Iron oxide hydroxide composite particles, pigment, paint and resin composition

Information

  • Patent Application
  • 20010011110
  • Publication Number
    20010011110
  • Date Filed
    December 08, 2000
    23 years ago
  • Date Published
    August 02, 2001
    22 years ago
Abstract
Iron oxide hydroxide composite particles having an average particle diameter of 0.005 to 1.0 μm, comprises:
Description


BACKGROUND OF THE INVENTION

[0001] The present invention relates to iron oxide hydroxide composite particles, a pigment composed of the same, a paint containing the pigment, a resin composition containing the pigment and a process for producing the iron oxide hydroxide composite particles. More particularly, the present invention relates to iron oxide hydroxide composite particles containing no harmful elements and exhibiting not only excellent chemical resistances such as acid resistance and alkali resistance, but also excellent heat resistance, a pigment such as a green-based pigment or a orange-based pigment, composed of the iron oxide hydroxide composite particles, a paint containing the pigment, a resin composition containing the pigment and a process for producing the iron oxide hydroxide composite particles.


[0002] At present, as green-based pigments, there have been widely used inorganic pigments such as chrome green, chromium oxide and zinc green, and organic pigments such as phthalocyanine green. Also, as orange-based pigments, there have been used chrome vermilion, chrome orange, permanent orange, benzidine orange or the like. These pigments have been extensively applied to colorants of resins, paints, printing inks or the like.


[0003] However, it is known that the inorganic pigments such as chrome green, chromium oxide and zinc green tend to be deteriorated in chemical resistances such as acid resistance and alkali resistance though they are excellent in light resistance, and are expensive.


[0004] In addition, the inorganic pigments such as chrome green, chromium oxide and zinc green contain harmful elements such as lead and chromium. For this reason, it has been strongly required to develop alternate materials for these green-based pigments from viewpoints of hygiene, safety and environmental protection.


[0005] On the other hand, the organic green-based pigments such as phthalocyanine green exhibit a high tinting strength and a clear hue. However, it is known that these organic pigments are deteriorated in light resistance, i.e., suffer from bronze-bleeding (so-called bronzing) upon outdoor exposure.


[0006] Chrome vermilion and chrome orange exhibit a very clear hue. However, it is known that these orange-based pigments are deteriorated in chemical resistances such acid resistance and alkali resistance as well as light resistance and heat resistance, and are extensive.


[0007] In addition, the inorganic orange-based pigments such as chrome vermilion and chrome orange also contain harmful elements such as lead and chromium. Therefore, it has been strongly required to develop alternate materials for these orange-based pigments from viewpoints of hygiene, safety and environmental protection.


[0008] It is also known that the organic orange-based pigments such as permanent orange and benzidine orange exhibit a clear hue, but are deteriorated in light resistance.


[0009] Further, resin compositions using thermoplastic resins such as polyolefins, for example, polyethylenes, polypropylenes, styrene polymers or the like, polyamides and ABS resins are usually molded at a temperature as high as not less than 200° C. For this reason, pigments added as colorants to these resin compositions are required to exhibit a good heat resistance.


[0010] In consequence, green and orange-based pigments added to these resin compositions are strongly required to have not only excellent chemical resistances and tinting strength but also excellent heat resistance.


[0011] Hitherto, in order to improve properties of the pigments, it has been attempted to use inorganic and organic pigments in combination. For example, there have been proposed methods of co-precipitating chrome yellow and phthalocyanine blue together or adhering organic pigments onto the surfaces of inorganic pigments (Japanese Patent Application Laid-Open (KOKAI) Nos. 4-132770(1992), 10-88032(1998) and 11-181329(1999), etc.).


[0012] Thus, it has been strongly demanded to provide green and orange-based pigments exhibiting both excellent chemical resistances and excellent heat resistance without containing harmful elements. However, such pigments capable of satisfying these requirements have not been provided until now.


[0013] Namely, in the above method of co-precipitating chrome yellow and phthalocyanine blue together, the obtained pigments show a toxicity due to chrome yellow. Further, paints containing such pigments are insufficient in storage stability due to the use of co-precipitated pigments, so that coating films formed therefrom tend to suffer from bleeding.


[0014] In the method of precipitating organic pigments in the presence of inorganic pigments as described in Japanese Patent Application Laid-Open (KOKAI) No. 4-132770, the organic pigments are insufficient in adhesion to the inorganic pigments.


[0015] In the method of mechanically mixing and milling inorganic and organic pigments together as described in Japanese Patent Application Laid-Open (KOKAI) No. 10-88032(1998), the organic pigments are also insufficient in adhesion to the inorganic pigments.


[0016] Further, in Japanese Patent Application Laid-Open (KOKAI) No. 11-181329(1999), there is described the method of adding organic pigments to a solution prepared by dissolving organopolysiloxane in cyclic silicone to disperse therein the pigments as fine particles, impregnating the fine organic pigments with high oil-absorption inorganic pigments, and then evaporating cyclic silicone from the pigments. In this method, the organic pigments are also insufficient in adhesion to the inorganic pigments.


[0017] Meanwhile, in Japanese Patent Application Laid-Open (KOKAI) No. 11-323174(1999), there are described iron-based black composite particles obtained by forming an organosilane coating layer on black iron oxide particles or black iron oxide hydroxide particles, and then forming a carbon black coat on the organosilane coating layer. Since the iron-based black composite particles are black iron oxide hydroxide composite particles having the carbon black coat, the iron-based black composite particles are quite different from composite particles having green or orange-based pigments.


[0018] As a result of the present inventors' earnest studies, it has been found that by mixing as core particles iron oxide hydroxide particles with at least one compound selected from the group consisting of:


[0019] (1) alkoxysilane compounds, and


[0020] (2) polysiloxanes or modified polysiloxanes, by using an apparatus capable of applying a shear force to the core particles, thereby coating the surface of the black iron oxide hydroxide particle with the compounds;


[0021] mixing the obtained iron oxide hydroxide particles coated with the compounds and organic blue or red-based pigment in an amount of 1 to 30 parts by weight based on 100 parts by weight of the core particles by using an apparatus capable of applying a shear force to the core particles, thereby forming organic blue or red-based pigment coat on the surface of a coating layer comprising the organosilicon compounds, the thus obtained iron oxide hydroxide composite particles are harmless pigments which are excellent not only in chemical resistances such as acid resistance and alkali resistance, but also in heat resistance. The present invention has been attained on the basis of the above finding.



