiol

A hydrazine derivative containing no active hydrogen or a quaternary chlorinating agent which is a mixture with a ternary amine.

Examples of the above-described hydrazine derivative (C) containing active hydrogen are the following.

(1) hydrazide compound such as carbohydrazide, propionic acid hydrazide, salicylic acid hydrazide, adipic acid hydrazide, sebacic acid hydrazide, dodecanic acid hydrazide, isophtharic acid hydrazide, thiocarbo-hydrazide, 4,4′-oxy-bis-benzenesulfonyl hydrazide, benzophenone hydrazone, amino-polyacrylamide hydrazide; (2) pyrazole compound such as pyrazole, 3,5-dimethylpyrazole, 3-methyl-5-pyrazolone, 3-amino-5-methylpyrazole; (3) triazole compound such as 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 5-amino-3-mercapto-1,2,4-triazole, 2,3-dihydro-3-oxo-1,2,4-triazole, 1H-benzotriazole, 1-hydroxybenzotriazole (mono hydrate), 6-methyl-8-hydroxytriazolopyridazine, 6-phenyl-8-hydroxytriazolopyrydazine, 5-hydroxy-7-methyl-1,3,8-triazaindolizine;

(4) tetrazole compound such as 5-phenyl-1,2,3,4-tetrazole, 5-mercapto-1-phenyl-1,2,3,4-tetrazole;

(5) thiadiazole compound such as 5-amino-2-mercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole;

(6) pyridazine compound such as maleic acid hydrazide, 6-methyl-3-pyridazone, 4,5-dichloro-3-pyridazone, 4,5-dibromo-3-pyridazone, 6-methyl-4,5-dihydro-3-pyridazone.

Among these compounds, particularly preferred ones are pyrazole compound and triazole compound which have cyclic structure of five- or six-membered ring and which have nitrogen atom in the cyclic structure.

These hydrazine derivatives may be applied separately or blending two or more of them together.

Examples of above-described amine compound having active hydrogen, which can be used as a part of the active-hydrogen-laden compound (B) are the following.

(1) a compound prepared by heating to react a primary amino group of an amine compound containing a single secondary amino group of diethylenetriamine, hydroxylaminoethylamine, ethylaminoethylamine, methylaminopropylamine, or the like and one or more of primary amino group, with ketone, aldehyde, or carboxylic acid, at, for example, approximate temperatures of from 100 to 230° C. to modify them to aldimine, ketimine, oxazoline, or imidazoline;

(2) a secondary monoamine such as diethylamine, diethanolamine, di-n- or -iso-propanolamine, N-methylethanolamine, N-ethylethanolamine;

(3) a secondary-amine-laden compound prepared by Michael addition reaction through the addition of monoalkanolamine such as monoethanolamine to dialkyl(meth)acrylamide;

(4) a compound prepared by modifying a primary amino group of alkanolamine such as monoethanolamine, neopentanolamine, 2-aminopropanol, 3-aminopropanol, 2-hydroxy-2′(aminopropoxy)ethylether to ketimine.

As for the above-described quaternary chlorinating agents which are able to be used as a part of the active-hydrogen-laden compound (B), the hydrazine derivative having active hydrogen or ternary amine has no reactivity with epoxy group as it is. Accordingly, they are mixed with an acid to make them reactive with epoxy group. The quaternary chlorinating agent reacts with epoxy group with the presence of water, at need, to form a quaternary salt with the expoxy-groupgroup-laden resin.

The acid used to obtain the quaternary chlorinating agent may be organic acid such as acetic acid and lactic acid, or inorganic acid such as hydrochloric acid. The hydrazine derivative containing no active hydrogen, which is used to obtain quaternary chlorinating agent may be 3,6-dichloropyridazine. The ternary amine may be dimethylethanolamine, triethylamine, trimethylamine, tri-isopropylamine, methyldiethanolamine.

The product of the reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen, may be prepared by reacting the film-forming organic resin (A) with the active-hydrogen-laden compound (B) at temperatures of from 10 to 300° C., preferably from 50 to 150° C., for about 1 to about 8 hours.

The reaction may be carried out adding an organic solvent. The kind of adding organic solvent is not specifically limited. Examples of the organic solvent are: ketone such as acetone, methyethylketone, methylisobutylketone, dibutylketone, cyclohexanone; alcohol or ether having hydroxyl group, such as ethanol, butanol, 2-ethylhexylalcohol, benzylalcohol, ethyleneglycol, ethyleneglycol mono-isopropylether, ethyleneglycol monobutylether, ethyleneglycol monohexylether, propyleneglycol, propyleneglycol monomethylether, diethyleneglycol, diethyleneglycol monoethylether, diethyleneglycol monobutylether; ester such as ethylacetate, butylacetate, ethyleneglycol monobutylether acetate; and aromatic hydrocarbon such as toluene and xylene. These compounds may be applied separately or blending two or more of them together. Among them, from the viewpoint of solubility and coating film-forming performance with epoxy resin, ketone group or ether group solvents are particularly preferred.

The blending ratio of the film-forming organic resin (A) and the active-hydrogen-laden compound (B), a part or whole of which compound consists of a hydrazine derivative (C) containing active hydrogen, is in a range of from 0.5 to 20 parts by weight of the active-hydrogen-laden compound (B), more preferably from 1.0 to 10 parts by weight, to 100 parts by weight of the film-forming organic resin (A).

When the film-forming organic resin (A) is an expoxy-group group-laden resin (D), the blending ratio of the expoxy-group group-laden resin (D) to the active-hydrogen-laden compound (B) is preferably, from the viewpoint of corrosion resistance and other performance, in a range of from 0.01 to 10 as the ratio of the number of active hydrogen groups in the active-hydrogen-laden compound (B) to the number of epoxy groups in the expoxy-group-laden resin (D), or [the number of active hydrogen groups/the number of epoxy groups], more preferably from 0.1 to 8, most preferably from 0.2 to 4.

A preferred range of hydrazine derivative (C) containing active hydrogen in the active-hydrogen-laden compound (B) is from 10 to 100 mole %, more preferably from 30 to 100 mole %, and most preferably from 40 to 100 mole %. If the rate of hydrazine derivative (C) containing active hydrogen is less than 10 mole %, the organic coating fails to have satisfactory rust-preventive function, thus the obtained rust-preventive effect becomes similar with the case of simple blending of a film-forming organic resin with a hydrazine derivative.

To form a dense barrier coating according to the present invention, it is preferable that a curing agent is blended into the resin composition, and that the organic coating is heated to cure.

Suitable methods for curing to form a resin composition coating include (1) a curing method utilizing a urethanation reaction between isocyanate and hydroxide group in the base resin, and (2) a curing method utilizing an ether reaction between hydroxide group in the base resin and an alkyletherified amino resin which is prepared by reacting between a part of or whole of a methylol compound which is prepared by reacting formaldehyde with one or more of melamine, urea, and benzoguanamine, and a C1-5 primary alcohol. As of these methods, particularly preferred one is to adopt a urethanation reaction between isocyanate and hydroxyl group in the base resin as the main reaction.

The polyisocyanate compound used in the curing method (1) described above is a compound prepared by partially reacting an aliphatic, alicyclic (including heterocyclic), or aromatic isocyanate compound, or a compound thereof using a polyhydric alcohol. Examples of that kind of polyisocyanate compound are the following.

(1) m- or p-phenylene diisocyanate, 2,4- or 2,6-trilene diisocyanate, o- or p-xylylene diisocyanate, hexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate;

(2) a compound of product of reaction between separate or mixture of the compounds given in-(1) with a polyhydric alcohol (for example, a dihydric alcohol such as ethyleneglycol and propyleneglycol, a trihydric alcohol such as glycerin and trimethylolpropane, a tetrahydric alcohol such as pentaerythritol, and hexahydric alcohol such as sorbitol and dipentaerythritol) leaving at least two isocyanate within a molecule.

These polyisocyanate compounds may be used separately or mixing two or more of them together.

Examples of protective agent (blocking agent) of the polyisocyanate compound are the following.

(1) Aliphatic monoalcohol such as methanol, ethanol, propanol, butanol, octylalcohol;

(2) Monoether of ethyleneglycol and/or diethyleneglycol, for example, monoether of methyl, ethyl, propyl (n-, iso-), butyl (n-, iso-, sec-);

(3) Aromatic alcohol such as phenol and cresol;

(4) Oxime such as acetoxime and methylethylketone oxime.

Through reaction between one or more of these compounds with above-described polyisocyanate compound, a polyisocyanate compound thus obtained is stably protected at least at normal temperature.

It is preferable to blend that kind of polyisocyanate compound (E) with a film-forming organic resin (A) as the curing agent at a range of (A)/(E)=95/5 to 55/45 (weight ratio of non-volatile matter), more preferably (A)/(E)=90/10 to 65/35. Since polyisocyanate compounds have water-absorbing property, blending of the compound at ratios above (A)/(E)=55/45 degrades the adhesiveness of the organic coating. If top coating is given on the organic coating, unreacted polyisocyanate compound migrates into the coating film to induce hindrance of curing or insufficient adhesiveness of the coating film. Accordingly, the blending ratio of the polyisocyanate compound (E) is preferably not more than (A)/(E)=55/45.

The film-forming organic resin (A) is fully cross-linked by the addition of above-described cross-linking agent (curing agent). For further increasing the cross-linking performance at a low temperature, it is preferable to use a known catalyst for enhancing curing. Examples of the curing-enhancing catalyst are N-ethylmorpholine, dibutyltin dilaurate, cobalt naphthenate, tin(II)chloride, zinc naphthenate, and bismuth nitrate.

When an expoxy-groupgroup-laden resin is used as the film-forming organic resin (A), the expoxy-groupgroup-laden resin may be blended with a known resin such as that of acrylic, alkyd, and polyester to improve the physical properties such as adhesiveness to some extent.

The organic coating of the organic coating steel sheet according to the present invention normally consists mainly of a product (resin composition) of reaction between a film-forming organic resin (A) and an active-hydrogenhydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen). And, at need, additives may be added to the organic coating, which additives include a lubricant (for example, polyethylene wax and fluororesin compound), a rust-preventive agent (for example, silica), an organic coloring pigment (for example, condensing polycyclic organic pigment, phthalocyanine base organic pigment), a coloring dye (for example, azo dye soluble in organic solvent, azo metal dye soluble in water), an inorganic pigment (for example, titanium oxide), a chelating agent (for example, thiol), a conductive pigment (for example, metallic powder of zinc, aluminum, nickel, or the like, iron phosphide, antimony-dope type tin oxide), a coupling agent (for example, silane coupling agent and titanium coupling agent), a melamine-cyanuric acid additive.

The paint composition for film-formation containing above-described main component and additive components normally contains solvent (organic solvent and/or water), and, at need, further a neutralizer or the like is added.

Applicable organic solvent described above has no specific limitation if only it dissolves or disperses the product of reaction between the above-described film-forming organic resin (A) and the active-hydrogenhydrogen-laden compound (B), and adjusts the product as the painting composition. Examples of the organic solvent are the organic solvents given above as examples.

The above-described neutralizers are blended, at need, to neutralize the film-forming organic resin (A) to bring it to water-type. When the film-forming organic resin (A) is a cationic resin, acid such as acetic acid, lactic acid, and formic acid may be used as the neutralizer.

The organic coatings described above are formed on the surface of zinc base plating steel sheet or aluminum base plating steel sheet without inserting chromated coating.

The dry thickness of the organic coating is in a range of from 0.1 to 5 μm. If the thickness of the organic coating is less than 0.1 μm, the corrosion resistance becomes insufficient. If the thickness of the organic coating exceeds 5 μm, the conductivity and the workability degrade. Further preferable thickness of the organic coating is in a range of from 0.5 to 3 μm.

The organic coating steel sheet according to the present invention is manufactured by applying a paint composition which contains the product of reaction between above-described film-forming organic resin (A) and an active-hydrogenhydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen, which product of reaction is preferably the main component, onto the surface of a zinc base plating steel sheet or aluminum base plating steel sheet, followed by heating to dry the product.

The surface of the plating steel sheet may be, at need, subjected to alkaline degreasing before applying the above-described treatment liquid, and may further be subjected to preliminary treatment such as surface adjustment treatment for further improving the adhesiveness and corrosion resistance.

The methods for applying the paint composition onto the surface of the zinc plating steel sheet or aluminum base plating steel sheet may be either one of coating method, dipping method, and spray method. The coating method may adopt any type such as roll coater (three-roll type, two-roll type, etc.), squeeze coater, die coater. After the coating step using squeeze coater and the like, the dipping step, or the spray step, it is possible to adjust the coating weight, the uniformizing appearance, and the uniformizing the film-thickness using air-knife method and roll-squeezing method.

After applying the paint composition, normally heating and drying are given without giving rinsing with water. However, the organic coating according to the present invention is bonded to the surface of the plating steel sheet as the base material by chemical adsorption or by reaction, so that there may be given water rinsing after applying the paint composition.

The heating and drying treatment is preferably conducted at reaching temperatures of from 50 to 300° C., more preferably from 80 to 200° C., and most preferably from 80 to 250° C. If the heating temperature is less than 50° C., excess amount of water is left in the coating, which results in insufficient corrosion resistance. If the heating temperature exceeds 300° C., the operation becomes uneconomical and defects likely appear in the coating to degrade the corrosion resistance.

As described above, the present invention includes a steel sheet having an organic coating on both sides or on side thereof. Accordingly, modes of the steel sheet according to the present invention include, for example, the followings.

(1) “Plating film—Organic coating” on one side of the steel sheet, and “Plating film” on other side of the steel sheet;

(2) “Plating film—Organic coating” on one side of the steel sheet, and “a known phosphate treatment coating” on other side of the steel sheet;

(3) “Plating film—Organic coating” on both sides of the steel sheet;

Embodiments

Following is the embodiments for synthesizing resin compositions for forming the coating according to the present invention.

SYNTHESIS EXAMPLE 1

A 1870 parts of EP828 (epoxy equivalent 187, manufactured by Yuka Shell Epoxy Co., Ltd.), 912 parts of bisphenol A, 2 parts of tetraethylammonium bromide, and 300 parts of methylethylketone were charged in a flask with four necks, which mixture was then heated to 140° C. to let them react for 4 hours. Thus, an epoxy resin having an epoxy equivalent of 1391 and a solid content of 90% was obtained. A 1500 parts of ethyleneglycol monobutylether was added to the epoxy resin, which were then cooled to 100° C. A 96 parts of 3,5-dimethylpyrazole (molecular weight 96) and 129 parts of dibutylamine (molecular weight 129) were added to the cooled resin, and they were reacted for 6 hours to eliminate the epoxy group. Then, a 205 parts of methylisobutylketone was added while the mixture was cooling, to obtain a pyrazole-modified epoxy resin having 60% of solid matter. The epoxy resin is defined as the resin composition (1). The resin composition (1) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogenhydrogen-laden compound that contains 50 mole % of hydrazine derivative (C) containing active hydrogen.

SYNTHESIS EXAMPLE 2

A 4000 parts of EP1007 (epoxy equivalent 2000, manufactured by Yuka Shell Epoxy Co., Ltd.) and 2239 parts of ethyleneglycol monobutylether were charged into a flask with four necks, which mixture was then heated to 120° C. to let them react for 1 hour to fully dissolve the epoxy resin. The mixture was cooled to 100° C. A 168 parts of 3-amino-1,2,4-triazole (molecular weight 84) was added to the mixture, and they were reacted for 6 hours to eliminate the epoxy group. Then, a 540 parts of methylisobutylketone was added while the mixture was cooling, to obtain a triazole-modified epoxy resin having 60% of solid matter. The epoxy resin is defined as the resin composition (2). The resin composition (2) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogenhydrogen-laden compound that contains 100 mole % of hydrazine derivative (C) containing active hydrogen.

SYNTHESIS EXAMPLE 3

A 222 parts of isophorone diisocyanate (epoxy equivalent 111) and 34 parts of methylisobutylketone were charged into a flask with four necks. A 87 parts of methylethylketoxime (molecular weight 87) was added to the mixture dropwise for 3 hours while keeping the mixture at temperatures ranging from 30 to 40° C., then the mixture was kept to 40° C. for 2 hours. Thus, a block isocyanate having isocyanate equivalent of 309 and solid content of 90% was obtained.

A 1489 parts of EP828 (epoxy equivalent 187, manufactured by Yuka Shell Epoxy Co., Ltd.), 684 parts of bisphenol A, 1 part of tetraethylammonium bromide, and 241 parts of methylisobutylketone were charged into a flask with four necks, which mixture was then heated to 140° C. to let them react for 4 hours. Thus, an epoxy resin having epoxy equivalent of 1090 and solid content of 90% was obtained. To the epoxy resin, 1000 parts of methylisobutylketone was added, then the mixture was cooled to 100° C., and 202 parts of 3-mercapto-1,2,4-triazole (molecular weight 101) was added to the mixture, and let the mixture react for 6 hours to fully eliminate the epoxy group. After that, the part-block isocyanate of the above-described 90% solid portion was added to the reaction product to let the mixture react at 100° C. for 3 hours, and the vanish of isocyanate group was confirmed. Further, 461 parts of ethyleneglycol monobutylether was added to the product to obtain a triazole-modified epoxy resin having 60% solid content. The product is defined as the resin composition (3). The resin composition (3) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogenhydrogen-laden compound that contains 100 mole % of hydrazine derivative (C) containing active hydrogen.

SYNTHESIS EXAMPLE 4

A 1870 parts of EP828 (epoxy equivalent 187, manufactured by Yuka Shell Epoxy Co., Ltd.), 912 parts of bisphenol A, 2 parts of tetraethylammonium bromide, and 300 parts of methylisobutylketone were charged into a flask with four necks, which mixture was then heated to 140° C. to let them react for 4 hours. Thus, an epoxy resin having epoxy equivalent of 1391 and solid content of 90% was obtained. To the epoxy resin, 1500 parts of ethyleneglycol monobutylether was added, then the mixture was cooled to 100° C., and 258 parts of dibutylamine (molecular weight 129) was added to the mixture, and let the mixture react for 6 hours to fully eliminate the epoxy group. While cooling the mixture, 225 parts of methylisobutylketone was further added to the mixture to obtain an epoxyamine adduct having 60% solid content. The product is defined as the resin composition (4). The resin composition (4) is a product of the reaction between the film-forming organic resin (A) and the active-hydrogenhydrogen-laden compound of hydrazine derivative (C) containing no active hydrogen.

A curing agent was blended to each of the synthesized resin compositions (1) through (4) to prepare the resin compositions (paint compositions) listed in Table 135.

To obtain organic coating steel sheets for household electric appliances, building materials, and automobile parts, the plating steel sheets shown in Table 136 were used as the target base plates, which plates were prepared by applying zinc base plating or aluminum base plating on the cold-rolled steel sheets having a plate thickness of 0.8 mm and a surface roughness Ra of 1.0 μm. The surface of the plating steel sheet was treated by alkaline degreasing and water washing, then the paint composition shown in Table 135 was applied to the surface using a roll coater, followed by heating to dry at various temperatures to form the organic coating steel sheets. The thickness of the organic coating was adjusted by the solid content in the paint composition (heating residue) or applying conditions (roll pressing force, rotational speed, and other variables).

To each of thus obtained organic coating steel sheets, evaluation was given in terms of quality performance (appearance of coating, white-rust resistance, paint adhesiveness). The results are given in Tables 137 and 138 along with the structure of organic coating.

TABLE 135
Resin composition
	Base resin	Curing agent		Adaptability to the
No.	Type*1	Blending rate	Type*2	Blending rate	Catalyst	conditions of the invention
1	(1)	100 parts	A	5 parts	Dibutyltin dilaurate (0.2 part)	Example
2	(1)	100 parts	B	25 parts	Dibutyltin dilaurate (1.0 part)	Example
3	(1)	100 parts	C	25 parts	—	Example
4	(2)	100 parts	A	50 parts	Dibutyltin dilaurate (2.0 part)	Example
5	(2)	100 parts	B	50 parts	Dibutyltin dilaurate (3.0 part)	Example
6	(2)	100 parts	C	80 parts	Dibutyltin dilaurate (4.0 part)	Example
7	(3)	100 parts	A	25 parts	Cobalt naphthenate (1.0 part)	Example
8	(3)	100 parts	B	10 parts	Tin (II) chloride (1.0 part)	Example
9	(3)	100 parts	C	50 parts	N-ethylmorpholine (1.0 part)	Example
10	(1)	100 parts	D	25 parts	—	Example
11	(3)	100 parts	D	30 parts	—	Example
12	(4)	100 parts	B	25 parts	Dibutyltin dilaurate (1.0 part)	Comparative example
13	Aqueous solution of a hydrazine derivative (aqueous solution of 5 wt. % 3,5-dimethylpyrazole)	Comparative example
14	Mixture of an epoxyamine adduct and a hydrazine derivative (3 parts by weight of	Comparative example
	3,5-dimethylpyrazole per 100 parts by weight of base resin is added to the composition No. 12,
	followed by agitating the mixture.)
*1 The resin compositions (1) through (4) which were synthesized in Synthesis Examples 1 through 4 described in the body of this specification.
*2
A An MEK oxime block body of IPDI, “TAKENATE B-870N” produced by Takeda Chemical Industries, Ltd.
B Isocyanurate type: “DESMODUR BL-3175” produced by Bayer A. G.
C An MEK oxime block body of HMDI, “DURANATE MF-B80M” produced by Asahi Chemical Industry Co., Ltd.
D A melamine resin of imino-base: “CYMEL 325” produced by Mitsui Cytech Co., Ltd.

 

TABLE 136
[Plating steel plate]
No.	Type	Coating weight (g/m 2 )
1	Electrolytically galvanized steel plate	20

 

	TABLE 137
	Performance
	Plating		Drying	Coating		White-rust	White-rust resistance
	steel	Resin	temperature	thickness		resistance:	after alkaline	Paint
No.	plate*1	composition*3	(° C.)	(μm)	Appearance	SST 72 hrs	SST 72 hrs	adhesiveness	Classification
1	1	1	150	1.5	∘	⊚	⊚	⊚	Example
2	1	2	150	1.5	∘	⊚	⊚	⊚	Example
3	1	3	150	1.5	∘	⊚	⊚	⊚	Example
4	1	4	150	1.5	∘	⊚	⊚	⊚	Example
5	1	5	150	1.5	∘	⊚	⊚	⊚	Example
6	1	6	150	1.5	∘	⊚	⊚	⊚	Example
7	1	7	150	1.5	∘	⊚	⊚	⊚	Example
8	1	8	150	1.5	∘	⊚	⊚	⊚	Example
9	1	9	150	1.5	∘	⊚	⊚	⊚	Example
10	1	10	150	1.5	∘	⊚	⊚	⊚	Example
11	1	11	150	1.5	∘	⊚	⊚	⊚	Example
12	1	12	150	1.5	∘	Δ	x	⊚	Comparative example
13	1	13	150	1.5	∘	x	x	x	Comparative example
14	1	14	150	1.5	∘	Δ	x	⊚	Comparative example
15	1	1	40	1.5	∘	x	x	x	Comparative example
16	1	1	50	1.5	∘	∘−	∘−	∘	Example
17	1	1	80	1.5	∘	∘	∘	∘+	Example
*1 Corresponding to No. given in Table 136
*2 Corresponding to No. given in Table 135

 

	TABLE 138
	Performance
	Plating		Drying	Coating		White-rust	White-rust resistance
	steel	Resin	temperature	thickness		resistance:	after alkaline	Paint
No.	plate*1	composition*3	(° C.)	(μm)	Appearance	SST 72 hrs	SST 72 hrs	adhesiveness	Classification
18	1	1	120	1.5	∘	⊚	∘+	⊚	Example
19	1	1	180	1.5	∘	⊚	⊚	⊚	Example
20	1	1	200	1.5	∘	⊚	⊚	⊚	Example
21	1	1	230	1.5	∘	⊚	⊚	⊚	Example
22	1	1	250	1.5	∘	⊚	⊚	⊚	Example
23	1	1	300	1.5	∘	⊚	⊚	⊚	Example
24	1	1	350	1.5	∘	Δ	Δ	⊚	Comparative example
25	1	1	200	0.01	∘	x	x	⊚	Comparative example
26	1	1	200	0.1	∘	∘−	∘−	⊚	Example
27	1	1	200	0.5	∘	∘	∘	⊚	Example
28	1	1	200	1.0	∘	⊚	⊚	⊚	Example
29	1	1	200	2.0	∘	⊚	⊚	⊚	Example
30	1	1	200	2.5	∘	⊚	⊚	⊚	Example
31	1	1	200	3.0	∘	⊚	⊚	⊚	Example
32	1	1	200	4.0	∘	⊚	⊚	⊚	Example
33	1	1	200	5.0	∘	⊚	⊚	⊚	Example
34	1	1	200	20	∘	⊚	⊚	⊚	Comparative&Asteriskpseud;1
									example
*1 Corresponding to No. given in Table 136
*2 Corresponding to No. given in Table 135
&Asteriskpseud;1 Unable to weld

 

Best Mode 6

According to a finding of the inventors of the present invention, an organic coating steel sheet inducing no pollution problem and providing excellent corrosion resistance is obtained without applying chromate treatment which may give bad influence to environment and human body, through the steps of: forming a specific composite oxide coating as the primary layer coating on the surface of a zinc base plating steel sheet or an aluminum base plating steel sheet; then, on the primary layer coating, forming an organic coating as the secondary layer coating having a specific organic polymer resin as the base resin; further preferably blending an adequate amount of a specific rust-preventive agent into the organic coating.

The organic coating steel sheet according to the present invention is basically characterized in that a composite oxide coating as the primary layer coating comprising (α) fine particles of oxide, (β) one or more of metal selected from the group consisting of Mg, Ca, Sr, and Ba (including the case that the metal is in a form of compound and/or composite compound), and (γ) phosphoric acid and/or phosphoric acid compound, is formed on the surface of a zinc base plating steel sheet or an aluminum base plating steel sheet, and that, further on the primary coating layer, an organic coating as the secondary layer coating containing an organic polymer resin (A) (preferably a thermosetting resin, and further preferably an epoxy resin and/or a modified epoxy resin) containing OH group and/or COOH group, as the second layer coating.

Preferably the above-described composite oxide coating as the primary layer coating contains: SiO 2 fine particles as the component (α) at a specific coating weight; one or more substance (magnesium component) selected from the group consisting of Mg, a compound containing Mg, a composite compound containing Mg, as the component (β) at a specific coating weight; and phosphoric acid and/or phosphoric acid compound as the component (γ) at a specific coating weight.

Although the mechanism of corrosion resistance in the dual layer coating structure consisting of a specific composite oxide coating and a specific organic coating is not fully analyzed, a thin coating provides corrosion resistance equivalent to that of chromate coating owing to the synergy effect of the corrosion-suppression effect of the composite oxide coating of the primary coating, described below, and the barrier action of the film-forming resin of the secondary layer coating.

The corrosion preventive mechanism of the composite oxide coating as the primary layer coating is not fully understood. The excellent corrosion-preventive performance, supposedly, owes to that the dense and slightly soluble composite oxide coating acts as a barrier coating to shut off corrosion causes, that the fine particles of oxide such as silicon oxide (SiO 2 ) form a stable and dense barrier coating along with an alkali earth metal such as Mg and phosphoric acid and/or phosphoric acid compound, and that, when the fine particles of oxide are those of silicon oxide (SiO 2 ), the silicic acid ion emitted from the silicon oxide forms basic zinc chloride under a corrosive environment to improve the barrier performance. Even when defects occur on the coating, it is supposed that a cathodic reaction generates OH ion to bring the interface to alkali side, and Mg ion and Ca ion, which are soluble matter in alkali earth metal, precipitates as Mg(OH) 2 and Ca(OH)2, respectively, which act as the dense and slightly soluble reaction products to seal the defects, thus resulting in suppressing the corrosion reactions. Also it is assumed that phosphoric acid and/or phosphoric acid compound contributes to the improvement of denseness of the composite oxide coating, further that the phosphoric acid component catches the zinc ion which is eluted during an anodic reaction as a corrosion reaction in the coating-defect section, then the phosphoric acid component is converted to a slightly soluble zinc phosphate compound to form a precipitate at that place. As described above, alkali earth metals and phosphoric acid and/or phosphoric acid compounds should perform self-repair action in the coating-defect section.

That kind of work effect appears particularly when the composite oxide coating contains, as described before, SiO 2 fine particles as the component (α) at a specific coating weight; a magnesium component as the component (β) at a specific coating weight; and phosphoric acid and/or phosphoric acid compound as the component (γ) at a specific coating weight.

The corrosion-preventive mechanism of the organic coating as the above-described secondary layer coating is also not fully analyzed. The mechanism is, however, presumably the following. An organic polymer resin (A) (preferably a thermosetting resin, and further preferably an epoxy resin and/or a modified epoxy resin) containing OH group and/or COOH group reacts with a cross-linking agent to form a dense barrier coating. The barrier coating has superior penetration-suppression performance against the corrosion causes such as oxygen, and provides strong bonding force with the base material, thus providing particularly excellent corrosion resistance.

According to the organic coating steel sheet of the present invention, further high anti-corrosive performance (self-repair work at coating-defect section) is attained by blending adequate amount of ion-exchanged silica (a) with an organic coating consisting of above-described specific organic polymer resin (A). The corrosion-preventive mechanism attained by blending an ion-exchanged silica (a) to the specific organic coating is presumably the following. When cation such as Na ion enters under a corrosion environment, the iron exchange action emits Ca ion and

Mg ion from the surface of silica. Furthermore, when OH ion is generated by the cathode reaction under the corrosive environment to increase pH value near the plating interface, the Ca ion (or Mg ion) emitted from the ion-exchanged silica precipitates in the vicinity of the plating interface in a form of Ca(OH) 2 or Mg(OH) 2 , respectively. The precipitate seals defects as a dense and slightly soluble product to suppress the corrosion reactions. There may given an effect that the eluted zinc ion is exchanged with Ca ion (or Mg ion) and is fixed onto the surface of silica.

According to the organic coating steel sheet of the present invention, the corrosion resistance can also be increased by blending an adequate amount of silica fine particles (b) with an organic coating consisting of a specific organic polymer resin (A) as described above. That is, by blending silica fine particles such as fumed silica and colloidal silica (having average primary particle sizes of from 5 to 50 nm, preferably from 5 to 20 nm, more preferably from 5 to 15 nm) having large specific surface area into a specific organic coating, the generation of dense and stable corrosion products such as basic zinc chloride is enhanced, thus suppressing the generation of zinc oxide (white-rust).

Furthermore, according to the organic coating steel sheet of the present invention, the corrosion resistance can further be increased by blending an ion-exchanged silica (a) and silica fine particles (b) together into the organic coating consisting of a specific organic polymer resin (A) as described above. The ion-exchanged silica consists mainly of porous silica, and generally has a relatively large particle size, 1 μm or more. Accordingly, after releasing Ca ion, the rust-preventive effect as silica is not much expectable. Consequently, by accompanying fine particle silica having a relatively large specific surface area, such as fumed silica and colloidal silica, (with primary particle sizes of from 5 to 50 nm, preferably from 5 to 20 nm, more preferably from 5 to 15 nm), the generation of dense and stable corrosion products such as basic zinc chloride may be enhanced, thus suppressing the generation of zinc oxide (white rust). Through the combined rust-preventive mechanisms of ion-exchanged silica and fine particle silica, particularly strong corrosion-preventive effect would appear.

The following is the description of the composite oxide coating as the primary layer coating which is formed on the surface of zinc base plating steel sheet or aluminum base plating steel sheet.

