Method for forming multi-layer coating film

BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a process for the formation of a leafing type aluminum flake-containing metallic multi-layer coating film.
2. Description of Related Art
There has already been known a technique to form, on a substrate such as an automobile body panel, a multi-layer coating film, by applying an aluminum flake pigment-containing metallic coating on said substrate, and then applying, on the resultant coated surface, a clear coating which is capable of forming a transparent film.
The aluminum flake pigment to be compounded in a metallic coating is classified into a leafing type and a non-leafing type. In a metallic coating film which contains a leafing type aluminum flake pigment, the aluminum flake pigment floats up to the surface of said coating film (which phenomenon is called leafing) to form a continuous and dense aluminum plane which is oriented substantially parallel to the coated surface, resulting in the achievement of special effects such as a chrome plating-like finish, glittering brightness and strong flip-flop properties.
This metallic coating film per se is, however, inferior in chemical resistance such as acid resistance since aluminum flake pigment floats up to the surface of said coating film. In order to overcome this defect, the coated surface of said metallic coating film is usually coated with a clear coating. However, when a clear coating is applied onto the coated surface of a metallic coating film while the metallic coating is uncured, the orientation of leafing type aluminum flake is disturbed, resulting in the deterioration of a chrome plating-like finish (which phenomenon is called mottling). On the other hand, when a clear coating is applied after the metallic coating film is heat-cured, the interlayer adhesivity between the metallic coating film and the clear coating film is caused to be insufficient. Hence, it has been impossible to fully produce the above-mentioned various advantageous effects of a leafing type aluminum flake-containing metallic coating film.
As for a non-leafing type aluminum flake, it is uniformly dispersed in the whole of a coating film without causing leafing. Hence, when a clear coating is applied onto the surface of a metallic coating, there occurs neither mottling nor the reduction in interlayer adhesivity. However, the brightness and flip-flop effects of the film are weak, and, moreover, it is difficult to achieve a metallic coating film having a chrome plating-like finish.
In view of the above situation, the inventors of this invention studied how to improve the interlayer adhesivity between a metallic coating film and an adjacent film, without causing reduction in the above-mentioned special effects (e.g., dense metallic appearance of the coated surface, a chrome plating-like finish, strong brightness and flip-flop effects) possessed by a leafing type aluminum flake pigment-containing metallic coating film.
SUMMARY OF THE INVENTION
As a result, the inventors have now found out that the interlayer adhesivity between a metallic coating film and a clear coating film can be improved, without reducing the above-mentioned peculiar effects, by means of applying a base coating which contains a phosphoric acid group-containing resin composition, and, without curing said base coating, applying a leafing type aluminum flake pigment-containing metallic composition on the coated surface of said base coating, and, after curing these coatings, applying on the resultant coated surface a composition which contains a phosphoric acid group-containing non-aqueous dispersion which comprises polymer particles dispersed in a solution of macromolecular dispersion stabilizer dissolved in an organic solvent, said polymer particles being particles of polymer which comprises, as a constituent component, a phosphoric acid group-containing polymerizable unsaturated monomeric unit, and then applying a clear coating, and, thus, the present invention has been completed.
Thus, this invention provides a process (hereinafter referred to as "the application process of this invention) for the formation of a multi-layer coating film which process is characterized by applying a base coating (A) which contains a phosphoric acid group-containing resin composition, and, without curing said base coating, applying a leafing type aluminum flake pigment-containing metallic composition (B) on the coated surface of said base coating, and, after curing these coatings, applying on the resultant coated surface a composition (C) which contains a phosphoric acid group-containing non-aqueous dispersion which comprises polymer particles dispersed in a solution of macromolecular dispersion stabilizer dissolved in an organic solvent, said polymer particles being particles of polymer which comprises, as a constituent component, a phosphoric acid group-containing polymerizable unsaturated monomeric unit, and then applying a clear coating (D).

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
The following is a further detailed explanation of the Application Process of this invention.
Base Coating (AL)Which Contains Phosphoric Acid Group-Containing Resin Composition
Base coating (A) is a paint which is to be applied on a material to be coated, prior to the application of metallic composition (B) which is mentioned later. By providing the coating film of this base coating (A) in adjacent to, and just under the coating film of said metallic composition (B), there can remarkably the adhesivity can be remarkably improved between metallic composition (B) and intermediate coating or primer coating which is applied under the metallic composition (B).
Base coating (A) is a paint which contains a phosphoric acid group-containing resin composition. As said phosphoric acid group-containing resin composition, one or more species may be selected for use from the followings:
(P-1) Polymer containing a phosphoric acid group and a hydroxyl group in one molecule, which is prepared with use of a phosphoric acid group-containing unsaturated monomer and a hydroxyl group-containing unsaturated monomer as constituent components.
(P-2) Phosphoric acid group-containing non-aqueous dispersion, which comprises polymer particles dispersed in a solution of macromolecular dispersion stabilizer dissolved in an organic solvent, polymer of said particles comprising a phosphoric acid group-containing unsaturated monomer unit as a constituent component.
The phosphoric acid group-containing polymerizable unsaturated monomers which may be used for the preparation of the polymer (P-1), include a compound which has, in one molecule, both at least one phosphoric acid group represented by formula
--OPO(OH)(R.sub.1) (1)
wherein R.sub.1 is a hydroxyl group, a phenyl group or an alkyl group having 1 to 20, especially 2 to 10, carbon atoms
and at least one polymerizable unsaturated bond. Concretely, there are mentioned acid-phosphoxy-C.sub.1-20 (especially C.sub.2-10)alkyl (meth)acrylates such as acid-phosphoxyethyl acrylate, acid-phosphoxyethyl methacrylate, acid-phosphoxypropyl acrylate, acid-phosphoxypropyl methacrylate, acid-phosphoxydecyl acrylate, acid-phosphoxydecyl methacrylate and the like.
As a phosphoric acid group-containing polymerizable unsaturated monomer, there can also be used an equimolar adduct of glycidyl (meth)acrylate with mono-C.sub.1-20 alkylphosphoric acid ester.
The hydroxyl group-containing unsaturated monomer is a compound having, in one molecule, a hydroxyl group and a polymerizable unsaturated bond. Examples of said monomer include C.sub.2-20, in particular C.sub.2-10 hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and the like. Examples of this monomer further include PLACCEL's FA-1, FA-2, FA-3, FA-4, FA-5, FM-1, FM-2, FM-3, FM-4, FM-5 and FM-6 (trade names of the products of Daicel Chemical Industries, Ltd.), which are each an ester of the above-mentioned hydroxyalkyl (meth)acrylate and caprolactone.
The polymer (P-1) can be produced by copolymerizing the phosphoric acid group-containing unsaturated monomer, the hydroxyl group-containing unsaturated monomer, and, if necessary, an N-alkoxymethylamide group-containing unsaturated monomer and/or other unsaturated monomer.
The N-alkoxymethylamide group-containing unsaturated monomer is a compound having an N-alkoxy-methylamide group and a polymerizable unsaturated bond in one molecule. Examples of said compound include N-C.sub.1-6 alkoxymethyl (meth)acrylamides such as N-methoxy-methyl (meth)acrylamide, N-ethoxymethyl (meth)acryl-amide, N-butoxymethyl (meth)acrylamide, N-propoxymethyl (meth)acrylamide and the like. Examples of said other unsaturated monomer include C.sub.1-22 alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylayte, propyl (meth)acrylate, butyl (meth)acrylate and the like; vinyl aromatic compounds such as styrene, vinyl-toluene and the like; vinyl monomers such as acrylonitrile, vinyl acetate, vinyl chloride and the like; olefins such as ethylene, propylene and the like; and carboxyl group-containing unsaturated compounds such as (meth)acrylic acid, maleic acid, maleic anhydride and the like.