SUMMARY OF THE INVENTION

[0022] An object of the present invention is to provide a harmless pigment such as a harmless green or orange-based pigment exhibiting not only excellent chemical resistances such as acid resistance and alkali resistance, but also high hiding power, high tinting powder and excellent heat resistance.


[0023] Another object of the present invention is to provide a fine pigment such as a green or orange-based fine pigment which contains no harmful elements and is improved not only in chemical resistances such as acid resistance and alkali resistance but also in heat resistance, and further is capable of producing a paint and a resin composition exhibiting an excellent transparency.


[0024] To accomplish the aim of the present invention, in a first aspect of the present invention, there are provided iron oxide hydroxide composite particles having an average particle diameter (average major axial diameter) of 0.005 to 1.0 μm, comprising:


[0025] iron oxide hydroxide particles as core particles,


[0026] a coating formed on surface of the iron oxide hydroxide particles, comprising at least one organosilicon compound selected from the group consisting of:


[0027] (1) organosilane compounds obtainable from alkoxysilane compounds, and


[0028] (2) polysiloxanes or modified polysiloxanes, and


[0029] an organic pigment coat formed on the coating layer comprising the organosilicon compound, in an amount of from 1 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0030] In a second aspect of the present invention, there are provided iron oxide hydroxide composite particles having an average particle diameter of 0.005 to 1.0 μm, comprising:


[0031] iron oxide hydroxide particles as core particles,


[0032] a coat formed on at least a part of the surface of the iron oxide hydroxide particles, comprising at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon;


[0033] a coating formed on surface of the said coat, comprising at least one organosilicon compound selected from the group consisting of:


[0034] (1) organosilane compounds obtainable from alkoxysilane compounds, and


[0035] (2) polysiloxanes or modified polysiloxanes, and


[0036] an organic pigment coat formed on the coating layer comprising the organosilicon compound, in an amount of from 1 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0037] In a third aspect of the present invention, there are provided iron oxide hydroxide composite particles having an average particle diameter of from 0.005 to less than 0.1 μm, comprising:


[0038] iron oxide hydroxide particles as core particles,


[0039] a coating formed on surface of the iron oxide hydroxide particles, comprising at least one organosilicon compound selected from the group consisting of:


[0040] (1) organosilane compounds obtainable from alkoxysilane compounds, and


[0041] (2) polysiloxanes or modified polysiloxanes, and


[0042] an organic blue-based pigment coat formed on the coating layer comprising the organosilicon compound, in an amount of from 5 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0043] In a fourth aspect of the present invention, there are provided iron oxide hydroxide composite particles having an average particle diameter of from 0.005 to less than 0.1 μm, comprising:


[0044] iron oxide hydroxide particles as core particles,


[0045] a coat formed on at least a part of the surface of the iron oxide hydroxide particles, comprising at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon;


[0046] a coating formed on surface of the said coat, comprising at least one organosilicon compound selected from the group consisting of:


[0047] (1) organosilane compounds obtainable from alkoxysilane compounds, and


[0048] (2) polysiloxanes or modified polysiloxanes, and


[0049] an organic blue-based pigment coat formed on the coating layer comprising the organosilicon compound, in an amount of from 5 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0050] In a fifth aspect of the present invention, there are provided iron oxide hydroxide composite particles having an average particle diameter of from 0.005 to less than 0.1 μm, comprising:


[0051] iron oxide hydroxide particles as core particles,


[0052] a coating formed on surface of the iron oxide hydroxide particles, comprising at least one organosilicon compound selected from the group consisting of:


[0053] (1) organosilane compounds obtainable from alkoxysilane compounds, and


[0054] (2) polysiloxanes or modified polysiloxanes, and


[0055] an organic red-based pigment coat formed on the coating layer comprising the organosilicon compound, in an amount of from 1 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0056] In a sixth aspect of the present invention, there are provided iron oxide hydroxide composite particles having an average particle diameter of from 0.005 to less than 0.1 μm, comprising:


[0057] iron oxide hydroxide particles as core particles,


[0058] a coat formed on at least a part of the surface of the iron oxide hydroxide particles, comprising at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon;


[0059] a coating formed on surface of the said coat, comprising at least one organosilicon compound selected from the group consisting of:


[0060] (1) organosilane compounds obtainable from alkoxysilane compounds, and


[0061] (2) polysiloxanes or modified polysiloxanes, and an organic red-based pigment coat formed on the coating layer comprising the organosilicon compound, in an amount of from 1 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0062] In a seventh aspect of the present invention, there are provided iron oxide hydroxide composite particles having an average particle diameter of from 0.1 to 1.0 μm, comprising:


[0063] iron oxide hydroxide particles as core particles,


[0064] a coating formed on surface of the iron oxide hydroxide particles, comprising at least one organosilicon compound selected from the group consisting of:


[0065] (1) organosilane compounds obtainable from alkoxysilane compounds, and


[0066] (2) polysiloxanes or modified polysiloxanes, and an organic blue-based pigment coat formed on the coating layer comprising the organosilicon compound, in an amount of from 5 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0067] In an eighth aspect of the present invention, there are provided iron oxide hydroxide composite particles having an average particle diameter of from 0.1 to 1.0 μm, comprising:


[0068] iron oxide hydroxide particles as core particles,


[0069] a coat formed on at least a part of the surface of the iron oxide hydroxide particles, comprising at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon;


[0070] a coating formed on surface of the said coat, comprising at least one organosilicon compound selected from the group consisting of:


[0071] (1) organosilane compounds obtainable from alkoxysilane compounds, and


[0072] (2) polysiloxanes or modified polysiloxanes, and


[0073] an organic blue-based pigment coat formed on the coating layer comprising the organosilicon compound, in an amount of from 5 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0074] In a ninth aspect of the present invention, there are provided iron oxide hydroxide composite particles having an average particle diameter of from 0.1 to 1.0 μm, comprising:


[0075] iron oxide hydroxide particles as core particles,


[0076] a coating formed on surface of the iron oxide hydroxide particles, comprising at least one organosilicon compound selected from the group consisting of:


[0077] (1) organosilane compounds obtainable from alkoxysilane compounds, and


[0078] (2) polysiloxanes or modified polysiloxanes, and


[0079] an organic red-based pigment coat formed on the coating layer comprising the organosilicon compound, in an amount of from 1 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0080] In a tenth aspect of the present invention, there are provided iron oxide hydroxide composite particles having an average particle diameter of from 0.1 to 1.0 μm, comprising:


[0081] iron oxide hydroxide particles as core particles,


[0082] a coat formed on at least a part of the surface of the iron oxide hydroxide particles, comprising at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon;


[0083] a coating formed on surface of the said coat, comprising at least one organosilicon compound selected from the group consisting of:


[0084] (1) organosilane compounds obtainable from alkoxysilane compounds, and


[0085] (2) polysiloxanes or modified polysiloxanes, and


[0086] an organic red-based pigment coat formed on the coating layer comprising the organosilicon compound, in an amount of from 1 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0087] In an eleventh aspect of the present invention, there is provided a pigment comprising iron oxide hydroxide composite particles having an average particle diameter of 0.005 to 1.0 μm, comprising:


[0088] iron oxide hydroxide particles as core particles,


[0089] a coating formed on surface of the iron oxide hydroxide particles, comprising at least one organosilicon compound selected from the group consisting of:


[0090] (1) organosilane compounds obtainable from alkoxysilane compounds, and


[0091] (2) polysiloxanes or modified polysiloxanes, and


[0092] an organic pigment coat formed on the coating layer comprising the organosilicon compound, in an amount of from 1 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0093] In a twelfth aspect of the present invention, there is provided a pigment comprising iron oxide hydroxide composite particles having an average particle diameter of 0.005 to 1.0 μm, comprising:


[0094] iron oxide hydroxide particles as core particles,


[0095] a coat formed on at least a part of the surface of the iron oxide hydroxide particles, comprising at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon;


[0096] a coating formed on surface of the said coat, comprising at least one organosilicon compound selected from the group consisting of:


[0097] (1) organosilane compounds obtainable from alkoxysilane compounds, and


[0098] (2) polysiloxanes or modified polysiloxanes, and


[0099] an organic pigment coat formed on the coating layer comprising the organosilicon compound, in an amount of from 1 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0100] In a thirteenth aspect of the present invention, there is provided a green-based pigment comprising iron oxide hydroxide composite particles having an average particle diameter of 0.005 to 1.0 μm, comprising:


[0101] iron oxide hydroxide particles as core particles,


[0102] a coating formed on surface of the iron oxide hydroxide particles, comprising at least one organosilicon compound selected from the group consisting of:


[0103] (1) organosilane compounds obtainable from alkoxysilane compounds, and


[0104] (2) polysiloxanes or modified polysiloxanes, and


[0105] an organic blue-based pigment coat formed on the coating layer comprising the organosilicon compound, in an amount of from 5 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0106] In fourteenth aspect of the present invention, there is provided an orange-based pigment comprising iron oxide hydroxide composite particles having an average particle diameter of 0.005 to 1.0 μm, comprising:


[0107] iron oxide hydroxide particles as core particles,


[0108] a coating formed on surface of the iron oxide hydroxide particles, comprising at least one organosilicon compound selected from the group consisting of:


[0109] (1) organosilane compounds obtainable from alkoxysilane compounds, and


[0110] (2) polysiloxanes or modified polysiloxanes, and


[0111] an organic red-based pigment coat formed on the coating layer comprising the organosilicon compound, in an amount of from 1 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0112] In a fifteenth aspect of the present invention, there is provided a paint comprising:


[0113] a paint base material, and


[0114] a pigment comprising iron oxide hydroxide composite particles having an average particle diameter of 0.005 to 1.0 μm, comprising:


[0115] iron oxide hydroxide particles as core particles,


[0116] a coating formed on surface of the iron oxide hydroxide particles, comprising at least one organosilicon compound selected from the group consisting of:


[0117] (1) organosilane compounds obtainable from alkoxysilane compounds, and


[0118] (2) polysiloxanes or modified polysiloxanes, and an organic pigment coat formed on the coating layer comprising the organosilicon compound, in an amount of from 1 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0119] In a sixteenth aspect of the present invention, there is provided a rubber or resin composition comprising:


[0120] a base material for rubber or resin composition, and


[0121] a pigment comprising iron oxide hydroxide composite particles having an average particle diameter of 0.005 to 1.0 μm, comprising:


[0122] iron oxide hydroxide particles as core particles,


[0123] a coating formed on surface of the iron oxide hydroxide particles, comprising at least one organosilicon compound selected from the group consisting of:


[0124] (1) organosilane compounds obtainable from alkoxysilane compounds, and


[0125] (2) polysiloxanes or modified polysiloxanes, and


[0126] an organic pigment coat formed on the coating layer comprising the organosilicon compound, in an amount of from 1 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.



DETAILED DESCRIPTION OF THE INVENTION

[0127] First, the pigment such as green or orange-based pigment according to the present invention will be explained below.


[0128] The pigment of the present invention is composed of iron oxide hydroxide composite particles which comprise iron oxide hydroxide particles as core particles, a coating layer of organosilicon compounds formed on the surface of the core particle, and an organic blue-based pigment or an organic red-based pigment adhered on the coating layer, and have an average major axial diameter of from 0.005 to 1.0 μm.


[0129] The above iron oxide hydroxide composite particles of the present invention are generally classified into:


[0130] (1) iron oxide hydroxide composite particles comprising iron oxide hydroxide particles as core particles, a coating layer of organosilicon compounds formed on the surface of the core particle, and an organic blue-based pigment or an organic red-based pigment adhered on the coating layer, and having an average major axial diameter of 0.1 to 1.0 μm; and


[0131] (2) fine iron oxide hydroxide composite particles comprising fine iron oxide hydroxide particles as core particles, a coating layer of organosilicon compounds formed on the surface of the core particle, and an organic blue-based pigment or an organic red-based pigment adhered on the coating layer, and having an average major axial diameter of from 0.005 to less than 0.1 μm.


[0132] The iron oxide hydroxide particles used as core particles in the present invention are of an acicular shape or a rectangular shape. The “acicular” shape used herein may include a spindle shape and a rice-ball shape in addition to literally acicular or needle-like shape.