Quite different from conventional alkali silicate treatment coating which is represented by the coating composition consisting of lithium oxide and silicon oxide, the composite oxide coating according to the present invention comprises:

(α) fine particles of oxide (preferably SiO 2 fine particles);

(β) one or more of metal selected from the group consisting of Mg, Ca, Sr, and Ba (including the case that the metal is in a form of compound and/or composite compound); and

(γ) phosphoric acid and/or phosphoric acid compound.

Particularly preferable oxide fine particles as the above-described component (α) are those of silicon oxide (fine particles of SiO 2 ), and most preferable one among the silicon oxides is colloidal silica.

Among these silicon oxides (SiO 2 fine particles), the ones having particle sizes of 14 nm or less, more preferably 8 nm or less are preferred from the viewpoint of corrosion resistance.

The silicon oxide may be used by dispersing dry silica fine particles in a coating composition solution. Examples of the dry silica are AEROSIL 200, AEROSIL 3000, AEROSIL 300CF, AEROSIL 380, (these are trade names) manufactured by Japan Aerosil Co., Ltd., and particularly the ones having particle sizes of 12 nm or less, more preferably 7 nm or less are preferred.

Other than above-described silicon oxides, the oxide fine particles may be colloidal liquid and fine particles of aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, and antimony oxide.

From the viewpoint of corrosion resistance and weldability, a preferred range of coating weight of the above-described component (α) is from 0.01 to 3,000 mg/m 2 , more preferably from 0.1 to 1,000 mg/m 2 , and most preferably from 1 to 500 mg/m 2 .

As for the specific alkali earth metal components (Mg, Ca, Sr , Ba), which a re the above-described component (β) one or more of these alkali earth metals are necessary to be contained in the coating. The form of these alkali earth metals existing in the coating is not specifically limited, and they may exist in a form of metal, or compound or composite compound of their oxide, hydroxide, hydrated oxide, phosphoric acid compound, coordination compound, or the like. The ionicity and solubility of these compound, hydroxide, hydrated oxide, phosphoric acid compound, coordination compound, o r the like are not specifically limited.

Among those alkali earth metals, it is most preferable to use Mg to obtain particularly superior corrosion resistance. The presumable reason of significant increase in corrosion resistance by the addition of Mg is that Mg shows lower solubility of its hydroxide than other alkali earth metals, thus likely forming slightly soluble salt.

The method to introduce the component (β) into coating may be the addition of phosphate, sulfate, nitrate, chloride, or the like of Mg, Ca, Sr, Ba to the coating composition.

From the standpoint of prevention of degradation in corrosion resistance and in coating appearance, a preferred range of coating weight of the above-described (β) is from 0.01 to 1,000 mg/m 2 as metal, more preferably from 0.1 to 500 mg/m 2 , and most preferably from 1 to 100 mg/m 2 .

The phosphoric acid and/or phosphoric acid compound as the above-described component (γ) may be blended by adding orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, or metallic salt or compound of them to the coating composition.

There is no specific limitation on the form of existing phosphoric acid and phosphoric acid compound in the coating, and they may be crystals or non-crystals. Also there is no specific limitation on the ionicity and solubility of phosphoric acid and phosphoric acid compound in the coating.

From the viewpoint of corrosion resistance and weldability, a preferred range of coating weight of the above-described component (γ) is from 0.01 to 3,000 mg/m 2 as P 2 O 5 , more preferably from 0.1 to 1,000 mg/m 2 , and most preferably from 1 to 500 mg/m 2 .

The composite oxide coating may further contain an organic resin for improving workability and corrosion resistance of the coating. Examples of the organic resin are epoxy resin, polyurethane resin, polyacrylic resin, acrylic-ethylene copolymer, acrylic-styrene copolymer, alkyd resin, polyester resin, polyethylene resin. These resins may be introduced into the coating in a form of water-soluble resin or water-dispersible resin.

Adding to these water type resins, it is effective to use water-soluble epoxy resin, water-soluble phenol resin, water-soluble polybutadiene rubber (SBR, NBR, MBR), melamine resin, block-polyisocyanate compound, oxazolane compound, and the like as the cross-linking agent.

For further improving the corrosion resistance, the composite oxide coating may further contain polyphosphate, phosphate (for example, zinc phosphate, aluminum dihydrogen phosphate, and zinc phosphite), molybdate, phospho molybdate (for example, aluminum phosphomolybdate), organic phosphate and its salt (for example, phytic acid, phytiate, phosphonic acid, phosphonate, their metal salt and alkali metal salt), organic inhibitor (for example, hydrazine derivative, thiol compound, dithiocarbamate), organic compound (polyethyleneglycol), and the like.

Other applicable additives include organic coloring pigments (for example, condensing polycyclic organic pigments, phthalocyanine base organic pigments), coloring dyes (for example, azo dye soluble in organic solvent, azo metal dye soluble in water), inorganic pigments (titanium oxide), chelating agents (for example, thiol), conductive pigments (for example, metallic powder of zinc, aluminum, nickel, or the like, iron phosphide, antimony-dope type tin oxide), coupling agents (for example, silane coupling agent and titanium coupling agent), melamine-cyanuric acid additives.

The composite oxide coating may contain one or more of iron group metallic ions (Ni ion, Co ion, Fe ion) to prevent blackening (an oxidizing phenomenon appeared on plating surface) under a use environment of organic coating steel sheets. As of these ions, addition of Ni ion is most preferable. In that case, concentration of the iron base metallic ion of 1/10,000 mole per 1 mole of the component (β), converted to the metal amount in the target composition, gives satisfactory effect. Although the upper limit of the iron group ion is not specifically limited, it is preferable to select a concentration level thereof not to give influence to the corrosion resistance.

A preferable range of the thickness of the composite oxide coating is from 0.005 to 3 μm, more preferably from 0.01 to 2 μm, further preferably from 0.1 to 1 μm, and most preferably from 0.2 to 0.5 μm. If the thickness of the composite oxide coating is less than 0.005 μm, the corrosion resistance degrades. If the thickness of the composite oxide coating exceeds 3 μm, conductive performance such as weldability degrades. When the composite oxide coating is specified in terms of coating weight, it is adequate to specify the sum of coating weight of the above-described component (α), the above-described component (β) converted to metal amount, and the above-described component (γ) converted to P 2 O 5 , to a range of from 6 to 3,600 mg/m 2 , more preferably from 10 to 1,000 mg/m 2 , and most preferably from 50 to 500 mg/m 2 . If the total coating weight is less than 6 mg/m 2 , the corrosion resistance degrades. If the total coating weight exceeds 3,600 mg/m 2 , the conductive performance such as weldability degrades.

To attain particularly superior performance of the present invention, it is preferable that the above-described oxide coating comprises: SiO 2 fine particles as the component (α) at a specific coating weight; one or more of magnesium components selected from the group consisting of Mg, a compound containing Mg, and a composite compound containing Mg, as the component (β) at a specific coating weight; and phosphoric acid and/or phosphoric acid compound as the component (γ) at a specific coating weight.

The preferred condition for SiO 2 fine particles as the above-described component (α) was described before.

A preferred range of the coating weight of the SiO 2 fine particles in the coating is from 0.01 to 3,000 mg/m 2 as SiO 2 , more preferably from 0.1 to 1,000 mg/m 2 , further preferably from 1 to 500 mg/m 2 , and most preferably from 5 to 100 mg/m 2 .

If the coating weight of SiO 2 fine particles is less than 0.01 mg/m 2 as SiO 2 , the contribution of the silicon component emitted from silicon oxide to the corrosion resistance becomes small to fail in attaining sufficient corrosion resistance. If the coating weight of SiO 2 fine particles exceeds 3,000 mg/m 2 as SiO 2 , the conductive performance such as weldability degrades.

Introduction of the above-described component (α) into the coating may be done by adding a silicic acid sol such as colloidal silica to the film-forming composition. Examples of preferred colloidal silica are described before.

The form of magnesium component as the above-described component (β) existing in the coating is not specifically limited, and it may be metal, or compound or composite compound such as oxide, hydroxide, hydrated oxide, phosphoric acid compound, coordination compound. The ionicity and solubility of these compound, hydroxide, hydrated oxide, phosphoric acid compound, coordination compound, or the like are not specifically limited.

A preferable range of the coating weight of the magnesium component in the coating is from 0.01 to 1,000 mg/ 2 as Mg, more preferably from 0.1 to 500 mg/m 2 , and most preferably from 1 to 100 mg/m 2 .

If the coating weight of magnesium component is less than 0.01 mg/m 2 as Mg, the contribution of the magnesium component to the corrosion resistance becomes small to fail in attaining sufficient corrosion resistance. If the coating weight of magnesium component exceeds 1,000 mg/m 2 as Mg, the excess amount of magnesium exists as a soluble component, which degrades the appearance of the coating.

Introduction of the above-described component (β) into the coating may be done by adding phosphate, sulfate, nitrate, chloride of magnesium, or magnesium oxide fine particles, to the film-forming composition.

In particular, the composite oxide according to the present invention contains phosphoric acid as a constitution component, it is preferable to add a phosphate such as magnesium phosphate to the target composition. In that case, the form of magnesium phosphate is not specifically limited, and it may be orthophosphate, pyrophosphate, tripolyphosphate, phosphite, hypophosphate.

For the methods and the forms in the coating of phosphoric acid and/or phosphoric acid compound as the above-described component (γ), there is no specific limitation as described before.

In the composite oxide coating, since the phosphoric acid component coexists with a magnesium component, the form of phosphoric acid compound in the coating may be phosphate or condensing phosphate of magnesium phosphate. Methods to introduce those phosphoric acid compounds into the coating may be the addition of phosphate or organic phosphoric acid or its salt (for example, phytic acid, phytiate, phosphonic acid, phosphonate, their metal salt) to the target composition.

A preferable range of coating weight of phosphoric acid and/or phosphoric acid compound in the coating is from 0.01 to 3,000 mg/m 2 as P 2 O 5 , more preferably from 0.1 to 1,000 mg/m 2 , and most preferably from 1 to 500 mg/m 2 .

If the coating weight of phosphoric acid and/or phosphoric acid compound is less than 0.01 mg/m 2 as P 2 O 5 , the corrosion resistance degrades. If the coating weight of phosphoric acid and/or phosphoric acid compound exceeds 3,000 mg/m 2 as P 2 O 5 , the conductive performance degrades and the weldability degrades.

To attain particularly superior corrosion resistance, it is preferred to select the ratio of the magnesium component as the component (β) to the SiO 2 fine particles as the component (α) in the composite oxide coating to a range of from 1/100 to 100/1 as the molar ratio of the component (β) as Mg to the component (α) as SiO 2 , or [Mg/SiO 2 ], more preferably from 1/10 to 10/1, and most preferably from 1/2 to 5/1.

The reason of giving particularly superior corrosion resistance when the ratio of coating weight of magnesium to SiO 2 fine particles is selected to the range given above is not fully analyzed. It is, however, speculated that, when the ratio of the magnesium component to the SiO 2 fine particles falls in the range given above, the synergy effect of the corrosion-suppressing actions of each of the silicon component emitted from the SiO 2 fine particles and the magnesium component markedly appears.

From the similar viewpoint, it is preferred to select the ratio of the phosphoric acid and/or phosphoric acid compound as the component (γ) to the magnesium component as the component (β) in the composite oxide coating to a range of from 1/100 to 100/1 as the molar ratio of the component (γ) as P 2 O 5 to the component (β) as Mg, or [P 2 O 5 /Mg], more preferably from 1/10 to 10/1, and most preferably from 1/2 to 2/1.

The reason of giving particularly superior corrosion resistance when the ratio of coating weight of phosphoric acid and/or phosphoric acid compound to magnesium is selected to the range given above is not fully analyzed. It is, however, speculated that, when the ratio of the phosphoric acid and/or phosphoric acid compound to the magnesium component falls in the range given above, the synergy effect of the corrosion-suppressing actions of each of the phosphoric acid and/or phosphoric acid compound and the magnesium component markedly appears.

To obtain most excellent corrosion resistance, it is preferred to select the ratio of the magnesium component as the component (β) and the SiO 2 fine particles as the component (α) in the composite oxide coating to a range of from 1/100 to 100/1 as the molar ratio of the component (β) as Mg to the component (α) as SiO 2 , or [Mg/SiO 2 ], more preferably from 1/10 to 10/1, and most preferably from 1/2 to 5/1, further to select the ratio of the phosphoric acid and/or phosphoric acid compound as the component (γ) to the magnesium component as the component (β) in the composite oxide coating to a range of from 1/100 to 100/1 as the molar ratio of the component (γ) as P 2 O 5 to the component (β) as Mg, or [P 2 O 5 /Mg], more preferably from 1/10 to 10/1, and most preferably from 1/2 to 2/1.

The reason of giving most excellent corrosion resistance when the ratio of magnesium component, SiO 2 fine particles, and phosphoric acid and/or phosphoric acid compound is selected to the range given above is presumably explained by the significant synergy effect of corrosion-suppressing actions of each component, as described above, and by the optimization of coating mode resulted from the reaction with base material for plating during the film-forming period.

A preferred range of the total coating weight in the composite oxide coating, or the sum of the coating weight of the above-described component (α) as SiO 2 , the coating weight of the above-described component (β) as Mg, and the coating weight of the above-described component (γ) as P 2 O 5 , is from 6 to 3,600 mg/m 2 , more preferably from 10 to 1,000 mg/m 2 , and most preferably from 50 to 500 mg/m 2 . If the total coating weight is less than 6 mg/m 2 , the corrosion resistance becomes insufficient. If the total coating weight exceeds 3,600 mg/m 2 , the conductive performance such as weldability degrades.

The following is the description about the organic coating formed as the secondary layer coating on the above-described oxide coating.

As the base resin of the organic coating, organic polymer resins (A) having OH group and/or COOH group are used. As of these resins, thermosetting resins are preferred, and epoxy resins or modified epoxy resins are particularly preferred.

Examples of the organic polymer resin containing OH group and/or COOH group are epoxy resin, polyhydroxypolyether resin, acrylic copolymer resin, ethylene-acrylic acid copolymer resin, alkyd resin, polybutadiene resin, phenol resin, polyurethane resin, polyamine resin, polyphenylene resin, and mixture or addition polymerization product of two or more of these resins.

(1) Epoxy Resin

Examples of epoxy resin are: epoxy resins which are prepared by glycidyl-etherifying bisphenol A, bisphenol F, novorak and the like; epoxy resins which are prepared by adding propyleneoxide, ethyleneoxide, or polyalkyleneglycol to bisphenol A, followed by glycidyl-etherifying; aliphatic epoxy resins, alicyclic epoxy resins, and polyether base epoxy resins.

As for these epoxy resins, particularly when they are necessary to be cured in low temperatures, preferably the number-average molecular weight of them is 1,500 or more. These epoxy resins may be used separately or mixing two or more of them.

The modified epoxy resins include the ones in which various types of modifiers are reacted with epoxy group or hydroxyl group in the above-described given epoxy resins. Examples of these modified epoxy resins are an epoxy-ester resin prepared by reacting carboxylic group in the drying oil fatty acid, an epoxy-acrylate resin prepared by modifying thereof using acrylic acid, methacrylic acid, or the like; a urethane-modified epoxy resin prepared by reacting with an isocyanate compound; and an amine-added-urethane-modified epoxy resin prepared by reacting an epoxy resin with an isocyanate compound to form a urethane-modified epoxy resin, followed by adding an alkanol amine to the urethane-modified epoxy resin.

The above-described hydroxypolyether resins are polymers prepared by polycondensation of a divalent phenol of a mononuclear or dinuclear divalent phenol or a mixture of mononuclear and dinuclear divalent phenols with a nearly equal moles of epihalohydrin under the presence of an alkali catalyst. Typical examples of the mononuclear divalent phenol are resorcin, hydroquinone, and catechol. Typical example of the dinuclear divalent phenol is bisphenol A. These divalent phenols may be used separately or two or more of them simultaneously.

(2) Polyurethane Resin

Examples of polyurethane resin are oil-modified polyurethane resin, alkyd base polyurethane resin, polyester base polyurethane resin, polyether base polyurethane resin, and polycarbonate base polyurethane resin.

(3) Alkyd Resin

Examples of alkyd resin are oil-modified alkyd resin, resin-modified alkyd resin, phenol-modified alkyd resin, styrenated alkyd resin, silicon-modified alkyd resin, acrylic-modified alkyd resin, oil-free alkyd resin, and high molecular weight oil-free alkyd resin.

(4) Polyacrylic Resin

Examples of polyacrylic resin are polyacrylic acid and its copolymer, polyacrylic ester and its copolymer, polymethacrylic acid ester and its copolymer, polymethacrylic acid ester and its copolymer, urethane-acrylic acid copolymer (or urethane-modified polyacrylic resin), styrene-acrylic acid copolymer. Further these resins may be modified by other alkyd resin, epoxy resin, phenol resin, and the like.

(5) Polyethylene Resin (Polyolefin Resin)

Examples of polyethylene resin are: ethylene base copolymers such as ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, carboxylic-modified polyolefin resin; ethylene-unsaturated carboxylic acid copolymers, and ethylene base ionomers. Further these resins may be modified by other alkyd resin, epoxy resin, and phenol resin.

(6) Acrylic Silicon Resin

Examples of acrylic silicon resin are the one which contains an acrylic base copolymer as a main component having hydrolyzable alcoxysilyl group at side chain or terminal of the acrylic base copolymer, further contains a curing agent. When that kind of acrylic silicon resin is used, superior weather-resistance is obtained.

(7) Fluororesin

Example of fluororesin is a fluoro-olefin base copolymer including a copolymer of a fluorine monomer (fluoro-olefin) with a monomer such as alkylvinylether, syncro-alkylvinylether, carboxylic acid modified vinylester, hydroxy-alkylallylether, tetrafluoropropylvinylether. When that kind of fluororesin is used, superior weather-resistance and hydrophobic property.

Aiming at reduction of resin drying temperature, there may be applied a resin having difference in resin kinds between the core and the shell of the resin particle, or a core-shell type water-dispersible resin comprising resins having different glass transition temperatures to each other.

By using a water-dispersible resin having self-cross-linking property, and by adding, for example, alkoxysilane group to the resin particles to generate silanol group by hydrolysis of alkoxysilane during the heating and drying process of the resin, it is possible to utilize cross-linking between particles using the dehydration condensation reaction of the silanol group between the resin particles.

As a resin to use for the organic coating, an organic composite silicate which is prepared by compositing an organic resin with a silane coupling agent is preferable.

According to the present invention, aiming at the improvement of corrosion resistance and workability of the organic coating, particularly the thermosetting resins are preferred. In this case, there may be added curing agent such as amino resins including urea resin (butylated urea resin, and the like), melamine resin (butylated melamine resin), butylated urea-melamine resin, and benzoguanamine resin, block isocyanate, oxazoline compound, and phenol resin.

Among these organic resins, epoxy resin and polyethylene base resin are preferable from the viewpoint of corrosion resistance, workability, and paintability, and, particularly preferred ones are thermosetting epoxy resin and modified epoxy resin which have excellent shut-off performance against corrosive causes such as oxygen. Examples of these thermosetting resins are thermosetting epoxy resin, thermosetting modified epoxy resin, acrylic base copolymer resin copolymerized with an expoxy-groupgroup-laden monomer, expoxy-groupgroup-laden polybutadiene resin, expoxy-groupgroup-laden polyurethane resin, and their adducts or condensates. These expoxy-groupgroup-laden resins may be used separately or mixing two or more of them.

According to the present invention, the organic coating may include ion-exchanged silica (a) and/or fine particle silica (b) as the rust-preventive additive.

The ion-exchanged silica is prepared by fixing metallic ion such as calcium and magnesium ions on the surface of porous silica gel powder. Under a corrosive environment, the metallic ion is released to form a deposit film. Among these ion-exchanged silicas, Ca ion-exchanged silica is most preferable.

Any type of Ca ion-exchanged silica may be applied. A preferred range of average particle size of Ca ion-exchanged silica is 6 μm or less, more preferably 4 μm or less. For example, Ca ion-exchanged silica having average particle sizes of from 2 to 4 μm may be used. If the average particle size of Ca ion-exchanged silica exceeds 6 μm, the corrosion resistance degrades and the dispersion stability in the coating composition degrades.

A preferred range of Ca concentration in the Ca ion-exchanged silica is 1 wt. % or more, more preferably from 2 to 8 wt. %. If the Ca concentration is below 1 wt. %, the rust-preventive effect by the Ca release becomes insufficient.

Surface area, pH, and oil-absorbance of the Ca ion-exchanged silica are not specifically limited.

The rust-preventive mechanism in the case of addition of ion-exchanged silica (a) to organic coating is described above. Particularly according to the present invention, markedly excellent corrosion preventive effect is attained by combining a specific organic polymer resin with ion-exchanged silica, thus inducing the combined effect of the barrier action of the specific organic polymer resin coating with the corrosion-suppression effect of the ion-exchanged silica at the cathodic reaction section.

A preferred range of blending ratio of the ion-exchanged silica (a) in the organic resin coating is 1 to 100 parts by weight (solid matter) to 100 parts by weight (solid matter) of the base resin, more preferably from 5 to 80 parts by weight (solid matter), and most preferably from 10 to 50 parts by weight (solid matter). If the blending ratio of the ion-exchanged silica (a) becomes less than 1 part by weight, the effect of improved corrosion resistance after alkaline degreasing becomes small. If the blending ratio of the ion-exchanged silica (a) exceeds 100 parts by weight, the corrosion resistance degrades, which is unfavorable.

The fine particle silica (b) may be either colloidal silica or fumed silica.

The fine particle silica contributes to forming dense and stable zinc corrosion products under a corrosive environment. Thus formed corrosion products cover the plating surface in a dense mode, thus presumably suppressing the development of corrosion.

From the viewpoint of corrosion resistance, the fine particle silica preferably has particle sizes of from 5 to 50 nm, more preferably from 5 to 20 nm, and most preferably from 5 to 15 nm.

A preferred range of blending ratio of the fine particle silica (b) in the organic resin coating is 1 to 100 parts by weight (solid matter) to 100 parts by weight (solid matter) of the base resin, more preferably from 5 to 80 parts by weight (solid matter), and most preferably from 10 to 30 parts by weight (solid matter). If the blending ratio of the fine particle silica (b) becomes less than 1 part by weight, the effect of improved corrosion resistance after alkaline degreasing becomes small. If the blending ratio of the fine particle silica (b) exceeds 100 parts by weight, the corrosion resistance and the workability degrade, which is unfavorable.

According to the present invention, markedly high corrosion resistance is attained by combined addition of an ion-exchanged silica (a) and a fine particle silica (b) to the organic coating. That is, the combined addition of ion-exchanged silica (a) and fine particle silica (b) induces above-described combined rust-preventive mechanism which gives markedly excellent corrosion-preventive effect.

The blending ratio of combined addition of ion-exchanged silica (a) and fine particle silica (b) to the organic coating is in a range of from 1 to 100 parts by weight (solid matter) of the base resin, preferably from 5 to 80 parts by weight (solid matter). Further the weight ratio of blending amount (solid matter) of the ion-exchanged silica (a) to the fine particle silica (b), (α)/(b), is selected to a range of from 99/1 to 1/99, preferably from 95/5 to 40/60, more preferably from 90/10 to 60/40.

If the blending ratio of sum of the ion-exchanged silica (a) and the fine particle silica (b) is less than 1 part by weight, the effect of improved corrosion resistance after alkaline degreasing becomes small. If the blending ratio of sum of the ion-exchanged silica (a) and the fine particle silica (b) exceeds 100 parts by weight, the coatability and the weldability degrade, which is unfavorable.

If the weight ratio of the ion-exchanged silica (α) to the fine particle silica (b), (a)/(b), is less than 1/99, the corrosion resistance degrades. If the weight ratio of the ion-exchanged silica (a) to the fine particle silica (b), (β)/(b), exceeds 99/1, the effect of combined addition of the ion-exchanged silica (a) and the fine particle silica (b) cannot fully be attained.

Adding to the above-described rust-preventive agents, the organic coating may contain other corrosion-suppressing agent such as polyphosphate (for example, aluminum polyphosphate such as TAICA K-WHITE 82, TAICA K-WHITE 105, TAICA K-WHITE G105, TAICA K-WHITE Ca650 (trade marks) manufactured by TAYCA CORPORATION), phosphate (for example, zinc phosphate, aluminum dihydrogenphosphate, zinc phosphate), molybdenate, phosphomolybdenate (for example, aluminum phosphomolybdenate), organic phosphoric acid and its salt (for example, phytic acid, phytiate, phosphonic acid, phosphonate, their metal salt and alkali metal salt, alkali earth metal salt), organic inhibitor (for example, hydrazine derivative, thiol compound).

The organic coating may, at need, further include a solid lubricant (c) to improve the workability of the coating.

Examples of applicable solid lubricant according to the present invention are the following.

(1) Polyolefin wax, paraffin wax: for example, polyethylene wax, synthetic paraffin, natural paraffin, microwax, chlorinated hydrocarbon;

(2) Fluororesin fine particles: for example, polyfluoroethylene resin (such as poly-tetrafluoroethylene resin), polyvinylfluoride resin, polyvinylidenefluoride resin.

In addition, there may be applied fatty acid amide base compound (such as stearic acid amide, palmitic acid amide, methylene bis-stearoamide, ethylene bis-stearoamide, oleic acid amide, ethyl acid amide, alkylene bis-fatty acid amide), metallic soap (such as calcium stearate, lead stearate, calcium laurate, calcium palmate), metallic sulfide (molybdenum disulfide, tungsten disulfide), graphite, graphite fluoride, boron nitride, polyalkyleneglycol, and alkali metal sulfate.

Among those solid lubricants, particularly preferred ones are polyethylene wax, fluororesin fine particles (particularly poly-tetrafluoroethylene resin fine particles).

A most preferred fluororesin fine particle is tetrafluoroethylene fine particle.

As of these compounds, combined use of polyolefin wax and tetrafluoroethylene fine particles is expected to provide particularly excellent lubrication effect.

A preferred range of blending ratio of the solid lubricant (c) in the organic resin coating is from 1 to 80 parts by weight (solid matter) to 100 parts by weight (solid matter) of the base resin, more preferably from 3 to 40 parts by weight (solid matter). If the blending ratio of the solid lubricant (c) becomes less than 1 part by weight, the effect of lubrication is small. If the blending ratio of the solid lubricant (c) exceeds 80 parts by weight, the painting performance degrade, which is unfavorable.

The organic coating of the organic coating steel sheet according to the present invention comprises an organic polymer resin (A) as the base resin. And, at need, an ion-exchanged silica (a), a fine particle silica (b), a solid lubricant (c), and a curing agent may further be added to the organic coating. Furthermore, at need, there may be added other additives such as organic coloring pigment (for example, condensing polycyclic organic pigment, phthalocyanine base organic pigment), coloring dye (for example, azo dye soluble in organic solvent, azo metal dye soluble in water), inorganic pigment (for example, titanium oxide), chelating agent (forexample, thiol), conductive pigment (for example, metallic powder of zinc, aluminum, nickel, or the like, iron phosphide, antimony-dope type tin oxide), coupling agent (for example, silane coupling agent and titanium coupling agent), melamine-cyanuric acid additive.

The paint composition for film-formation containing above-described main component and additive components normally contains solvent (organic solvent and/or water), and, at need, further a neutralizer or the like is added.

The organic coatings described above are formed on the above-described composite oxide coating.

The dry thickness of the organic coating is in a range of from 0. 1 to 5 μm preferably from 0. 3 to 3 μm, and most preferably from 0.5 to 2 μm If the thickness of the organic coating is less than 0. 1 μ, the corrosion resistance becomes insufficient. If the thickness of the organic coating exceeds 5 μm, the conductivity and the workability degrade.

The following is the description about the method for manufacturing an organic coating steel sheet according to the present invention.

The organic coating steel sheet according to the present invention is manufactured by the steps of: treating the surface (applying a treatment liquid to the surface) of a zinc base plating steel sheet or an aluminum base plating steel sheet using a treatment liquid containing the components of above-described composite oxide coating; heating and drying the plate; applying a paint composition which contains the above-described organic polymer resin (A) as the base resin, and at need, further contains an ion-exchanged silica (a), a fine particle silica (b), and a solid lubricant (c), and the like; heating to dry the product.

The surface of the plating steel sheet may be, at need, subjected to alkaline degreasing before applying the above-described treatment liquid, and may further be subjected to preliminary treatment such as surface adjustment treatment for further improving the adhesiveness and corrosion resistance.

For treating the surface of the zinc base plating steel sheet or the aluminum base plating steel sheet with a treatment liquid and for forming a composite oxide coating thereon, it is preferred that the plate is treated by an acidic aqueous solution, at pH ranging from 0.5 to 5, containing:

(aa) oxide fine particles ranging from 0.001 to 3.0 mole/liter;

(ab) one or more of the substances selected from the group consisting of either one metallic ion of Mg, Ca, Sr, Ba; a compound containing at least one metal given above; a composite compound containing at least one metal given above; ranging from 0.001 to 3.0 mole/liter as metal given above;

(ac) phosphoric acid and/or phosphoric acid compound ranging from 0.001 to 6.0 mole/liter as P 2 O 5 ;

further adding, at need, above-described additive components (organic resin components, iron group metal ions, corrosion-suppression agents, other additives); then heating and drying the product.

The added components (ab) in the treatment liquid is in a range of from 0.001 to 3.0 mole/liter as metal, preferably from 0.01 to 0.5 mole/liter. If the sum of the added amount of these components is less than 0.001 mole/liter, the effect of addition cannot be fully attained. If the sum of the added amount of these components exceeds 3.0 mole/liter, these components interfere the network of coating, thus failing in forming dense coating. Furthermore, excess amount of addition of these components makes the metallic components likely elute from the coating, which results in defects such as discoloration of appearance under some environmental conditions.

A s of above-described given additive components (ab), Mg most significantly increases the corrosion resistance. The form of Mg in the treatment liquid may be compound or composite compound. To attain particularly excellent corrosion resistance, however, a metallic ion or a water-soluble ion form containing Mg is particularly preferred.

For supplying ion of the additive components (ab) in a form of metallic salt, the treatment liquid may contain anion such as chlorine ion, nitric acid ion, sulfuric acid ion, acetic acid ion, and boric acid ion.

It should be emphasized that the treatment liquid is an acidic aqueous solution. That is, by bringing the treatment liquid to acidic, the plating components such as zinc are readily dissolved. As a result, at the interface between the chemical conversion treatment film and the plating, a phosphoric acid compound layer containing plating components such as zinc is presumably formed, which layer strengthens the interface bonding of both sides to structure a coating having excellent corrosion resistance.

As the oxide fine particles as an additive component (aa), silicon oxide (SiO 2 ) fine particles are most preferred. The silicon oxide may be commercially available silica sol and water-dispersion type silicic acid oligomer or the like if only the silicon oxide is water-dispersion type SiO 2 fine particles which are stable in an acidic aqueous solution. Since, however, fluoride such as hexaf luoro silicic acid is strongly corrosive and gives strong effect to human body, that kind of compound should be avoided from the point of influence to work environment.

A preferred range of blending ratio of the fine particle oxide (the blending ratio as SiO 2 in the case of silicon oxide) in the treating liquid is from 0.001 to 3.0 mole/liter, more preferably from 0.05 to 1.0 mole/liter, and most preferably from 0.1 to 0.5 mole/liter. If the blending ratio of the fine particle oxide becomes less than 0.001 mole/liter, the effect of addition is not satisfactory. If the blending ratio of the fine particle oxide exceeds 3.0 mole/liter, the water-resistance of coating degrades, resulting in degradation of corrosion resistance.