As for the ratio of the phosphoric acid group-containing monomer to the hydroxyl group-containing monomer in polymer (P-1), the phosphoric acid group-containing monomer preferably acounts for 1 to 50% by weight, in particular 5 to 30% by weight, while the hydroxyl group-containing monomer accounts for 1 to 50% by weight, in particular 5 to 30% by weight, based on the total monomers constituting the polymer (P-1). N-alkoxymethylamide group-containing unsaturated monomer preferably accounts for 30% by weight or less, in particular 1 to 20% by weight, based on the total monomers constituting the polymer (P-1). The remainder is the other unsaturated monomer.
The copolymerization of these monomers is preferably conducted by solution polymerization. The resulting polymer (P-1) preferably has a hydroxyl value of 5 to 150 mg KOH/g, in particular 10 to 120 mg KOH/g, more desirably 30 to 110 mg KOH/g; an acid value, based on the phosphoric acid group, of generally 10 to 150 mg KOH/g, in particular 20 to 130 mg KOH/g; and a number-average molecular weight of 1,000 to 100,000, in particular 3,000 to 50,000, more desirably 5,000 to 30,000.
When comprising N-alkoxymethylamide group-containing monomer unit, this polymer (P-1) becomes self crosslinkable.
Polymer (P-1), when free from any N-alkoxy-methylamide group-containing monomer unit, has no self-crosslinkability or self-curability. When used in combination with an N-alkoxymethylamide group-containing monomer, however, polymer (P-1) can be subjected to crosslinking. When polymer (P-1) which is free from any N-alkoxymethylamide group-containing monomer unit is used in combination with a polymer having N-alkoxymethylamide group-containing monomer units in base coating (A), the base coating (A) becomes crosslinkable.
The non-aqueous dispersion (P-2) is the one which comprises polymer particles dispersed in a solution of macromolecular dispersion stabilizer dissolved in an organic solvent, said polymer particles being produced by polymerizing monomeric unit which contains a phosphoric acid group-containing polymerizable unsaturated monomer.
The polymer of the polymer particles in the non-aqueous dispersion (P-2) can be produced by polymerizing either a phosphoric acid group-containing polymerizable unsaturated monomer alone or a monomeric component which comprises a phosphoric acid group-containing polymerizable unsaturated monomer and another copolymerizable monomer.
As the phosphoric acid group-containing unsaturated monomer which is a constituent component of the polymer particles of non-aqueous dispersion (P-2), there is usable, for example, a compound which has both a phosphoric acid group represented by formula (1) which is explained in the above with respect to polymer (P-1) and a polymerizable unsaturated bond.
Furthermore, as a phosphoric acid group-containing polymerizable unsaturated monomer, there can also be used compounds represented by the formula
CH.sub.2 .dbd.CX--CO--(YO).sub.n --OPO(OH).sub.2 (2)
wherein X denotes hydrogen atom or methyl group; Y denotes alkylene group having 2 to 4 carbon atoms; and n denotes an integer of 3 to 30, especially 3 to 20.
This monomer can be prepared for example by adding alkylene oxide to (meth)acrylic acid to form polyalkylene glycol monoester, which is then allowed to react with phosphorus oxychloride to form phosphate monoester, which is then hydrolyzed. This phosphorus oxychloride can be replaced with orthophosphoric acid, metaphosphoric acid, phosphoric acid anhydride, phosphorus trichloride or phosphorus pentachloride. The above-mentioned alkylene oxide can be used in an amount of at least stoichiometric amount in accordance with the number "n" in the above formula (2), preferably for example, in an amount ranging from 3 to 60 moles per mole of (meth)acrylic acid. Alkylene oxide has preferably 2 to 4 carbon atoms, and its examples include ethylene oxide, propylene oxide and butylene oxide. The above-mentioned addition reaction can be completed within 0.5 to 5 hours at a temperature of 40 to 200.degree. C. The reaction of monoesterification of phosphorus oxychloride after the above addition reaction can be completed within 0.5 to 5 hours at a temperature of 0 to 100.degree. C. Phosphorus oxychloride may be used almost in a stoichiometric amount. According to necessity, it may be used in an amount ranging from 1 to 3 moles per mole of the adduct. Thereafter, the resultant monoester is hydrolyzed by a usual method, and, thus, the compounds of formula (2) are obtained. Examples of said compounds include acid-phosphoxyhexa (or dodeca) (oxypropylene) monomethacrylate.
Among the above-mentioned phosphoric acid group-containing polymerizable unsaturated monomers, acid-phosphoxy-C.sub.2-10 alkyl (meth)acrylates are especially preferable.
These phosphoric acid group-containing polymerizable unsaturated monomers may be used either alone or in combination of two or more species.
As another monomeric unit which is copolymerizable with the above-mentioned phosphoric acid group-containing polymerizable unsaturated monomers, there can be used compounds which have at least one polymerizable unsaturated bond in one molecule. Concretely, the following can be mentioned:
a) Esters of (meth)acrylic acid:
For example, C.sub.1-18 alkyl esters of (meth)acrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate and stearyl (meth)acrylate; glycidyl ester such as glycidyl (meth)acrylate; C.sub.2-8 alkenyl esters of (meth)acrylic acid such as allyl (meth)acrylate; C.sub.2-8 hydroxyalkyl esters of (meth)acrylic acid such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; C.sub.3-18 alkenyloxy alkyl esters of (meth)acrylic acid such as allyloxyethyl (meth)acrylate; esters between C.sub.2-8 hydroxyalkyl esters of (meth)acrylic acid and caprolactone which are available under tradenames PLACCEL FA-1, FA-2, FA-3, FA-4, FA-5, FM-1, FM-2, FM-3, FM-4, FM-5 and FM-6 (produced by Daicel Chemical Industries, Ltd.); diesters between (meth)acrylic acid and glycols such as ethylene glycol and propylene glycol.
b) Vinyl aromatic compounds:
For example, styrene, .alpha.-methylstyrene, vinyl toluene, p-chlorostyrene, vinylpyridine and divinyl benzene, and the like.
c) .alpha., .beta.-Ethylenically unsaturated acids:
For example, (meth)acrylic acid, maleic acid and itaconic acid.
d) (Meth)acrylic acid amides:
For example, (meth)acrylamide, n-butoxymethyl (meth)acrylamide and n-methylol (meth)acrylamide.
e) Others:
For example, (meth)acrylonitrile, methylisopropenyl ketone, vinyl acetate, Veova monomer (tradename of a product produced by Shell Chemical), vinyl propionate, vinyl pivalate, isocyanate ethyl (meth)acrylate, perfluorocyclohexyl (meth)acrylate, p-styrene sulfonamide, N-methyl-p-styrene sulfonamide and .gamma.-methacryloxy propyltrimethoxy silane.
Among the above monomers, esters of (meth)acrylic acid are preferably used. It is desirable that at least a part of the same should be hydroxyl group-containing unsaturated monomers such as C.sub.2-8 hydroxyalkyl esters of (meth)acrylic acid or esters between C.sub.2-8 hydroxyalkyl esters of (meth)acrylic acid and caprolactone.