[0133] The iron oxide hydroxide particles used in the present invention include goethite (α-FeOOH) particles and lepidocrocite (γ-FeOOH) particles. In the consideration of heat resistance of the obtained pigments, iron oxide hydroxide particles obtained by subjecting iron oxide hydroxide particles to heat resistance-imparting treatments is preferred. More specifically, the preferred iron oxide hydroxide particles used as core particles in the present invention may include iron oxide hydroxide particles whose surfaces are coated with at least one compound selected from the group consisting of hydroxides of aluminum and oxides of aluminum; iron oxide hydroxide particles containing aluminum inside thereof; iron oxide hydroxide particles having a coating layer composed of an iron and aluminum oxide hydroxide composite on the surface thereof; and iron oxide hydroxide particles subjected to any two or more of the above heat resistance-imparting treatments.


[0134] In the case of the iron oxide hydroxide particles whose surfaces are coated with at least one compound selected from the group consisting of hydroxides of aluminum and oxides of aluminum, the aluminum content thereof is 0.1 to 20.0% by weight (calculated as Al) based on the weight of the iron oxide hydroxide particles coated. In the case of the iron oxide hydroxide particles containing aluminum inside thereof, the aluminum content thereof is 0.05 to 50% by weight (calculated as Al) based on the weight of the iron oxide hydroxide particles containing aluminum inside thereof. In the case of the iron oxide hydroxide particles having a coasting layer composed of an iron and aluminum oxide hydroxide composite on the surfaces thereof, the aluminum content thereof is 0.1 to 10% by weight (calculated as Al) based on the weight of the iron oxide hydroxide particles, and the iron content thereof is 0.1 to 30% by weight (calculated as Fe) based on the weight of the iron oxide hydroxide particles.


[0135] The iron oxide hydroxide particles used in the present invention have an average major axial diameter of 0.005 to 1.0 μm; an average minor axial diameter of 0.0025 to 0.5 μm; an aspect ratio of 2:1 to 20:1; a BET specific surface area value of 5 to 300 m2/g; and a geometrical standard deviation of major axial diameters of 1.01 to 2.0. As to the hue of the iron oxide hydroxide particles, the L* value thereof is 40 to 80; the a* value thereof is −57.7 to +57.7 (a* value≢0); and the b* value thereof is from more than 0 to +100; and the h value thereof is from more than 60° to less than 120°.


[0136] More specifically, the following two kinds of iron oxide hydroxide particles as classified based on average major axial diameter thereof, are individually explained.


[0137] (1) In the case of iron oxide hydroxide particles having an average major axial diameter of 0.1 to 1.0 μm:


[0138] The average major axial diameter of the iron oxide hydroxide particles (1) is usually 0.1 to 1.0 μm, preferably 0.15 to 0.9 μm.


[0139] When the average major axial diameter is more than 1.0 μm, the obtained pigments become coarse particles, resulting in deteriorated tinting strength.


[0140] The average minor axial diameter of the iron oxide hydroxide particles (1) is usually 0.05 to 0.5 μm, preferably 0.075 to 0.45 μm.


[0141] The aspect ratio (ratio of average major axial diameter to average minor axial diameter; hereinafter referred to merely as “aspect ratio”) is usually not more than 20:1, preferably 2:1 to 15:1.


[0142] When the aspect ratio is more than 20:1, the particles may tend to be entangled or interlaced with each other, so that it may be difficult to uniformly form a coating layer of organosilicon compounds on the surface of each iron oxide hydroxide particle and uniformly adhere the organic pigment thereonto.


[0143] The geometrical standard deviation value of major axial diameters is usually not more than 2.0, preferably not more than 1.8, more preferably not more than 1.6.


[0144] When the geometrical standard deviation value is more than 2.0, a large amount of coarse particles may be present, so that the particles may be inhibited from being uniformly dispersed. As a result, it may be difficult to uniformly form a coating layer of organosilicon compounds on the surface of each iron oxide hydroxide particle and uniformly adhere the organic pigment thereonto. The lower limit of the geometrical standard deviation value is 1.01. It is difficult to industrially produce iron oxide hydroxide particles having a geometrical standard deviation value of less than 1.01.


[0145] The BET specific surface area value is usually 5 to 150 m2/g, preferably 10 to 120 m2/g, more preferably 15 to 100 m2/g.


[0146] When the BET specific surface area value is less than 5 m2/g, the iron oxide hydroxide particles may become coarse or tend to be sintered together. As a result, the obtained particles may become coarse, resulting in deteriorated tinting strength.


[0147] As to the hue of the iron oxide hydroxide particles (1), the L* value thereof is 40 to 80; the a* value thereof is −57.7 to +57.7 (a* value≢0); the b* value thereof is from more than 0 to +100; and the h value thereof is from more than 60° to less than 120°. When any of the L*, a*, b* and h values is out of the above specified range, the aimed pigments such as green or orange-based pigments according to the present invention may not be obtained.


[0148] (2) In the case of iron oxide hydroxide fine particles having an average major axial diameter of from 0.005 μm to less than 0.1 μm:


[0149] The average major axial diameter thereof is usually from 0.005 μm to less than 0.1 μm. When the average major axial diameter is less than 0.005 μm, the particles may tend to be agglomerated together due to increase in intermolecular force therebetween. As a result, it may be difficult to uniformly form a coating layer of organosilicon compounds on the surface of each iron oxide hydroxide fine particle and uniformly adhere the organic pigment thereonto.


[0150] In the consideration of uniform formation of the coating layer of organosilicon compounds on the surface of each iron oxide hydroxide fine particle, uniform adhesion of the organic pigment thereonto, and the average major axial diameter is preferably 0.008 to 0.096 μm, more preferably 0.01 to 0.092.


[0151] The average minor axial diameter thereof is usually from 0.0025 to less than 0.05 μm, preferably 0.004 to 0.048 μm, more preferably 0.005 to 0.046 μm; the aspect ratio thereof is usually not more than 20:1, preferably not more than 15:1, more preferably not more than 10:1 (lower limit of the aspect ratio: 2:1); the BET specific surface area value thereof is usually 50 to 300 m2/g, preferably 70 to 280 m2/g, more preferably 80 to 250 m2/g; and the geometrical standard deviation value of major axial diameters thereof is usually not more than 2.0, preferably not more than 1.8, more preferably not more than 1.6 (lower limit of the geometrical standard deviation value: 1.01).