The phosphoric acid and/or phosphoric acid compound as the additive component (ac) includes: a mode of aqueous solution in which a compound specific to phosphoric acid, such as polyphosphoric acid such as orthophosphoric acid, pyrophosphoric acid, and tripolyphosphoric acid, methaphosphoric acid, inorganic salt of these acids (for example, primary aluminum phosphate), phosphorous acid, phosphate, phosphinic acid, phosphinate, exists in a form of anion or complex ion combined with a metallic cation which are generated by dissolving the compound in the aqueous solution; and a mode of aqueous solution in which that kind of compound exists in a form of inorganic salt dispersed therein. The amount of phosphoric acid component according to the present invention is specified by the sum of all these modes of acidic aqueous solution thereof as converted to P 2 O 5 amount.

A preferred range of blending ratio of the phosphoric acid and/or phosphoric acid compound as P 2 O 5 is from 0.001 to 6.0 mole/liter, more preferably from 0.02 to 1.0 mole/liter, and most preferably from 0.1 to 0.8 mole/liter. If the blending ratio of the phosphoric acid and/or phosphoric acid compound becomes less than 0.001 mole/liter, the effect of addition is not satisfactory and the corrosion resistance degrades. If the blending ratio of the phosphoric acid and/or phosphoric acid compound exceeds 6.0 mole/liter, excess amount of phosphoric acid ion reacts with the plating film under a humid environment, which enhances the corrosion of plating base material to cause discoloration and stain-rusting under some corrosive environments.

For obtaining a composite oxide coating providing particularly excellent corrosion resistance, or for preparing a composite oxide coating comprising components (α), (β), and (γ) given below, and having the coating weight of the sum of these components (α), (β), and (γ) in a range of from 6 to 3,600 mg/m 2 , it is preferable that the above-described composite oxide coating contains the additive components (aa), (ab), and (ac) in the acidic aqueous solution, further, the composite oxide coating is treated by an acidic aqueous solution of pH of from 0.5 to 5 containing, at need, above-described additive components (organic resin component, iron group metallic ion, corrosion-suppression agent, and other additives), followed by heating and drying. The above-described given composite oxide coating components (α), (β), and (γ), and the above-described given additive components (aa), (ab), and (ac) are specified below.

(α) SiO 2 fine particles in a range of from 0.01 to 3,000 mg/m 2 as SiO 2 ,

(β) One or more of Mg, compound containing Mg, and composite compound containing Mg in a range of from 0.01 to 1,000 mg/m 2 as Mg,

(γ) Phosphoric acid and/or phosphoric acid compound in a range of from 0.01 to 3,000 mg/m 2 as P 2 O 5 ;

(aa) SiO 2 fine particles in a range of from 0.001 to 3.0 mole/liter as SiO 2 , preferably from 0.05 to 1.0 mole/liter, more preferably from 0.1 to 0.5 mole/liter,

(ab) One or more of the substances selected from the group consisting of Mg ion, water-soluble ion containing Mg, compound containing Mg, composite compound containing Mg in a range of from 0.001 to 3.0 mole/liter as Mg, preferably from 0.01 to 0.5 mole/liter,

(ac) phosphoric acid and/or phosphoric acid compound in a range of from 0.001 to 6.0 mole/liter as P 2 O 5 , preferably from 0.02 to 1.0 mole/liter, more preferably from 0.1 to 0.8 mole/liter.

The reason to specify the conditions and amount of the above-described given additives (aa), (ab), and (ac) is described before.

To prepare the range of the ratio of the component (β) to the component (α) in the composite oxide coating, molar ratio [Mg/SiO 2 ], or the component (β) as Mg to the component (α) as SiO 2 , from 1/100 to 100/1, the ratio of the additive component (ab) to the additive component (aa) in the acidic aqueous solution for forming the composite oxide coating may be adjusted to a range of from 1/100 to 100/1 as the molar ratio [Mg/SiO 2 ], or the additive component (ab) as Mg to the additive component (aa) as SiO 2 .

To adjust the ratio of the component (β) to the component (α) in the composite oxide coating to a preferred range of from 1/10 to 10/1, more preferably from 1/2 to 5/1, as the molar ratio [Mg/SiO 2 ], or the ratio of the component (β) as Mg to the component (α) as SiO 2 , it is adequate to adjust the ratio of the additive component (ab) to the additive component (aa) in the acidic aqueous solution for forming the composite oxide coating to a range of from 1/10 to 10/1, more preferably from 1/2 to 5/1, as the molar ratio [Mg/SiO 2 ], or the ratio of the additive component (ab) as Mg to the additive component (aa) as SiO 2 .

To adjust the ratio of the component (γ) to the component (β) in the composite oxide coating to a range of from 1/100 to 100/1 as the molar ratio [P 2 O 5 /Mg], or the ratio of the component (γ) as P 2 O 5 to the component (β) as Mg, it is adequate to adjust the ratio of additive component (ac) to the additive component (ab) in the acidic aqueous solution for forming the composite oxide coating to a range of from 1/100 to 100/1 as the molar ratio [P 2 O 5 /Mg] represented by the ratio of the additive component (ac) as P 2 O 5 to the additive component (ab) as Mg.

To adjust the ratio of the component (γ) to the component (β) in the composite oxide coating to a further preferable range of from 1/10 to 10/1 as the molar ratio [P 2 O 5 /Mg], or the ratio of the component (γ) as P 2 O 5 to the component (β) as Mg, more preferably from 1/2 to 2/1, it is adequate to adjust the ratio of additive component (ac) to the additive component (ab) in the acidic aqueous solution for forming the composite oxide coating to a range of from 1/10 to 10/1, more preferably from 1/2 to 2/1, as the molar ratio [P 2 O 5 /Mg], or the ratio of the additive component (ac) as P 2 O 5 to the additive component (ab) as Mg.

For adjusting the ratio of the additive component (ac) to the additive component (ab) in the acidic aqueous solution for forming the composite oxide coating, it is preferable to use an aqueous solution of primary magnesium phosphate or the like which is prepared by limiting the molar ratio of the magnesium component to the phosphoric acid component, in advance, because other anionic components are prevented from existing in the treatment liquid.

On applying the aqueous solution of primary magnesium phosphate, however, lowered molar ratio [P 2 O 5 /Mg] degrades the stability of the compound in the aqueous solution. Accordingly, a suitable molar ratio [P 2 O 5 /Mg] is not less than 1/2.

On the other hand, increased molar ratio [P 2 O 5 /Mg] in the aqueous solution of primary magnesium phosphate decreases the pH of treatment liquid, which increases the reactivity with the plating base material, which then induces irregular coating caused by non-uniform reaction to give an influence to corrosion resistance. Consequently, when an aqueous solution of primary magnesium phosphate which is prepared by limiting the molar ratio of the magnesium component to the phosphoric acid component, the molar ratio [P 2 O 5 /Mg] is preferably set to not more than 2/1.

To attain the most excellent corrosion resistance, it is preferred that the ratio of the component (β) to the component (α) in the composite oxide coating is adjusted to a range of from 1/100 to 100/1 as the molar ratio [Mg/SiO 2 ], or the component (β) as Mg to the component (α) as SiO 2 , more preferably from 1/10 to 10/1, most preferably from 1/2 to 5/1. And, to adjust the ratio of the component (γ) to the component (β) in the composite oxide coating to a range of from 1/100 to 100/1 as the molar ratio [P 2 O 5 /Mg], or the component (γ) as P 2 O 5 to the component (β) as Mg in the composite oxide coating, more preferably from 1/10 to 10/1, and most preferably from 1/2 to 2/1, it is preferred that the ratio of the additive component (ab) to the additive component (aa) in the acidic aqueous solution for forming the composite oxide coating is adjusted to a range of from 1/100 to 100/1 as the molar ratio [Mg/SiO 2 ], or the additive component (ab) as Mg to the additive component (aa) as SiO 2 , more preferably from 1/10 to 10/1, and most preferably from 1/2 to 5/1, and further the ratio of the additive component (ac) to the additive component (b) is adjusted to a range of from 1/100 to 100/1 as the molar ratio [P 2 O 5 /Mg], or the additive component (ac) as P 2 O 5 to the additive component (ab) as Mg, preferably from 1/10 to 10/1, more preferably from 1/2 to 2/1.

The treatment liquid may further include an adequate amount of an additive component (ad) which is one or more ions selected from the group consisting of: either one metallic ion of Ni, Fe, and Co; and water-soluble ion containing at least one of the above-described listed metals. By adding that kind of iron group metal, blackening phenomenon is avoided. The blackening phenomenon occurs in the case of non-addition of iron group metals caused from corrosion on the plating polar surface layer under a humid environment. Among these iron group metals, Ni provides particularly strong effect even with a slight amount thereof. Since, however, excessive addition of iron group metals such as Ni and Co induces degradation of corrosion resistance, the added amount should be kept at an adequate level.

A preferred range of the added amount of the above-described additive component (ad) is from 1/10,000 to 1 mole as metal per one mole of the additive component (ac), more preferably from 1/10,000 to 1/100. If the added amount of the additive component (ad) is less than 1/10,000 mole to one mole of the additive component (ac), the effect of the addition is not satisfactory. If the added amount of the additive component (ad) exceeds 1 mole, the corrosion resistance degrades as described above.

Adding to the above-described additive components (aa) through (ad), the treatment liquid may further contain an adequate amount of additive components to the coating, which are described before.

A preferable range of pH of the treatment liquid is from 0.5 to 5, more preferably from 2 to 4. If the pH of treatment liquid is less than 0.5, the reactivity of the treatment liquid becomes excessively strong so that micro-defects appear on the surface of the coating to degrade the corrosion resistance. If the pH of the treatment liquid exceeds 5, the reactivity of the treatment liquid becomes poor, and the bonding at interface between the plating face and the coating becomes insufficient, as described above, thus degrading the corrosion resistance.

The methods for applying the treatment liquid onto the plating steel sheet may be either one of coating method, dipping method, and spray method. The coating method may adopt any type such as roll coater (three-roll type, two-roll type, etc.), squeeze coater, die coater. After the coating step using squeeze coater and the like, the dipping step, or the spray step, it is possible to adjust the coating weight, the uniformizing appearance, and the uniformizing the film-thickness using air-knife method and roll-squeezing method.

Although there is no specific limitation on the temperature of the treatment liquid, a preferable range thereof is from normal temperature to around 60° C. Below the normal temperature is uneconomical because a cooling unit or other additional facilities are required. On the other hand, temperatures above 60° C. enhances the vaporization of water, which makes the control of the treatment liquid difficult.

After the coating of treatment liquid as described above, generally the plate is heated to dry without rinsing with water. The treatment liquid according to the present invention forms a slightly soluble salt by a reaction with the substrate plating steel sheet, so that rinsing with water may be applied after the treatment.

Method for heating to dry the coated treatment liquid is not limited. For example, dryer, hot air oven, high frequency induction heating furnace, infrared heating furnace may be applied.

The heating and drying treatment is preferably conducted at reaching temperatures of from 50 to 300° C., more preferably from 80 to 200° C., and most preferably from 80 to 160° C. If the heating temperature is less than 50° C., excess amount of water is left in the coating, which results in insufficient corrosion resistance. If the heating temperature exceeds 300° C., the operation becomes uneconomical and defects likely appear in the coating to degrade the corrosion resistance.

After forming the composite oxide coating on the surface of the zinc base plating steel sheet or the aluminum base plating steel sheet, as described above, a paint composition for forming an organic coating is applied on the composite oxide coating. Method for applying the paint composition is not limited, and examples of the method are coating method, dipping method, and spray method. The coating method may adopt any type such as roll coater (three-roll type, two-roll type, etc.), squeeze coater, die coater. After the coating step using squeeze coater and the like, the dipping step, or the spray step, it is possible to adjust the coating weight, the uniformizing appearance, and the uniformizing the film-thickness using air-knife method and roll-squeezing method.

After applying the paint composition, generally the plate is heated to dry without rinsing with water. After applying the paint composition, however, water-rinse step may be given.

Method for heating to dry the paint composition is not limited. For example, dryer, hot air oven, high frequency induction heating furnace, infrared heating furnace may be applied. The heating treatment is preferably conducted at reaching temperatures of from 50 to 350° C., more preferably from 80 to 250° C. If the heating temperature is less than 50° C., excess amount of water is left in the coating, which results in insufficient corrosion resistance. If the heating temperature exceeds 350° C., the operation becomes uneconomical and defects likely appear in the coating to degrade the corrosion resistance.

As described above, the present invention includes a steel sheet having an organic coating on both sides or on side thereof. Accordingly, modes of the steel sheet according to the present invention include, for example, the followings.

(1) “Plating film—Composite oxide coating—Organic coating” on one side of the steel sheet, and “Plating film” on other side of the steel sheet;

(2) “Plating film—Composite oxide coating—Organic coating” on one side of the steel sheet, and “Plating film—Known coating treated by phosphoric acid, or the like” on other side of the steel sheet;

(3) “Plating film—Composite oxide coating—Organic coating” on both sides of the steel sheet;

(4) “Plating film—Composite oxide coating—Organic coating” on one side of the steel sheet, and “Plating film—Composite oxide coating” on other side of the steel sheet;

(5) “Plating film—Composite oxide coating—Organic coating” on one side of the steel sheet, and “Plating film—Organic coating” on other side of the steel sheet.

Embodiments

Treatment liquids (coating compositions) for forming the primary layer coating, which are listed in Tables 140 through 155, and resin compositions for forming the secondary layer coating, which are listed in Table 156, were prepared.

To the resin compositions shown in Table 156, an ion-exchanged silica, a fine particle silica shown in Table 157, and a solid lubricant shown in Table 158 were added at respective adequate amount, which additives were dispersed in the resin composition for a necessary time using a paint dispersion apparatus (a sand grinder) to prepare respective desired paint compositions. As the above-described ion-exchanged silica, SHIELDEX C303 (average particle sizes of from 2.5 to 4.5 μm, Ca concentration of 3 wt. %) which is a Ca-exchanged silica produced by W.R. Grace & Co. was used.

To obtain organic coating steel sheets for household electric appliances, building materials, and automobile parts, the plating steel sheets shown in Table 139 were used as the target base plates, which plates were prepared by applying zinc base plating or aluminum base plating on the cold-rolled steel sheets having a plate thickness of 0.8 mm and a surface roughness Ra of 1.0 μm. The surface of the plating steel sheet was treated by alkaline degreasing and water washing, then the treatment liquids (coating compositions) shown in Tables 140 through 155 were applied to the surface using a roll coater, followed by heating to dry to form the first layer coating. The thickness of the first layer coating was adjusted by the solid content in the treatment liquid (heating residue) or applying conditions (roll pressing force, rotational speed, and other variables). Then, the paint composition given in Table 156 was applied using a roll coater, which was then heated to dry to form the secondary layer coating, thus manufactured the organic coating steel sheets as Examples and Comparative Examples. The thickness of the second layer coating was adjusted by the solid content in the treatment liquid (heating residue) or applying conditions (roll pressing force, rotational speed, and other variables).

In the Table 156, each of *1 through *7 appeared in the table expresses the following.

*1: A butylcellove-cellosolve solution of epoxy resin (solid 40%) produced by Yuka Shell Epoxy Co., Ltd.

*2: A urea resin (solid 60%) produced by Dainippon Ink & Chemicals, Inc.

*3: A diethanol-modified epoxy resin (solid 50%) produced by Kansai Paint Co., Ltd.

*4: A block-polyurethane resin (solid 60t) produced by Asahi Chemical Industry Co., Ltd.

*5 A high molecular weight oil-free alkyd resin (solid 60t) produced by Dainippon Ink & Chemicals, Inc.

*6: A melamine resin (solid 80%) produced by Mitsui Sytech Co.

*7 A high molecular weight oil-free alkyd resin (solid 40%) produced by Toyobo Co., Ltd.

To each of thus obtained organic coating steel sheets, evaluation was given in terms of quality performance (appearance of coating, white-rust resistance, white-rust resistance after alkaline degreasing, paint adhesiveness, and workability). The results are given in Tables 159 through 190 along with the structure of primary layer coating and of secondary layer coating. In the Tables 159 through 190, each of *1 through *13 appeared in the table expresses the following.

*1: Corresponding to No. given in Table 139.

*2: Corresponding to No. given in Tables 140 through 155.

*3: Corresponding to No. given in Table 156.

*4: Coating weight of SiO 2 fine particles (α)=Coating weight of SiO 2 fine particles converted to SiO 2

 : Coating weight of Mg component (γ)=Coating weight of one ore more substances selected from the group consisting of Mg, compound containing Mg, composite compound containing Mg, converted to Mg.

 : Coating weight of P 2 O 5 component (γ)=Coating weight of phosphoric acid and/or phosphoric acid compound, converted to P 2 O 5 .

 : Total coating weight=(α)+(β)+(γ)

*5: Molar ratio of Mg component (β) as Mg to SiO 2 fine particles (α) as SiO 2 .

*6: Molar ratio of P 2 O 5 component (γ) as P 2 O 5 to Mg component (β) as Mg.

*7: Blending ratio (weight parts) of solid portion of ion-exchanged silica to 100 parts by weight of solid portion of resin composition.

*8: Corresponding to No. given in Table 157.

*9: Blending ratio (weight parts) of solid portion of fine particle silica to 100 parts by weight of solid portion of resin composition.

*10: Blending ratio (weight parts) of solid portion of the sum of ion-exchanged silica (a) and fine particle silica (b) to 100 parts by weight of solid portion of resin composition.

*11: Weight ratio of solid portion of ion-exchanged silica (a) to fine particle silica (b).

*12: Corresponding to No. given in Table 158.

*13: Blending ratio (weight parts) of solid portion of solid lubricant to 100 parts by weight of solid portion of resin composition.

As the conventional reaction type chromate steel sheet treatment liquid, a solution containing 30 g/l of anhydrous chromic acid, 10 g/l of phosphoric acid, 0.5 g/l of NaF, and 4 g/l of K 2 TiF 6 was used. After spray treatment at a bath temperature of 40° C., the steel sheet was washed with water and was dried, thus a chromated steel sheet having a chromium coating weight of 20 mg/m 2 as metallic chromium as prepared. Thus obtained steel sheet was subjected to the salt spray test under the same condition that applied to Examples, and the plate generated white-rust within about 24 hours. Consequently, the results of Examples show that the organic coating steel sheets according to the present invention provide remarkably superior corrosion resistance to the conventional type chromate treated steel sheets.

TABLE 139
		Coating weight
No.	Kind	(mg/m 2 )
1	Electrolytically galvanized steel plate	20
2	Hot dip galvanized steel plate	60
3	Alloyed hot dip galvanized steel plate	60
	(Fe: 10 wt %)
4	Zn—Ni alloy plating steel plate (Ni: 12 wt %)	20
5	Zn—Co alloy plating steel plate (Co: 0.5 wt %)	20
6	Zn—Cr alloy plating steel plate (Cr: 12 wt %)	20
7	Hot dip Zn—Al alloy plating steel plate	90
	(Al: 55 wt %)
8	Hot dip Zn-5 wt % Al-0.5 wt % Mg alloy plating	90
	steel plate
9	Electrolytically Zn—SiO2 composite plating	20
	steel plate
10	Hot dip aluminized steel plate (Al-6 wt % Si ally	60
	plating)
11	Electrolytically Al-Mn alloy plating steel plate	40
	(Mn: 30 wt %)
12	Electrolytically aluminized steel plate	40
13	Hot dip Zn—Mg alloy plating steel plate	150
	(Mg: 0.5 wt %)

 

TABLE 140
Composition of primary layer coating
		Alkali	Phosphoric acid,
		earth metal	phosphoric acid
	Oxide fine particles (aa)	(ab)	compound (ac)	Organic resin
				Concen-		Concen-		Concen-		Concen-
			Particle size	tration		tration		tration		tration
No.	Type	Trade name	(nm)	(M/L)	Type	(M/L)	Type	(M/L)*1	Type	(g/l)
1	Colloidal silica	Nissan Chemical	12 to 14	0.11	Mg 2+	0.20	orthophosphoric	0.42	—	—
		Industries, Ltd.					acid
		SNOWTEX-O
2	Colloidal silica	Nissan Chemical	12 to 14	0.18	Mg 2+	0.17	orthophosphoric	0.36	—	—
		Industries, Ltd.					acid
		SNOWTEX-O
3	Colloidal silica	Nissan Chemical	12 to 14	0.40	Mg 2−	0.40	orthophosphoric	0.80	—	—
		Industries, Ltd.					acid
		SNOWTEX-O
4	Colloidal silica	Nissan Chemical	8 to 10	0.18	Mg 2−	0.17	orthophosphoric	0.36	—	—
		Industries, Ltd.					acid
		SNOWTEX-OS
5	Colloidal silica	Nissan Chemical	6 to 8	0.11	Mg 2+	0.20	orthophosphoric	0.42	—	—
		Industries, Ltd.					acid
		SNOWTEX-OXS
6	Alumina sol	Nissan Chemical	&Asteriskpseud;	0.20	Mg 2+	0.30	orthophosphoric	0.60	—	—
		Industries, Ltd.					acid
		Alumina sol 200
7	Zirconia sol	Nissan Chemical	60 to 70	0.40	Mg 2+	0.40	orthophosphoric	0.80	—	—
		Industries, Ltd.					acid
		NZS-30A
8	Colloidal silica	Nissan Chemical	12 to 14	0.30	Mg 2+	0.10	orthophosphoric	0.20	Acrylic-styrene	180
		Industries, Ltd.					acid		base water-
		SNOWTEX-O							dispersible resin
*1 Converted to P 2 O 5
&Asteriskpseud;Feather-shape particles (10 nm × 100 nm)

 

TABLE 141
				Adaptability to the
	Molar ratio	Molar ratio	Composition	condition of the
No.	(ab)/(aa)	(ac)/(ab)	pH	invention* 2
1	1.82	2.10	3.1	◯
2	0.94	2.12	3.1	◯
3	1.00	2.00	2.7	◯
4	0.94	2.12	3.1	◯
5	1.82	2.10	3.0	◯
6	1.50	2.00	3.5	◯
7	1.00	2.00	3.2	◯
8	0.33	2.00	2.5	◯
* 2 ◯: Satisfies the conditions of the invention
X: Dissatisfies the conditions of the invention

 

TABLE 142
Composition of primary layer coating
		Alkali	Phosphoric acid,
		earth metal	phosphoric acid
	Oxide fine particles (aa)	(ab)	compound (ac)	Organic resin
				Concen-		Concen-		Concen-		Concen-
			Particle size	tration		tration		tration		tration
No.	Type	Trade name	(nm)	(M/L)	Type	(M/L)	Type	(M/L)*1	Type	(g/l)
9	Colloidal silica	Nissan Chemical Industries, Ltd.	12 to 14	0.20	Ca 2+	0.20	orthophosphoric	0.40	—	—
		SNOWTEX-O					acid
10	Colloidal silica	Nissan Chemical Industries, Ltd.	12 to 14	0.10	Sr 2−	0.10	orthophosphoric	0.20	—	—
		SNOWTEX-O					acid
11	Colloidal silica	Nissan Chemical Industries, Ltd.	12 to 14	0.05	Ba 2+	0.10	orthophosphoric	0.20	—	—
		SNOWTEX-O					acid
12	—	—	—	—	Mg 2−	0.30	orthophosphoric	0.60	—	—
							acid
13	Colloidal silica	Nissan Chemical Industries, Ltd.	12 to 14	0.40	—	—	orthophosphoric	0.30	—	—
		SNOWTEX-O					acid
14	Colloidal silica	Nissan Chemical Industries, Ltd.	12 to 14	0.40	Mg 2+	0.20	—	—	—	—
		SNOWTEX-O
15	Lithium silicate	Nissan Chemical Industries, Ltd.	—	1.00	—	—	—	—	—	—
		LSS-35
*1 Converted to P 2 O 5

 

TABLE 143
				Adaptability to the
	Molar ratio	Molar ratio	Composition	condition of the
No.	(ab)/(aa)	(ac)/(ab)	pH	invention* 2
9	1.00	2.00	3.0	◯
10	1.00	2.00	3.1	◯
11	2.00	2.00	3.2	◯
12	—	2.00	2.8	X
13	—	—	3.0	X
14	0.50	—	2.1	X
15	—	—	11	X
* 2 ◯: Satisfies the conditions of the invention
X: Dissatisfies the conditions of the invention

 

TABLE 144
Composition of primary layer coating
		Alkali	Phosphoric acid,
		earth metal	phosphoric acid
	Oxide fine particles (aa)	(ab)	compound (ac)	Organic resin
				Concen-		Concen-		Concen-		Concen-
			Particle size	tration		tration		tration		tration
No.	Type	Trade name	(nm)	(M/L)	Type	(M/L)	Type	(M/L)*1	Type	(g/l)
16	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.2	Mg 2+	0.4	orthophosphoric	0.46	—	—
		SNOWTEX-OS					acid
17	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.1	Mg 2−	0.2	orthophosphoric	0.23	—	—
		SNOWTEX-OS					acid
18	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.3	Mg 2+	0.3	orthophosphoric	0.31	—	—
		SNOWTEX-OS					acid
19	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.15	Mg 2+	0.2	orthophosphoric	0.4	—	—
		SNOWTEX-OS					acid
20	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.3	Mg 2+	0.35	orthophosphoric	0.4	—	—
		SNOWTEX-OS					acid
21	Alumina sol	Nissan Chemical Industries, Ltd.	8 to 10	0.1	Mg 2+	0.5	orthophosphoric	0.5	—	—
		SNOWTEX-OS					acid
22	Zirconia sol	Nissan Chemical Industries, Ltd.	8 to 10	0.3	Mg 2+	0.15	orthophosphoric	0.16	—	—
		SNOWTEX-OS					acid
23	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.3	Mg 2+	0.4	orthophosphoric	0.2	—	—
		SNOWTEX-OS					acid
*1 Converted to P 2 O 5

 

TABLE 145
				Adaptability to the
	Molar ratio	Molar ratio	Composition	condition of the
No.	(ab)/(aa)	(ac)/(ab)	pH	invention* 2
16	2.00	1.2	2.7	◯
16	2.00	1.2	2.7	◯
17	2.00	1.2	2.8	◯
18	1.00	1.0	3.0	◯
19	1.33	2.0	1.9	◯
20	1.17	1.1	2.8	◯
21	5.00	1.0	3.1	◯
22	0.50	1.1	3.3	◯
23	1.33	0.5	3.0	◯
* 2 ◯: Satisfies the conditions of the invention
X: Dissatisfies the conditions of the invention

 

TABLE 146
[Composition of primary layer coating]
		Alkali
	Oxide fine particles (aa)	earth metal (ab)	Phosphoric acid,	Organic resin
	Particle	Concen-		Concen-	phosphoric acid compound (ac)		Concen-
			size	tration		tration		Concentration		tration
No.	Type	Trade name	(nm)	(M/L)	Type	(M/L)	Type	(M/L) *1	Type	(g/l)
24	Colloidal silica	Nissan Chemical Industries, Ltd.	6 to 8	0.2	Mg 2+	0.4	orthophosphoric	0.4	—	—
		SNOWTEX-OXS					acid
25	Colloidal silica	Nissan Chemical Industries, Ltd.	6 to 8	0.2	Mg 2+	0.4	orthophosphoric	0.4	—	—
		SNOWTEX-OXS					acid
26	Colloidal silica	Nissan Chemical Industries, Ltd.	12 to 14	0.2	Mg 2+	0.4	orthophosphoric	0.4	—	—
		SNOWTEX-O					acid
27	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.5	Mg 2−	0.05	orthophosphoric	0.1	—	—
		SNOWTEX-OS					acid
28	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.05	Mg 2+	0.5	orthophosphoric	0.6	—	—
		SNOWTEX-OS					acid
29	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.2	Mg 2+	0.3	orthophosphoric	0.03	—	—
		SNOWTEX-OS					acid
30	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.1	Mg 2+	0.1	orthophosphoric	1.0	—	—
		SNOWTEX-OS					acid
31	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.04	Mg 2−	0.3	orthophosphoric	0.32	—	—
		SNOWTEX-OS					acid
*1: Converted to P 2 O 5

 

TABLE 147
				Adaptability to the
	Molar ratio	Molar ratio	Composition	condition of the
No.	(ab)/(aa)	(ac)/(ab)	pH	invention* 2
24	2.00	1.0	2.9	◯
25	2.00	1.0	2.9	◯
26	2.00	1.0	2.9	◯
27	0.10	2.0	2.5	◯
28	10.00	1.2	1.8	◯
29	1.50	0.1	3.0	◯
30	1.00	10.0	1.5	◯
31	7.50	1.1	2.6	◯
* 2 ◯: Satisfies the conditions of the invention
X: Dissatisfies the conditions of the invention

 

TABLE 148
[Composition of primary layer coating]
		Alkali
	Oxide fine particles (aa)	earth metal (ab)	Phosphoric acid,	Organic resin
	Particle	Concen-		Concen-	phosphoric acid compound (ac)		Concen-
			size	tration		tration		Concentration		tration
No.	Type	Trade name	(nm)	(M/L)	Type	(M/L)	Type	(M/L) *1	Type	(g/l)
32	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.01	Mg 2+	0.5	orthophosphoric	0.51	—	—
		SNOWTEX-OS					acid
33	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.5	Mg 2+	0.01	orthophosphoric	0.3	—	—
		SNOWTEX-OS					acid
34	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	1.0	Mg 2−	0.01	orthophosphoric	0.5	—	—
		SNOWTEX-OS					acid
35	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.02	Mg 2−	2.0	orthophosphoric	0.5	—	—
		SNOWTEX-OS					acid
36	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.01	Mg 2+	2.0	orthophosphoric	0.5	—	—
		SNOWTEX-OS					acid
37	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	2.0	Mg 2+	0.01	orthophosphoric	0.5	—	—
		SNOWTEX-OS					acid
38	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	2.0	Mg 2+	0.01	orthophosphoric	2.5	—	—
		SNOWTEX-OS					acid
39	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.02	Mg 2−	2.5	orthophosphoric	0.01	—	—
		SNOWTEX-OS					acid
*1: Converted to P 2 O 5

 

TABLE 149
				Adaptability to the
	Molar ratio	Molar ratio	Composition	condition of the
No.	(ab)/(aa)	(ac)/(ab)	pH	invention* 2
32	50	1.0	2.0	◯
33	0.02	30.0	2.5	◯
34	0.01	50.0	2.2	◯
35	100	0.3	2.0	◯
36	200	0.3	1.9	◯
37	0.005	50.0	2.1	◯
38	0.005	250.0	1.6	◯
39	125	0.004	2.5	◯
* 2 ◯: Satisfies the conditions of the invention
X: Dissatisfies the conditions of the invention

 

TABLE 150
[Composition of primary layer coating]
		Alkali
	Oxide fine particles (aa)	earth metal (ab)	Phosphoric acid,	Organic resin
	Particle	Concen-		Concen-	phosphoric acid compound (ac)		Concen-
			size	tration		tration		Concentration		tration
No.	Type	Trade name	(nm)	(M/L)	Type	(M/L)	Type	(M/L) *1	Type	(g/l)
40	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.001	Mg 2−	2.0	orthophosphoric	0.5	—	—
		SNOWTEX-OS					acid
41	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.002	Mg 2+	3.0	orthophosphoric	0.5	—	—
		SNOWTEX-OS					acid
42	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	2.5	Mg 2+	0.02	orthophosphoric	0.5	—	—
		SNOWTEX-OS					acid
43	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	3.0	Mg 2+	0.05	orthophosphoric	0.3	—	—
		SNOWTEX-OS					acid
44	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.5	Mg 2−	0.001	orthophosphoric	0.6	—	—
		SNOWTEX-OS					acid
45	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.2	Mg 2+	0.6	orthophosphoric	0.001	—	—
		SNOWTEX-OS					acid
46	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.5	Mg 2+	2.0	orthophosphoric	4.0	—	—
		SNOWTEX-OS					acid
47	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.001	Mg 2−	3.0	orthophosphoric	6.0	—	—
		SNOWTEX-OS					acid
*1: Converted to P 2 O 5

 