The monomeric component from which to prepare the polymer of polymer particles in the non-aqueous dispersion (P-2) comprises a phosphoric acid group-containing polymerizable unsatureated monomer as an essential ingredient and, if necessary, another copolymerizable monomer. The ratio of these monomers are not specifically restricted, and may optionally be changed according to objective. Generally, however, phosphoric acid group-containing polymerizable unsaturated monomer accounts for 0.1-100% by weight, especially 0.5-50% by weight, most desirably 3-30% by weight based on the total of phosphoric acid group-containing polymerizable unsatureated monomer and the other monomer, and said other monomer accounts for 99.9-0% by weight, especially 99.5-50% by weight, most preferably 97-70% by weight.
As for the above-mentioned hydroxyl group-containing unsaturated monomer, it is usable in an amount of 0-80% by weight, especially 1-50% by weight, most desirably 5-40% by weight based on the total monomers.
The non-aqueous dispersion (P-2) can be prepared by polymerizing the above-mentioned monomeric components into the form of particles in a solution of macromolecular dispersion stabilizer in an organic solvent. There can resultantly be obtained a non-aqueous dispersion wherein polymer particles derived from the above-mentioned monomeric components are dispersed in a solution of macromolecular dispersion stabilizer dissolved in an organic solvent.
The purpose of using a macromolecular dispersion stabilizer is to disperse polymer particles stably in a dispersion. Usable macromolecular dispersion stabilizer is compatible with organic solvent in said dispersion, but is substantially incompatible with coexistent particles of polymer which comprises, as a constituent component, a phosphoric acid group-containing polymerizable unsaturated monomer unit.
Examples of such a macromolecular dispersion stabilizer include the followings, which may be used either alone or in combination of two or more species.
1) Polyester macromonomer (1a) which is produced by adding, by esterification, a glycidyl ester of (meth)acrylic acid to a carboxyl group of a self condensation polyester resin of a fatty acid which has a hydroxyl group such as 12-hydroxystearic acid; and Polymer (1b) which is produced by polymerizing a polymerizable monomer with a polymerizable unsaturated bond in said polyester macromonomer (1a).
2) Polymer which is produced by polymerizing the above-mentioned polyester macromonomer (1a) with a polymerizable monomer which contains a glycidyl ester of (meth)acrylic acid, and by further adding .alpha., .beta.-ethylenically unsaturated acid to glycidyl group in the resultant polymer so as to introduce polymerizable unsaturated bond. Usually, the amount of said polymerizable unsaturated bond to be introduced is preferably, on average, 0.2 to 1.2 in number, especially 0.5 to 1 in number, per molecule.
3) Hydroxyl group-containing acrylic resin which is produced by polymerizing a polymerizable monomeric component which contains both C.sub.4-22 alkyl ester of (meth)acrylic acid and a hydroxyl group-containing polymerizable monomer.
4) Acrylic resin (4a) which is produced by introducing a polymerizable unsaturated bond, by means of adding .alpha., .beta.-ethylenically unsaturated acid, into a glycidyl group of a hydroxyl group-containing acrylic resin which is produced by polymerizing a polymerizable monomeric component which contains C.sub.4-22 alkyl ester of (meth)acrylic acid, a hydroxyl group-containing polymerizable monomer such as C.sub.2-8 hydroxyalkyl esters of (meth)acrylic acid and glycidyl ester of (meth)acrylic acid; and Acrylic resin (4b) which is produced by introducing a polymerizable unsaturated bond, by means of adding glycidyl ester of (meth)acrylic acid, into a carboxyl group of a hydroxyl group-containing acrylic resin which is produced by polymerizing a polymerizable monomeric component which contains monoester between an alkyl having four or more carbon atoms and (meth)acrylic acid, a hydroxyl group-containing polymerizable monomer and .alpha., .beta.-ethylenically unsaturated acid. In each of these resins (4a) and (4b), usually 0.2 to 1.2 in number, especially 0.5 to 1 in number, on average, of said polymerizable unsaturated bond is preferably introduced per one molecule.
5) Alkyl-etherified melamine resin which has a high allowability for mineral spirit.
6) Oil-modified alkyd resin having an oil length of at least 15% by weight, preferably 20 to 40% by weight. Or alkyd resin into which a polymerizable unsaturated bond has been introduced by means of adding glycidyl ester of (meth)acrylic acid to carboxyl group in said oil-modified alkyd resin. On average, 0.2 to 1.2 in number, especially 0.5 to 1 in number, of said polymerizable unsaturated bond is preferably introduced into one molecule.
7) Alkyd resin which is produced by adding, by urethane formation, an equimolar reaction product between polyisocyanate and a hydroxyl group-containing polymerizable monomer to hydroxyl group of an oil-modified alkyd resin having at least 15% by weight, preferably 20 to 40% by weight, of oil length so as to introduce a polymerizable unsaturated bond. On average, 0.2 to 1.2 in number, especially 0.5 to 1 in number, of said polymerizable unsaturated bond is preferably introduced into one molecule.
8) Cellulose acetate butyrate having a polymerizable unsaturated bond which is prepared by subjecting a hydroxyl group of cellulose acetate butyrate to a urethane reaction with a monomer such as isocyanate ethyl(meth)acrylate and an equimolar adduct of isophorone diisocyanate with hydroxyethyl acrylate, each of which has both an isocyanate group and a polymerizable unsaturated bond. On average, 0.2 to 1.2 in number, especially 0.5 to 1 in number, of said polymerizable unsaturated bond is preferably introduced into one molecule.
As for the glycidyl ester of (meth)acrylic acid, polymerizable monomer, .alpha., .beta.-ethylenically unsaturated acid, C.sub.4-22 alkyl ester of (meth)acrylic acid, a hydroxyl group-containing polymerizable monomer and C.sub.2-8 hydroxyalkyl esters of (meth)acrylic acid in the above dispersion stabilizers, there are usable one or more species which are selected from the afore-mentioned examples.
Generally, the above-mentioned various dispersion stabilizers have a weight average molecular weight ranging from about 1,000 to about 50,000, preferably from about 2000 to about 35,000, and most desirably from about 3,000 to about 20,000.
Moreover, said dispersion stabilizers have a hydroxyl value which ranges generally from 0.5 to 200, especially from 5 to 170, and most desirably from 20 to 140, and have an acid value which ranges generally from 0.5 to 100, especially from 3 to 60, and most desirably from 5 to 40.
Especially preferable among the above dispersion stabilizers are acrylic resins mentioned in the above 3) and 4) which are easily dissolved in a low polarity organic solvent such as aliphatic hydrocarbon, and which have good weatherability. Acrylic resin type dispersion stabilizer which has preferably an average of 0.2 to 1.2 polymerizable unsaturated bonds per one molecule is most desirable since it graft-polymerizes with polymer particles to improve the stability of dispersion. Especially desirable is a polymer (dispersion stabilizer) which is prepared with use of a low polarity monomer, as a main component, such as C4q22 alkyl ester of methacrylic acid like n-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, lauryl methacrylate and stearyl methacrylate, and, if necessary, together with styrene, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate. To said polymer, furthermore, glycidyl (meth)acrylate, (meth)acrylic acid or isocyanate ethyl-methacrylate is preferably added so as to introduce polymerizable double bond.