[0152] When the average minor axial diameter is less than 0.0025 μm, the intermolecular force between the particles may become large due to fineness thereof, so that it may become difficult to uniformly form a coating layer of organosilicon compounds on the surface of each iron oxide hydroxide fine particle and uniformly adhere the organic pigment thereonto.


[0153] When the BET specific surface area value is more than 300 m2/g, the intermolecular force between the particles may become large due to fineness thereof, so that it may be difficult to uniformly form a coating layer of organosilicon compounds on the surface of each iron oxide hydroxide fine particle and uniformly adhere the organic pigment thereonto.


[0154] As to the hue of the iron oxide hydroxide fine particles (2) used in the present invention, the L* value thereof is 40 to 80; the a* value thereof is −57.7 to +57.7 (a* value≢0); the b* value thereof is from more than to +100; and the h value thereof is from more than 60° to less than 120°. When any of the L*, a* and b* values is out of the above specified range, the aimed fine pigments such as green or orange-based fine pigments according to the present invention may not be obtained.


[0155] The iron oxide hydroxide fine particles (2) used in the present invention have a hiding power of preferably less than 600 cm2/g, more preferably not more than 500 cm2/g. When the hiding power is not less than 600 cm2/g, the fine pigments obtained using the iron oxide hydroxide fine particles as core particles may show a too high hiding power.


[0156] As to the chemical resistances of the iron oxide hydroxide fine particles (2) used in the present invention, the acid resistance (ΔE*) thereof is preferably not more than 3.0, more preferably not more than 2.5; and the alkali resistance (ΔE*) thereof is preferably not more than 3.0, more preferably not more than 2.5, when measured by the evaluation methods described hereinafter. When any of the acid and alkali resistances (ΔE*) is more than 3.0, it may be difficult to obtain the aimed fine pigments such as green or orange-based fine pigments having excellent chemical resistances according to the present invention.


[0157] As to the heat resistance of the iron oxide hydroxide particles used in the present invention, the heat resistance temperature thereof is preferably not less than 180° C., more preferably not less than 185° C. In the consideration of the heat resistance of the obtained pigments such as green or orange-based pigments, the use of iron oxide hydroxide particles subjected to heat resistance-imparting treatments is preferred. In the case of the iron oxide hydroxide particles whose surfaces are coated with at least one compound selected from the group consisting of hydroxides of aluminum and oxides of aluminum, the heat resistance temperature thereof is about 240° C. In the case of the iron oxide hydroxide particles containing aluminum inside thereof, the heat resistance temperature thereof is about 245° C. Also, in the case of the iron oxide hydroxide particles having a coating layer composed of an aluminum and iron oxide hydroxide composite on the surfaces thereof, the heat resistance temperature thereof is about 250° C.


[0158] The coating formed on the surface of the core particle comprises at least one organosilicon compound selected from the group consisting of (1) organosilane compounds obtainable from alkoxysilane compounds; and (2) polysiloxanes and modified polysiloxanes selected from the group consisting of (2-A) polysiloxanes modified with at least one compound selected from the group consisting of polyethers, polyesters and epoxy compounds (hereinafter referred to merely as “modified polysiloxanes”), and (2-B) polysiloxanes whose molecular terminal is modified with at least one group selected from the group consisting of carboxylic acid groups, alcohol groups and a hydroxyl group (hereinafter referred to merely as “terminal-modified polysiloxanes”).


[0159] The organosilane compounds (1) may be produced by drying or heat-treating alkoxysilane compounds represented by the formula (I):


R1aSiX4−a  (I)


[0160] wherein R1 is C6H5—, (CH3)2CHCH2— or n-CbH2b+1— (wherein b is an integer of 1 to 18); X is CH3O— or C2H5O—; and a is an integer of 0 to 3.


[0161] The drying or heat-treatment of the alkoxysilane compounds may be conducted, for example, at a temperature of usually 40 to 200° C., preferably 60 to 150° C. for usually 10 minutes to 12 hours, preferably 30 minutes to 3 hours.


[0162] Specific examples of the alkoxysilane compounds may include methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethyoxysilane, diphenyldiethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane or the like. Among these alkoxysilane compounds, in view of the desorption percentage and the adhering effect of organic pigments, methyltriethoxysilane, phenyltriethyoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane and isobutyltrimethoxysilane are preferred, and methyltriethoxysilane and methyltrimethoxysilane are more preferred.


[0163] As the polysiloxanes (2), there may be used those compounds represented by the formula (II):
1


[0164] wherein R2 is H— or CH3—, and d is an integer of 15 to 450.


[0165] Among these polysiloxanes, in view of the desorption percentage and the adhering effect of the organic pigments, polysiloxanes having methyl hydrogen siloxane units are preferred.


[0166] As the modified polysiloxanes (2-A), there may be used:


[0167] (a) polysiloxanes modified with polyethers represented by the formula (III):
2


[0168]  wherein R3 is —(—CH2—)h—; R4 is —(—CH2—)i—CH3; R5 is —OH, —COOH, —CH═CH2, —C(CH3)═CH2 or —(—CH2—)j—CH3; R6 is —(—CH2—)k—CH3; g and h are an integer of 1 to 15; i, j and k are an integer of 0 to 15; e is an integer of 1 to 50; and f is an integer of 1 to 300;


[0169] (b) polysiloxanes modified with polyesters represented by the formula (IV):
3


[0170]  wherein R7, R8 and R9 are —(—CH2—)q— and may be the same or different; R10 is —OH, —COOH, —CH═CH2, —C(CH3)═CH2 or —(—CH2—)r—CH3; R11 is —(—CH2—)s—CH3; n and q are an integer of 1 to 15; r and s are an integer of 0 to 15; e′ is an integer of 1 to 50; and f′ is an integer of 1 to 300;


[0171] (c) polysiloxanes modified with epoxy compounds represented by the formula (V):
4


[0172]  wherein R12 is —(—CH2—)v—; v is an integer of 1 to 15; t is an integer of 1 to 50; and u is an integer of 1 to 300; or a mixture thereof.


[0173] Among these modified polysiloxanes (2-A), in view of the desorption percentage and the adhering effect of the organic pigments, the polysiloxanes modified with the polyethers represented by the formula (III), are preferred.