TABLE 151
				Adaptability to the
	Molar ratio	Molar ratio	Composition	condition of the
No.	(ab)/(aa)	(ac)/(ab)	pH	invention* 2
40	2000	0.3	1.9	◯
41	1500	0.2	1.9	◯
42	0.008	25.0	2.0	◯
43	0.017	6.0	2.2	◯
44	0.002	600.0	1.9	◯
45	3	0.002	3.2	◯
46	4	2.0	0.51	◯
47	3000	2.0	0.5	◯
* 2 ◯: Satisfies the conditions of the invention
X: Dissatisfies the conditions of the invention

 

TABLE 152
[Composition of primary layer coating]
		Alkali	Phosphoric acid, phosphoric
	Oxide fine particles (aa)	earth metal (ab)	acid compound (ac)	Organic resin
	Particle	Concen-		Concen-		Concen-		Concen-
			size	tration		tration		tration		tration
No.	Type	Trade name	(nm)	(M/L)	Type	(M/L)	Type	(M/L) *1	Type	(g/l)
48	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.01	Mg 2+	0.02	orthophosphoric	0.02	—	—
		SNOWTEX-OS					acid
49	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.05	Mg 2+	0.1	orthophosphoric	0.1	—	—
		SNOWTEX-OS					acid
50	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	2.0	Mg 2+	3.0	orthophosphoric	4.2	—	—
		SNOWTEX-OS					acid
51	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.3	Mg 2+	0.001	orthophosphoric	0.2	Acrylic-styrene	180
		SNOWTEX-OS					acid		base water-
									dispersible
									resin
52	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.3	Mg 2−	0.4	orthophosphoric	0.42	Acrylic-styrene	180
		SNOWTEX-OS					acid		base water-
									dispersible
									resin
53	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.3	Mg 2+	0.02	orthophosphoric	0.2	Acrylic-styrene	180
		SNOWTEX-OS					acid		base water-
									dispersible
									resin
*1: Converted to P 2 O 5

 

TABLE 153
				Adaptability to the
	Molar ratio	Molar ratio	Composition	condition of the
No.	(ab)/(aa)	(ac)/(ab)	pH	invention* 2
48	2	1.0	4.0	◯
49	2	1.0	3.3	◯
50	1.5	1.4	0.8	◯
51	0.003	200	2.5	◯
52	1.3	1.1	2.2	◯
53	0.1	10	2.5	◯
* 2 ◯: Satisfies the conditions of the invention
X: Dissatisfies the conditions of the invention

 

TABLE 154
[Composition of primary layer coating]
		Alkali
	Oxide fine particles (aa)	earth metal (ab)	Phosphoric acid,	Organic resin
	Particle	Concen-		Concen-	phosphoric acid compound (ac)		Concen-
			size	tration		tration		Concentration		tration
No.	Type	Trade name	(nm)	(M/L)	Type	(M/L)	Type	(M/L) *1	Type	(g/l)
54	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	3.2	Mg 2+	0.1	orthophosphoric	0.3	—	—
		SNOWTEX-OS					acid
55	—	—	—	—	Mg 2+	0.5	orthophosphoric	2.0	—	—
							acid
56	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.2	Mg 2−	4.0	orthophosphoric	0.5	—	—
		SNOWTEX-OS					acid
57	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	3.0	Mg 2+	—	orthophosphoric	0.5	—	—
		SNOWTEX-OS					acid
58	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.02	Mg 2+	3.0	orthophosphoric	6.5	—	—
		SNOWTEX-OS					acid
59	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.5	Mg 2+	0.2	orthophosphoric	—	—	—
		SNOWTEX-OS					acid
60	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.001	Mg 2−	0.02	orthophosphoric	0.001	—	—
		SNOWTEX-OS					acid
61	Colloidal silica	Nissan Chemical Industries, Ltd.	8 to 10	0.5	Mg 2+	3.0	orthophosphoric	6.0	—	—
		SNOWTEX-OS					acid
*1: Converted to P 2 O 5

 

TABLE 155
				Adaptability to the
	Molar ratio	Molar ratio	Composition	condition of the
No.	(ab)/(aa)	(ac)/(ab)	pH	invention* 2
54	0.03	3.0	3.5	X
55	—	4.0	1.5	X
56	20	0.1	2.0	X
57	—	—	2.2	X
58	150	2.2	0.4	X
59	0.4	—	2.2	X
60	20	0.05	5.2	X
61	6	2.0	0.4	X
* 2 ◯: Satisfies the conditions of the invention
X: Dissatisfies the conditions of the invention

 

TABLE 156
		Type
No.	Group	(main component/curing agent)	Base resin
1	Thermosettting	Epoxy resin/ureea resin	Epicoat E-1009 (*1)/BECKAMINE P196M (*2) = 85/15
	resin
2	Thermosetting	Diethanol-modified epoxy resin/	ER-007 (*3)/Duranate NF-K60X (*4) = 90/10
	resin	block-urethane resin
3	Thermosetting	High molecular weight oil-free	BECKOLITE M-6206 (*5)/CYMEL 352 (*6) = 85/15
	resin	alkyd resin/melamine resin
4	Thermosetting	High molecular weight oil-free	BYRON GK-19CS (*7)/CYMEL 325 (*6) = 85/15
	resin	alkyd resin/melamine resin
5	Water-type	Ethylene ionomer resin	Mitsui Petrochemical Industries, Ltd. CHEMIPEARL S-650 (solid 27%)
	resin
6	Water-type	Polyurethane dispersion	Dai-ichi Kogyo Seiyaku Co., Ltd.
	resin		SUPERFLEX 150 (solid 30%)
7	Water-type	Epoxy dispersion	EPOMIC WR-942 (solid 27%) produced by Mitsui Chemical Industry
	resin		Co.
8	Water-type	Vinylidene chloride latex	Kurcha Chemical Industry Co.
	resin		KUREHALON LATEX AO (solid 48%)

 

TABLE 157
[Fine particle silica]
No.	Type	Trade name
1	Dry silica	AEROSIL R811 produced by Japan Aerosil Co., Ltd.

 

TABLE 158
[Solid lubricant]
No.	Type	Trade name
1	Polyethylene wax	LUVAX 1151 produced by Nippon Seiro Co.

 

	TABLE 159
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of
	Plating	Coating	Drying	Coating	coating	particles	component	component	coating components
	steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6
1	1	1	140	0.3	366	34	25	307	1.82	2.1
2	1	1	140	0.3	366	34	25	307	1.82	2.1
3	1	1	140	0.3	366	34	25	307	1.82	2.1
4	1	1	140	0.3	366	34	25	307	1.82	2.1
5	1	1	140	0.3	366	34	25	307	1.82	2.1
6	1	1	140	0.3	366	34	25	307	1.82	2.1
7	1	1	140	0.3	366	34	25	307	1.82	2.1
8	1	1	140	0.3	366	34	25	307	1.82	2.1
	Secondary layer coating
	Fine particles
	silica (b)
		Resin		Blending	Drying	Coating
		composition	Type	rate	temperature	thickness
	No.	*3	*8	*9	(° C.)	(μm)	Classification
	1	1	1	10	230	1	Example
	2	2	1	10	230	1	Example
	3	3	1	10	230	1	Example
	4	4	1	10	230	1	Example
	5	5	9	10	140	1	Example
	6	6	9	10	140	1	Example
	7	7	9	10	140	1	Example
	8	8	9	10	140	1	Example

 

	TABLE 160
	Performance
			White-rust resistance
		White-rust resistance:	after alkaline degreasing:	Paint
No.	Appearance	SST 72 hrs	SST 72 hrs	adhesiveness	Classification
1	◯	⊚	⊚	⊚	Example
2	◯	⊚	⊚	⊚	Example
3	◯	◯ +	◯	⊚	Example
4	◯	◯ +	◯	⊚	Example
5	◯	◯	◯ −	⊚	Example
6	◯	◯	◯ −	⊚	Example
7	◯	◯	◯ −	⊚	Example
8	◯	◯	◯ −	⊚	Example

 

	TABLE 161
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of
	Plating	Coating	Drying	Coating	coating	particles	component	component	coating components
	steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6
43	1	1	140	0.3	366	34	25	307	1.82	2.1
44	1	1	140	0.3	366	34	25	307	1.82	2.1
45	1	1	140	0.3	366	34	25	307	1.82	2.1
46	1	1	140	0.3	366	34	25	307	1.82	2.1
47	1	1	140	0.3	366	34	25	307	1.82	2.1
48	1	1	140	0.3	366	34	25	307	1.82	2.1
49	1	1	140	0.3	366	34	25	307	1.82	2.1
50	1	1	140	0.3	366	34	25	307	1.82	2.1
51	1	1	140	0.3	366	34	25	307	1.82	2.1
52	1	1	140	0.3	366	34	25	307	1.82	2.1
	Secondary layer coating
	Fine particles
	silica (b)
		Resin		Blending	Drying	Coating
		composition	Type	rate	temperature	thickness
	No.	*3	*8	*9	(° C.)	(μm)	Classification
	43	1	1	10	230	0.01	Comparative
							example
	44	1	1	10	230	0.1	Example
	45	1	1	10	230	0.5	Example
	46	1	1	10	230	0.5	Example
	47	1	1	10	230	2	Example
	48	1	1	10	230	2.5	Example
	49	1	1	10	230	3	Example
	50	1	1	10	230	4	Example
	51	1	1	10	230	5	Example
	52	1	1	10	230	20	Comparative
							example

 

	TABLE 162
	Performance
			White-rust resistance
		White-rust resistance:	after alkaline degreasing:
No.	Appearance	SST 72 hrs	SST 72 hrs	adhesiveness	Classification
43	◯	×	×	⊚	Comparative
					example
44	◯	◯−	◯−	⊚	Example
45	◯	◯	◯−	⊚	Example
46	◯	◯+	◯+	⊚	Example
47	◯	⊚	⊚	⊚	Example
48	◯	⊚	⊚	⊚	Example
49	◯	⊚	⊚	⊚	Example
50	◯	⊚	⊚	⊚	Example
51	◯	⊚	⊚	⊚	Example
52	◯	⊚	⊚	⊚	Comparative
					example&Asteriskpseud;1
&Asteriskpseud;1: Unable to weld

 

	TABLE 163
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	Plating	Coating	Drying	Coating	coating	particles	component	component	components
	steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	Classification
63	1	1	140	0.3	366	34	25	307	1.82	2.1	Example

 

	TABLE 164
	Secondary layer coating
	Fine particles silica (b)	Solid lubricant (c)	Drying	Coating
	Resin composition	Type	Blending rate	Type	Blending rate	temperature	thickness
No.	*3	*8	*9	*12	*13	(° C.)	(μm)	Classification
63	1	1	10	1	5	230	1	Example

 

	TABLE 165
	Performance
			White-rust resistance
		White-rust resistance:	after alkaline degreasing:	Paint
No.	Appearance	SST 72 hrs	SST 72 hrs	adhesiveness	Workability	Classification
63	◯	⊚	⊚	⊚	⊚	Example

 

	TABLE 166
	Primary layer coating
	Coating weight *4
	Plating				Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	steel	Coating	Drying	Coating	coating	particles	component	component	components
	plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg	Class-
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	ification
91	1	1	140	0.3	366	34	25	307	1.82	2.1	Example

 

	TABLE 167
	Secondary layer coating
		Ion-exchanged			(a)/(b)
	Resin	silica (a)	Fine particles silica (b)	(a) + (b)	Weight	Solid lubricant (c)	Drying	Coating
	composition	Blending rate	Type	Blending rate	Blending rate	ratio	Type	Blending rate	temperature	thickness	Classi-
No.	*3	*7	*8	*9	*10	*11	*12	*13	(° C.)	(μm)	fication
91	1	30	—	—	—	—	—	—	230	1	Example

 

	TABLE 168
	Performance
			White-rust resistance
		White-rust resistance:	after alkaline degreasing:	Paint
No.	Appearance	SST 72 hrs	SST 72 hrs	adhesiveness	Workability	Classification
91	◯	⊚	⊚	⊚	—	Example

 

	TABLE 169
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	Plating	Coating	Drying	Coating	coating	particles	component	component	components
	steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	Classiciation
141	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
142	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
143	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
144	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
145	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
146	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
147	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
148	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
149	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
150	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
151	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
152	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
153	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
154	1	1	140	0.3	366	34	25	307	1.82	2.1	Example

 

	TABLE 170
	Secondary layer coating
		Ion-exchanged			(a)/(b)
	Resin	silica (a)	Fine particles silica (b)	(a) + (b)	Weight	Solid lubricant (c)	Drying	Coating
	composition	Blending rate	Type	Blending rate	Blending rate	ratio	Type	Blending rate	temperature	thickness	Classi-
No.	*3	*7	*8	*9	*10	*11	*12	*13	(° C.)	(μm)	fication
141	1	30	1	5	35	6/1	—	—	230	1.5	Example
142	1	30	1	5	35	6/1	—	—	230	1.5	Example
143	1	30	1	5	35	6/1	—	—	230	1.5	Example
144	1	30	1	5	35	6/1	—	—	230	1.5	Example
145	1	30	1	5	35	6/1	—	—	230	1.5	Example
146	1	30	1	5	35	6/1	—	—	230	1.5	Example
147	1	30	1	5	35	6/1	—	—	230	1.5	Example
148	1	30	1	5	35	6/1	—	—	230	1.5	Example
149	1	30	—	—	30	30/0	—	—	230	1.5	Example
150	1	29.9	1	0.1	30	299/1	—	—	230	1.5	Example
151	1	29	1	1	30	29/1	—	—	230	1.5	Example
152	1	20	1	10	30	2/1	—	—	230	1.5	Example
153	1	15	1	15	30	1/1	—	—	230	1.5	Example
154	1	10	1	20	30	1/2	—	—	230	1.5	Example

 

	TABLE 171
	Performance
			White-rust resistance
		White-rust resistance:	after alkaline degreasing:	Paint
No.	Appearance	SST 120 hrs	SST 120 hrs	adhesiveness	Workability	Classification
141	◯	⊚	⊚	⊚	—	Example
142	◯	⊚	⊚	⊚	—	Example
143	◯	◯ +	◯	⊚	—	Example
144	◯	◯ +	◯	⊚	—	Example
145	◯	◯	◯ −	⊚	—	Example
146	◯	◯	◯ −	⊚	—	Example
147	◯	◯	◯ −	⊚	—	Example
148	◯	◯	◯ −	⊚	—	Example
149	◯	◯	◯	⊚	—	Example
150	◯	◯	◯	⊚	—	Example
151	◯	◯ +	◯ +	⊚	—	Example
152	◯	⊚	⊚	⊚	—	Example
153	◯	⊚	⊚	⊚	—	Example
154	◯	◯	◯	⊚	—	Example

 

	TABLE 172
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	Plating	Coating	Drying	Coating	coating	particles	component	component	components
	steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	Classiciation
155	1	1	140	0.3	366	34	25	307	1.82	2.1	Example
156	1	1	140	0.3	366	34	25	307	1.82	2.1	Example

 

	TABLE 173
	Secondary layer coating
		Ion-exchanged			(a)/(b)
	Resin	silica (a)	Fine particles silica (b)	(a) + (b)	Weight	Solid lubricant (c)	Drying	Coating
	composition	Blending rate	Type	Blending rate	Blending rate	ratio	Type	Blending rate	temperature	thickness	Classi-
No.	*3	*7	*8	*9	*10	*11	*12	*13	(° C.)	(μm)	fication
155	1	1	1	29	30	1/29	—	—	230	1	Example
156	1	0.1	1	29.9	30	1/299	—	—	230	1	Example

 

	TABLE 174
	Performance
			White-rust
			resistance after
		White-rust	alkaline
		resistance:	degreasing:	Paint
No.	Appearance	SST 120 hrs	SST 120 hrs	adhesiveness	Workability	Classification
155	◯	◯	◯	⊚	—	Example
156	◯	◯ −	◯ −	⊚	—	Example

 

	TABLE 175
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	Plating	Coating	Drying	Coating	coating	particles	component	component	components
	steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	Classiciation
181	1	1	140	0.3	366	34	25	307	1.82	2.1	Example

 

	TABLE 176
	Secondary layer coating
		Ion-exchanged			(a)/(b)
	Resin	silica (a)	Fine particles silica (b)	(a) + (b)	Weight	Solid lubricant (c)	Drying	Coating
	composition	Blending rate	Type	Blending rate	Blending rate	ratio	Type	Blending rate	temperature	thickness	Classi-
No.	*3	*7	*8	*9	*10	*11	*12	*13	(° C.)	(μm)	fication
181	1	30	—	—	—	—	1	10	230	1	Example

 

	TABLE 177
	Performance
			White-rust resistance
		White-rust resistance:	after alkaline degreasing:	Paint
No.	Appearance	SST 96 hrs	SST 96 hrs	adhesiveness	Workability	Classification
181	◯	⊚	⊚	⊚	⊚	Example

 

	TABLE 178
	Primary layer coating
	Coating weight *4
	Plating				Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	steel	Coating	Drying	Coating	coating	particles	component	component	components
	plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6	ification
203	1	1	140	0.001	1	0.14	0.1	1	1.82	2.1	Comparative
											example
204	1	1	140	0.005	5.9	0.54	0.4	5	1.82	2.1	Example
205	1	1	140	0.01	15	1.4	1	12	1.82	2.1	Example
206	1	1	140	0.1	146	14	10	123	1.82	2.1	Example
207	1	1	140	0.5	585	54	40	491	1.82	2.1	Example
208	1	1	140	1	1170	109	80	982	1.82	2.1	Example
209	1	1	140	2	2341	217	160	1963	1.82	2.1	Example
210	1	1	140	3	3511	326	240	2945	1.82	2.1	Example
211	1	1	140	5	5851	543	400	4909	1.82	2.1	Comparative
											example

 

	TABLE 179
	Secondary layer coating
		Ion-exchanged			(a)/(b)
	Resin	silica (a)	Fine particles silica (b)	(a) + (b)	Weight	Solid lubricant (c)	Drying	Coating
	composition	Blending rate	Type	Blending rate	Blending rate	ratio	Type	Blending rate	temperature	thickness	Classi-
No.	*3	*7	*8	*9	*10	*11	*12	*13	(° C.)	(μm)	fication
203	1	30	—	—	—	—	—	—	230	1	Example
											example
204	1	30	—	—	—	—	—	—	230	1	Example
205	1	30	—	—	—	—	—	—	230	1	Example
206	1	30	—	—	—	—	—	—	230	1	Example
207	1	30	—	—	—	—	—	—	230	1	Example
208	1	30	—	—	—	—	—	—	230	1	Example
209	1	30	—	—	—	—	—	—	230	1	Example
210	1	30	—	—	—	—	—	—	230	1	Example
211	1	30	—	—	—	—	—	—	230	1	Compara-
											tive
											example

 

	TABLE 180
	Performance
			White-rust resistance
		White-rust resistance:	after alkaline degreasing:	Paint
No.	Appearance	SST 96 hrs	SST 96 hrs	adhesiveness	Workability	Classification
203	◯	×	×	⊚	—	Comparative
						example
204	◯	◯ −	◯ −	⊚	—	Example
205	◯	◯	◯	⊚	—	Example
206	◯	◯+	◯ +	⊚	—	Example
207	◯	⊚	⊚	⊚	—	Example
208	◯	⊚	⊚	⊚	—	Example
209	◯	⊚	⊚	⊚	—	Example
210	◯	⊚	⊚	⊚	—	Example
211	◯	⊚	⊚	⊚	—	Comparative
						example&Asteriskpseud;1
&Asteriskpseud;1: Unable to weld

 

	TABLE 181
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	Plating	Coating	Drying	Coating	coating	particles	component	component	components
	steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6
220	1	2	140	0.3	400	66	25	310	0.94	2.12
221	1	3	140	0.3	303	49	20	234	1	2
222	1	4	140	0.3	320	53	20	248	0.94	2.12
223	1	5	140	0.3	293	27	20	245	1.82	2.1
224	1	6	140	0.3	317	(Al 2 O 3 )	25	292	1.5	2
225	1	7	140	0.3	317	(ZrO 2 )	25	292	1.5	2
226	1	8	140	0.3	403	150	20	234	0.33	2
227	1	9	140	0.3	320	95	(ca)	225	—	—
228	1	10	140	0.3	320	90	(Sr)	230	—	—
229	1	11	140	0.3	329	89	(Ba)	240	2	8
230	1	12	140	0.3	320	—	40	280	—	1.2
231	1	13	140	0.3	300	50	—	250	—	—
232	1	14	140	0.3	416	346	70	0	0.5	—
233	1	15	140	0.3	500	—	—	0	—	—
	Secondary layer coating
		Resin	Drying	Coating
		composition	temperature	thickness
	No.	*3	(° C.)	(μm)	Classification
	220	1	230	1	Example
	221	1	230	1	Example
	222	1	230	1	Example
	223	1	230	1	Example
	224	1	230	1	Example
	225	1	230	1	Example
	226	1	230	1	Example
	227	1	230	1	Example
	228	1	230	1	Example
	229	1	230	1	Example
	230	1	230	1	Comparative
					example
	231	1	230	1	Comparative
					example
	232	1	230	1	Comparative
					example
	233	1	230	1	Comparative
					example

 

	TABLE 182
	Performance
			White-rust resistance
			White-rust resistance
		White-rust resistance:	after alkaline degreasing:	Paint
No.	Appearance	SST 48 hrs	SST 48 hrs	adhesiveness	Classification
220	◯	⊚	⊚	⊚	Example
221	∘	⊚	⊚	⊚	Example
222	∘	⊚	⊚	⊚	Example
223	∘	⊚	⊚	⊚	Example
224	◯	◯	◯	⊚	Example
225	◯	◯	◯	⊚	Example
226	◯	⊚	⊚	⊚	Example
227	◯	◯ +	◯ +	⊚	Example
228	◯	◯	◯	⊚	Example
229	◯	◯	◯	⊚	Example
230	◯	Δ	Δ	⊚	Example
231	◯	Δ	Δ	⊚	Comparative
					example
232	◯	Δ	Δ	⊚	Comparative
					example
233	◯	×	Δ	⊚	Comparative
					example

 

	TABLE 183
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	Plating	Coating	Drying	Coating	coating	particles	component	component	components
	steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6
234	1	16	140	0.3	324	43.2	35	245.4	2	1.2
235	1	17	140	0.3	324	43.2	35	245.4	2	1.2
236	1	18	140	0.3	335	88.9	36	210.4	1	1
237	1	19	140	0.3	292	38.0	20	233.7	1.3	2
238	1	20	140	0.3	332	72.0	35	225.0	1.2	1.1
239	1	21	140	0.3	330	22.2	45	263.0	5	1
240	1	22	140	0.3	371	148.1	30	192.8	0.5	1.1
241	1	23	140	0.3	349	114.0	60	175.3	1.3	0.5
242	1	24	140	0.3	323	49.4	40	233.7	2.0	1.0
243	1	25	140	0.3	323	49.4	40	233.7	2.0	1.0
244	1	26	140	0.3	323	49.4	40	233.7	2.0	1.0
245	1	27	140	0.3	374	246.9	10	116.9	0.1	2.0
	Secondary layer coating
		Resin	Drying	Coating
		composition	temperature	thickness
	No.	*3	(° C.)	(μm)	Classification
	234	1	230	1	Example
	235	1	230	1	Example
	236	1	230	1	Example
	237	1	230	1	Example
	238	1	230	1	Example
	239	1	230	1	Example
	240	1	230	1	Example
	241	1	230	1	Example
	242	1	230	1	Example
	243	1	230	1	Example
	244	1	230	1	Example
	245	1	230	1	Example

 

	TABLE 184
	Performance
			White-rust resistance
		White-rust resistance:	after alkaline degreasing:	Paint
No.	Appearance	SST 48 hrs	SST 48 hrs	adhesiveness	Classification
234	◯	⊚	⊚	⊚	Example
235	◯	⊚	⊚	⊚	Example
236	◯	⊚	⊚	⊚	Example
237	◯	⊚	⊚	⊚	Example
238	◯	⊚	⊚	⊚	Example
239	◯	⊚	⊚	⊚	Example
240	◯	⊚	⊚	⊚	Example
241	◯	⊚	⊚	⊚	Example
242	◯	⊚	⊚	⊚	Example
243	◯	⊚	⊚	⊚	Example
244	◯	⊚	◯ +	⊚	Example
245	◯	⊚	◯ +	⊚	Example

 

	TABLE 185
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	Plating	Coating	Drying	Coating	coating	particles	component	component	components
	steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6
246	1	28	140	0.3	330	9.9	40	280.5	10.0	1.2
247	1	29	140	0.3	323	164.6	100	58.4	1.5	0.1
248	1	30	140	0.3	310	12.3	5	292.2	1.0	10.0
249	1	31	140	0.3	310	13.2	40	257.1	7.5	1.1
250	1	32	140	0.3	310	2.2	45	263.0	50.0	1.0
251	1	33	140	0.3	300	123.5	1	175.3	0.02	30
252	1	34	140	0.3	324	148.1	0.6	175.3	0.01	50
253	1	35	140	0.3	389	3.5	140	245.4	100	0.3
254	1	36	140	0.3	401	1.8	145	254.2	100	0.3
255	1	37	140	0.3	394	246.9	0.5	146.1	0.005	50
256	1	38	140	0.3	293	74.1	0.15	219.1	0.005	250
257	1	39	140	0.3	365	6.9	350	8.2	125	0.004
	Secondary layer coating
		Resin	Drying	Coating
		composition	temperature	thickness
	No.	*3	(° C.)	(μm)	Classification
	246	1	230	1	Example
	247	1	230	1	Example
	248	1	230	1	Example
	249	1	230	1	Example
	250	1	230	1	Example
	251	1	230	1	Example
	252	1	230	1	Example
	253	1	230	1	Example
	254	1	230	1	Example
	255	1	230	1	Example
	256	1	230	1	Example
	257	1	230	1	Example

 

	TABLE 186
	Performance
			White-rust resistance
		White-rust resistance:	after alkaline degreasing:	Paint
No.	Appearance	SST 48 hrs	SST 48 hrs	adhesiveness	Classification
246	◯	⊚	◯ +	⊚	Example
247	◯	⊚	◯ +	⊚	Example
248	◯	⊚	◯ +	⊚	Example
249	◯	⊚	◯ +	⊚	Example
250	◯	⊚	◯	⊚	Example
251	◯	⊚	◯	⊚	Example
252	◯	⊚	◯	⊚	Example
253	◯	⊚	◯	⊚	Example
254	◯	⊚	◯ −	⊚	Example
255	◯	⊚	◯ −	⊚	Example
256	◯	◯ +	◯ +	⊚	Example
257	◯	◯ +	◯ +	⊚	Example

 

	TABLE 187
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	Plating	Coating	Drying	Coating	coating	particles	component	component	components
	steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6
258	1	40	140	0.3	394	0.2	160	233.7	2000	0.25
259	1	41	140	0.3	391	0.3	180	210.4	1500	0.2
260	1	42	140	0.3	365	246.9	0.8	116.9	0.008	25
261	1	43	140	0.3	399	319.5	2.2	77.1	0.017	6
262	1	44	140	0.3	379	98.8	0.08	280.5	0.002	600
263	1	45	140	0.3	404	181.1	220	2.6	3	0.002
264	1	46	140	0.3	399	18.5	30	350.6	4	2
265	1	47	140	0.3	321	0.03	40	280.5	3000	1.2
266	1	48	140	0.3	323	49.4	40	233.7	2	1
267	1	49	140	0.3	323	49.4	40	233.7	2	1
268	1	50	140	0.3	379	57.6	35	286.3	1.5	1.4
	Secondary layer coating
		Resin	Drying	Coating
		composition	temperature	thickness
	No.	*3	(° C.)	(μm)	Classification
	258	1	230	1	Example
	259	1	230	1	Example
	260	1	230	1	Example
	261	1	230	1	Example
	262	1	230	1	Example
	263	1	230	1	Example
	264	1	230	1	Example
	265	1	230	1	Example
	266	1	230	1	Example
	267	1	230	1	Example
	268	1	230	1	Example

 

	TABLE 188
	Performance
			White-rust resistance
		White-rust resistance:	after alkaline degreasing:	Paint
No.	Appearance	SST 48 hrs	SST 48 hrs	adhesiveness	Classification
258	◯	◯ +	◯ +	⊚	Example
259	◯	◯ +	◯ +	⊚	Example
260	◯	◯ +	◯ +	⊚	Example
261	◯	◯ +	◯ +	⊚	Example
262	◯	◯ +	◯ +	⊚	Example
263	◯	◯ +	◯ +	⊚	Example
264	◯	◯ +	◯ +	⊚	Example
265	◯	◯ +	◯ +	⊚	Example
266	◯	⊚	◯ +	⊚	Example
267	◯	⊚	◯ +	⊚	Example
268	◯	⊚	⊚	⊚	Example

 

	TABLE 189
	Primary layer coating
	Coating weight *4
					Total	SiO 2 fine	Mg	P 2 O 5	Molar ratio of coating
	Plating	Coating	Drying	Coating	coating	particles	component	component	components
	steel plate	composition	temperature	thickness	weight	(α)	(β)	(γ)	Mg/SiO 2	P 2 O 5 /Mg
No.	*1	*2	(° C.)	(μm)	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	(mg/m 2 )	*5	*6
269	1	51	140	0.3	399	164.6	0.2	233.7	0.003	200
270	1	52	140	0.3	326	66.5	35	225.0	1.3	1.1
271	1	53	140	0.3	337	98.8	4	233.7	0.1	10
272	1	54	140	0.3	393	318.6	4	70.1	0.031	3
273	1	55	140	0.3	366	0.0	15	350.6	—	4
274	1	56	140	0.3	359	25.9	210	122.7	20	0.1
275	1	57	140	0.3	400	280.0	0	120.0	—	—
276	1	58	140	0.3	347	0.40	25	321.4	150	2.2
277	1	59	140	0.3	359	308.6	50	0.0	0.4	—
278	1	60	140	0.3	297	25.9	210	61.4	20	0.05
279	1	61	140	0.3	327	10.3	25	292.2	6	2
	Secondary layer coating
		Resin	Drying	Coating
		composition	temperature	thickness
	No.	*3	(° C.)	(μm)	Classification
	269	1	230	1	Example
	270	1	230	1	Example
	271	1	230	1	Example
	272	1	230	1	Example
	273	1	230	1	Example
	274	1	230	1	Example
	275	1	230	1	Example
	276	1	230	1	Example
	277	1	230	1	Example
	278	1	230	1	Example
	279	1	230	1	Example

 

	TABLE 190
	Performance
			White-rust resistance
		White-rust resistance:	after alkaline degreasing:	Paint
No.	Appearance	SST 48 hrs	SST 48 hrs	adhesiveness	Classification
269	◯	⊚	⊚	⊚	Example
270	◯	⊚	⊚	⊚	Example
271	◯	⊚	⊚	⊚	Example
272	◯	◯	Δ	Δ	Comparative
					example
273	◯	×	×	⊚	Comparative
					example
274	×	Δ	◯	⊚	Comparative
					example
275	◯	Δ	×	⊚	Comparative
					example
276	×	Δ	Δ	⊚	Comparative
					example
277	◯	Δ	Δ	⊚	Comparative
					example
278	◯	×	Δ	⊚	Comparative
					example
279	◯	◯	◯	×	Comparative
					example

 

Best Mode 7

According to a finding of the inventors of the present invention, an organic coating steel sheet inducing no pollution problem and providing excellent corrosion resistance is obtained without applying chromate treatment which may give bad influence to environment and human body, through the steps of: forming a specific composite oxide coating as the primary layer coating on the surface of a zinc base plating steel sheet or an aluminum base plating steel sheet; then, on the primary layer coating, further forming an organic resin as the secondary layer coating comprising a specific organic polymer resin as the base resin.