Preferably used in the non-aqueous dispersion (P-2) is an organic solvent which dissolves macromolecular dispersion sabilizer, and which is capable of dispersing polymer particles without substantially dissolving the same, and which, in particular, has a boiling point at most 150.degree. C. There are concretely mentioned the followings, which may be employed either alone or in combination of two or more species.
Hydrocarbon solvent such as heptane, octane, toluene, xylene and mineral spirit; ester solvent such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl Cellosolve acetate and butyl Carbitol acetate; ketone solvent such as methylethyl ketone, methylisobutyl ketone and diisobutyl ketone; alcohol solvent such as methanol, ethanol, isopropanol, n-butanol and sec-butanol; ether solvent such as n-butyl ether, dioxane, ethyleneglycol monomethylether and ethyleneglycol mono-ethylether; SWASOL 310, SWASOL 1000 and SWASOL 1500 which are tradenames of petroleum type aromatic hydrocarbon solvent produced by Cosmo Oil Co.
The non-aqueous dispersion (P-2) can be produced, for example, by uniformly dissolving the above-mentioned macromolecular dispersion stabilizer in an organic solvent, and subsequently dispersion-polymerizing a monomeric component which contains phosphoric acid group-containing polymerizable unsaturated monomer. It is important that said monomeric component before the dispersion-polymerization should be readily soluble in the solution of macromolecular dispersion stabilizer dissolved in an organic solvent, but that the polymer particles which are formed after the dispersion-polymerization should substantially be insoluble in said solution. In thus obtained non-aqueous dispersion of this invention, the polymer which is derived from monomeric component which comprises a phosphoric acid group-containing polymerizable unsaturated monomer is dispersed, in the form of particles, in a solution of organic solvent which contains a macromolecular dispersion stabilizer dissolved therein. The average particle size of the dispersed polymer particles preferably ranges from 0.01 to 1 .mu.m, especially from 0.05 to 0.6 .mu.m.
Dispersion polymerization of the monomeric component which contains a phosphoric acid group-containing polymerizable unsaturated monomer in a solution of a macromolecular dispersion stabilizer dissolved in an organic solvent can easily be conducted by a known method such as radical polymerization. The constituent ratio of these components in the polymerization reaction is not particularly restricted. As for the preferable ratio of macromolecular dispersion stabilizer to monomeric component for example, macromolecular dispersion stabilizer accounts for 3 to 90%, in particular 5 to 70%, while monomeric component accounts for 97 to 10%, in particular 95 to 30%, based on the total weight of solid contents of these two components. On the basis of the total weight of macromolecular dispersion stabilizer, monomeric component and organic solvent, the total amount of macromolecular dispersion stabilizer and monomeric component accounts for 5 to 70%, in particular 10 to 60%, while organic solvent accounts for 95 to 30%, in particular 90 to 40%.
Thus produced non-aqueous dispersion can have an acid value which ranges generally from 0.1 to 500, preferably from 1 to 300, and most desirably from 5 to 100, on account of the phosphoric acid group-containing unsaturated monomer used as a raw material.
When a crosslinkable functional group such as hydroxyl group is existent in the molecule of macromolecular dispersion stabilizer and/or polymer particles, a three-dimensionally crosslinked coating film can be formed by means of compounding a crosslinking agent with the non-aqueous dispersion (P-2).
Base coating (A) can be prepared by dissolving or dispersing, in an organic solvent, a phosphoric acid group-containing resin composition such as the above-mentioned polymer (P-1) and the non-aqueous dispersion of this invention (P-2), together with, if necessary, resin for coating composition, crosslinking agent, other polymer particles, extender pigment, curing catalyst, UV light absorber, painted surface adjustor, antioxidant, fluidity adjustor, pigment dispersing agent and silane coupling agent.
Examples of resin for coating composition include polyester resin, alkyd resin, acrylic resin, epoxy resin and cellulose acetate butyrate. Examples of crosslinking agent include melamine resin, polyisocyanate compound which may be blocked and epoxy compound.
As for the amount of the above-mentioned resin for coating composition and crosslinking agent compounded, generally, resin for coating composition and crosslinking agent, in total, preferably account for 99.09 to 0% by weight, in particular 98 to 50% by weight, and phosphoric acid group-containing resin composition preferably accounts for 0.01 to 100% by weight, in particular 2 to 50% by weight, each on the basis of solid contents of the total of the resin for coating composition, crosslinking agent and phosphoric acid group-containing resin composition. As for the weight ratio of (resin for coating composition/crosslinking agent), it preferably ranges from 50/50 to 90/10, in particular 65/35 to 85/15.
As an example of said other polymer particles, there can be mentioned both a powder which can be produced by separating particles from an aqueous dispersion of polymer particles, and a dispersion which can be produced by replacing water of said aqueous dispersion of polymer particles with an organic solvent, said aqueous dispersion of polymer particles being obtained by subjecting a polymerizable monomeric component which contains a small amount of monomer having at least two polymerizable unsaturated bonds to emulsion-polymerization in an aqueous medium with use of an anionic or nonionic surfactant. Generally, said other polymer particles compounded preferably account for 0.1 to 30 parts by weight, in particular 1 to 20 parts by weight, on the basis of 100 parts by weight of solid contents of the phosphoric acid group-containing resin composition.
In Application Process of this invention, base coating (A) is to be applied prior to the application of metallic composition (B) which is mentioned later. Base coating (A) can be applied onto a metallic or a plastic substrate such as an automobile body panel, either directly or after coating said substrate with a primer (e.g., a cationic electrocoating), heat-curing the primer, and, if necessary, further applying an intermediate coating, and then appropriately heat-curing the intermediate coating. Wet-on-wet application of the base coating (A) on uncured film of intermediate coating can effectively shorten the application step.
Base coating (A) is applied by air spray, airless spray or electrostatic coating. Thus applied coating film has preferably a thickness ranging from 5 to 20 .mu.m, in particular from 10 to 15 .mu.m, as a cured film.
The film of base coating (A) per se can be crosslinked and cured either at a normal temperature or by heating. In this Application Process II, however, base coating (A) is applied, and, without crosslinking or curing the resulting coating film, metallic composition (B) which is mentioned later is applied on the uncured film of base coating (A).
Leafing Type Aluminum Flake-Containing Metallic Composition (B)
A composition to be applied on uncured film of base coating (A). This composition mainly comprises a leafing type aluminum flake pigment and an organic solvent.
Examples of the aluminum of leafing type aluminum flake pigment which is used for metallic composition (B) are, when mechanically ground, preferably coated on its surface with a low surface tension component such as stearic acid. Said leafing type aluminum flake pigment appropriately has a lengthwise direction size of 2 to 50 .mu.m and a thickness of 0.1 to 2 .mu.m. When a coating composition which contains such a leafing type aluminum flake pigment is applied, the aluminum flake floats up to the surface layer of the coated surface, and is oriented almost parallel to the coated surface, and, thus, there can be formed a metallic coating film having a high density, strong brightness and a chrome plating-like finish.
As for the organic solvent used for metallic composition (B), any solvent for painting may be employed without special restriction. Particularly preferable is a solvent for painting which contains an organic solvent having a surface tension as high as at least 27 dyn/cm, especially 30 dyn/cm. Examples of such solvents include hydrocarbon type ones such as xylene, toluene, tetralin and solvent naphtha; ester type ones such as Cellosolve and butyl Cellosolve; alcohol type ones such as decanol, dodecanol and benzylalcohol; ketone type ones such as cycloheptane and cyclohexane.