[0174] As the terminal-modified polysiloxanes (2-B), there may be used those represented by the formula (VI):
5


[0175] wherein R13 and R14 are —OH, R16OH or R17COOH and may be the same or different; R15 is —CH3 or —C6H5; R16 and R17 are —(—CH2—)y—; y is an integer of 1 to 15; w is an integer of 1 to 200; and x is an integer of 0 to 100.


[0176] Among these terminal-modified polysiloxanes, in view of the desorption percentage and the adhering effect of the organic pigments, the polysiloxanes whose terminals are modified with carboxylic acid groups are preferred.


[0177] The coating amount of the organosilicon compounds is usually 0.02 to 5.0% by weight, preferably 0.03 to 4.0% by weight, more preferably 0.05 to 3.0% by weight (calculated as Si) based on the weight of the iron oxide hydroxide particles coated with the organosilicon compounds.


[0178] When the coating amount of the organosilicon compounds is less than 0.02% by weight, it may be difficult to adhere the organic pigments in a predetermined.


[0179] When the coating amount of the organosilicon compounds is more than 5.0% by weight, the organic pigments can be adhered in a predetermined. Therefore, it is unnecessary and meaningless to coat the core particles with such a large amount of the organosilicon compounds.


[0180] As to the organic pigments used in the present invention, organic blue-based pigments and organic red-based pigments may be exemplified. The amount of the organic pigment such as organic blue-based pigments and organic red-based pigments adhered on the coating layer composed of organosilicon compounds is usually 1 to 30 parts based on 100 parts by weight of the iron oxide hydroxide particles.


[0181] As the organic blue-based pigments used in the present invention, there may be used phthalocyanine-based pigments such as metal-free phthalocyanine blue, phthalocyanine blue (copper phthalocyanine) and fast sky blue (sulfonated copper phthalocyanine), and alkali blue pigments, or the like. In the consideration of the hue of the obtained green-based fine pigments, among these pigments, the use of phthalocyanine blue is preferred.


[0182] In particular, in the consideration of light resistance, the use of low-chlorinated copper phthalocyanine, NC-type (non-crystallization-type) copper phthalocyanine or NC-type low-chlorinated copper phthalocyanine is preferred.


[0183] The amount of the organic blue-based pigment adhered is preferably 5 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0184] When the amount of the organic blue-based pigment adhered is out of the above-mentioned range, it may be difficult to obtain the aimed green-based pigment of the present invention. The amount of the organic blue-based pigment adhered is more preferably 7.5 to 25 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0185] As the organic red-based pigments used in the present invention, there may be used quinacridone-based pigments such as quinacridone red, azo-based pigments such as permanent red, condensed azo-based pigments such as condensed azo red, and perylene-based pigments such as perylene red. In the consideration of heat resistance and light resistance of the obtained orange-based pigments, the use of quinacridone-based pigments is preferred.


[0186] The amount of the organic red-based pigment adhered is usually 1 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles. When the amount of the organic red-based pigment adhered is less than 1 part by weight or more than 30 parts by weight, it may be difficult to obtain the aimed orange-based pigment of the present invention. The amount of the organic red-based pigment adhered is preferably 3 to 25 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles.


[0187] Phe shape and size of the green or orange-based pigments of the present invention considerably varies depending upon those of the iron oxide hydroxide particles as core particles, and usually have an analogous configuration to that of the iron oxide hydroxide particles.


[0188] For example, the green or orange-based pigment according to the present invention has an average major axial diameter of 0.005 to 1.0 μm; an average minor axial diameter of 0.0025 to 0.5 μm; an aspect ratio of 2.0:1 to 20:1; a BET specific surface area value of 6 to 300 m2/g; a geometrical standard deviation value of major axial diameters of 1.01 to 2.0; and a desorption percentage of the organic pigment of not more than 15%. As to the heat resistance of the green or orange-based pigment, the heat resistance temperature thereof is higher by +5 to +40° than that of the iron oxide hydroxide particles. As to the chemical resistances of the green or orange-based pigment, the acid resistance (ΔE* value) thereof is not more than 1.5, and the alkali resistance thereof is not more than 1.5, when evaluated by the method specified hereinafter.


[0189] Next, the properties of the green or orange-based pigments used on the present invention are more concretely explained as follows.


[0190] (1) In the case where iron oxide hydroxide particles having an average major axial diameter of 0.1 to 1.0 μm are used as core particles:


[0191] The green or orange-based pigment according to the present invention has an average major axial diameter of usually 0.1 to 1.0 μm, preferably 0.15 to 0.9 μm.


[0192] When the average major axial diameter of the green or orange-based pigment is more than 1.0 μm, the pigment particles may be larger, resulting in deteriorated tinting strength.


[0193] The green or orange-based pigment according to the present invention is of an acicular or rectangular shape.


[0194] The green or orange-based pigment according to the present invention has an aspect ratio of usually not more than 20:1, preferably 2:1 to 15:1, more preferably 2:1 to 10:1. When the aspect ratio of the green or orange-based pigment is more than 20:1, the pigment particles may tend to be entangled or interlaced with each other, resulting in poor dispersibility in vehicles or resin compositions as well as increased viscosity of the coating solution.


[0195] The green or orange-based pigment according to the present invention suitably has a geometrical standard deviation value of particle sizes of not more than 2.0. When the geometrical standard deviation value of particle sizes of the green or orange-based pigment is more than 2.0, a considerable amount of coarse particles are present, so that it may be difficult to uniformly disperse the pigment in vehicles or resin compositions. In the consideration of uniform dispersion in vehicles or resin compositions, the geometrical standard deviation value of particle sizes of the green or orange-based pigment is preferably not more than 1.8, more preferably not more than 1.6. In the consideration of industrial productivity, the lower limit of the geometrical standard deviation value of particle sizes of the green or orange-based pigment is 1.01, since it is difficult to industrially produce those pigments having a geometrical standard deviation value of less than 1.01.


[0196] The green or orange-based pigment according to the present invention has a BET specific surface area value of usually 6 to 160 M2/g, preferably 11 to 130 m2/g, more preferably 16 to 110 m2/g. When the BET specific surface area value of the green or orange-based pigment is less than 6 m2/g, the obtained green or orange-based pigment particles may be coarser, resulting in deteriorated tinting strength.