The organic coating steel sheet according to the present invention is basically characterized in that a composite oxide coating is formed on a zinc base plating steel sheet or an aluminum base steel sheet as the primary layer coating comprising (α) fine particles of oxide and (β) phosphoric acid and/or phosphoric acid compound, and at need, further comprising one or more of metal selected from the group consisting of Li, Mn, Fe, Co, Ni, Zn, Al, La, and Ce, and that, further on the primary layer coating, an organic coating as the secondary layer coating with a base resin of an organic polymer resin (A) containing OH group and/or COOH group, (preferably a thermosetting resin, more preferably an epoxy resin and/or a modified epoxy resin).

According to the present invention, there provided a dual-layer coating structure in which the primary layer is the lower layer, and the secondary layer is the upper layer of the coating. Owing to the synergy effect of the dual-layer structure, even a thin coating provides corrosion resistance equivalent to that of chromate coating. Although the mechanism of corrosion resistance in the dual layer coating structure consisting of a specific composite oxide coating and a specific organic coating is not fully analyzed, the corrosion-preventive effect of the dual layer coating structure presumably comes from the combination of corrosion-suppression actions of individual coatings, which is described below.

The corrosion preventive mechanism of the composite oxide coating as the primary layer coating is not fully understood. The excellent corrosion-preventive performance, supposedly, owes to that the dense and slightly soluble composite oxide coating acts as a barrier coating to shut-off corrosion causes, that the fine particles of oxide such as silicon oxide form a stable and dense barrier coating along with phosphoric acid and/or phosphoric acid compound, and that, when the fine particles of oxide are those of silicon oxide, the silicic acid ion emitted from the silicon oxide forms basic zinc chloride under a corrosive environment to improve the barrier performance. Also it is assumed that phosphoric acid and/or phosphoric acid compound contributes to the improvement of denseness of the composite oxide coating, further that the phosphoric acid component catches the zinc ion which is eluted during an anodic reaction as a corrosion reaction in the coating-defect section, then the phosphoric acid component is converted to a slightly soluble zinc phosphate compound to form a precipitate at that place.

When the composite oxide further contains one or more of elements selected from the group consisting of Li, Mn, Fe, Co, Ni, Zn, Al, La, and Ce, the corrosion resistance further improves. Although the reason that these elements further improves the corrosion resistance, presumably the effect comes from that any of these substances likely form a slightly soluble salt with phosphate in alkaline region, and generates OH ion resulted from cathodic reaction of oxygen in a corrosion reaction, which then seals the corrosion sites when the environment becomes alkaline state, thus providing high barrier effect.

Among these elements, Mn and Ni gave particularly excellent corrosion resistance. The reason of providing excellent corrosion resistance of Mn and Ni is not fully understood, the presumable cause is that these phosphates are difficult to be dissolved under alkaline environments.

Although the corrosion-preventive mechanism of the organic coating as the above-described secondary layer is not fully analyzed, the mechanism is speculated as follows.

The corrosion-preventive mechanism of the organic coating as the above-described secondary layer coating is also not fully analyzed. The mechanism is, however, presumably the following. An organic polymer resin (A) having OH group or COOH group, (preferably a thermosetting resin, more preferably an epoxy resin and/or a modified epoxy resin) reacts with a cross-linking agent to form a dense barrier coating. The barrier coating has excellent penetration-suppression performance against corrosion causes such as oxygen, and provides strong bonding force to the base material owing to the OH group and COOH group in the molecule. As a result, particular superior corrosion resistance would be obtained.

As described above, the corrosion-preventive effects of the primary layer, and the corrosion-preventive effects of the secondary layer totally function in combining and synergetic effects, thus the excellent corrosion resistance has been attained without using chromium even with a thin coating film.

The following is the detail description of the present invention and the reasons of specified conditions thereof.

Examples of the zinc base plating steel sheet as the base of the organic coating steel sheet according to the present invention are, galvanized steel sheet, Zn—Ni alloy plating steel sheet, Zn—Fe alloy plating steel sheet (electroplating steel sheet and alloyed hot dip galvanized steel sheet), Zn—Cr alloy plating steel sheet, Zn—Mn alloy plating steel sheet, Zn—Co alloy plating steel sheet, Zn—Co—Cr alloy plating steel sheet, Zn—Cr—Ni alloy plating steel sheet, Zn—Cr—Fe alloy plating steel sheet, Zn—Al alloy plating steel sheet (for example, Zn—5%Al alloy plating steel sheet and Zn—55%Al alloy plating steel sheet), Zn—Mg alloy plating steel sheet, Zn—Al—Mg plating steel sheet, zinc base composite plating steel sheet (for example, Zn—SiO 2 dispersion plating steel sheet) which is prepared by dispersing a metallic oxide, a polymer, or the like in the plating film of these plating steel sheets.

Among the platings described above, the same kind or different kinds of them may be plated into two or more layers to form a multi-layered plating steel sheet.

The aluminum base plating steel sheet which is a base of the organic coating steel sheet of the present invention may be an aluminum plating steel sheet, an Al—Si alloy plating steel sheet, or the like.

The plating steel sheet may be prepared from a steel sheet by applying plating of Ni or the like thereon at a small coating weight in advance, followed by the above-described various kinds of platings.

The plating method may be either applicable one of electrolytic method (electrolysis in an aqueous solution or in a non-aqueous solvent) and vapor phase method.

To prevent occurrence of coating defects and nonuniformity during the step for forming the dual layer coating on the surface of the plating film, there may be applied at need, alkaline degreasing, solvent degreasing, surface-adjustment treatment (alkaline surface-adjustment treatment or acidic surface-adjustment treatment) and the like to the surface of plating film in advance. To prevent blackening (a kind of oxidization on the plating surface) of organic coating steel sheet under the use conditions, the surface of plating film may be subjected to, at need, surface-adjustment treatment using acidic or alkaline aqueous solution containing iron group metal ion(s) (Ni ion, Co ion, Fe ion) in advance. When an electrolytically galvanized steel sheet is used as the base steel sheet, the electroplating bath may contain 1 ppm or more of iron group metal ion(s) (Ni ion, Co ion, Fe ion), thus letting these metals in the plating film perform to prevent blackening. In that case, there is no specific limitation on the upper limit of iron group metal concentration in the plating film.

The following is the description of the composite oxide coating as the primary layer coating which is formed on the surface of zinc base plating steel sheet or aluminum base plating steel sheet.

Quite different from conventional alkali silicate treatment coating which is represented by the coating composition consisting of lithium oxide and silicon oxide, the composite oxide coating according to the present invention comprises (α) fine particles of oxide (preferably SiO 2 fine particles) and (β) phosphoric acid and/or phosphoric acid compound, and at need, further comprises (γ) at least one element selected from the group consisting of Li, Mn, Fe, Co, Ni, Zn, Al, La, and Ce.

Particularly preferable oxide fine particles as the above-described component (α) are those of silicon oxide (fine particles of SiO 2 ), and most preferable one among the silicon oxides is colloidal silica.

Among these silica oxides (SiO 2 fine particles), the ones having particle sizes of 14 nm or less, more preferably 8 nm or less are preferred from the viewpoint of corrosion resistance.

The silicon oxide may be used by dispersing dry silica fine particles in a coating composition solution. Examples of the dry silica are AEROSIL 200, AEROSIL 3000, AEROSIL 300CF, AEROSIL 380, (these are trade names) manufactured by Japan Aerosil Co., Ltd., and particularly the ones having particle sizes of 12 nm or less, more preferably 7 nm or less are preferred.

Other than above-described silicon oxides, the oxide fine particles may be colloidal liquid and fine particles of aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, and antimony oxide.

The phosphoric acid and/or phosphoric acid compound as the above-described component (β) may be blended by adding orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, methaphosphoric acid, or metallic salt or compound of them to the coating composition. The target composition may include organic phosphoric acid and salt thereof (for example, phytic acid, phytiate, phosphonic acid, phosphonate, their metal salt). Among them, primary phosphonic acid is preferable from the point of stability of the coating composition. When primary ammonium phosphate, secondary ammonium phosphate, or ternary ammonium phosphate was added as the phosphate to the coating composition solution, the corrosion resistance was improved. Although the reason is not fully analyzed, the presumable reason is that, when those kinds of ammonium salts are used, the liquid does not gel even at high pH region of the coating composition solution. Since generally metallic salts become insoluble in alkaline region, when the metallic salts are formed from a composition solution of high pH, compounds of further difficult to dissolve are generated during the drying step.

There is no specific limitation on the form of existing phosphoric acid and phosphoric acid compound in the coating, and they may be crystals or non-crystals. Also there is no specific limitation on the ionicity and solubility of phosphoric acid and phosphoric acid compound in the coating.

The form of the above-described component (γ) existing in the coating is not specifically limited, and it may be metal, or compound or composite compound such as oxide, hydroxide, hydrated oxide, phosphoric acid compound, or composite compound or metal. The ionicity and solubility of these compound, hydroxide, hydrated oxide, phosphoric acid compound, coordination compound, or the like are not specifically limited.

There is no specific limitation on introducing the component (γ) into the coating, and the component (γ) may be added to the coating composition in a form of phosphate, sulfate, nitrate, and chloride of Li, Mn, Fe, Co, Ni, Zn, Al, La, and Ce. A preferable range of coating weight of the composite oxide is, when the oxide fine particles (α) and the above-described composition (β) as P 2 O 5 , and further the component (γ) exist, from 5 to 4,000 mg/m 2 as the sum of (α), (β), and (γ) as metal, more preferably from 50 to 1,000 mg/m 2 , further preferably from 100 to 500 mg/m2, and most preferably from 200 to 400 mg/m 2 . If the coating weight is less than 5 mg/m 2 , the corrosion resistance degrades. If the coating weight exceeds 4,000 mg/m 2 , the conductive performance degrades and the weldability degrades. To attain particularly superior corrosion resistance, it is preferred to select the ratio of silicon oxide as the component (α), converted to SiO 2 , to the total composite oxide coating to a range of from 5 to 95 wt. %, more preferably from 10 to 60 wt. %.

The reason of giving particularly superior corrosion resistance when the ratio of the silicon oxide is selected to the range given above is not fully analyzed. It is, however, speculated that the phosphoric acid component supports the barrier effect which cannot be attained solely by silicon oxide, thus contributing to forming a dense film, further that the synergy effect of corrosion-suppression actions of each of phosphoric acid component and silicon oxide component, resulting in obtaining the excellent corrosion resistance.

From the similar viewpoint, it is preferred to select the ratio of the phosphoric acid and/or phosphoric acid compound as the component (β) to the metallic component as the component (γ) (if there are two or more metals, the sum of each of them converted to respective metals) in the composite oxide coating to a range of from 1/2 to 2/1 as the molar ratio of the component (β) as P 2 O 5 to the component (γ) as metal, or [P 2 O 5 /Me] for attaining further excellent corrosion resistance.

The reason of giving particularly superior corrosion resistance when the ratio of phosphoric acid component to metallic component is selected to the range given above is not fully analyzed. It is, however, speculated that, since the solubility of phosphoric component varies with the ratio of phosphoric acid to metal, the corrosion resistance becomes particularly high when the coating non-soluble property stays within the range given above, so that the barrier performance of the coating increases.

For further improving the workability and the corrosion resistance of the coating, the composite oxide coating may further contain organic resins. Examples of the organic resin are epoxy resin, polyurethane resin, polyacrylic resin, acrylic-ethylene copolymer resin, acrylic-styrene copolymer resin, alkyd resin, polyester resin, polyethylene resin. These resins may be introduced into the coating in a form of water-soluble resin or water-dispersible resin.

Adding to these water-dispersible resins, it is effective to use water-soluble epoxy resin, water-soluble phenol resin, water-soluble polybutadiene rubber (SBR, NBR, MBR), melamine resin, block-polyisocyanate compound, oxazolane compound, and the like as the cross-linking agent.

For further improving the corrosion resistance, the composite oxide coating may further contain polyphosphate, phosphate (for example, zinc phosphate, aluminum dihydrogen phosphate, and zinc phosphate), molybdate, phospho molybdate (for example, aluminum phosphomolybdate), organic phosphate and its salt (for example, phytic acid, phytiate, phosphonic acid, phosphonate, their metal salt and alkali metal salt), organic inhibitor (for example, hydrazine derivative, thiol compound, dithiocarbamate), organic compound (polyethyleneglycol), and the like.

Other applicable additives include organic coloring pigments (for example, condensing polycyclic organic pigments, phthalocyanine base organic pigments), coloring dyes (for example, azo dye soluble in organic solvent, azo metal dye soluble in water), inorganic pigments (titanium oxide), chelating agents (for example, thiol), conductive pigments (for example, metallic powder of zinc, aluminum, nickel, or the like, iron phosphide, antimony-dope type tin oxide), coupling agents (for example, silane coupling agent and titanium coupling agent), melamine-cyanuric acid additives.

The following is the description about the organic coating formed as the secondary layer coating on the above-described oxide coating.

As the base resin of the organic coating, organic polymer resins (A) having OH group and/or COOH group are used. As of these resins, thermosetting resins are preferred, and epoxy resins or modified epoxy resins are particularly preferred.

Examples of the organic polymer resin containing OH group and/or COOH group are epoxy resin, polyhydroxypolyether resin, acrylic copolymer resin, ethylene-acrylic acid copolymer resin, alkyd resin, polybutadiene resin, phenol resin, polyurethane resin, polyamine resin, polyphenylene resin, and mixture or addition polymerization product of two or more of these resins.

(1) Epoxy Resin

Examples of epoxy resin are: epoxy resins which are prepared by glycidyl-etherifying bisphenol A, bisphenol F, novorak and the like; epoxy resins which are prepared by adding propyleneoxide, ethyleneoxide, or polyalkyleneglycol to bisphenol A, followed by glycidyl-etherifying; aliphatic epoxy resins, alicyclic epoxy resins, and polyether base epoxy resins.

As for these epoxy resins, particularly when they are necessary to be cured in low temperatures, preferably the number-average molecular weight of them is 1,500 or more. These epoxy resins may be used separately or mixing two or more of them.

The modified epoxy resins include the ones in which various types of modifiers are reacted with epoxy group or hydroxyl group in the above-given epoxy resins. Examples of these modified epoxy resins are an epoxy-ester resin prepared by reacting carboxylic group in the drying oil fatty acid, an epoxy-acrylate resin prepared by modifying thereof using acrylic acid, methacrylic acid, or the like; a urethane-modified epoxy resin prepared by reacting with an isocyanate compound; and an amine-added-urethane-modified epoxy resin prepared by reacting an epoxy resin with an isocyanate compound to form a urethane-modified epoxy resin, followed by adding an alkanol amine to the urethane-modified epoxy resin.

The above-described hydroxypolyether resins are polymers prepared by polycondensation of a divalent phenol of a mononuclear or dinuclear divalent phenol or a mixture of mononuclear and dinuclear divalent phenols with a nearly equal moles of epihalohydrin under the presence of an alkali catalyst. Typical examples of the mononuclear divalent phenol are resorcin, hydroquinone, and catechol. Typical example of the dinuclear divalent phenol is bisphenol A. These divalent phenols may be used separately or two or more of them simultaneously.

(2) Polyurethane Resin

Examples of polyurethane resin are oil-modified polyurethane resin, alkyd base polyurethane resin, polyester base polyurethane resin, polyether base polyurethane resin, and polycarbonate base polyurethane resin.

(3) Alkyd Resin

Examples of alkyd resin are oil-modified alkyd resin, resin-modified alkyd resin, phenol-modified alkyd resin, styrenated alkyd resin, silicon-modified alkyd resin, acrylic-modified alkyd resin, oil-free alkyd resin, and high molecular weight oil-free alkyd resin.

(4) Polyacrylic Resin

Examples of polyacrylic resin are polyacrylic acid and its copolymer, polyacrylic ester and its copolymer, polymethacrylic acid ester and its copolymer, polymethacrylic acid ester and its copolymer, urethane-acrylic acid copolymer (or urethane-modified polyacrylic resin), styrene-acrylic acid copolymer. Further these resins may be modified by other alkyd resin, epoxy resin, phenol resin, and the like.

(5) Polyethylene Resin (Polyolefin Resin)

Examples of polyethylene resin are: ethylene base copolymers such as ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, carboxylic-modified polyolefin resin; ethylene-unsaturated carboxylic acid copolymers, and ethylene base ionomers. Further these resins may be modified by other alkyd resin, epoxy resin, and phenol resin.

(6) Acrylic Silicon Resin

Examples of acrylic silicon resin are the one which contains an acrylic base copolymer as a main component having hydrolyzable alcoxysilyl group at side chain or terminal of the acrylic base copolymer, further contains a curing agent. When that kind of acrylic silicon resin is used, superior weather-resistance is obtained.

(7) Fluororesin

Example of fluororesin is a fluoro-olefin base copolymer including a copolymer of a fluorine monomer (fluoro-olefin) with a monomer such as alkylvinylether, Syncro-alkylvinylether, carboxylic acid modified vinylester, hydroxy-alkylallylether, tetrafluoropropylvinylether. When that kind of fluororesin is used, superior weather-resistance and hydrophobic property.

Aiming at reduction of resin drying temperature, there may be applied a resin having difference in resin kinds between the core and the shell of the resin particle, or a core-shell type water-dispersible resin comprising resins having different glass transition temperatures to each other.

By using a water-dispersible resin having self-cross-linking property, and by adding, for example, alkoxysilane group to the resin particles to generate silanol group by hydrolysis of alkoxysilane during the heating and drying process of the resin, and to utilize cross-linking between particles using the dehydration condensation reaction of the silanol group between the resin particles.

As a resin to use for the organic coating, an organic composite silicate which is prepared by compositing an organic resin with a silane coupling agent is preferable.

According to the present invention, aiming at the improvement of corrosion resistance and workability of the organic coating, particularly the thermosetting resins are preferred. In this case, there may be added curing agent such as amino resins including urea resin (butylated urea resin, and the like), melamine resin (butylated melamine resin), butylated urea-melamine resin, and benzoguanamine resin, block isocyanate, oxazoline compound, and phenol resin.

Among these organic resins, epoxy resin and polyethylene base resin are preferable from the viewpoint of corrosion resistance, workability, and paintability, and, particularly preferred ones are thermosetting epoxy resin and modified epoxy resin which have excellent shut-off performance against corrosive causes such as oxygen. Examples of these thermosetting resins are thermosetting epoxy resin, thermosetting modified epoxy resin, acrylic base copolymer resin copolymerized with an epoxy-group-laden monomer, epoxy-group-laden polybutadiene resin, epoxy-group-laden polyurethane resin, and their adducts or condensates. These epoxy-group-laden resins may be used separately or mixing two or more of them.

According to the present invention, the organic coating further includes an inorganic rust-preventive pigment (a).

Examples of the inorganic rust-preventive pigment are: silica compound such as ion-exchanged silica and fine particle silica; celium oxide; aluminum oxide; zirconium oxide; antimonium oxide; polyphosphoric acid (for example, aluminum polyphosphate, TAICA K-WHITE 80, 84, 105, G105, 90, 90, (produced by TAYCA CORPORATION); molybdenate; phospho-molybdenate (such as aluminum-phosphomolybdenate). Particularly improved corrosion resistance is obtained when the system includes at least one of silica compound such as ion-exchanged silica (c), fine particle silica (d), phosphate such as zinc phosphate (e) and aluminum phosphate (f), and calcium compound.

The adding amount of inorganic rust-preventive pigment is in a range of from 1 to 100 parts by weight (solid matter) as the total inorganic rust-preventive pigment to 100 parts by weight of the reaction product as the resin composition for forming coating (the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen), preferably from 5 to 80 parts by weight (solid matter).

The ion-exchanged silica is prepared by fixing metallic ion such as calcium and magnesium ions on the surface of porous silica gel powder. Under a corrosive environment, the metallic ion is released to form a deposit film. Among these ion-exchanged silicas, Ca ion-exchanged silica is most preferable.

The corrosion-preventive mechanism obtained by blending ion-exchanged silica (a) in the organic coating is presumably the following. That is, when cation such as Na ion enters under the corrosion environment, the iron exchange action emits Ca ion and Mg ion from the surface of silica. Furthermore, when OH ion is generated by the cathode reaction under the corrosive environment to increase pH value near the plating interface, the Ca ion (or Mg ion) emitted from the ion-exchanged silica precipitates in the vicinity of the plating interface in a form of Ca(OH) 2 or Mg(OH) 2 , respectively. The precipitate seals defects as a dense and slightly soluble product to suppress the corrosion reactions. Furthermore, the eluted Zn ion exchanges Ca ion (or Mg ion) to be fixed onto the surface of silica.

Any type of Ca-exchanged silica may be used, and a preferred one has an average particle size not more than 6 μm, more preferably not more than 4 μm. For example, Ca-exchanged silica having average particle sizes of from 2 to 4 μm may be used. If the average particle size of the Ca-exchanged silica exceeds 6 μm, the corrosion resistance degrades, and the dispersion stability in a paint composition degrades.

A preferred range of the Ca concentration in the Ca-exchanged silica is 1 wt. % or more, more preferably from 2 to 8 wt. %. Ca content of less than 1 wt. % fails to obtain satisfactory rust-preventive effect under the Ca emission.

There is no specific limitation on the surface area, pH, and oil absorbing capacity of Ca-exchanged silica.

The corrosion-preventive mechanism in the case that ion-exchanged silica (c) is added to the organic coating is described before. In particular, according to the present invention, when an ion-exchanged silica is blended with an organic coating consisting of a specific chelate-modified resin, the corrosion-preventive effect at anode reaction section owing to the chelate-modified resin and the corrosion-preventive effect at cathode reaction section owing to the ion-exchanged silica are combined to suppress both the anode and the cathode corrosion reactions, which should provide markedly strong corrosion-preventive effect.

The adding amount of ion-exchanged silica (c) in the organic resin coating is in a range of from 1 to 100 parts by weight (solid matter) to 100 parts by weight of the reaction product as the resin composition for forming coating (the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen), preferably from 5 to 80 parts by weight (solid matter), more preferably from 10 to 50 parts by weight (solid matter). When the amount of ion-exchanged silica (c) is less than 1 part by weight, the effect to improve the corrosion resistance after alkaline degreasing becomes small. If the amount of ion-exchanged silica (c) exceeds 100 parts by weight, the corrosion resistance degrades, which is unfavorable.

The fine particle silica (d) may be either colloidal silica or fumed silica.

Particularly an organic solvent dispersible silica sol has superior dispersibility, and shows superior corrosion resistance to fumed silica.

Fine particle silica is supposed to contribute to forming dense and stable zinc corrosion products under a corrosive environment. Thus formed corrosion products cover the plating surface in a dense mode, thus presumably suppressing the development of corrosion.

From the viewpoint of corrosion resistance, the fine particle silica preferably has particle sizes of from 5 to 50 nm, more preferably from 5 to 20 nm, and most preferably from 5 to 15 nm.

The adding amount of fine particle silica (d) in the organic resin coating is in a range of from 1 to 100 parts by weight (solid matter) to 100 parts by weight of the reaction product as the resin composition for forming coating (the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part or whole of which compound (B) consists of a hydrazine derivative (C) containing active hydrogen), preferably from 5 to 80 parts by weight (solid matter), more preferably from 10 to 30 parts by weight (solid matter). When the amount of fine particle silica (d) is less than 1 part by weight, the effect to improve the corrosion resistance after alkaline degreasing becomes small. If the amount of fine particle silica (d) exceeds 100 parts by weight, the corrosion resistance degrades, which is unfavorable.

According to the present invention, combined addition of ion-exchanged silica (c) and fine particle silica (d) to the organic coating provides particularly excellent corrosion resistance. That is, the combined addition of ion-exchanged silica (c) and fine particle silica (d) induces combined rust-preventive mechanism of both components as described before to give particularly excellent corrosion-preventive effect.

A preferred range of ratio of combined blend of ion-exchanged silica (c) and fine particle silica (d) in the organic resin coating is 1 to 100 parts by weight (solid matter) of the sum of the ion-exchanged silica (c) and the fine particle silica (d) to 100 parts by weight (solid matter) of the base resin, more preferably from 5 to 80 parts by weight (solid matter), and a preferred range of blending ratio of the ion-exchanged silica (c) to the fine particle silica (d), (solid matter), or (c)/(d), is from 99/1 to 1/99, more preferably from 95/5 to 40/60, and most preferably from 90/10 to 16/40.

If the blending ratio of the sum of the ion-exchanged silica (c) and the fine particle silica (d) becomes less than 1 part by weight, the effect of improved corrosion resistance after alkaline degreasing becomes small. If the blending ratio of the sum of the ion-exchanged silica (c) and the fine particle silica (d) exceeds 100 parts by weight, the paintability and the workability degrade, which is unfavorable.

If the weight ratio of the ion-exchanged silica (c) to the fine particle silica (d), (c)/(d), is less than 1/99, the corrosion resistance degrades. If the weight ratio of the ion-exchanged silica (c) to the fine particle silica (d), (c)/(d), exceeds 99/1, the effect of combined addition of the ion-exchanged silica (c) and the fine particle silica (d) cannot fully be attained.

There is no specific limitation on the skeleton and degree of condensation of phosphoric acid ions for the zinc phosphate (e) and the aluminum phosphate (f) blended in the organic coating. They may be normal salt, dihydrogen salt, monohydrogen salt, or phosphate. The normal salt includes orthophosphoric acid and all the condensed phosphates such as polyphosphate. For example, zinc phosphate may be LF-BOSEI ZP-DL produced by Kikuchi Color Co., and aluminum phosphate may be K-WHITE produced by TAYCA CORPORATION.

These zinc phosphates and aluminum phosphates dissociate to phosphoric acid ion by hydrolysis under a corrosive environment, and form a protective coating through the complex-forming reaction with the eluted metals.

A preferred range of blending amount of zinc phosphate and/or aluminum phosphate (e, f) in the organic resin coating is from 1 to 100 parts by weight to 100 parts by weight (solid matter) of the film-forming organic resin (A), more preferably from 5 to 80 parts by weight (solid matter), and most preferably from 10 to 50 parts by weight. If the blending amount of the zinc phosphate and/or aluminum phosphate (e, f) is less than 1 part by weight, the improved effect of corrosion resistance after alkaline degreasing becomes small. If the blending amount of the zinc phosphate and/or aluminum phosphate (e, f) exceeds 100 parts by weight, the corrosion resistance degrades, which is unfavorable.

According to the present invention, combined addition of zinc phosphate and/or aluminum phosphate (e, f) and calcium compound (g) to the organic coating provides particularly excellent corrosion resistance. That is, the combined addition of zinc phosphate and/or aluminum phosphate (e, f) and calcium compound (g) to the organic coating provides particularly excellent corrosion resistance which induces combined rust-preventive mechanism of both components as described before to give particularly excellent corrosion-preventive effect.

Calcium compound (g) may be either one of calcium oxide, calcium hydroxide, and calcium salt, and at least one of them is adopted. There is no specific limitation on the kind of calcium salt, and the salt may be a single salt containing only calcium as cation, for example, calcium silicate, calcium carbonate, and calcium phosphate, and may be complex salt containing cation other than calcium cation, for example, zinc calcium phosphate, magnesium calcium phosphate.

Since calcium compounds elute preferentially to metals under a corrosive environment, it presumably induces a complex-forming reaction with phosphoric acid ion without triggering the elution of plating metal, thus forming a dense and slightly-soluble protective coating to suppress the corrosion reactions.

A preferred blending ratio of combined addition of zinc phosphate and/or aluminum phosphate (e, f) and calcium compound (g) to the organic resin coating is from 1 to 100 parts by weight (solid matter) to 100 parts by weight (solid matter) of the film-forming organic resin (A), more preferably from 5 to 80 parts by weight (solid matter), and a preferred blending weight ratio (solid matter) of the zinc phosphate and/or aluminum phosphate (e, f) and the calcium compound (g), (e, f)/(g), is from 99/1 to 1/99, more preferably from 95/5 to 40/60, and most preferably from 90/10 to 60/40.

If the blending amount of the sum of zinc phosphate and/or aluminum phosphate (e, f) and calcium compound (g) is less than 1 part by weight, the improved effect of corrosion resistance after alkaline degreasing becomes small. If the blending amount of the sum of zinc phosphate and/or aluminum phosphate (e, f) and calcium compound (g) exceeds 100 parts by weight, the corrosion resistance degrades, which is unfavorable. If the blending ratio (solid matter) of zinc phosphate and/or aluminum phosphate (e, f) to calcium compound (g), or (e, f)/(g), is less than 1/99, the corrosion resistance is inferior. If the blending ratio (solid matter) of zinc phosphate and/or aluminum phosphate (e, f) to calcium compound (g), or (g, f)/(g), exceeds 99/1, the effect of combined addition of zinc phosphate and/or aluminum phosphate (e, f) and calcium compound (g) cannot be fully attained.

The organic coating may further contain, adding to the above-described inorganic rust-preventive pigments, corrosion-suppression agents such as organic inhibitors including organic phosphate and its salt (for example, phytic acid, phytiate, phosphonic acid, phosphonate, their metal salt, alkali metal salt, and alkali earth metal salt), hydrazine derivative, thiol compound, dithiocarbamate.

The organic coating may, at need, further include a solid lubricant (b) to improve the workability of the coating.

Examples of applicable solid lubricant according to the present invention are the following.

(1) Polyolefin wax, paraffin wax: for example, polyethylene wax, synthetic paraffin, natural paraffin, microwax, chlorinated hydrocarbon;

(2) Fluororesin fine particles: for example, polyfluoroethylene resin (such as poly-tetrafluoroethylene resin), polyvinylfluoride resin, polyvinylidenefluoride resin.

In addition, there may be applied fatty acid amide base compound (such as stearic acid amide, palmitic acid amide, methylene bis-stearoamide, ethylene bis-stearoamide, oleic acid amide, ethyl acid amide, alkylene bis-fatty acid amide), metallic soap (such as calcium stearate, lead stearate, calcium laurate, calcium palmate), metallic sulfide (molybdenum disulfide, tungsten disulfide), graphite, graphite fluoride, boron nitride, polyalkyleneglycol, and alkali metal sulfate.

Among those solid lubricants, particularly preferred ones are polyethylene wax, fluororesin fine particles (particularly poly-tetrafluoroethylene resin fine particles).

Applicable polyethylene wax include: Sheridust 9615A, Sheridust 3715, Sheridust 3620, Sheridust 3910 (trade names) manufactured by Hoechst Co., Ltd.; SUNWAX 131-P, SUNWAX 161-P (trade names) manufactured by Sanyo Chemical Industries, Ltd.; CHEMIPEARL W-100, CHEMIPEARL W-200, CHEMIPEARL W-500, CHEMIPEARL W-800, CHEMIPEARL W-950 (trade names) manufactured by Mitsui Petrochemical Industries, Ltd.

A most preferred fluororesin fine particle is tetrafluoroethylene fine particle. Examples of the fine particles are LUBRON L-2, LUBRON L-5 (trade names) manufactured by Daikin Industries, Ltd.; MP 1100, MP 1200 (trade names; manufactured by Du Pont-Mitsui Company, Ltd.); FLUON DISPERSION AD1, FLUON DISPERSION AD2, FLUON L141J, FLUON L150J, FLUON L155J (trade names) manufactured by Asahi ICI Fluoropolymers Co., Ltd.

As of these compounds, combined use of polyolefin wax and tetrafluoroethylene fine particles is expected to provide particularly excellent lubrication effect.

A preferred range of blending ratio of the solid lubricant (b) in the organic resin coating is from 1 to 80 parts by weight (solid matter) to 100 parts by weight (solid matter) of the reaction product as the resin composition for film-forming (that is, the product of reaction between the film-forming organic resin (A) and the active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen), more preferably from 3 to 40 parts by weight (solid matter). If the blending ratio of the solid lubricant (b) becomes less than 1 part by weight, the effect of lubrication is small. If the blending ratio of the solid lubricant (b) exceeds 80 parts by weight, the painting performance degrade, which is unfavorable.