The organic solvent used for metallic composition (B) may either consist of the above-mentioned high surface tension organic solvent alone or be a mixture system comprising said high surface tension organic solvent and other organic solvent. In said mixture system, the above-mentioned high surface tension organic solvent preferably accounts for at least 50% by weight, in particular at least 60% by weight, based on the total solvents in the mixture system.
As for the proportion of leafing type aluminum flake pigment to organic solvent in metallic composition (B), the leafing type aluminum flake pigment accounts for 1 to 10% by weight, in particular 3 to 7% by weight, while the organic solvent accounts for 99 to 90% by weight, in particular 97 to 93% by weight, on the basis of the total amount of these two components.
The metallic composition (B) can be produced by mixing and dispersing a leafing type aluminum flake pigment in an organic solvent. With the resultant dispersion, if necessary, an anti-settling agent, a UV light absorber, etc. may be further compounded.
The metallic composition (B) can be applied on uncured coated surface of base coating (A) by electrostatic coating, spray coating or the like. Generally, the film of the metallic composition (D) has preferably a thickness ranging from 0.5 to 5 .mu.m, in particular from 0.8 to 3 .mu.m, as a cured film (which is composed of a leafing type aluminum flake pigment only, or may sometimes contain other solid contents).
After the metallic composition (B) is applied, it is preferably heated at a temperature of about 100 to about 180.degree. C. for about 10 to 40 minutes, so that the coating film of base coating (A) may be cured, and that the base coating (A) and the metallic composition (B) may be tightly adhered to each other.
Composition (C) which Contains a Phosphoric Acid Group-Containing Non-aqueous Dispersion
Composition (C) is a composition which contains a phosphoric acid group-containing non-aqueous dispersion which comprises polymer particles dispersed in a solution of macromolecular dispersion stabilizer dissolved in an organic solvent, said polymer particles being particles of polymer which comprises, as a constituent component, a phosphoric acid group-containing polymerizable unsaturated monomeric unit. This composition (C) plays a role of improving the interlayer adhesivity between the metallic composition (B) and clear coating (D) which is mentioned later. A composition which is usable as composition (C) is required to form either a colorless transparent coating film or a colored transparent coating film which is clear enough so that the metallic feeling of the underlying metallic composition (B) can be seen through.
As for the application of composition (C), after applying metallic composition (B) and heating both base coating (A) and metallic composition (B), then composition (C) is applied on the resultant coated surface of metallic composition (B).
As the phosphoric acid group-containing non-aqueous dispersion of composition (C), there is usable a non-aqueous dispersion which is selected from "(P-2) Phosphoric acid group-containing non-aqueous dispersion which comprises polymer particles dispersed in a solution of macromolecular dispersion stabilizer dissolved in an organic solvent, polymer of said particles comprising a phosphoric acid group-containing unsaturated monomer unit as a constituent component" which is mentioned above as an example of phosphoric acid group-containing resin composition usable for base coating (A).
Composition (C) can be prepared by dissolving or dispersing said phosphoric acid group-containing non-aqueous dispersion in an organic solvent, if necessary together with other normal resin for paint, crosslinking agent, solid color pigment, metallic pigment, coherent pigment or UV light absorber, etc.
In the composition (C), the content (as solid) of the phosphoric acid group-containing non-aqueous dispersion may be varied in a wide range. Generally, however, said content preferably ranges from 0.01 to 100% by weight, in particular from 2 to 20% by weight, most desirably from 3 to 15% by weight, based on the total solid contents.
Examples of other usual resin for paint which may be compounded with the composition (C) include acrylic resin, polyester resin, alkyd resin, fluoro-resin, urethane resin and silicon-containing resin, each of which has a crosslinkable functional group such as hydroxyl group, epoxy group, carboxyl group, silanol group or the like. Crosslinkable functional group-containing acrylic resin is preferable in particular. A resin which contains the above-mentioned crosslinkable functional group may be used in combination with a crosslinking agent such as melamine resin, urea resin, (blocked) polyisocyanate compound, epoxy compound or resin, carboxyl group-containing compound or resin, acid anhydride and alkoxysilane group-containing compound or resin, each of which is reactive with the above-mentioned functional group. As melamine resin, there is preferably used a partially or fully etherified methylol melamine resin having 1 to 5 triazine nuclei wherein a part or the whole of the methylol groups of methylol melamine has been etherified with a monohydric alcohol having 1 to 8 carbon atoms. An imino group-containing melamine resin is also usable. As for the compounding ratio of the crosslinkable functional group-containing resin to the crosslinking agent in said other usual resin for paint, the crosslinkable functional group-containing resin accounts for 50 to 90% by weight, particularly 65 to 80% by weight, while the crosslinking agent accounts for 50 to 10% by weight, particularly 45 to 20% by weight, based on the total of the solid contents of these two components.
In the composition (C), the constituent proportion of the phosphoric acid group-containing non-aqueous dispersion to said other usual resin for paint (including crosslinking agent) may be optional depending on the objective. Generally, however, the phosphoric acid group-containing non-aqueous dispersion accounts for 0.01 to 100% by weight (as solid), in particular 2 to 20% by weight (as solid), further especially desirably 3 to 15% by weight (as solid), while said other usual resin for paint accounts for 99.99 to 0% by weight, in particular 98 to 80% by weight, and most desirably 97 to 85% by weight, based on the total amount of solid contents of these two components.
As examples of organic solvent in composition (C), there are mentioned solvents like hydrocarbon type ones such as hexane, heptane, xylene, toluene and cyclohexane; ester type ones such as methyl acetate, ethyl acetate, ethylene glycol acetate monomethyl ether and diethylene glycol acetate monomethyl ether; ether type ones such as isopropylether, ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; alcohol type ones such as ethyl alcohol, butyl alcohol and hexyl alcohol; ketone type ones such as methyl isobutyl ketone, methylethyl ketone, isophorone and acetophenone.
In the application process of this invention, after base coating (A) and metallic composition (B) are applied and heat-cured, composition (C) whose solid content concentration at the time of application has been adjusted to about 10 to about 80% by weight is applied by electrostatic coating, spray coating or the like, so that the cured film may have a thickness ranging from 1 to 25 .mu.m, preferably from 5 to 15 .mu.m. The coating film of composition (C) can be cured when heated at a temperature of about 100 to about 180.degree. C. for about 10 to 40 minutes. In the application process of this invention, however, it is preferable that the coated surface of said coating film of composition (C), while uncured, is coated with clear coating (D) mentioned below.
Clear Coating (ID
Clear coating (D) is applied onto cured or uncured coated surface of composition (C), and forms either a colorless transparent coating film or a colored transparent coating film.
As clear coating (D), there is usable a liquid coating composition which contains base resin, crosslinking agent and organic solvent, and, if necessary, is further compounded with solid color pigment, metallic pigment, coherent pigment or UV light absorber, etc., and which is capable of forming a coating film transparent enough so that the metallic feeling of the underlying metallic composition (B) can be seen through.