[0197] The green or orange-based pigment according to the present invention has a desorption percentage of the organic pigment of preferably not more than 15%, more preferably not more than 12%. When the desorption percentage of the organic pigment is more than 15%, the pigment particles may tend to be inhibited from being uniformly dispersed in vehicles or resin compositions due to desorbed organic pigment particles. Further, a portion of the surface of the iron oxide hydroxide core particle from which the organic pigment is desorbed, is exposed to outside, so that the obtained iron oxide hydroxide composite particles fail to exhibit a uniform hue.


[0198] Especially, as to the hue of the green-based pigment according to the present invention, the L* value thereof is 25 to 80; the a* value thereof is from −100 to less than 0; the b* value thereof is −100 to +100; and the h value thereof is 120° to 240°.


[0199] In addition, as to the hue of the orange-based pigment according to the present invention, the L* value thereof is 25 to 80; the a* value thereof is from more than 0 to +100; the b* value thereof is from more than 0 to +100; and the h value thereof is 30° to 60°.


[0200] As to the heat resistance of the green or orange-based pigment according to the present invention, the heat resistance temperature thereof is higher by +5 to +40° than that of the iron oxide hydroxide particles as core particles.


[0201] The green or orange-based pigment according to the present invention has a tinting strength of preferably not less than 115%, more preferably not less than 120%, when measured by the evaluation method specified hereinafter.


[0202] The green or orange-based pigment according to the present invention has a hiding power of preferably not less than 1,750 cm2/g, more preferably not less than 1,800 cm2/g, when measured by the evaluation method specified hereinafter.


[0203] As to the chemical resistances of the green or orange-based pigment according to the present invention, the acid resistance (ΔE* value) thereof is preferably not more than 1.5, more preferably not more than 1.2; and the alkali resistance (ΔE* value) thereof is preferably not more than 1.5, more preferably not more than 1.2, when measured by the evaluation method specified hereinafter.


[0204] (2) In the case where iron oxide hydroxide particles having an average major axial diameter of from 0.005 μm to less than 0.1 μm are used as core particles:


[0205] The green or orange-based fine pigment of the present invention has an average major axial diameter of from usually 0.005 μm to less than 0.1 μm, preferably 0.008 to 0.096 μm, more preferably 0.01 to 0.092 μm.


[0206] When the average major axial diameter of the green or orange-based fine pigment is less than 0.005 μm, the intermolecular force between the pigment particles may be increased due to fineness thereof, so that the particles may tend to be agglomerated together, resulting in poor dispersibility in vehicles or resin compositions.


[0207] The green or orange-based fine pigment of the present invention is also of an acicular or rectangular shape.


[0208] The green or orange-based fine pigment of the present invention has an aspect ratio of preferably not more than 20:1, more preferably 2:1 to 15:1, still more preferably 2:1 to 10:1. When the aspect ratio of the green or orange-based pigment is more than 20:1, the pigment particles may tend to be entangled or interlaced with each other, resulting in poor dispersibility in vehicles or resin compositions as well as increased viscosity of the obtained coating solution.


[0209] The green or orange-based fine pigment according to the present invention has an average minor axial diameter of usually from 0.0025 μm to less than 0.05 μm, preferably 0.004 to 0.048 μm, more preferably 0.005 to 0.046 μm. When the average minor axial diameter of the green or orange-based fine pigment is less than 0.0025 μm, the intermolecular force between the pigment particles may be increased due to fineness thereof, so that the particles may tend to be agglomerated together, resulting in poor dispersibility in vehicles or resin compositions.


[0210] The green or orange-based fine pigment according to the present invention suitably has a geometrical standard deviation value of particle sizes of usually not more than 2.0. When the geometrical standard deviation value of particle sizes of the green or orange-based fine pigment is more than 2.0, a considerable amount of coarse particles may be present, so that it may be difficult to uniformly disperse the fine pigment particles in vehicles or resin compositions. In the consideration of uniform dispersion in vehicles or resin compositions, the geometrical standard deviation value of particle sizes of the green or orange-based fine pigment is preferably not more than 1.8, more preferably not more than 1.6. In the consideration of industrial productivity, the lower limit of the geometrical standard deviation value of particle sizes of the green or orange-based fine pigment is 1.01, since it is difficult to industrially produce those pigments having a geometrical standard deviation value of less than 1.01.


[0211] The green or orange-based fine pigment according to the present invention has a BET specific surface area value of usually 50 to 300 m2/g, preferably 70 to 280 m2/g, more preferably 80 to 250 m2/g. When the BET specific surface area value of the green or orange-based fine pigment is less than 50 m2/g, the obtained green or orange-based fine pigment particles may be coarser, resulting in too high hiding power. As a result, coating films or resin compositions obtained using the green or orange-based fine pigment may fail to exhibit a sufficient transparency. On the other hand, when the BET specific surface area value of the green or orange-based fine pigment is more than 300 m2/g, the intermolecular force between the fine pigment particles may be increased due to fineness thereof, so that the particles may tend to be agglomerated together, resulting in poor dispersibility in vehicles or resin compositions.


[0212] The organic pigment constituting the green or orange-based fine pigment according to the present invention has a desorption percentage of the organic pigment of usually not more than 15%, preferably not more than 12%. When the desorption percentage of the organic pigment is more than 15%, the fine pigment particles tends to be inhibited from being uniformly dispersed in vehicles or resin compositions due to desorbed organic pigment particles. Further, a portion of the surface of the iron oxide hydroxide fine particles as core particle from which the organic pigment particles are desorbed, is exposed to outside, so that the obtained iron oxide hydroxide composite fine particles fail to exhibit a uniform hue.


[0213] Especially, as to the hue of the green-based fine pigment according to the present invention, the L* value thereof is usually 25 to 80; the a* value thereof is usually from −100 to less than 0; the b* value thereof is −100 to +100; and the h value thereof is usually 120 to 240°.


[0214] In addition, as to the hue of the orange-based fine pigment according to the present invention, the L* value thereof is usually 25 to 80; the a* value thereof is usually from more than 0 to +100; the b* value thereof is usually from more than 0 to +100; and the h value thereof is usually from 30° to 60°.