The organic coating of the organic coating steel sheet according to the present invention normally consists mainly of a product (resin composition) of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B) a part of or whole of which consists of a hydrazine derivative (C) containing active hydrogen). And, at need, an inorganic rust-preventive pigment (a), a solid lubricant (b), a curing agent, or the like may further be added to the organic coating. Furthermore, at need, there may be added other additives such as organic coloring pigment (for example, condensing polycyclic organic pigment, phthalocyanine base organic pigment), coloring dye (for example, azo dye soluble in organic solvent, azo metal dye soluble in water), inorganic pigment (for example, titanium oxide), chelating agent (for example, thiol), conductive pigment (for example, metallic powder of zinc, aluminum, nickel, or the like, iron phosphide, antimony-dope type tin oxide), coupling agent (for example, silane coupling agent and titanium coupling agent), melamine-cyanuric acid additive.

The paint composition for film-formation containing above-described main component and additive components normally contains solvent (organic solvent and/or water), and, at need, further a neutralizer or the like is added.

The organic coatings described above are formed on the above-described composite oxide coating.

The dry thickness of the organic coating is in a range of from 0.1 to 5 μm, preferably from 0.3 to 3 μm, and most preferably from 0.5 to 2 μm. If the thickness of the organic coating is less than 0.1 μm, the corrosion resistance becomes insufficient. If the thickness of the organic coating exceeds 5 μm, the conductivity and the workability degrade.

The following is the description about the method for manufacturing an organic coating steel sheet according to the present invention.

The organic coating steel sheet according to the present invention is manufactured by the steps of: treating the surface (applying a treatment liquid to the surface) of a zinc base plating steel sheet or an aluminum base plating steel sheet using a treatment liquid containing the components of above-described composite oxide coating; heating and drying the plate; applying a paint composition which contains the above-described organic polymer resin (A) as the base resin, and at need, further contains an inorganic rust-preventive pigment (a), a solid lubricant (b) and the like; heating to dry the product.

The surface of the plating steel sheet may be, at need, subjected to alkaline degreasing before applying the above-described treatment liquid, and may further be subjected to preliminary treatment such as surface adjustment treatment for further improving the adhesiveness and corrosion resistance.

For treating the surface of the zinc base plating steel sheet or the aluminum base plating steel sheet with a treatment liquid and for forming a composite oxide coating thereon, it is preferred that the plate is treated by an aqueous solution containing:

(aa) oxide fine particles ranging from 0.001 to 3.0 mole/liter; and

(ab) phosphoric acid and/or phosphoric acid compound ranging from 0.001 to 6.0 mole/liter as P 2 O 5 ; followed by heating to dry.

The aqueous solution may further contain:

(ac) one or more of the substances selected from the group consisting of either one metallic ion of Li, Mn, Fe, Co, Ni, Zn, Al, La, and Ce; a compound containing at least one metal given above; a composite compound containing at least one metal given above; ranging from 0.001 to 3.0 mole/liter as metal given above.

As the oxide fine particles as an additive component (aa), silicon oxide (SiO 2 ) fine particles are most preferred. The silicon oxide may be commercially available silica sol and water-dispersion type silicic acid oligomer or the like if only the silicon oxide is water-dispersion type SiO 2 fine particles which are stable in an acidic aqueous solution. Since, however, fluoride such as hexafluoro silicic acid is strongly corrosive and gives strong effect to human body, that kind of compound should be avoided from the point of influence to work environment.

A preferred range of blending ratio of the fine particle oxide (the blending ratio as SiO 2 in the case of silicon oxide) in the treating liquid is from 0.001 to 3.0 mole/liter, more preferably from 0.05 to 1.0 mole/liter, and most preferably from 0.1 to 0.5 mole/liter. If the blending ratio of the fine particle oxide becomes less than 0.001 mole/liter, the effect of addition is not satisfactory. If the blending ratio of the fine particle oxide exceeds 3.0 mole/liter, the water-resistance of coating degrades, resulting in degradation of corrosion resistance.

The phosphoric acid and/or phosphoric acid compound as the additive component (ab) includes: a mode of aqueous solution in which a compound specific to phosphoric acid, such as polyphosphoric acid such as orthophosphoric acid, pyrophosphoric acid, and tripolyphosphoric acid, methaphosphoric acid, inorganic salt of these acids (for example, primary aluminum phosphate), phosphorous acid, phosphate, phosphinic acid, phosphinate, exists in a form of anion or complex ion combined with a metallic cation which are generated by dissolving the compound in the aqueous solution; and a mode of aqueous solution in which that kind of compound exists in a form of inorganic salt dispersed therein. The amount of phosphoric acid component according to the present invention is specified by the sum of all these modes of acidic aqueous solution thereof as converted to P 2 O 5 mount.

A preferred range of blending ratio of the phosphoric acid and/or phosphoric acid compound as P 2 O 5 is from 0.001 to 6.0 mole/liter, more preferably from 0.02 to 1.0 mole/liter, and most preferably from 0.1 to 0.8 mole/liter. If the blending ratio of the phosphoric acid and/or phosphoric acid compound becomes less than 0.001 mole/liter, the effect of addition is not satisfactory and the corrosion resistance degrades. If the blending ratio of the phosphoric acid and/or phosphoric acid compound exceeds 6.0 mole/liter, excess amount of phosphoric acid ion reacts with the plating film under a humid environment, which enhances the corrosion of plating base material to cause discoloration and stain-rusting under some corrosive environments.

As the component (ab), use of ammonium phosphate is also effective because the compound provides a highly anti-corrosive composite oxide. As for the ammonium phosphate, primary ammonium phosphate and secondary ammonium phosphate are preferred.

The added components (ac) in the treatment liquid is in a range of from 0.001 to 3.0 mole/liter as metal, preferably from 0.01 to 0.5 mole/liter. If the sum of the added amount of these components is less than 0.001 mole/liter, the effect of addition cannot be fully attained. If the sum of the added amount of these components exceeds 3.0 mole/liter, these components become soluble cations to interfere the network of coating.

For supplying ion of the additive components (ac) in a form of metallic salt, the treatment liquid may contain anion such as chlorine ion, nitric acid ion, sulfuric acid ion, acetic acid ion, and boric acid ion.

The treatment liquid may further contain an organic resin (ad) for improving workability and corrosion resistance of the composite oxide coating. Examples of the organic resin are water-soluble resins and/or water-dispersible resins such as epoxy resin, polyurethane resin, polyacrylic resin, acrylic-ethylene copolymer, acrylic-styrene copolymer, alkyd resin, polyester resin, polyethylene resin.

Adding to these water-dispersible resins, it is also possible to use water-soluble epoxy resin, water-soluble phenol resin, water-soluble polybutadiene rubber (SBR, NBR, MBR), melamine resin, block-polyisocyanate compound, oxazolane compound, and the like as the cross-linking agent.

Adding to the above-described additive components (aa) through (ad), the treatment liquid may further contain an adequate amount of additive components to the coating, which are described before.

The methods for applying the treatment liquid onto the plating steel sheet may be either one of coating method, dipping method, and spray method. The coating method may adopt any type such as roll coater (three-roll type, two-roll type, etc.), squeeze coater, die coater. After the coating step using squeeze coater and the like, the dipping step, or the spray step, it is possible to adjust the coating weight, the uniformizing appearance, and the uniformizing the film-thickness using air-knife method and roll-squeezing method.

Although there is no specific limitation on the temperature of the treatment liquid, a preferable range thereof is from normal temperature to around 60° C. Below the normal temperature is uneconomical because a cooling unit or other additional facilities are required. On the other hand, temperatures above 60° C. enhances the vaporization of water, which makes the control of the treatment liquid difficult.

After the coating of treatment liquid as described above, generally the plate is heated to dry without rinsing with water. The treatment liquid according to the present invention forms a slightly soluble salt by a reaction with the substrate plating steel sheet, so that rinsing with water may be applied after the treatment.

Method for heating to dry the coated treatment liquid is not limited. For example, dryer, hot air oven, high frequency induction heating furnace, infrared heating furnace may be applied.

The heating and drying treatment is preferably conducted at reaching temperatures of from 50 to 300° C., more preferably from 80 to 200° C., and most preferably from 80 to 160° C. If the heating temperature is less than 50° C., excess amount of water is left in the coating, which results in insufficient corrosion resistance. If the heating temperature exceeds 300° C., the operation becomes uneconomical and defects likely appear in the coating to degrade the corrosion resistance.

After forming the composite oxide coating on the surface of the zinc base plating steel sheet or the aluminum base plating steel sheet, as described above, a paint composition for forming an organic coating is applied on the composite oxide coating. Method for applying the paint composition is not limited, and examples of the method are coating method, dipping method, and spray method. The coating method may adopt any type such as roll coater (three-roll type, two-roll type, etc.), squeeze coater, die coater. After the coating step using squeeze coater and the like, the dipping step, or the spray step, it is possible to adjust the coating weight, the uniformizing appearance, and the uniformizing the film-thickness using air-knife method and roll-squeezing method.

After applying the paint composition, generally the plate is heated to dry without rinsing with water. After applying the paint composition, however, water-rinse step may be given.

Method for heating to dry the paint composition is not limited. For example, dryer, hot air oven, high frequency induction heating furnace, infrared heating furnace may be applied. The heating treatment is preferably conducted at reaching temperatures of from 50 to 350° C., more preferably from 80 to 250° C. If the heating temperature is less than 50° C., excess amount of water is left in the coating, which results in insufficient corrosion resistance. If the heating temperature exceeds 350° C., the operation becomes uneconomical and defects likely appear in the coating to degrade the corrosion resistance.

As described above, the present invention includes a steel sheet having an organic coating on both sides or on side thereof. Accordingly, modes of the steel sheet according to the present invention include, for example, the followings.

(1) “Plating film—Composite oxide coating—Organic coating” on one side of the steel sheet, and “Plating film” on other side of the steel sheet;

(2) “Plating film—Composite oxide coating—Organic coating” on one side of the steel sheet, and “Plating film—Known coating treated by phosphoric acid, or the like” on other side of the steel sheet;

(3) “Plating film—Composite oxide coating—Organic coating” on both sides of the steel sheet;

(4) “Plating film—Composite oxide coating—Organic coating” on one side of the steel sheet, and “Plating film—Composite oxide coating” on other side of the steel sheet;

(5) “Plating film—Composite oxide coating—Organic coating” on one side of the steel sheet, and “Plating film—Organic coating” on other side of the steel sheet.

Embodiments

Treatment liquids (coating compositions) for forming the primary layer coating, which are listed in Tables 192 and 194, and resin compositions for forming the secondary layer coating, which are listed in Table 195, were prepared.

To the resin compositions shown in Table 195, inorganic rust-preventive pigments shown in Tables 196 through 198, and solid lubricants shown in Table 199 were added at respective adequate amount, which additives were dispersed in the resin compositions for a necessary time using a paint dispersion apparatus (a sand grinder) to prepare respective desired paint compositions.

To obtain organic coating steel sheets for household electric appliances, building materials, and automobile parts, the plating steel sheets shown in Table 1 were used as the target base plates, which plates were prepared by applying zinc base plating or aluminum base plating on the cold-rolled steel sheets having a plate thickness of 0.8 mm and a surface roughness Ra of 1.0 μm. The surface of the plating steel sheet was treated by alkaline degreasing and water washing, then the treatment liquids (coating compositions) shown in Tables 192 through 194 were applied to the surface using a roll coater, followed by heating to dry to form the first layer coating. The thickness of the first layer coating was adjusted by the solid content in the treatment liquid (heating residue) or applying conditions (roll pressing force, rotational speed, and other variables). Then, the paint composition given in Table 195 was applied using a roll coater, which was then heated to dry to form the secondary layer coating, thus manufactured the organic coating steel sheets as Examples and Comparative Examples. The thickness of the second layer coating was adjusted by the solid content in the treatment liquid (heating residue) or applying conditions (roll pressing force, rotational speed, and other variables).

To each of thus obtained organic coating steel sheets, evaluation was given in terms of quality performance (appearance of coating, white-rust resistance, white-rust resistance after alkaline degreasing, paint adhesiveness, and workability). The results are given in Tables 200 through 205 along with the structure of primary layer coating and of secondary layer coating.

In the Tables 200 through 205, each of *1 through *11 appeared in the table expresses the following.

*1: Corresponding to No. given in Table 191.

*2: Corresponding to No. given in Tables 192 through 194.

*3: Weight ratio to the total weight of the primary layer (composite oxide).

*4: Ratio of the sum of moles of the component (γ) converted to metal concerned to moles of the phosphoric acid and/or phosphoric acid compound (β) converted to P 2 O 5 weight.

*5: Total coating weight=(α)+(β)+(γ)

*6: Corresponding to No. given in Table 195.

*7: Corresponding to No. given in Tables 196 through 198.

*8: Blending ratio (weight parts) of solid portion to 100 parts by weight of solid portion of resin composition.

*9: Weight amount of solid portion of inorganic rust-preventive pigment 1 to inorganic rust-preventive pigment 2.

*10: Weight ratio of solid portion of inorganic rust-preventive pigment 1 to inorganic rust-preventive pigment 2.

*11: Corresponding to No. given in Table 199.

*12: Blending ratio (weight parts) of solid portion of solid lubricant to 100 parts by weight of solid portion of resin composition.

TABLE 191
No.	Plating steel plate	Coating weight (g/m 2 )
1	Electrolytically galvanized steel plate	20

 

	TABLE 192
		Phosphoric acid/phosphoric acid
	Oxide fine particles (α)	compound (β)
				Concen-		Con-
			Particle	tration		Centration	Molar
			size	*1		*2	ratio
No.	Type	Thickness	(nm)	(mol/L)	Type	(mol/L)	(β)/(γ)
1	Silicic	SNOWTEX-OS produced	6 to 8	0.33	orthophosphoric	0.30	1.00
	acid	by Nissan Chemical			acid
		Industries, Ltd.
2	Silicic	SNOWTEX-OS produced	6 to 8	0.33	orthophosphoric	0.06	1.47
	acid	by Nissan Chemical			acid
		Industries, Ltd.
3	Silic	SNOWTEX-OS produced	6 to 8	0.40	orthophosphoric	0.13	1.30
	acid	by Nissan Chemical			acid
		Industries, Ltd.
4	Silicic	SNOWTEX-OS produced	6 to 8	0.30	orthophosphoric	0.22	1.21
	acid	by Nissan Chemical			acid
		Industries, Ltd.
5	Silicic	SNOWTEX-OS produced	6 to 8	0.33	orthophosphoric	0.15	1.21
	acid	by Nissan Chemical			acid
		Industries, Ltd.
6	Silicic	SNOWTEX-OS produced	6 to 8	0.33	orthophosphoric	0.22	1.10
	acid	by Nissan Chemical			acid
		Industries, Ltd.
7	Silicic	SNOWTEX-OS produced	6 to 8	0.33	orthophosphoric	0.15	1.50
	acid	by Nissan Chemical			acid
		Industries, Ltd.
8	Silicic	SNOWTEX-OS produced	6 to 8	0.33	orthophosphoric	0.09	1.80
	acid	by Nissan Chemical			acid
		Industries, Ltd.
9	Silicic	SNOWTEX-OS produced	6 to 8	0.33	orthophosphoric	0.09	1.80
	acid	by Nissan Chemical			acid
		Industries, Ltd.
10	Silicic	AEROSIL 200 produced by	12	0.50	orthophosphoric	0.15	1.47
	acid	Japan Aerosil Co., Ltd.			acid
11	Silicic	AEROSIL 201 produced by	12	0.50	orthophosphoric	0.10	1.20
	acid	Japan Aerosil Co., Ltd.			acid
				Adaptability
	Metal component (γ)	Organic resin		to the
	Component 1	Component 2		(δ)		conditions
		Concen-		Concen-			Concen-		of the
		tration		tration	Total		tration	Composition	invention
No.	Type	(mol/L)	Type	(mol/L)	moles	Type	(g/l)	pH	*3
1	Li	0.30			0.30			4.3	◯
2	Mn	0.04			0.04			2.6	◯
3	Fe	0.10			0.10			0.8	◯
4	Co	0.18			0.18			1.3	◯
5	Ni	0.12			0.12			3	◯
6	Zn	0.20			0.20			2.4	◯
7	Al	0.10			0.10			2.1	◯
8	La	0.05			0.05			1.5	◯
9	Ce	0.05			0.05			2	◯
10	Mn	0.10			0.10			2.6	◯
11	Ni	0.08			0.08			3	◯
*1 Converted to SiO 2
*2 Converted to P 2 O 5
*3  ◯ : Satisfies the conditions of the invention
×: Dissatisfies the conditions of the invention

 

	TABLE 193
		Phosphoric acid/phosphoric acid
	Oxide fine particles (α)	compound (β)
				Concen-		Con-
			Particle	tration		Centration	Molar
			size	*1		*2	ratio
No.	Type	Trade name	(nm)	(mol/L)	Type	(mol/L)	(β)/(γ)
12	Silicic	AEROSIL 200 produced by	12	0.33	orthophosphoric	0.10	1.21
	acid	Japan Aerosil Co., Ltd.			acid
13	Silicia	AEROSIL 200 produced by	12	0.33	orthophosphoric	0.12	1.50
	acid	Japan Aerosil Co., Ltd.			acid
14	Silicic	SNOWTEX-OUP produced	12 to 14	0.20	orthophosphoric	0.12	1.20
	acid	by Nissan Chemical			acid
		Industries, Ltd.
15	Silicic	SNOWTEX-OUP produced	12 to 14	0.20	orthophosphoric	0.12	1.20
	acid	by Nissan Chemical			acid
		Industries, Ltd.
16	Aluminum	Alumina sol 200 produced by			orthophosphoric	0.10	1.03
	acid	Nissan Chemical Industries,			acid
		Ltd.
17	Zirconium	NZS-30A produced by Nissan	60 to 70		orthophosphoric	0.15	1.47
	oxide	Chemical Industries, Ltd.			acid
18	Silicic	SNOWTEX-N produced by	12 to 14	0.33	Phosphoric acid	0.15
	acid	Nissan Chemical Industries,			ammonium
		Ltd.
19	Silicic	AEROSIL 200 produced by	12	0.33	orthophosphoric	0.12	1.20
	acid	Jpana Aerosil Co., Ltd.			acid
20	Silicic	AEROSIL 200 produced by	12	0.33	orthophosphoric	0.12	1.05
	acid	Japan Aerosil Co., Ltd.
21	Silicic	AEROSIL 200 produced by	6 to 8	0.33	orthophosphoric	0.25	2.50
	acid	Japan Aerosil Co., Ltd.			acid
	Metal component (γ)	Organic resin
	Component 1	Component 2		(δ)
		Con-		Con-			Con-		Adaptability to the
		tration		tration	Total		tration	Composition	conditions of the
No.	Type	(mol/L)	Type	(mol/L)	moles	Type	(g/l)	pH	invention *3
12	Co	0.08			0.08			2.8	◯
13	Al	0.08			0.08			2.9	◯
14	Ni	0.10			0.10			1.5	◯
15	Al	0.10			0.10			2	◯
16	Mn	0.10			0.10			3.1	◯
17	Mn	0.10			0.10			2.6	◯
18								8	◯
19	Ni	0.08	Mn	0.02	0.10			2.8	◯
20	Al	0.08	Mg	0.03	0.11			2.9	◯
21	Ni	0.10			0.10			2.1	◯
*1 Converted to SiO 2
*2 Converted to P 2 O 5
*3  ◯ : Satisfies the conditions of the invention
×: Dissatisfies the conditions of the invention
*Feather-shape particles (10 nm × 100 nm)

 

	TABLE 194
		Phosphoric acid/phosphoric acid
	Oxide fine particles (α)	compound (β)
				Concen-		Con-
			Particle	tration		Centration	Molar
			size	*1		*2	ratio
No.	Type	Trade name	(nm)	(mol/L)	Type	(mol/L)	(β)/(γ)
22	Silicic	SNOWTEX-OS produced	6 to 8	0.90	orthophosphoric	0.01	1.03
	acid	by Nissan Chemical			acid
		Industries, Ltd.
23	Silicic	SNOWTEX-OS produced	6 to 8	0.005	orthophosphoric	0.240	1.200
	acid	by Nissan Chemical			acid
		Industries, Ltd.
24	Silicic	SNOWTEX-OS produced	6 to 8	0.16	orthophosphoric	0.08	1.33
	acid	by Nissan Chemical			acid
		Industries, Ltd.
25	Silicic	SNOWTEX-N produced by	12 to 14	0.33	diphosphoric acid	0.20	1.00
	acid	Nissan Chemical Industries,
		Ltd.
26	Silicic	SNOWTEX-N produced by	12 to 14	0.33	orthophosphoric	0.13
	acid	Nissan Chemical Industries,
		Ltd.
27	Silicic	SNOWTEX-OS produced	6 to 8	1.00	orthophosphoric	0.72	1.20
	acid	by Nissan Chemical			acid
		Industries, Ltd.
28					orthophosphoric	0.22	1.10
					acid
29	Silicic	SNOWTEX-OS produced	6 to 8	0.3	diphosphoric acid	0.3
	acid	by Nissan Chemical
		Industries, Ltd.
30	Silicic	SNOWTEX-OS produced	6 to 8	0.50
	acid	by Nissan Chemical
		Industries, Ltd.
	Metal component (γ)	Organic resin
	Component 1	Component 2		(δ)
		Con-		Con-			Con-		Adaptability to the
		tration		tration	Total		tration	Composition	conditions of the
No.	Type	(mol/L)	Type	(mol/L)	moles	Type	(g/l)	pH	invention *3
22	Ni	0.005			0.01		3.5	◯
23	Ni	0.20			0.20	Acrylic-styrene	2	◯
						resin
24	Ni	0.06			0.06		90	3.5	◯
25	Li	0.20			0.20			4	◯
26								2.9	◯
27	Ni	0.60			0.60			2.1	◯
28		0.200			0.20			3.5	×
29								2	◯
30	Ni	0.20			0.20			2.2	×
*1 Converted to SiO 2
*2 Converted to P 2 O 5
*3  ◯ : Satisfies the conditions of the invention
×: Dissatisfies the conditions of the invention

 

TABLE 195
		Type
		(main component/
No.	Group	curing agent)	Base resin
1	Thermosetting resin	Epoxy resin/	Epicoat E-1009 (*1)/
		urea resin	BECKAMINE
			P196M (*2) = 85/15
* 1 A butycelob solution of epoxy resin (30% solid), produced by Yuka Shell Epoxy Co., Ltd.
* 2 Urea resin (20% solid) produced by Dainippon Ink & Chemicals, Inc.

 

TABLE 196
(Ion-exchanged silica, fine particle silica)
No.	Type	Trade name
1	Ca-exchanged silica	SHIELDEX C303 (average particle size
		2.5-3.5 μm, Ca Conc. 3 wt. %) produced
		by W. R. Graco & Co.

 

TABLE 197
(Zinc phosphate, aluminum phosphate)
No. Type and composition
13  Orthophosphoric acid

 

TABLE 198
(Calcium compound)
No. Type and composition
28  Calcium carbonate (60 wt. %) + calcium silicate (40 wt. %)

 

TABLE 199
[Solid lubricant]
No.	Type	Trade name
1	Polyethylene wax	LUVAX 1151 produced by Nippon Seira Co.

 

	TABLE 200
	Primary layer coating
		Coating	Drying	Blending ratio		Molar ratio of
	Plating steel plate	composition	temperature	converted to SiO 2		phosphoric acid	Total coating weight
No.	*1	*2	(° C.)	(wt %) *3	(γ) Component	component (β)/(γ) *4	(mg/m 2 ) *5
1	1	5	120	40	Ni	1.2	300
	Secondary layer coating
	Inorganic rust-preventive pigment	Solid
	(Pigment 1)	(Pigment 2)	(Pigment 1) +	(Pigment 1)/	lubricant
	Resin		Blending		Blending	(Pigment 2)	(Pigment 2)		Blending	Drying	Coating
	composition	Type	ratio	Type	ratio	Total amount	Ratio	Type	ratio	temperature	thickness
No.	*6	*7	*8	*7	*8	*9	*10	*11	*12	(° C.)	(μm)
1	1	1	30							230	1
	Performance
			White-rust resistance				Classification
		White-rust resistance:	after alkaline degreasing:	Paint			Example/
No.	Appearance	SST 96 hrs	SST 96 hrs	adhesiveness	Workability	Remark	Comparative Example
1	◯	⊚	⊚	⊚			Example

 

	TABLE 201
	Primary layer coating
		Coating	Drying	Blending ratio		Molar ratio of
	Plating steel plate	composition	temperature	converted to SiO 2		phosphoric acid	Total coating weight
No.	*1	*2	(° C.)	(wt %) *3	(γ) Component	component (β)/(γ) *4	(mg/m 2 ) *5
15	1	1	120	40	Li	1	320
16	1	2	120	40	Mn	1.47	290
17	1	3	120	40	Fe	1.3	320
18	1	4	120	40	Co	1.21	315
19	1	6	120	40	Zn	1.1	280
20	1	7	120	40	Al	1.5	350
21	1	8	120	40	La	1.8	350
22	1	9	120	40	Ce	1.8	350
23	1	10	120	60	Mn	1.47	360
24	1	11	120	60	Ni	1.2	290
25	1	12	120	40	Co	1.2	290
26	1	13	120	40	Al	1.5	280
27	1	14	120	20	Ni	1.2	320
28	1	15	120	20	Al	1.2	330
	Secondary layer coating
	Inorganic rust-preventive pigment	Solid
	(Pigment 1)	(Pigment 2)	(Pigment 1) +	(Pigment 1)/	lubricant
	Resin		Blending		Blending	(Pigment 2)	(Pigment 2)		Blending	Drying	Coating
	composition	Type	ratio	Type	ratio	Total amount	Ratio	Type	ratio	temperature	thickness
No.	*6	*7	*8	*7	*8	*9	*10	*11	*12	(° C.)	(μm)
15	1	1	30							230	1
16	1	1	30							230	1
17	1	1	30							230	1
18	1	1	30							230	1
19	1	1	30							230	1
20	1	1	30							230	1
21	1	1	30							230	1
22	1	1	30							230	1
23	1	1	30							230	1
24	1	1	30							230	1
25	1	1	30							230	1
26	1	1	30							230	1
27	1	1	30							230	1
28	1	1	30							230	1
	Performance
			White-rust resistance				Classification
		White-rust resistance:	after alkaline degreasing:	Paint			Example/
No.	Appearance	SST 96 hrs	SST 96 hrs	adhesiveness	Workability	Remark	Comparative Example
15	◯	◯	◯	⊚			Example
16	◯	⊚	⊚	⊚			Example
17	◯	⊚	◯	⊚			Example
18	◯	⊚	◯ +	⊚			Example
19	◯	⊚	◯	⊚			Example
20	◯	⊚	◯ +	⊚			Example
21	◯	⊚	◯	⊚			Example
22	◯	⊚	◯	⊚			Example
23	◯	⊚	⊚	⊚			Example
24	◯	⊚	⊚	⊚			Example
25	◯	⊚	◯ +	⊚			Example
26	◯	⊚	◯ +	⊚			Example
27	◯	⊚	⊚	⊚			Example
28	◯	⊚	◯ +	⊚			Example

 

	TABLE 202
	Primary layer coating
		Coating	Drying	Blending ratio		Molar ratio of
	Plating steel plate	composition	temperature	converted to SiO 2		phosphoric acid	Total coating weight
No.	*1	*2	(° C.)	(wt %) *3	(γ) Component	component (β)/(γ) *4	(mg/m 2 ) *5
29	1	16	120		Mn	1.03	290
30	1	17	120		Mn	1.47	320
31	1	18	120	40			320
32	1	19	120	40	Ni, Mn	1.2	290
33	1	20	120	40	Al, Mg	1.05	300
34	1	21	120	40	Ni	2.5	320
35	1	22	120	98	Ni	1.03	280
36	1	23	120	4	Ni	1.2	320
37	1	24	120	40	Ni	1.33	350
38	1	25	120	40	Li	1	280
39	1	26	120	40			500
40	1	27	120	40	Ni	1.2	4200
41	1	28	120	0	Ni	1.1	360
42	1	29	120	60			290
43	1	30	120	60	Ni	0	290
	Secondary layer coating
	Inorganic rust-preventive pigment	Solid
	(Pigment 1)	(Pigment 2)	(Pigment 1) +	(Pigment 1)/	lubricant
	Resin		Blending		Blending	(Pigment 2)	(Pigment 2)		Blending	Drying	Coating
	composition	Type	ratio	Type	ratio	Total amount	Ratio	Type	ratio	temperature	thickness
No.	*6	*7	*8	*7	*8	*9	*10	*11	*12	(° C.)	(μm)
29	1	1	30							230	1
30	1	1	30							230	1
31	1	1	30							230	1
32	1	1	30							230	1
33	1	1	30							230	1
34	1	1	30							230	1
35	1	1	30							230	1
36	1	1	30							230	1
37	1	1	30							230	1
38	1	1	30							230	1
39	1	1	30							230	1
40	1	1	30							230	1
41	1	1	30							230	1
42	1	1	30							230	1
43	1	1	30							230	1
	Performance
			White-rust resistance				Classification
		White-rust resistance:	after alkaline degreasing:	Paint			Example/
No.	Appearance	SST 96 hrs	SST 96 hrs	adhesiveness	Workability	Remark	Comparative Example
29	◯	⊚	⊚	⊚			Example
30	◯	⊚	⊚	⊚			Example
31	◯	⊚	◯	⊚			Example
32	◯	⊚	⊚	⊚			Example
33	◯	⊚	◯ +	⊚			Example
34	◯	⊚	⊚	⊚			Example
35	◯	⊚	◯ −	⊚			Example
36	◯	⊚	◯ −	⊚			Example
37	◯	⊚	⊚	⊚			Example
38	◯	⊚	◯ +	⊚			Example
39	◯	⊚	◯ +	⊚			Example
40	×	⊚	⊚	×			Comparative
							Example
41	◯	Δ	Δ	Δ			Comparative
							Example
42	◯	⊚	◯ +	⊚			Example
43	◯	×	×	×			Comparative
							Example

 

	TABLE 203
	Primary layer coating
		Coating	Drying	Blending ratio		Molar ratio of
	Plating steel plate	composition	temperature	converted to SiO 2		phosphoric acid	Total coating weight
No.	*1	*2	(° C.)	(wt %) *3	(γ) Component	component (β)/(γ) *4	(mg/m 2 ) *5
73	1	5	120	40	Ni	1.2	300
	Secondary layer coating
	Inorganic rust-preventive pigment	Solid
	(Pigment 1)	(Pigment 2)	(Pigment 1) +	(Pigment 1)/	lubricant
	Resin		Blending		Blending	(Pigment 2)	(Pigment 2)		Blending	Drying	Coating
	composition	Type	ratio	Type	ratio	Total amount	Ratio	Type	ratio	temperature	thickness
No.	*6	*7	*8	*7	*8	*9	*10	*11	*12	(° C.)	(μm)
73	1	13	30							230	1
	Performance
			White-rust resistance				Classification
		White-rust resistance:	after alkaline degreasing:	Paint			Example/
No.	Appearance	SST 96 hrs	SST 96 hrs	adhesiveness	Workability	Remark	Comparative Example
73	◯	⊚	⊚	⊚			Example

 

	TABLE 204
	Primary layer coating
		Coating	Drying	Blending ratio		Molar ratio of
	Plating steel plate	composition	temperature	converted to SiO 2		phosphoric acid	Total coating weight
No.	*1	*2	(° C.)	(wt %) *3	(γ) Component	component (β)/(γ) *4	(mg/m 2 ) *5
81	1	5	120	40	Ni	1.2	300
	Secondary layer coating
	Inorganic rust-preventive pigment	Solid
	(Pigment 1)	(Pigment 2)	(Pigment 1) +	(Pigment 1)/	lubricant
	Resin		Blending		Blending	(Pigment 2)	(Pigment 2)		Blending	Drying	Coating
	composition	Type	ratio	Type	ratio	Total amount	Ratio	Type	ratio	temperature	thickness
No.	*6	*7	*8	*7	*8	*9	*10	*11	*12	(° C.)	(μm)
81	1	13	30	28	20	50	3/2			230	1
	Performance
			White-rust resistance				Classification
		White-rust resistance:	after alkaline degreasing:	Paint			Example/
No.	Appearance	SST 96 hrs	SST 96 hrs	adhesiveness	Workability	Remark	Comparative Example
81	◯	⊚	⊚	⊚			Example

 

	TABLE 205
	Primary layer coating
		Coating	Drying	Blending ratio		Molar ratio of
	Plating steel plate	composition	temperature	converted to SiO 2		phosphoric acid	Total coating weight
No.	*1	*2	(° C.)	(wt %) *3	(γ) Component	component (β)/(γ) *4	(mg/m 2 ) *5
134	1	5	120	40	Ni	1.2	300
	Secondary layer coating
	Inorganic rust-preventive pigment	Solid
	(Pigment 1)	(Pigment 2)	(Pigment 1) +	(Pigment 1)/	lubricant
	Resin		Blending		Blending	(Pigment 2)	(Pigment 2)		Blending	Drying	Coating
	composition	Type	ratio	Type	ratio	Total amount	Ratio	Type	ratio	temperature	thickness
No.	*6	*7	*8	*7	*8	*9	*10	*11	*12	(° C.)	(μm)
1	1	13	30	28	20	50	3/2	1	10	230	1
	Performance
			White-rust resistance				Classification
		White-rust resistance:	after alkaline degreasing:	Paint			Example/
No.	Appearance	SST 120 hrs	SST 120 hrs	adhesiveness	Workability	Remark	Comparative Example
134	◯	⊚	⊚	⊚	⊚		Example

 

Best Mode 8

The method for manufacturing a surf ace-treated steel sheet comprises the steps of: preparing a zinc base plating steel sheet or an aluminum base plating steel sheet; treating thus prepared plating steel sheet in an acidic aqueous solution within a pH range of from 0.5 to 5; and forming a chemical conversion treatment coating having a thickness in a range of from 0.005 to 2 μm on the surface of the plating steel sheet by heating and drying thereof.