As said base resin which is compounded in clear coating (D), there may be employed usual resin for paint, include acrylic resin, polyester resin, alkyd resin, fluororesin, urethane resin and silicon-containing resin, each of which has a crosslinkable functional group such as hydroxyl group, epoxy group, carboxyl group, silanol group or the like. Crosslinkable functional group-containing acrylic resin is preferable in particular. A resin which contains the above-mentioned crosslinkable functional group may be used in combination with a crosslinking agent such as melamine resin, urea resin, (blocked) polyisocyanate compound, epoxy compound or resin, carboxyl group-containing compound or resin, acid anhydride and alkoxysilane group-containing compound or resin, each of which is reactive with the above-mentioned functional group. As melamine resin, there is preferably used a partially or fully etherified methylol melamine resin having 1 to 5 triazine nuclei wherein a part or the whole of the methylol groups of methylol melamine has been etherified with a monohydric alcohol having 1 to 8 carbon atoms. An imino group-containing melamine resin is also usable. As for the compounding ratio of the crosslinkable functional group-containing resin to the crosslinking agent in said other usual resin for paint, the crosslinkable functional group-containing resin accounts for 50 to 90% by weight, particularly 65 to 80% by weight, while the crosslinking agent accounts for 50 to 10% by weight, particularly 45 to 20% by weight, based on the total of the solid contents of these two components.
As examples of organic solvent in clear coating (D), there are mentioned solvents like hydrocarbon type ones such as hexane, heptane, xylene, toluene and cyclohexane; ester type ones such as methyl acetate, ethyl acetate, ethylene glycol acetate monomethyl ether and diethylene glycol acetate monomethyl ether; ether type ones such as isopropylether, ethylene glycol mono-methyl ether and diethylene glycol monobutyl ether; alcohol type ones such as ethyl alcohol, butyl alcohol and hexyl alcohol; ketone type ones such as methyl isobutyl ketone, methylethyl ketone, isophorone and acetophenone.
In the application process of this invention, onto cured or uncured coated surface of composition (C), clear coating (D) whose solid content concentration at the time of application has been adjusted to about 30 to about 80% by weight is applied by electrostatic coating, spray coating or the like, so that the cured film may have a thickness ranging from 5 to 100 .mu.m, preferably from 20 to 80.mu.m, and, then, the applied coating is cured. How to cure clear coating (D) may optionally be chosen according to its composition. In the case of heat curing, the coating is preferably heated at a temperature of about 100 to about 180.degree. C. for about 10 to 40 minutes.
The coating film of clear coating (D) is thereby cured. When the coating film of composition (C) was uncured, it is now cured concurrently with the coating film of clear coating (D), and, thus, the multi-layer coating film which is the object of this invention is produced.
The above-mentioned Application Process of this invention gives the following effects:
1 In a multi-layer coating film which comprises leafing type aluminum flake-containing metallic coating film and clear coating film, when both overlying and underlying layers which are adjacent to said metallic coating film are made to contain a specific phosphoric acid group-containing component, there can remarkably the interlayer adhesivity can be remarkably improved between said metallic coating film and other adjacent coating films, without decreasing the effects of a chrome plating-like finish with dense and strongly bright coated surface which is derived from leafing type aluminum plane.
2 Thus formed multi-layer coating film has good heat insulation as compared with other coating films. Therefore, in an automobile whose body panel is coated with the multi-layer coating film of this invention, the inside temperature is hardly affected by outdoor conditions.
3 The leafing type aluminum flake has its surface coated with stearic acid etc. and has low surface tension. Hence, when the coated surface of this leafing type aluminum flake is coated with clear coating, wettability sometimes decreases. In this invention, however, wettability of clear coating is improved.
4 Since clear coating (D) and metallic composition (B) are separated from each other by composition (C) any composition is usable as clear coating (D) according to objective.
This invention is described below in more detail by way of Examples. Part and % used in the following each mean a value based on weight.
1. Sample Preparation
1) Piece to Be Coated
Onto a zinc phosphate-treated dull-finish steel plate having a thickness of 0.8 mm, there was applied a thermosetting epoxy resin type cationic electrocoating [Elecron 9600 (trade name of a product of Kansai Paint Co., Ltd.] so as to form a film of about 20 .mu.m in thickness as cured. After the applied coating was cured at 170.degree. C. for 30 minutes, there was air sprayed, on thus cured coating film, an intermediate coating for automobile [TP-37 Primer Surfacer (trade name of a thermosetting polyester resin-melamine resin type organic solvent of Kansai Paint Co., Ltd.)] so as to form a film of about 25 .mu.m in thickness as cured. Thus coated plate was then left to stand at room temperature for 3 minutes, and was used for the test piece.
2) Base coatings (A)
(A-1):
In a mixed organic solvent (xylene/toluene=1/1 by weight), there were mixed and dispersed 65 parts of a polyester resin (*1), 35 parts of a melamine resin (*2) and 10 parts of a resin containing both phosphoric acid group and hydroxyl group (*3), and, thus, the viscosity was adjusted to 13 seconds by Ford Cup No. 4 (20.degree. C.).
(*1) Polyester resin:
Phthalic anhydride-hexahydrophthalic anhydride type polyester resin, having a number-average molecular weight of about 3,500, a hydroxyl value of 82 mg KOH/g and an acid value of 8 mg KOH/g.
(*2) UBAN 28-60:
Trade name of a melamine resin produced by Mitsui Toatsu Chemicals, Inc.
(*3) Resin containing both phosphoric acid group and hydroxyl group:
Prepared by mixing, in an organic solvent (xylene), a resin containing phosphoric acid group, hydroxyl group and alkoxymethylamide group, said resin having an acid value of 21 mg KOH/g, a hydroxyl value of 72 mg KOH/g and a number average molecular weight of 11,000, and the same resin being produced by polymerizing 5 parts of acid-phosphoxyethyl methacrylate, 15 parts of 2-hydroxyethyl methacrylate, 15 parts of N-butoxymethylacrylamide, 20 parts of styrene, 15 parts of butyl-methacrylate and 30 parts of 2-ethylhexyl methacrylate in an equal weight solvent mixture of xylene and butanol.
(A-2):
In SWASOL 1000 (trade name of a hydrocarbon type solvent produced by Cosmo Oil Co., Ltd.), there were mixed and dispersed 65 parts of a polyester resin (*1), 35 parts of a melamine resin (*2), 10 parts (solid) of the phosphoric acid group-containing non-aqueous dispersion (a) (*4), 1 part of TINUBIN 900 (trade name of an ultraviolet absorber of Ciba-Geigy), 2 parts of an equal equivalent mixture of tetrabutylammonium bromide with monobutylphosphoric acid, and 0.1 part of BYK 300 (trade name of a surface conditioner of BYK Chemie). Then, the viscosity of the resulting mixture was adjusted to 13 seconds by Ford Cup No. 4 at 20.degree. C.
(*4) Phosphoric acid group-containing non-aqueous dispersion (a):
Into a usual reactor for the production of acrylic resin which was equipped with stirrer, thermometer, reflux condenser, etc., there were introduced 120 parts of xylene, 64 parts of heptane and 55 parts of dispersion stabilizer 1 (*5), which were then heated and stirred. When the temperature reached 100.degree. C., a mixture of the following monomers and dispersion stabilizer 1 was added dropwise over a period of five hours.