The treatment liquid for applying chemical conversion treatment to the plating steel sheet according to the present invention is an acidic aqueous solution within a pH range of from 0.5 to 5, containing (a) silica and/or silica sol in a range of from 0.001 to 3 mole/liter as SiO 2 , (b) phosphoric acid ion and/or phosphoric acid compound in a range of from 0.001 to 6 mole/liter as P 2 O 5 , and (c) one or more substances selected from the group consisting of: either one metallic ion selected from the group consisting of Al, Mg, Ca, Sr, Ba, Hf, Ti, Y, Sc, Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Ni, Co, Fe, and Mn; a water-soluble ion containing at least one of the above-given metals; an oxide containing at least one of the above-given metals; and a hydroxide containing at least one of the above-given metals, in a range of from 0.001 to 3 mole/liter as the total of above-given metals converted to the metal concerned.

Even when a plating steel sheet is treated by a treatment liquid containing solely silica or silica sol, the obtained coating cannot have satisfactory corrosion resistance. The reason is presumably that, during the process of drying the silica or silica sol from wet state, the dehydration condensation of the silica occurs only in local positions, which fails to form a coating. To the contrary, when phosphoric acid coexists with silica or silica sol in the treatment liquid, significant improvement in the corrosion resistance appears compared with a treatment liquid containing solely silica or silica sol. Although the reason of significant improvement in corrosion resistance is not fully analyzed, the reason is presumably that the phosphoric acid ion or the phosphoric acid compound forms a slightly soluble salt with the plating composition (for example, zinc) in the plating steel sheet, which salt holds the silica fine particles.

The above-described coating of phosphoric acid base, containing silica or silica sol, gives, however, not a fully satisfactory level of corrosion resistance, though the corrosion resistance is superior to the case of treatment with a treatment liquid containing solely silica or silica sol. To this point, a study was given on, adding to the two components of silica and/or silica sol, further additives. The study revealed that the corrosion resistance is further improved by adding an adequate amount of above-described component (c) further improves the corrosion resistance, which component (c) is one or more substances selected from the group consisting of: either one metallic ion selected from the group consisting of Al, Mg, Ca, Sr, Ba, Hf , Ti, Y, Sc, Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Ni, Co, Fe, and Mn; a water-soluble ion containing at least one of the above-given metals; an oxide containing at least one of the above-given metals; and a hydroxide containing at least one of the above-given metals.

Although the reason of improving the corrosion resistance by adding the additive component (c) is not fully analyzed, metals structuring the additive component (c) have their stable domain in alkaline side, and further their solubility is relatively low and they likely form slightly soluble salts, so that presumably these components existing in the coating deposit as hydroxides at the sites where pH increases during the corrosion process, thus contribute to the suppression of corrosion reactions.

The sum of the added amount of above-described additive components (c) in the treatment liquid is in a range of from 0.01to 3 mole/liter as metal concerned, preferably from 0.01 to 0.5 mole/liter. If the added total amount is less than 0.001 mole/liter, the effect of addition is not fully obtained. If the added total amount exceeds 3 mole/liter, these component s interfere the network of the coating, which makes the forming of dense coating difficult, and the metallic components tend to be eluted from the coating, which induces defects such as discoloration of appearance depending on environment.

Furthermore, it was found that, among the above-described additive components (c), alkali earth metals (Mg, Ca, Sr, Ba) are particularly effective for improving the corrosion resistance, and that, as of these alkali earth metals, Mg most significantly improves the corrosion resistance. The reason that Mg addition improves the corrosion resistance most effectively is presumably that Mg has lower solubility of its hydroxide than hydroxide of other alkali earth metals and that Mg likely forms slightly soluble salts. In addition, the form of these alkali earth metals such as Mg in the treatment liquid may be oxide or hydroxide. To attain particularly excellent corrosion resistance, a form of metallic ion or a water-soluble ion containing Mg is particularly preferred.

When the additive components (c) contain one or more of substances selected from the group consisting of Mg ion, water-soluble ion containing Mg, oxide containing Mg, and hydroxide containing Mg, particularly when one or more of the substances selected from the group consisting of Mg ion and water-soluble ion containing Mg, the relation between the molar ratio of Mg to silica sol and the corrosion resistance was investigated. The investigation revealed that particularly excellent corrosion resistance is attained in a range of the molecular ratio of Mg as metal to silica and/or silica sol as Si in the additive components (c), or [Mg/Si], from 100/1 to 1/10.

FIG. 1 shows the state of white-rust generation in terms of area percentage of white-rust. FIG. 1 was plotted under the conditions given below. Treatment liquid of different molar ratios of primary magnesium phosphate (Mg content 3%, manufactured by Taihei Chemicals Co., Ltd.) to silica sol (SNOWTEX-0, manufactured by Nissan Chemical Industries, Ltd.), or [Mg/Si], were applied onto electrolytically galvanized steel sheets (coating weight of 20 g/m 2 ) separately, which applied plates were then dry-baked at reaching temperature of 140° C. to prepare chemical conversion treatment steel sheets having the coatings (thickness of about 0.4 μm, Mg coating weights of from 0.01 to 200 mg/m 2 ). Thus prepared steel sheets were tested by salt spray test (JIS Z2371) for 96 hours. The horizontal axis of FIG. 1 is expressed by logarithmic unit of molar ratio [Mg/Si] in the treatment liquid.

FIG. 1 shows that the corrosion resistance of the coating becomes favorable when the molar ratio [Mg/Si] is in a range of from 100/1 to 1/10, or within a range of (1) given in the figure. Further excellent corrosion resistance is attained when the ratio is in a range of from 10/1 to 1/5, or within a range of (2) given in the figure, and when the ratio is in a range of from 5/1 to 1/2, or within a range of (3) given in the figure. The reason of giving these results is not fully analyzed. According to a speculation on the reason, when the molar ratio [Mg/Si] is less than 1/10, the Mg effect cannot be fully attained, or the existing excess amount of SiO 2 degrades the barrier performance of the coating, which reduces the corrosion resistance. The degradation of corrosion resistance observed in the case that the molar ratio [Mg/Si] exceeds 100/1 presumably owes to insufficient corrosion-suppression effect of Zn by silica, (for example, inhibitor effect of silicic acid ion).

Consequently, when Mg exists as an additive component (c), it is preferred to set the molar ratio of Mg as metal to silica and/or silica sol as Si, [Mg/Si], to a range of from 100/1 to 1/10. Further preferred range of the molar ratio [Mg/Si] is from 10/1 to 1/5, and most preferable range is from 5/1 to 1/2.

The form of metals structuring the additive components (c) in the treatment liquid is not limited, and may be hydrated ion, complex ion, oxide sol, and hydroxide sol, if only they are in a state to be dissolved or dispersed in water. From the point of corrosion resistance, existence in a form of hydrated ion or complex ion is preferable.

In that case, when the ion of additive component (c) is supplied as hydrated ion or complex ion, supply as a phosphate such as primary phosphate is preferable. The reason is presumably that, when the ion is supplied from a phosphate, phosphoric acid and a part of metallic cation form a complex ion even in an acidic aqueous solution, so that the bonding of metallic cation with phosphoric acid relatively easily proceeds even in the process of forming the coating.

The ion of the additive components (c) may be supplied in other metallic salt. For example, anion such as chlorine ion, nitric acid ion, sulfuric acid ion, acetic acid ion, and boric acid ion may be added to the treatment liquid.

It should be emphasized that the treatment liquid according to the present invention is an acidic aqueous solution. That is, by bringing the treatment liquid to acidic, the plating components such as zinc are readily dissolved. As a result, at the interface between the chemical conversion treatment film and the plating, a phosphoric acid compound layer containing plating components such as zinc is presumably formed, which layer strengthens the interface bonding of both sides to structure a coating having excellent corrosion resistance.

The following is the description on the additive components (a) and (b).

The silica and/or silica sol as an additive component (a) may be commercially available silica sol and water-dispersion type silicic acid oligomer or the like if only the silicon oxide is water-dispersion type silica fine particles which are stable in an acidic aqueous solution. Since, however, fluoride such as hexafluoro silicic acid is strongly corrosive and gives strong effect to human body, that kind of compound should be avoided from the point of influence to work environment.

A preferred range of added amount of silica and/or silica sol as SiO 2 is from 0.001 to 3 mole/liter. If the added amount of silica and/or silica sol becomes less than 0.001 mole/liter, the effect of addition is not satisfactory. If the added amount of silica and/or silica sol exceeds 3 mole/liter, the water-resistance of coating degrades, resulting in degradation of corrosion resistance.

The effect of the present invention is acquired only when silica fine particles having a specified size exist in the coating. Although the reason is not fully analyzed, the corrosion resistance depends on the sizes of the silica.

A preferable range of silica particle sizes is from 5 to 20 nm, more preferably from 5 to 14 nm, and most preferably from 5 to 10 nm. If the silica particle size is less than 5 nm, the stability of the treatment liquid degrades, and the liquid tends to gel. If the silica particle size exceeds 20 nm, the corrosion resistance degrades.

Regarding phosphoric acid ion and/or phosphoric acid compound as the additive component (b), all kinds of modes thereof are included: for example, a mode of aqueous solution in which a compound specific to phosphoric acid, such as polyphosphoric acid such as orthophosphoric acid, pyrophosphoric acid, and tripolyphosphoric acid, methaphosphoric acid, inorganic salt of these acids (for example, primary aluminum phosphate), phosphorous acid, phosphate, phosphinic acid, phosphinate, exists in a form of anion or complex ion combined with a metallic cation which are generated by dissolving the compound in the aqueous solution; a mode of aqueous solution in which that kind of compound exists as free acids; and a mode of aqueous solution in which that kind of compound exists in a form of inorganic salt dispersed therein. The amount of phosphoric acid component according to the present invention is specified by the sum of all these modes of acidic aqueous solution thereof as converted to P 2 O 5 amount.

A preferred range of blending ratio of the phosphoric acid ion and/or phosphoric acid compound as P 2 O 5 is from 0.001 to 6 mole/liter, and more preferably from 0.02 to 1.0 mole/liter. If the blending ratio of the phosphoric acid ion and/or phosphoric acid compound becomes less than 0.001 mole/liter, the effect of addition is not satisfactory and the corrosion resistance degrades. If the blending ratio of the phosphoric acid ion and/or phosphoric acid compound exceeds 6 mole/liter, excess amount of phosphoric acid ion reacts with the plating film under a humid environment, which enhances the corrosion of plating base material to cause discoloration and stain-rusting under some corrosive environments.

When the additive component (c) is one or more of the substances selected from the group consisting of Mg ion, water-soluble ion containing Mg, oxide containing Mg, and hydroxide containing Mg, and particularly when the additive component (c) is one or more of Mg ion and water-soluble ion containing Mg, an adequate amount of one or more of the substances selected from the group consisting of either one metallic ion of Ni, Fe, and Co, and a water-soluble ion containing at least one of the above-given metals may be applied as the additive component (d). By adding that kind of iron group metal, blackening phenomenon is avoided. The blackening phenomenon occurs in the case of non-addition of iron group metals caused from corrosion on the plating polar surface layer under a humid environment. Among these iron group metals, Ni provides particularly strong effect even with a slight amount thereof. Since, however, excessive addition of iron group metals such as Ni and Co induces degradation of corrosion resistance, the added amount should be kept at an adequate level.

A preferred range of the added amount of the above-described additive component (d) is from 1/10,000 to 1 mole as metal per one mole of the additive component (c), more preferably from 1/10,000 to 1/100. If the added amount of the additive component (d) is less than 1/10,000 mole to one mole of the additive component (c), the effect of the addition is not satisfactory. If the added amount of the additive component (d) exceeds 1 mole, the corrosion resistance degrades as described above.

Similar effect is also obtained by surface adjustment treatment (treatment to make iron group metals substitute to deposit on the surface of plating) applied before the chemical conversion treatment, which surface adjustment treatment is described later.

The treatment liquid may, adding to the above-described additive components (a) through (d), further contain: water-soluble or water-dispersible resins such as acrylic base resin, polyethylene resin (polyolefin resin), alkydresin, epoxy resin, and polyurethane resin; water-soluble polymers such as high molecular weight polyol; coloring dyes such as water-soluble azo metallic dyes; chelating agents such as tannic acid and thiol; and silane coupling agent, in order to improve the denseness of coating, improve the corrosion resistance, improve the paintability, and add flexibility, and the like. Furthermore, the treatment liquid may contain components such as other metal additive compounds such as Zn and Mn, nitric acid ion, sulfuric acid ion, chloride ion, acetic acid ion; and boric acid ion, and etching assistant such as oxidation agent, at adequate amounts not giving bad effect to corrosion resistance.

The range of pH of the treatment liquid (acidic aqueous solution) is from 0.5 to 5. If the pH of the treatment liquid is less than 0.5, the reactivity of the treatment liquid becomes excessively strong, and micro-defects appear on the coating, thus degrading the corrosion resistance. If the pH of the treatment liquid exceeds 5, the reactivity of the treatment liquid becomes low, and the bonding between the plating face and the coating at the interface becomes insufficient, which also degrades the corrosion resistance.

According to the present invention, the plating steel sheets are treated by the treatment liquid of above-described acidic aqueous solution, then heating and drying are applied to the plates to form chemical conversion treatment coating having thicknesses of from 0.005 to 2 μm onto the surface of the plating steel sheets.

If the thickness of the chemical conversion treatment coating is less than 0.005 μm, the coating fails to uniformly cover the plating surface, and local defects occur on the coating, which results in insufficient corrosion resistance. If the thickness of the coating exceeds 2 μm, performance other than corrosion resistance, such as weldability and coating adhesiveness, degrades.

The plating steel sheets which are the base material to form the chemical conversion treatment coating according to the present invention are zinc base plating steel sheets or aluminum base plating steel sheets.

The plating method may be either applicable one of electrolytic method (electrolysis in an aqueous solution or in a non-aqueous solvent) and vapor phase method.

The methods for applying the treatment liquid onto the plating steel sheet may be either one of coating method, dipping method, and spray method. The coating method may adopt any type such as roll coater (three-roll type, two-roll type, etc.), squeeze coater, die coater. After the coating step using squeeze coater and the like, the dipping step, or the spray step, it is possible to adjust the coating weight, the uniformizing appearance, and the uniformizing the film-thickness using air-knife method and roll-squeezing method.

Although there is no specific limitation on the temperature of the treatment liquid, a preferable range thereof is from normal temperature to around 60° C. Below the normal temperature is uneconomical because a cooling unit or other additional facilities are required. On the other hand, temperatures above 60° C. enhances the vaporization of water, which makes the control of the treatment liquid difficult.

After the coating of treatment liquid as described above, generally the plate is heated to dry without rinsing with water. The treatment liquid according to the present invention forms a slightly soluble salt by a reaction with the substrate plating steel sheet, so that rinsing with water may be applied after the treatment. The present invention also includes the case that rinsing with water after the treatment.

Method for heating to dry the coated treatment liquid is not limited. For example, dryer, hot air oven, high frequency induction heating furnace, infrared heating furnace may be applied. In particular, the high frequency induction heating furnace is preferred because the furnace dries the work within a short time while effectively heating the base materials and the coating interface. The heating and drying treatment is preferably conducted at reaching temperatures of from 50 to 300° C., more preferably from 80 to 200° C. If the heating temperature is less than 50° C., excess amount of water is left in the coating, which results in insufficient corrosion resistance. If the heating temperature exceeds 300° C., the operation becomes uneconomical and defects likely appear in the coating to degrade the corrosion resistance.

Before the above-described chemical conversion treatment using an acidic aqueous solution, the surface of the plating steel sheet is brought to contact with an aqueous solution (acidic or alkaline aqueous solution) which contains adequate amount of one or more substances selected from the group consisting of either one of metallic ions of iron group metals, and water-soluble ion containing at least one of the iron group metals, and the surface of the plating film is subjected to surface adjustment treatment that deposits iron group metals onto the surface of the plating film. Thus, blackening phenomenon caused from the corrosion of the plating polar surface layer under a humid environment is avoided.

The added amount of the iron group metal (water-soluble ion containing at least one of iron group metal ion and/or iron group metal) in the treatment liquid (aqueous solution) used to the surface adjustment treatment is preferably in a range of from 0.001 to 10 g/liter. If the added amount of iron group metal is less than 0.001 g/liter, the effect of addition is not satisfactory. If the added amount of iron group metal exceeds 10 g/liter, the plating surface and the treatment liquid react nonuniformly, thus likely inducing problems such as insufficient appearance.

The deposition of iron group metal on the surface of plating film by the surface adjustment treatment is preferably in a rang e of from 0.01 to 100 mg/m 2 as the sum of metal. If the deposition of iron group metal on the surface of plating film is less than 0.01 mg/m the effect of addition is not satisfactory. If the deposition of iron group metal on the surface of plating film exceeds 100 mg/m 2 , problems such as insufficient appearance likely occur.

As for the iron group metal ions add ed to the treatment liquid, Ni most significantly improves the blackening resistance.

Similar improvement effect to blackening resistance is attained also by coexisting Ni, Co, and other components as ions in the plating bath for manufacturing plating steel sheets by electroplating or the like, and by u sing a plating steel sheet in which Ni, Co, or the like is co-deposited into the plating film at rates of from 1 to 5,000 ppm, (for example, zinc base plating steel sheet).

The surface treated steel sheet manufactured conforming to the present invention has sufficiently favorable corrosion resistance as it is. However, to improve corrosion resistance and paintability after the alkaline degreasing, the formed chemical conversion treatment coating may be coated by an organic resin coating or an organic composite silicate coating as the upper layer. The upper layer coating may contain rust-preventive pigment such as silica, and solid lubricant of, for example, hydrocarbon compound, fluororesin base compound, fatty acid amide base compound, molybdenum disulfide, metallic soap, graphite fluoride, boron nitride, polyalkyleneglycol.

A preferred thickness of the upper layer coating (dry thickness) is in a range of approximately from 0.1 to 5 μm, and more preferably from 0.5 to 3 μm. If the thickness of the upper layer coating is less than 0.1 μm, the effect of improved corrosion resistance and of improved paintability after the alkaline degreasing is not satisfactory. If the thickness of the upper layer coating exceeds 5 μm, the product cannot be used to portions which need spot welding.

As described above, the present invention includes a steel sheet having an organic coating on both sides or on side thereof. Accordingly, modes of the steel sheet according to the present invention include, for example, the followings.

(1) “Plating film—Chemical conversion treatment coating according to the present invention—Upper layer coating” on one side of the steel sheet, and “Plating film” on other side of the steel sheet;

(2) “Plating film—Chemical conversion treatment coating according to the present invention—Upper layer coating” on one side of the steel sheet, and “Known coating treated by phosphoric acid, or the like” on other side of the steel sheet;

(3) “Plating film—Chemical conversion treatment coating according to the present invention” on both sides of the steel sheet;

(4) “Plating film—Chemical conversion treatment coating according to the present invention” on one side of the steel sheet, and “Plating film” on other side of the steel sheet;

(5) “Plating film—Chemical conversion treatment coating according to the present invention—Upper layer coating” on one side of the steel sheet, and “Plating film—Chemical conversion treatment coating according to the present invention” on other side of the steel sheet;

(6) “Plating film—Chemical conversion treatment coating according to the present invention: on both sides of the steel sheet.

EXAMPLE 1

To obtain organic coating steel sheets for household electric appliances, building materials, and automobile parts, the surface-treated steel sheets described below were prepared.

The surface of each of the plating steel sheets was treated by alkaline degreasing and water washing, followed by drying. Then, each of the treatment liquids for chemical conversion treatment which was adjusted in composition and pH shown in Tables 206 through 208 was applied to the surface using a roll coater, followed by heating to dry in a hot air oven. The thickness of the chemical conversion treatment coating was adjusted by the concentration of the treatment liquid and applying conditions (roll pressing force, rotational speed, and other variables). The drying temperature was determined by direct measurement of the plate temperature using thermocouples.

In Tables 206 through 208, * and *1 through *4 mean the following.

*: A silica gel “SNOWTEX-0” produced by Nissan Chemical Industries, Ltd.

*1: SiO 2 amount

*2: Converted to P 2 O 5

*3: Converted to metal.

*4: Examples and Comparative Examples.

For thus obtained surface-treated steel sheets, the corrosion resistance and the coating adhesiveness were evaluated by the following-given procedures. The results are shown in Tables 209 through 212 along with the kind, coating weight, chemical conversion treatment condition, and thickness of chemical conversion treatment coating of the plating steel sheets used as the target base plates. In Tables 209 through 212, *1 through *4 mean the following.

*1: Corresponding to treatment liquid No. in Tables 206 through 208.

*2: EG: Electrolytically galvanized steel sheet GI: Hot dip galvanized steel sheet GF: Hot dip Zn-55wt. %Al-0.1 wt. %misch metal alloy plating steel sheet GL: Hot dip Zn—55%Al alloy plating steel sheet EN: Electrolytically Zn—Ni alloy plating steel sheet

*3: Coating weight per single side of the plate

*4: Reaching temperature

(1) Corrosion Resistance (White-rust Resistance)

For each sample, the salt spray test (JIS Z2371) was applied, and the evaluation was given by the area percentage of white-rust after 48 hours have passed.

The criteria for evaluation are the following.

⊚: White-rust area less than 5%

◯: White-rust area not less than 5% and less than 10%

Δ: White-rust area not less than 10% and less than 50%

X: White-rust area not less than 50%

(2) Adhesiveness (Coating Adhesiveness)

For each sample, a 0T bending was applied, and the bent section was observed by SEM. The adhesiveness of the chemical conversion treatment coating was evaluated by the criteria given below.

∘: Peeled area is slight

X: Lack of chemical conversion treatment coating is significant resulted from peeling

According to Examples given in Tables 209 through 212, all the surface-treated steel sheets obtained by the method according to the present invention have superior performance to the surface-treated steel sheets in Comparative Examples.

EXAMPLE 2

To obtain surface-treated steel sheets for household electric appliances, building materials, and automobile parts, the following-described surface-treated steel sheets were prepared.

Plating steel sheets shown in Table 213 were used as the target base plates, which plates were prepared by applying various kinds of platting on cold-rolled steel sheets having a plate thickness of 0.8 mm and a surface roughness Ra of 1.0 μm. The surface of the plating steel sheet was treated by alkaline degreasing and water rinsing. For some of these plating steel sheets, surface adjustment treatment (spray treatment or immersion treatment) using the treatment liquids shown in Table 214 to let iron group metals substitute-deposit onto the surface of the plating film. Then, the treatment liquids for chemical conversion treatment adjusted to specific compositions and pH values given in Tables 215 through 217 were applied to the surface using a roll coater, followed by heating to dry in a hot air oven or a high frequency induction heating furnace. The drying temperature was directly determined using thermocouples.

In Tables 215 through 217, *1 through *6 express the following.

*1: SiO 2 amount.

*2: Converted to metal concerned.

*3: Molar ratio of [Mg as metal]/[Silica gel as Si].

*4: Converted to P 2 O 5 .

*5: Molar ratio of [Additive component (d)]/[Additive component (c) as metal].

*6: Examples and Comparative Examples.

After that, some of the surface-treated steel sheets were subjected to form an organic resin coating on the chemical conversion treatment coating.

To each of thus obtained surface-treated steel sheets, evaluation was given in terms of appearance of coating, white-rust resistance, white-rust resistance after alkaline degreasing, paintability, blackening resistance, and coating adhesiveness. The results are given in Tables 218 through 227 along with the kinds, surface adjustment treatment conditions, chemical conversion treatment conditions, and thickness of chemical conversion treatment coating.

In Tables 218, 220, 222, 224, and 226, *1 through *3 express the following.

*1: Plating steel sheets given in Table 213.

*2: Corresponding to the treatment liquid Nos. given in Table 214.

*3: Corresponding to the treatment liquid composition Nos. given in Tables 215 through 217.

(1) Apperarance of Coating

For each sample, visual observation was given on the uniformity of coating appearance (presence/absence of irregular appearance.). The criteria for evaluation are the following.

◯: No irregularity appeared

X: Irregularity appeared

(2) White-rust Resistance

For each sample, the salt spray test (JIS Z2371) was applied, and the evaluation was given by the area percentage of white-rust after 48 hours and 72 hours have passed, respectively.

The criteria for evaluation are the following.

⊚: White-rust area less than 5%

◯: White-rust area not less than 5% and less than 10%

Δ: White-rust area not less than 10% and less than 50%

X: White-rust area not less than 50%

(3) White-rust Resistance After Alkaline Degreasing

For each sample, alkaline degreasing was applied (using the alkali treatment liquid CLN-364S, produced by Nihon Parkerizing Co.), followed by salt spray test (JIS Z2371). The result was evaluated by the white-rust area percentage after 48 hours and 72 hours have past, respectively.

The criteria for evaluation are the following.

⊚: White-rust area less than 5%

◯: White-rust area not less than 5% and less than 25%

Δ: White-rust area not less than 25% and less than 50%

X: White-rust area not less than 50%

(4) Paintability (Paint Adhesiveness)

For each sample, a melamine base paint (film thickness of 30 μm) was applied and baked, and the sample was dipped in a boiling water for 2 hours. Immediately after 2 hours of dipping, cross-cut (10×10 squares with 10 mm of spacing) was given to the surface of the sample. Then the test of attaching and peeling of adhesive tapes was given to the sample to evaluate the paint adhesiveness by the peeled paint film area percentage.

The criteria for evaluation are the following.

⊚: No peeling occurred

◯: Peeled area less than 5%

Δ: Peeled area not less than 5% and less than 20%

X: Peeled area not less than 20%

(5) Blackening Resistance

Each sample was held under a humid environment at 95% or higher relative humidity for 24 hours. The degree of discoloration of whiteness of the sample was determined before and after the humid test, thus giving the evaluation on the blackening resistance .

The criteria for evaluation are the following.

◯: Excellent (change in L value≧−2)

Δ: Poor (change in L value<−2)

(6) Adhesiveness (Coating Adhesiveness)

For each sample, 0T bending was applied, and the bent section was observed by SEM. The adhesiveness of chemical conversion treatment coating was evaluated in accordance with the criteria given below.

◯: Peeled area is slight

X: Lack of chemical conversion treatment coating is significant resulted from peeling.

The results of Examples given in Tables 218 through 227 show that the surface-treated steel sheets according to the present invention provide superior performance to the surface-treated steel sheets of Comparative Examples.

TABLE 206
[Treatment liquid for chemical conversion coating]
		Phosphoric
		acid/
	Silica sol	phosphoric	Water-soluble ion, oxide, hydroxide of specific metal	Treatment
	concentration	acid	Metal		Added amount		liquid	Classification
No.	(mol/L) *1	(mol/L) *2	species	Mode of addition	(mol/L) *3	Added reagent	pH	*4
1	0.20	0.40	Al	Hydrated ion	0.20	Primary aluminum phosphate	2.1	Example
2	0.40	0.20	Al	Hydrated ion	0.02	Aluminum sulfate	2.8	Example
3	0.15	0.02	Al	Hydroxide sol	0.15	Alumina sol	3.0	Example
4	0.15	0.30	Mg	Hydrated ion	0.20	Primary magnesium	2.6	Example
						phosphate
5	0.50	0.50	Mg	Hydrated ion	0.002	Magnesium sulfate	2.5	Example
6	0.20	0.25	Al, Mg	Hydrated ion	Al = 0.15, Mg = 0.05	Primary phosphate	1.5	Example
7	0.20	0.25	Al, Sr	Hydrated ion	Al = 0.15, Sr = 0.05	Primary phosphate	2.2	Example
8	0.20	0.20	Al, Ca	Hydrated ion	Al = 0.15, Ca = 0.05	Primary phosphate	2.2	Example
9	0.30	0.30	Ba	Hydrated ion	0.001	Barium sulfate	1.8	Example
10	0.30	0.25	Hf	Oxide	0.02	Hafnium oxide powder	2.0	Example
11	0.30	0.25	Ti	Oxide sol	0.05	Titania sol	1.2	Example
12	0.30	0.25	Se	Hydrated ion	0.05	Scandium nitrate	2.2	Example
13	0.30	0.25	Ce	Oxide sol	0.05	Cerium oxide sol	2.2	Example
14	0.30	0.05	La	Hydrated ion	0.01	Lanthanum nitrate	3.5	Example

 

TABLE 207
[Treatment liquid for chemical conversion coating]
		Phosphoric
		acid/
	Silica sol	phosphoric	Water-soluble ion, oxide, hydroxide of specific metal	Treatment
	concentration	acid	Metal		Added amount		liquid	Classification
No.	(mol/L) *1	(mol/L) *2	species	Mode of addition	(mol/L) *3	Added reagent	pH	*4
15	0.30	0.20	Pr	Hydrated ion	0.002	Praseodymium chloride	2.5	Example
16	0.30	0.20	Nd	Hydrated ion	0.001	Neodymium fluoride	2.5	Example
17	0.35	0.20	Sm	Hydrated ion	0.005	Samarium chloride	2.5	Example
18	0.30	0.20	Eu	Hydrated ion	0.05	Europium chloride	2.2	Example
19	0.40	0.20	Al, Gd	Hydrated ion	Al = 0.15, Gd = 0.001	Phosphate, gadolinium	2.2	Example
						fluoride
20	0.30	0.25	Al, Tb	Hydrated ion	Al = 0.15, Tb = 0.001	Phosphate, terbium nitride	2.2	Example
21	0.30	0.25	Dy	Hydrated ion	0.005	Dysprosium nitride	2.2	Example
22	0.30	0.25	Ho	Hydrated ion	0.005	Holmium chloride	2.2	Example
23	0.30	0.25	Er	Hydrated ion	0.005	Erbium carbonate	2.2	Example
24	0.30	0.25	Yb	Hydrated ion	0.005	Ytterbium nitride	2.2	Example
25	0.30	0.25	Lu	Hydrated ion	0.005	Lutetium nitride	2.2	Example
26	0.15	0.25	Al, Ni	Hydrated ion	Al = 0.15, Ni = 0.05	Primary phosphate	2.3	Example
27	0.15	0.20	Mg, Co	Hydrated ion	Mg = 0.15, Co = 0.05	Primary phosphate	1.8	Example

 

TABLE 208
[Treatment liquid for chemical conversion coating]
		Phosphoric
		acid/
	Silica sol	phosphoric	Water-soluble ion, oxide, hydroxide of specific metal	Treatment
	concentration	acid	Metal		Added amount		liquid	Classification
No.	(mol/L) *1	(mol/L) *2	species	Mode of addition	(mol/L) *3	Added reagent	pH	*4
28	0.15	0.25	Fe	Hydrated ion	0.20	Primary phosphate	1.5	Example
29	0.15	0.25	Mg, Fe	Hydrated ion	Mg = 0.15, Fe = 0.05	Primary phosphate	2.1	Example
30	0.15	0.25	Mn	Hydrated ion	0.10	Primary phosphate	2.5	Example
31	0.15	0.25	Al, Fe	Hydrated ion	Al = 0.15, Fe = 0.05	Primary phosphate	1.7	Example
32	2.50	3.00	Al	Hydrated ion	1.80	Primary phosphate	3.1	Example
33	0.02	0.01	Al	Hydrated ion	0.05	Primary phosphate	4.0	Example
34	—	0.30	Al	Hydrated ion	0.20	Primary phosphate	2.0	Comparative
								example
35	3.20	0.10	Al	Hydrated ion	0.05	Primary phosphate	3.5	Comparative
								example
36	0.20	0.20	—	—	—	—	3.5	Comparative
								example
37	0.30	7.00	Al	Hydrated ion	2.0	Primary phosphate	0.5	Comparative
								example
38	0.20	—	Mg	Hydrated ion	0.20	Nitrate	2.0	Comparative
								example
39	0.20	0.20	Al	Hydrated ion	3.5	Primary phosphate, sulfate	2.0	Comparative
								example
40	0.20	3.90	Al	Hydrated ion	0.50	Primary phosphate	0.4	Comparative
								example
41	0.05	0.002	Sr	Hydrated ion	0.01	Primary phosphate	5.2	Comparative
								example

 

	TABLE 209
		Target
	Treatment	treatment substrate	Drying
	liquid		Coating weight	temperature	Coating
	No.	Type	(g/m 2 )	*4	thickness	Corrosion
No.	*1	*2	*3	(° C.)	(μm)	resistance	Adhesiveness	Classification
1	1	EG	20	110	0.20	⊚	◯	Example
2	2	EG	20	130	0.40	⊚	◯	Example
3	3	EG	20	110	0.20	⊚	◯	Example
4	3	GI	90	90	0.20	⊚	◯	Example
5	4	EG	20	110	0.15	⊚	◯	Example
6	4	EG	20	120	0.20	⊚	◯	Example
7	4	EG	20	230	0.20	⊚	◯	Example
8	4	GI	120	120	0.15	⊚	◯	Example
9	4	GL	85	120	0.20	⊚	◯	Example
10	4	EN	30	110	0.20	⊚	◯	Example
11	5	EG	20	110	0.40	⊚	◯	Example
12	5	EG	20	110	0.40	⊚	◯	Example
13	5	EG	20	110	0.10	⊚	◯	Example

 

	TABLE 210
		Target
	Treatment	treatment substrate	Drying
	liquid		Coating weight	temperature	Coating
	No.	Type	(g/m 2 )	*4	thickness	Corrosion
No.	*1	*2	*3	(° C.)	(μm)	resistance	Adhesiveness	Classification
14	6	EG	20	120	0.35	⊚	◯	Example
15	7	EG	20	110	0.30	⊚	◯	Example
16	8	EG	20	80	0.35	⊚	◯	Example
17	9	EG	20	110	0.30	⊚	◯	Example
18	10	EG	20	120	0.30	⊚	◯	Example
19	11	EG	20	140	0.30	⊚	◯	Example
20	12	EG	20	110	0.30	⊚	◯	Example
21	13	EG	20	110	0.30	⊚	◯	Example
22	14	EG	20	120	0.30	⊚	◯	Example
23	15	EG	20	110	0.30	⊚	◯	Example
24	16	EG	10	110	0.30	⊚	◯	Example
25	17	EG	10	110	0.30	⊚	◯	Example
26	18	EG	20	120	0.30	⊚	◯	Example

 

	TABLE 211
		Target
	Treatment	treatment substrate	Treatment
	liquid		Coating weight	temperature	Coating
	No.	Type	(g/m 2 )	*4	thickness	Corrosion
No.	*1	*2	*3	(° C.)	(μm)	resistance	Adhesiveness	Classification
27	19	EG	20	110	0.20	⊚	◯	Example
28	20	EG	20	110	0.30	⊚	◯	Example
29	21	EG	20	120	0.35	⊚	◯	Example
30	22	EG	20	120	0.30	⊚	◯	Example
31	23	EG	20	150	0.30	⊚	◯	Example
32	24	EG	20	100	0.25	⊚	◯	Example
33	25	EG	20	100	0.30	⊚	◯	Example
34	25	EG	20	100	1.0	⊚	◯	Example
35	26	EG	20	100	0.50	⊚	◯	Example
36	27	EG	20	110	0.20	⊚	◯	Example
37	28	EG	20	110	0.20	⊚	◯	Example
38	29	EG	20	110	0.20	⊚	◯	Example
39	30	EG	20	110	0.20	⊚	◯	Example

 

	TABLE 212
		Target
	Treatment	treatment substrate	Drying
	liquid		Coating weight	temperature	Coating
	No.	Type	(g/m 2 )	*4	thickness	Corrosion
No.	*1	*2	*3	(° C.)	(μm)	resistance	Adhesiveness	Classification
40	31	EG	20	110	0.20	⊚	◯	Example
41	32	EG	20	110	2.2	⊚	×	Comparative
								example
42	33	EG	20	110	0.003	×	◯	Comparative
								example
43	34	EG	20	110	0.30	×	◯	Comparative
								example
44	35	EG	20	110	0.20	Δ	◯	Comparative
								example
45	36	EG	20	110	0.20	×	◯	Comparative
								example
46	37	EG	20	100	0.30	×	◯	Comparative
								example
47	38	EG	20	110	0.20	×	◯	Comparative
								example
48	39	EG	20	120	0.20	×	◯	Comparative
								example
49	40	EG	20	110	0.20	×	◯	Comparative
								example
50	41	EG	20	110	0.20	×	◯	Comparative
								example

 

TABLE 213
[Plating steel plate]
No.	Type	Coating weight (g/m 2 )
1	Electrolytically galvanized steel plate	20

 

TABLE 214
[Treatment liquid for surface adjustment]
	Composition (1)	Composition (2)	Ion group metal
		Concentration		Concentration		Concentration
No.	Type	(g/l)	Type	(g/l)	Type	(g/l)	pH
1	Na 4 P 2 O 7 .10H 2 O	10	NiSO 4 .6H 2 O	0.05	Ni	0.01	10
2	Na 4 P 2 O 7 .10H 2 O	10	NiSO 4 .6H 3O	0.10	Ni	0.02	10
3	Na 4 P 2 O 7 .10H 2 O	10	NiSO 4 .6H 4O	1.0	Ni	0.22	10
4	—	—	NiSO 4 .6H 5O	5.0	Ni	1.12	5
5	Commercial Na base pyrophosphoric acid	10	NiSO 4 .6H 6O	0.05	Ni	0.01	10
	degreasing agent*
6	Na 4 P 2 O 7 .10H 2 O	10	NiSO 4 .6H 7O	0.20	Co	0.07	10
*CL-342 produced by Nihon Parkerizing Co.

 

TABLE 215
[Treatment liquid for chemical conversion coating]
			Phosphoric acid/phosphoric
	Silica sol (a)	Alkali earth metal (c)	acid compound (b)
			Particle	Concentration		Concentration			Concentration
			size	(mol/L)		(mol/L)	Mg/Si		(mol/L)
No.	Type	Trade name	(nm)	*1	Type	*2	*3	Type	*4
1	Colloidal	Nissan Chemical	12 to 14	0.1	Mg 2+	0.20	1.82	orthophosphoric	0.21
	silica	Industries, Ltd.						acid
		SNOWTEX-O
2	Colloidal	Nissan Chemical	12 to 14	0.2	Mg 2+	0.17	0.94	orthophosphoric	0.18
	silica	Industries, Ltd.						acid
		SNOWTEX-O
3	Colloidal	Nissan Chemical	13 to 14	0.4	Mg 2+	0.40	1.00	orthophosphoric	0.40
	silica	Industries, Ltd.						acid
		SNOWTEX-O
4	Colloidal	Nissan Chemical	8 to 10	0.2	Mg 2+	0.17	0.94	orthophosphoric	0.18
	silica	Industries, Ltd.						acid
		SNOWTEX-O
5	Colloidal	Nissan Chemical	6 to 8	0.1	Mg 2+	0.20	1.82	orthophosphoric	0.18
	silica	Industries, Ltd.						acid
		SNOWTEX-O
6	Colloidal	Nissan Chemical	8 to 10	0.2	Mg 2+	0.30	1.50	orthophosphoric	0.21
	silica	Industries, Ltd.						acid
		SNOWTEX-O
7	Colloidal	Nissan Chemical	12 to 14	0.4	Mg 2+	0.40	1.00	orthophosphoric	0.30
	silica	Industries, Ltd.						acid
		SNOWTEX-O
8	Colloidal	Catalysts & Chemicals	10 to 20	0.3	Mg 2+	0.10	0.33	orthophosphoric	0.10
	silica	Industries Co., LTD.						acid
		Cataloid-SN
9	Colloidal	Nissan Chemical	12 to 14	0.2	Mg 2+	0.30	1.50	orthophosphoric	0.30
	silica	Industries, Ltd.						acid
		SNOWTEX-O
	Added metal (d)
				Molar
				ratio
				(d)/(c)	Treatment	Classification
	No.	Type	Concentration	*5	liquid pH	*6
	1	—	—	—	3.1	Example
	2	—	—	—	3.1	Example
	3	—	—	—	2.7	Example
	4	—	—	—	3.1	Example
	5	—	—	—	3.0	Example
	6	—	—	—	3.5	Example
	7	—	—	—	3.2	Example
	8	—	—	—	2.5	Example
	9	—	—	—	3.5	Example

 

TABLE 216
[Treatment liquid for chemical conversion coating]
			Phosphoric acid/phosphoric
	Silica sol (a)	Alkali earth metal (c)	acid compound (b)
			Particle	Concentration		Concentration			Concentration
			size	(mol/L)		(mol/L)	Mg/Si		(mol/L)
No.	Type	Trade name	(nm)	*1	Type	*2	*3	Type	*4
10	Colloidal	Nissan Chemical	12 to 14	0.4	Mg 2+	0.40	1.00	orthophosphoric	0.40
	silica	Industries, Ltd.						acid
		SNOWTEX-O
11	Colloidal	Nissan Chemical	12 to 14	0.4	Mg 2+	1.40	1.00	orthophosphoric	0.40
	silica	Industries, Ltd.						acid
		SNOWTEX-O
12	Colloidal	Nissan Chemical	8 to 10	0.3	Mg 2+	0.10	0.33	orthophosphoric	0.40
	silica	Industries, Ltd.						acid
		SNOWTEX-O
13	Colloidal	Catalysts & Chemicals	10 to 20	0.3	Mg 2+	0.10	0.33	orthophosphoric	0.10
	silica	Industries, Co., LTD.						acid
		Cataloid-SN
14	Colloidal	Nissan Chemical	12 to 14	1.0	Mg 2+	0.05	0.05	orthophosphoric	0.40
	silica	Industries, Ltd.						acid
		SNOWTEX-O
15	Colloidal	Nissan Chemical	12 to 14	0.1	Mg 2+	1.10	110.00	orthophosphoric	0.40
	silica	Industries, Ltd.						acid
		SNOWTEX-O
16	Colloidal	Nissan Chemical	12 to 14	0.2	Ca 2+	0.20	—	orthophosphoric	0.20
	silica	Industries, Ltd.						acid
		SNOWTEX-O
17	Colloidal	Nissan Chemical	12 to 14	0.1	Sr 2+	0.10	—	orthophosphoric	0.10
	silica	Industries, Ltd.						acid
		SNOWTEX-O
	Added metal (d)
				Molar
				ratio
				(d)/(c)	Treatment	Classification
	No.	Type	Concentration	*5	liquid pH	*6
	10	Ni 2+	0.001	0.0025	3.2	Example
	11	Co 2+	0.02	0.05	3.2	Example
	12	—	—	—	2.5	Example&Asteriskpseud;
	13	—	—	—	2.5	Example
	14	—	—	—	3.2	Example
	15	—	—	—	3.2	Example
	16	—	—	—	3	Example
	17	—	—	—	3.1	Example
	&Asteriskpseud;*Ethyl-styrene type moisture acid resin: 160 g/L added

 

TABLE 217
[Treatment liquid for chemical conversion coating]
			Phosphoric acid/phosphoric
	Silica sol (a)	Alkali earth metal (c)	acid compound (b)
			Particle	Concentration		Concentration			Concentration
			size	(mol/L)		(mol/L)	Mg/Si		(mol/L)
No.	Type	Trade name	(nm)	*1	Type	*2	*3	Type	*4
18	Colloidal	Nissan Chemical	12 to 14	0.1	Ba 2+	0.10	—	orthophosphoric	0.10
	silica	Industries, Ltd.						acid
		SNOWTEX-O
19	—	—	—	—	Mg 2+	0.30	—	orthophosphoric	0.30
								acid
20	Colloidal	Nissan Chemical	12 to 14	3.5	Mg 2+	0.30	0.09	orthophosphoric	0.30
	silica	Industries, Ltd.						acid
		SNOWTEX-O
21	Colloidal	Nissan Chemical	12 to 14	0.4	—	—	—	orthophosphoric	0.15
	silica	Industries, Ltd.						acid
		SNOWTEX-O
22	Colloidal	Nissan Chemical	12 to 14	0.4	Mg 2+	3.50	8.75	orthophosphoric	0.30
	silica	Industries, Ltd.						acid
		SNOWTEX-O
23	Colloidal	Nissan Chemical	12 to 14	0.4	Mg 2+	0.30	0.75	—	—
	silica	Industries, Ltd.
		SNOWTEX-O
24	Colloidal	Nissan Chemical	12 to 14	0.4	Mg 2+	0.30	0.75	orthophosphoric	6.2
	silica	Industries, Ltd.						acid
		SNOWTEX-O
25	Colloidal	Nissan Chemical	12 to 14	0.4	Mg 2+	2.50	6.25	orthophosphoric	5.0
	silica	Industries, Ltd.						acid
		SNOWTEX-O
26	Lithium	Nissan Chemical	—	1.0	—	—	—	—	—
	silicate	Industries, Ltd.
		LSS-35
	Added metal (d)
				Molar
				ratio
				(d)/(c)	Treatment	Classification
	No.	Type	Concentration	*5	liquid pH	*6
	18	—	—	—	3.2	Example
	19	—	—	—	2.8	Comparative
						example
	20	—	—	—	2.5	Comparative
						example
	21	—	—	—	3.0	Comparative
						example
	22	—	—	—	2.5	Comparative
						example
	23	—	—	—	2.8	Comparative
						example
	24	—	—	—	2.1	Comparative
						example
	25	—	—	—	0.4	Comparative
						example
	26	—	—	—	11	Comparative
						example

 

	TABLE 218
			Upper layer
	Surface adjustment	Chemical conversion treatment conditions	organic resin coating
	Plating base	Treatment	Treatment		Coating	Target	Drying	Coating		Coating
	plate	liquid	time	Deposition/	weight	composition	temperature	thickness	Presence/	thickness	Classi-
No.	*1	*2	(second)	Metal species	(mg/m 2 )	*3	(° C.)	(μm)	Absence	(μm)	fication
1	1	—	—	—	—	1	140	0.2	Absence	—	Example
2	1	—	—	—	—	2	140	0.2	Absence	—	Example
3	1	—	—	—	—	3	140	0.2	Absence	—	Example
4	1	—	—	—	—	4	140	0.2	Absence	—	Example
5	1	—	—	—	—	5	140	0.2	Absence	—	Example
6	1	—	—	—	—	6	140	0.2	Abscnce	—	Example
7	1	—	—	—	—	7	140	0.2	Absence	—	Example
8	1	—	—	—	—	8	140	0.2	Absence	—	Example
9	1	—	—	—	—	9	140	0.2	Absence	—	Example
10	1	—	—	—	—	10	140	0.2	Absence	—	Example
11	1	—	—	—	—	11	140	0.2	Absence	—	Example
12	1	—	—	—	—	12	140	0.2	Absence	—	Example
13	1	—	—	—	—	13	140	0.2	Absence	—	Example
14	1	—	—	—	—	14	140	0.2	Absence	—	Example
15	1	—	—	—	—	15	140	0.2	Absence	—	Example

 

	TABLE 219
	Performance
		White-rust resistance after		Resistance
	White-rust resistance	alkaline degreasing		to	Coating
No.	Appearance	SST 48 hrs	SST 72 hrs	SST 48 hrs	SST 72 hrs	Paintability	blackening	adhesiveness	Classification
1	∘	⊚	∘	Δ	x	Δ	x	∘	Example
2	∘	⊚	∘	Δ	x	Δ	x	∘	Example
3	∘	⊚	⊚	Δ	x	Δ	x	∘	Example
4	∘	⊚	⊚	Δ	x	Δ	X	∘	Example
5	∘	⊚	⊚	Δ	x	Δ	x	∘	Example
6	∘	⊚	⊚	Δ	x	Δ	x	∘	Example
7	∘	⊚	∘	Δ	X	Δ	x	∘	Example
8	∘	⊚	Δ	Δ	x	Δ	x	∘	Example
9	∘	⊚	∘	Δ	x	Δ	x	∘	Example
10	∘	⊚	∘	Δ	x	Δ	∘	∘	Example
11	∘	⊚	∘	Δ	x	Δ	∘	∘	Example
12	∘	⊚	⊚	Δ	x	Δ	x	∘	Example
13	∘	⊚	◯	Δ	x	Δ	x	∘	Example
14	∘	⊚	Δ	Δ	x	Δ	x	∘	Example
15	∘	⊚	Δ	Δ	x	Δ	x	∘	Example

 

	TABLE 220
		Chemical	Upper layer
	Surface adjustment	conversion treatment conditions	organic resin coating
	Plating base	Treatment	Treatment		Coating	Target	Drying	Coating		Coating
	plate	liquid	time	Deposition/	weight	composition	temperature	thickness	Presence/	thickness	Classi-
No.	*1	*2	(second)	Metal species	(mg/m 2 )	*3	(° C.)	(μm)	Absence	(μm)	fication
16	1	—	—	—	—	16	140	0.2	Absence	—	Example
17	1	—	—	—	—	17	140	0.2	Absence	—	Example
18	1	—	—	—	—	18	140	0.2	Absence	—	Example
19	1	—	—	—	—	19	140	0.2	Absence	—	Comparative
											Example
20	1	—	—	—	—	20	140	0.2	Absence	—	Comparative
											Example
21	1	—	—	—	—	21	140	0.2	Absence	—	Comparative
											Example
22	1	—	—	—	—	22	140	0.2	Absence	—	Comparative
											Example
23	1	—	—	—	—	23	140	0.2	Absence	—	Comparative
											Example
24	1	—	—	—	—	24	140	0.2	Absence	—	Comparative
											Example
25	1	—	—	—	—	25	140	0.2	Absence	—	Comparative
											Example
26	1	—	—	—	—	26	140	0.2	Absence	—	Comparative
											Example
27	1	1	2	Ni	0.1	1	140	0.2	Absence	—	Example
28	1	2	3	Ni	0.2	1	140	0.2	Absence	—	Example
29	1	3	3	Ni	1.0	1	140	0.2	Absence	—	Example
30	1	4	3	Ni	5.0	1	140	0.2	Absence	—	Example

 

	TABLE 221
	Performance
		White-rust resistance after		Resistance
	White-rust resistance	alkaline degreasing		to	Coating
No.	Appearance	SST 48 hrs	SST 72 hrs	SST 48 hrs	SST 72 hrs	Paintability	blackening	adhesiveness	Classification
16	∘	⊚	Δ	Δ	x	Δ	x	∘	Example
17	∘	⊚	Δ	Δ	x	Δ	x	∘	Example
18	∘	⊚	Δ	Δ	x	Δ	x	∘	Example
19	∘	x	x	x	x	x	x	∘	Comparative
									example
20	x	x	x	x	x	x	x	x	Comparative
									example
21	∘	x	x	x	x	x	x	∘	Comparative
									example
22	∘	Δ	x	x	x	x	x	x	Comparative
									example
23	∘	x	x	x	x	x	x	◯	Comparative
									example
24	∘	x	x	x	x	x	x	◯	Comparative
									example
25	∘	x	x	x	x	x	x	◯	Comparative
									example
26	∘	x	x	x	x	x	x	∘	Comparative
									example
27	∘	⊚	∘	Δ	x	Δ	∘	∘	Example
28	∘	⊚	∘	Δ	x	Δ	∘	∘	Example
29	∘	⊚	∘	Δ	x	Δ	∘	∘	Example
30	∘	⊚	◯	Δ	x	Δ	∘	∘	Example

 

	TABLE 222
		Chemical	Upper layer
	Surface adjustment	conversion treatment conditions	organic resin coating
	Plating base	Treatment	Treatment		Coating	Target	Drying	Coating		Coating
	plate	liquid	time	Deposition/	weight	composition	temperature	thickness	Presence/	thickness	Classi-
No.	*1	*2	(second)	Metal species	(mg/m 2 )	*3	(° C.)	(μm)	Absence	(μm)	fication
31	1	5	3	Ni	0.2	1	140	0.2	Absence	—	Example
32	1	6	3	Co	1.0	1	140	0.2	Absence	—	Example
33	1	4	20	Ni	120	1	140	0.2	Absence	—	Comparative
											Example

 

	TABLE 223
	Performance
		White-rust resistance after		Resistance
	White-rust resistance	alkaline degreasing		to	Coating
No.	Appearance	SST 48 hrs	SST 72 hrs	SST 48 hrs	SST 72 hrs	Paintability	blackening	adhesiveness	Classification
31	∘	⊚	∘	Δ	x	Δ	∘	∘	Example
32	∘	⊚	∘	Δ	x	Δ	∘	∘	Example
33	x	x	x	x	x	Δ	∘	∘	Comparative
									example

 

	TABLE 224
		Chemical	Upper layer
	Surface adjustment	conversion treatment conditions	organic resin coating
	Plating base	Treatment	Treatment		Coating	Target	Drying	Coating		Coating
	plate	liquid	time	Deposition/	weight	composition	temperature	thickness	Presence/	thickness	Classi-
No.	*1	*2	(second)	Metal species	(mg/m 2 )	*3	(° C.)	(μm)	Absence	(μm)	fication
51	1	—	—	—	—	1	80	0.1	Absence	—	Example
52	1	—	—	—	—	1	110	0.1	Absence	—	Example
53	1	—	—	—	—	1	250	0.1	Absence	—	Example
54	1	—	—	—	—	14	140	0.002	Absence	—	Comparative
											Example
55	1	—	—	—	—	15	140	2.5	Absence	—	Comparative
											Example
56	1	—	—	—	—	1	140	0.2	Presence	0.7	Example
57	1	—	—	—	—	2	140	0.2	Presence	0.7	Example
58	1	—	—	—	—	3	140	0.2	Presence	0.7	Example
59	1	—	—	—	—	4	140	0.2	Presence	0.7	Example
60	1	—	—	—	—	5	140	0.2	Prcsence	0.7	Example

 

	TABLE 225
	Performance
		White-rust resistance after		Resistance
	White-rust resistance	alkaline degreasing		to	Coating
No.	Appearance	SST 48 hrs	SST 72 hrs	SST 48 hrs	SST 72 hrs	Paintability	blackening	adhesiveness	Classification
51	∘	⊚	Δ	Δ	x	Δ	x	∘	Example
52	∘	⊚	∘	Δ	x	Δ	x	∘	Example
53	∘	⊚	∘	Δ	x	Δ	x	∘	Example
54	∘	x	x	x	x	Δ	x	∘	Comparative
									example
55	∘	⊚	⊚	⊚	⊚	x	x	x	Comparative
									example
56	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example
57	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example
58	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example
59	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example
60	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example

 

	TABLE 226
		Chemical	Upper layer
	Surface adjustment	conversion treatment conditions	organic resin coating
	Plating base	Treatment	Treatment		Coating	Target	Drying	Coating		Coating
	plate	liquid	time	Deposition/	weight	composition	temperature	thickness	Presence/	thickness	Classi-
No.	*1	*2	(second)	Metal species	(mg/m 2 )	*3	(° C.)	(μm)	Absence	(μm)	fication
61	1	—	—	—	—	6	140	0.2	Presence	0.7	Example
62	1	—	—	—	—	7	140	0.2	Presence	0.7	Example
63	1	—	—	—	—	8	140	0.2	Presence	0.7	Example
64	1	—	—	—	—	9	140	0.2	Presence	0.7	Example
65	1	—	—	—	—	10	140	0.2	Presence	0.7	Example
66	1	—	—	—	—	11	140	0.2	Presence	0.7	Example
67	1	—	—	—	—	12	140	0.2	Presence	0.7	Example
68	1	—	—	—	—	13	140	0.2	Presence	0.7	Example
69	1	—	—	—	—	14	140	0.2	Presence	0.7	Example
70	1	—	—	—	—	15	140	0.2	Presence	0.7	Example
71	1	—	—	—	—	16	140	0.2	Presence	0.7	Example
72	1	—	—	—	—	17	140	0.2	Presence	0.7	Example
73	1	—	—	—	—	18	140	0.2	Presence	0.7	Example

 

	TABLE 227
	Performance
		White-rust resistance after		Resistance
	White-rust resistance	alkaline degreasing		to	Coating
No.	Appearance	SST 48 hrs	SST 72 hrs	SST 48 hrs	SST 72 hrs	Paintability	blackening	adhesiveness	Classification
61	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example
62	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example
63	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example
64	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example
65	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example
66	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example
67	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example
68	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example
69	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example
70	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example
71	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example
72	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example
73	∘	⊚	⊚	⊚	⊚	⊚	∘	∘	Example

 

Claims

1. A coated steel sheet having corrosion resistance comprising:a zinc or a zinc alloy plated steel sheet or an aluminum or an aluminum alloy plated steel sheet; a composite oxide coating formed on the surface of the plated steel sheet; an organic coating formed on the composite oxide coating; said composite oxide coating containing: (α) oxide particles; (β) at least one metal selected from the group consisting of Mg, Ca, Sr and Ba, or said metal in a form of at least one of a compound and a composite compound; and (γ) at least one of a phosphoric acid and a phosphoric acid compound, the composite oxide coating has a thickness of from 0.005 to 3 μm, or has a total coating weight of the component (α), the component (β) converted to said metal, and the component (γ) converted to P2O5, of from 6 to 3,600 mg/m2; said organic coating comprising a product of a reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) comprises a hydrazine compound (C) containing active hydrogen, wherein the hydrazine compound (C) containing active hydrogen is at least one compound selected from the group consisting of an active-hydrogen-laden pyrazole compound and an active-hydrogen-laden triazole compound; and the organic coating having a thickness of from 0.1 to 5 μm.

2. The coated steel sheet having corrosion resistance of claim 1, wherein the organic coating contains a product of a reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) comprises a hydrazine compound (C) containing active hydrogen, and an ion-exchanged silica, the ion-exchanged silica being in an amount of from 1 to 100 parts by weight of solid matter to 100 parts by weight of solid matter of the reaction product.

3. The coated steel sheet having corrosion resistance of claim 1, wherein the organic coating contains a product of a reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) comprises a hydrazine compound (C) containing active hydrogen, and silica particles, the silica particles being in an amount of from 1 to 100 parts by weight of solid matter to 100 parts by weight of solid matter of the reaction product.

4. The coated steel sheet having corrosion resistance of claim 1, wherein the organic coating contains a product of a reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) comprises a hydrazine compound (C) containing active hydrogen, an ion-exchanged silica, and silica particles, the sum of the ion-exchanged silica and silica particles is from 1 to 100 parts by weight of solid matter to 100 parts by weight of solid matter of the reaction product, and the weight ratio of the solid matter content of the ion-exchanged silica to the solid matter content of the silica particles is from 1/99 to 99/1.

5. The coated steel sheet having corrosion resistance of claim 1, wherein the organic coating contains a product of reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) comprises a hydrazine compound (C) containing active hydrogen, and a solid lubricant, the solid lubricant being in an amount of from 1 to 80 parts by weight of solid matter to 100 parts by weight of solid matter of the reaction product.

6. The coated steel sheet having corrosion resistance of claim 1, wherein the organic coating contains a product of a reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) comprises a hydrazine compound (C) containing active hydrogen, an ion-exchanged silica, and a solid lubricant, the ion-exchanged silica being in an amount of from 1 to 100 parts by weight of solid matter to 100 parts by weight of solid matter of the reaction product, the solid lubricant being in an amount of from 1 to 80 parts by weight of solid matter to 100 parts by weight of solid matter of the reaction product.

7. The coated steel sheet having corrosion resistance of claim 1, wherein the organic coating contains a product of a reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) comprises a hydrazine compound (C) containing active hydrogen, silica particles, and a solid lubricant, the silica particles being in an amount of from 1 to 100 parts by weight of solid matter to 100 parts by weight of solid matter of the reaction product, the solid lubricant being in an amount of from 1 to 80 parts by weight of solid matter to 100 parts by weight of solid matter of the reaction product.

8. The coated steel sheet having corrosion resistance of claim 1, wherein the organic coating contains a product of a reaction between a film-forming organic resin (A) and an active-hydrogen-laden compound (B), a part or whole of which compound (B) comprises a hydrazine compound (C) containing active hydrogen, an ion-exchanged silica, silica particles, and a solid lubricant, the sum of the ion-exchanged silica and the silica particles is from 1 to 100 parts by weight of solid matter to 100 parts by weight of solid matter of the reaction product, the weight ratio of the solid matter content of the ion-exchanged silica to the solid matter content of the silica particles is from 1/99 to 99/1, the solid lubricant being in an amount of from 1 to 80 parts by weight of solid matter to 100 parts by weight of solid matter of the reaction product.

9. The coated steel sheet having corrosion resistance of claim 1, wherein the oxide particles in the composite oxide coating are SiO2 particles.

10. The coated steel sheet having corrosion resistance of claim 1, wherein the composite oxide coating comprises: (α) SiO2 particles; (β) at least one element selected from the group consisting of Mg, a compound containing Mg and a composite compound containing Mg; and (γ) at least one of a phosphoric acid and a phosphoric acid compound.

11. The coated steel sheet having corrosion resistance of claim 1, wherein the film-forming organic resin (A) is a epoxy-group-laden resin.

12. The coated steel sheet having corrosion resistance of claim 1, wherein the coated steel sheet does not contain hexavalent chromium.