______________________________________Methyl methacrylate 55 partsMethylacrylate 10 parts2-Hydroxyethyl acrylate 20 partsAcid-phosphoxyethyl methacrylate 15 partsDispersion stabilizer 1 55 parts.alpha., .alpha.'-Azobisisobutyronitrile 1 parts______________________________________
After the dropwise addition of the above mixture was over, the resultant mixture was kept at 100.degree. C. for further 30 minutes. Then, to said mixture, there was added dropwise a mixture of 0.5 part of azo-bisdimethyl valeronitrile and 20 parts of xylene over a period of one hour. The resultant mixture was stirred, while kept at 100IC for two hours. Then, said mixture was cooled, and, thus, there was produced the phosphoric acid group-containing non-aqueous dispersion (a). In this dispersion, solid content was 45%, acid value was 70, and phosphoric acid group-containing polymer particles had a particle size of 300 nm.
(*5) Dispersion Stabilizer 1:
Into a usual reactor for the production of acrylic resin which was equipped with stirrer, thermometer, reflux condenser, etc., there were introduced 52 parts of xylene and 10 parts of n-butanol, which were then heated and stirred. When the temperature reached 125.degree. C., a mixture of the following monomers was added dropwise over a period of four hours.
______________________________________Styrene 20 partsn-Butylacrylate 17 parts2-Ethylhexyl methacrylate 47 parts2-Hydroxyethyl acrylate 10 partsMethacrylic acid 6 parts.alpha., .alpha.'-Azobisisobutyronitrile 3 parts______________________________________
After the dropwise addition of the above monomeric mixture was over, the resultant mixture was kept at 125.degree. C. for 30 minutes. Then, to said mixture, there was added dropwise a mixture of 0.5 part of azo-bisdimethyl valeronitrile and 5 parts of xylene over a period of one hour. The resultant mixture was stirred, while kept at 125.degree. C. for three hours. Thus obtained resin solution had a solid content of 60% and an acid value of 86.5. To this resin solution, 1.2 parts of glycidyl methacrylate was added, and the resultant mixture was subjected to addition reaction at 120.degree. C. until acid value became 83, and, thus, dispersion stabilizer 1 was produced. This dispersion stabilizer 1 had a weight average molecular weight of 12,000, a hydroxyl value of 48.4, an acid value of 83 and a solid content of 60%.
(A-3):
In SWASOL 1000 (trade name of a hydrocarbon type solvent produced by Cosmo Oil Co., Ltd.), there were mixed and dispersed 65 parts of a polyester resin (*1), 35 parts of a melamine resin (*2), 10 parts (solid) of the phosphoric acid group-containing non-aqueous dispersion (b) (*6), 1 part of TINUBIN 900 (trade name of an ultraviolet absorber of Ciba-Geigy), 2 parts of an equal equivalent mixture of tetrabutylammonium bromide with monobutylphosphoric acid, and 0.1 part of BYK 300 (trade name of a surface conditioner of BYK Chemie). Then, the viscosity of the resulting mixture .sub.-- was adjusted to 13 seconds by Ford Cup No. 4 at 20.degree. C.
(*6) Phosphoric acid group-containing non-aqueous dispersion (b):
Into a usual reactor for the production of acrylic resin which was equipped with stirrer, thermometer, reflux condenser, etc., there were introduced 120 parts of xylene, 64 parts of heptane and 55 parts of dispersion stabilizer 2 (*7), which were then heated and stirred. When the temperature reached 100.degree. C., a mixture of the following monomers and dispersion stabilizer 2 was added dropwise over a period of five hours.
______________________________________Methyl methacrylate 53 partsGlycidyl methacrylate 2 partsMethyl acrylate 10 parts2-Hydroxyethyl acrylate 20 partsAcid-phosphoxyethyl methacrylate 15 partsDispersion stabilizer 2 55 parts.alpha., .alpha.'-Azobisisobutyronitrile 1 parts______________________________________
After the dropwise addition of the above mixture was over, the resultant mixture was kept at 100.degree. C. for further 30 minutes. Then, to said mixture, there was added dropwise a mixture of 0.5 part of azo-bisdimethyl valeronitrile and 20 parts of xylene over a period of one hour. The resultant mixture was stirred, while kept at 100.degree. C. for two hours. Then, said mixture was cooled, and, thus, there was produced the phosphoric acid group-containing non-aqueous dispersion (b) which contained intraparticle-crosslinked polymer particles. In this dispersion (b), solid content was 45%, acid value was 44, and phosphoric acid group-containing polymer particles had a particle size of 250 nm.
(*7) Dispersion Stabilizer 2:
Into a usual reactor for the production of acrylic resin which was equipped with stirrer, thermometer, reflux condenser, etc., there were introduced 52 parts of xylene and 10 parts of n-butanol, which were then heated and stirred. When the temperature reached 125.degree. C., a mixture of the following monomers was added dropwise over a period of four hours.
______________________________________Methyl methacrylate 30 partsn-Butylacrylate 15 parts2-Ethylhexyl methacrylate 47 parts2-Hydroxyethyl methacrylate 15 partsMethacrylic acid 3 parts.alpha., .alpha.'-Azobisisobutyronitrile 3 parts______________________________________
After the dropwise addition of the above monomeric mixture was over, the resultant mixture was kept at 125.degree. C. for 30 minutes. Then, to said mixture, there was added dropwise a mixture of 0.5 part of azo-bisdimethyl valeronitrile and 5 parts of xylene over a period of one hour. The resultant mixture was stirred, while kept at 125.degree. C. for three hours. Thus obtained resin solution had a solid content of 60% and an acid value of 19.2. To this resin solution, 1.2 parts of glycidyl methacrylate was added, and the resultant mixture was subjected to addition reaction at 120.degree. C. until acid value became 16, and, thus, dispersion stabilizer 2 was produced. This dispersion stabilizer 2 had a weight average molecular weight of 12,000, a hydroxyl value of 64.7, an acid value of 16 and a solid content of 60%.
(A-iv): (For Comparison)
There were mixed and dispersed, in an organic solvent mixture (xylene/toluene=1/1 by weight), 65 parts of a polyester resin (*1) and 35 parts of a melamine resin (*2). Then, the viscosity of the resulting mixture was adjusted to 13 seconds by Ford Cup No. 4 at 20.degree. C.
3) Metallic Compositions (B)
(B-i):
A mixture of 5 parts of a leafing type aluminum flake (*13) with 95 parts of an organic solvent (*9).
(*8) Leafing Aluminum Flake:
[01320MS] (trade name of a paste containing 32 % of mineral spirit, each flake having a lengthwise direction size of 13.6 .mu.m and a thickness of 0.4 .mu.m; product of Toyo Aluminium K. K.)
(*9) Organic solvent:
An equal-weight solvent mixture of toluene (surface tension: 30.9 dyn/cm) with m-xylene (surface tension: 31.23 dyn/cm)
(B-ii):
A mixture of 3 parts of a leafing type aluminum flake (*10) with 97 parts of an organic solvent (*9).
(*10) Hi Print 60T
Trade name of a paste containing 32% of mineral spirit produced by Toyo Aluminium K.K., each flake having a lengthwise direction size of 4.4 .mu.m and a thickness of 0.2 .mu.m.
4) Composition (C)
(C-1):
In SWASOL 1000, there were mixed and dispersed 75 parts of a hydroxyl group-containing acrylic resin (*11), 25 parts of a butyl etherified melamine resin (*2) and 15 parts (solid content) of phosphoric acid group-containing non-aqueous dispersion (a) (*4). The viscosity of the resulting mixture was adjusted to 13 seconds by Ford Cup No. 4 at 20.degree. C.
(*11) Hydroxyl group-containing acrylic resin:
A polymer composed of 38% of methyl methacrylate, 17% of ethyl acrylate, 17% of n-butyl acrylate, 7% of hydroxyethyl methacrylate, 20% of lauryl methacrylate and 1% of acrylic acid, which has a number average molecular weight of 50,000 and a hydroxyl value of 4 mg KOH/g.
(C-2):
In SWASOL 1000, there were mixed and dispersed 75 parts of a hydroxyl group-containing acrylic resin (*11), 25 parts of a butyl etherified melamine resin (*2), 15 parts (solid content) of phosphoric acid group-containing non-aqueous dispersion (b) (*6), 1 part of a phthalocyanine blue pigment (produced by Dainichi Seika Colour & Chemicals MFG. CO., LTD.). The viscosity of the resulting mixture was adjusted to 13 seconds by Ford Cup No. 4 at 20.degree. C.
(C-3)-: For Comparison
In SWASOL 1000, there were mixed and dispersed 75 parts of a hydroxyl group-containing acrylic resin (*11) and 25 parts of a butyl etherified melamine resin (*2). The viscosity of the resulting mixture was adjusted to 13 seconds by Ford Cup No. 4 at 20.degree. C.
5) Clear Coating (D)
(D-1):
In SWASOL 1000, there were mixed and dispersed 50 parts of a carboxyl group-containing acrylic resin (*12), 50 parts of an epoxy group-containing acrylic resin (*13), 1 part of TINUBIN 900 (trade name of an ultraviolet absorber of Ciba-Geigy), 2 parts of an equal equivalent mixture of tetrabutylammonium bromide with monobutylphosphoric acid, and 0.1 part of BYK 300 (trade name of a surface conditioner of BYK Chemie). The viscosity of the resulting mixture was adjusted to 13 seconds by Ford Cup No. 4 at 20.degree. C.
(*12) Carboxyl group-containing acrylic resin:
A polymer composed of 20% of methanol half ester of maleic anhydride, 20% of 4-hydroxy n-butyl acrylate, 40% of n-butyl acrylate and 20% of styrene, which has a number average molecular weight of 3,500, an acid value of 86 mg KOH/g and a hydroxyl value of 78 mg KOH/g.
(*13) Epoxy group-containing acrylic resin:
A polymer composed of 30% of glycidyl methacrylate, 20% of 4-hydroxy n-butyl acrylate, 30% of n-butyl acrylate and 20% of styrene, which has a number average molecular weight of 3,000, an epoxy group content of 2.12 mmole/g and a hydroxyl value of 78 mg KOH/g.
2. Examples and Comparative Examples
Uncured surface of intermediate coating which had been applied on each piece to be coated was coated with one of base coatings (A-1)-(A-4) respectively, and, without curing, was further coated with one of metallic compositions; (B-1)-(B-2). Then, after left to stand at room temperature for three minutes, each piece was heated at 140.degree. C. for 30 minutes so that the resultant multi-layer coating film might be cured at the same time. Subsequently, each piece was coated with one of compositions (C-1)-(C-3) respectively, and, without curing, was further coated with clear coating (D-1). Then, each piece was heated at 140.degree. C. for 30 minutes so that these compositions and clear coating might be cured.
Table 1 shows both the above-mentioned application steps and the results of property test of thus obtained multi-layer coating films.
TABLE 1______________________________________ Comparative Examples Examples 1 2 3 1 2______________________________________Base coatingName A-1 A-2 A-3 -- A-4Film thickness 10-15 .mu.m as a cured filmDrying Left at room temperature for 3 minutes (uncured)Metallic compositionName B-1 B-1 B-2 B-1 B-1Film thickness 1.3-2 .mu.m as a cured filmCuring 140.degree. C. for 30 minutesCompositionName C-1 C-1 C-2 C-3 C-3Film thickness 5-15 .mu.m as a cured filmDrying Left at room temperature for 3 minutes (uncured)Clear coatingName D-1Film thickness 35-45 .mu.m as a cured filmCuring 140.degree. C. for 30 minutesResults of PropertyTestWettability (*1) .largecircle. .largecircle. .largecircle. .DELTA. .DELTA.Adhesivity (*2) .largecircle. .largecircle. .largecircle. X XIV value (*3) 385 382 59 381 377SV value (*4) 13.6 13.8 4.7 13.8 13.8FF value (*5) 1.86 1.86 1.70 1.86 1.86C* value (*6) 2.0 1.8 71 1.6 2.0Appearance (*7) .largecircle. .largecircle. .circleincircle. .largecircle. .largecircle.______________________________________
Property test was conducted in the same manner as in Table 1.
Method of Property Test
(*1) Wettability:
Clear coating was spray-applied on the surface of cured metallic coating, and the degree of wetting was visually evaluated. The mark .largecircle. shows good wetting, .DELTA. poor wetting, and X very poor wetting.
(*2) Adhesivity:
Cross-cut lines were made with a cutter so that the cutter edge might reach the base plate through the multi-layer coating film, and, thus, there were formed 100 squares each having a size of 1 mm.times.1 mm. Next, Scotch tape was applied on the surface of said squares, and, then, the tape was peeled off rapidly, and, thus, the surface of the coated film was observed The mark .largecircle. shows that no square had been peeled off at all, while X shows that 10 or more squares had been peeled off.
(*3) IV value:
Y value at the light-reception angle of 15.degree. was measured with use of a portable goniophotometer MA 68 (produced by X-Rite Go.). This IV value indicates the brightness of a coating film, and shows the luminous feeling of highlight portion of metallic coating film.
This value means that, the larger it is, the more luminous is the coating film.
(*4) SV value:
Y value at the light-reception angle of 45.degree. was measured with use of MA 68. This SV value indicates the brightness of coating film, and shows the frontal colour brightness of coating film. The lower this value is, the darker is the coating film, which means that aluminum flake is horizontally oriented to give little diffuse light.
(*5) FF value:
Calculated from the equation:
FF=(IV-SV)/[(IV+SV)/2]
with use of the above-mentioned IV value and SV value measured by MA 68. This FF value shows contrast between the highlight luminance and the frontal brightness. The higher this FF value is, the stronger is light-dark contrast feeling, which means that a chrome plating-like finish has been achieved.
(*6) C* value:
CIE metric chroma at the light-reception angle of 15.degree. was measured with use of MA 68. This C* value indicates chroma in the highlight of coating film. The higher this value is, the more vivid is the color of coating film.
(*7) Appearance:
Results of visual evaluation of coating film. The mark .largecircle. shows that a chrome plating-like finish has been achieved. The mark .circleincircle. shows that a chrome plating-like finish with candy tone has been achieved. The mark X shows that not a chrome plating-like finish but an ordinary metallic-feeling finish has been achieved.

Number	Name	Date
2139824	Higgins	Dec 1938
3577257	Hutzler et al.	May 1971
4097639	Millar	Jun 1978
4141760	Baldi	Feb 1979
4220675	Imazaki	Sep 1980
4415698	Fan	Nov 1983
5244696	Hazan et al.	Sep 1993
5439710	Vogt et al.	Aug 1995
5466752	Barsotti et al.	Nov 1995
5780113	Masuda et al.	Jul 1998
5830581	Masuda et al.	Nov 1998
5929140	Fujii et al.	Jul 1999

Method for forming multi-layer coating film

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