[0215] As to the heat resistance of the green or orange-based fine pigment according to the present invention, the heat resistance temperature thereof is usually higher by +5 to +40° than that of the iron oxide hydroxide fine particles as core particles, and is preferably not less than 210° C., more preferably not less than 215° C.


[0216] The green or orange-based fine pigment according to the present invention has a tinting strength of preferably not less than 115%, more preferably not less than 120%, when measured by the evaluation method specified hereinafter.


[0217] The green or orange-based fine pigment according to the present invention has a hiding power of preferably less than 600 cm2/g, more preferably not more than 500 cm2/g. When the hiding power of the green or orange-based fine pigment is not less than 600 cm2/g, coating films or resin compositions obtained using the green or orange-based fine pigment may fail to exhibit a sufficient transparency due to a too high hiding power thereof.


[0218] As to the chemical resistances of the green or orange-based fine pigment according to the present invention, the acid resistance (ΔE* value) thereof is preferably not more than 1.5, more preferably not more than 1.3; and the alkali resistance (ΔE* value) thereof is preferably not more than 1.5, more preferably not more than 1.3, when measured by the evaluation method specified hereinafter.


[0219] Before forming the coating layer comprising the organosilicon compound onto the iron oxide hydroxide particles, the surfaces of the core particles may be preliminarily coated with at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon (hereinafter referred to merely as “hydroxides and/or oxides of aluminum and/or silicon”). When the coating layer is formed on the surfaces of the core particles, the desorption percentage of the organic pigment from the surfaces of the iron oxide hydroxide particles can be reduced as compared to those having no coating layer, and the heat resistance of the obtained composite particles can be slightly increased.


[0220] The total coating amount of the hydroxides and/or oxides of aluminum and/or silicon is 0.01 to 20% by weight (calculated as Al, Si or a sum of Al and Si) based on the weight of the coated iron oxide hydroxide particles.


[0221] When the coating amount of the hydroxides and/or oxides of aluminum and/or silicon is less than 0.01% by weight, the effect of reducing the desorption percentage of the organic pigment may not be obtained. Since a sufficient effect of reducing the desorption percentage of the organic pigment can be obtained by adjusting the coating amount of the hydroxides and/or oxides of aluminum and/or silicon to 0.01 to 20% by weight, it is unnecessary and meaningless to coat the core particles with the hydroxides and/or oxides of aluminum and/or silicon in an amount of more than 20% by weight.


[0222] The green or orange-based pigment in which the iron oxide hydroxide particles coated with the hydroxides and/or oxides of aluminum and/or silicon are used as core particles, are substantially identical in particle size, geometrical standard deviation value, BET specific surface area value, hue, tinting strength, hiding power and chemical resistances to those used for the core particles having no coating layer composed of the hydroxides and/or oxides of aluminum and/or silicon. Also, by forming such a coating layer composed of the hydroxides and/or oxides of aluminum and/or silicon on the core particles, the desorption percentage of the organic pigment is improved, i.e., can be reduced to preferably not more than 12%, more preferably not more than 10%, and the heat resistance of the obtained composite particles becomes higher by +5 to +30° C. than those obtained by using the core particles having no coating layer composed of the hydroxides and/or oxides of aluminum and/or silicon.


[0223] Next, the paint containing the green or orange-based pigment according to the present invention, is described.


[0224] The paint containing the green or orange-based pigment according to the present invention has a storage stability (ΔE* value) of usually not more than 1.5, a gloss of 70 to 115% (in a coating film), a heat resistance temperature of usually not less than 220° C. (in a coating film), an acid resistance (ΔG value) as a chemical resistances of usually not more than 12% (in a coating film), an alkali resistance (ΔG value) as a chemical resistances of usually not more than 12% (in a coating film), and a L* value of usually 25 to 85 (in a coating film).


[0225] (A) Paint Containing the Green-Based Piment Having an Average Major Axial Diameter of 0.1 to 1.0 μm


[0226] The paint containing the green-based pigment according to the present invention has a storage stability (ΔE* value) of usually not more than 1.5, preferably not more than 1.2. When a coating film is produced by using the solvent-based paints, the gloss of the coating film is usually 75 to 110%, preferably 80 to 110%; and the heat resistance temperature of the coating film is usually not less than 240° C., preferably not less than 245° C. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%; and the alkali resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%. As to the hue of the coating film produced from the paint, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from −100 to less than 0; the b* value thereof is −100 to +100; and the h value thereof is usually 120 to 240°.


[0227] The paint containing the green-based pigment obtained by using the core particles coated with the hydroxides and/or oxides of aluminum and/or silicon according to the present invention, has a storage stability (ΔE* value) of usually not more than 1.5, preferably not more than 1.2. When a coating film is produced by using the solvent-based paints, the gloss of the coating film is usually 80 to 115%, preferably 85 to 115%; and the heat resistance temperature of the coating film is usually not less than 245° C., preferably not less than 250° C. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%; and the alkali resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%. As to the hue of the coating film produced from the paint, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from −100 to less than 0; the b* value thereof is −100 to +100; and the h value thereof is usually 120 to 240°.


[0228] The water-based paint containing the green-based pigment according to the present invention, has a storage stability (ΔE* value) of usually not more than 1.5, preferably not more than 1.2. When a coating film is produced by using the water-based paints, the gloss of the coating film is usually 70 to 110%, preferably 75 to 110%; and the heat resistance temperature of the coating film is usually not less than 235° C., preferably not less than 240° C. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%; and the alkali resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%. As to the hue of the coating film produced from the water-based paint, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from −100 to less than 0; the b* value thereof is −100 to +100; and the h value thereof is usually 120 to 240°.


[0229] The water-based paint containing the green-based pigment obtained by using as the core particles iron oxide hydroxide particles coated with the hydroxides and/or oxides of aluminum and/or silicon according to the present invention, has a storage stability (ΔE* value) of usually not more than 1.5, preferably not more than 1.2. When a coating film is produced by using the water-based paints, the gloss of the coating film is usually 75 to 115%, preferably 80 to 115%; and the heat resistance temperature of the coating film is usually not less than 240° C., preferably not less than 245° C. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%; and the alkali resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%. As to the hue of the coating film produced from the water-based paint, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from −100 to less than 0; the b* value thereof is −100 to +100; and the h value thereof is usually 120 to 240°.


[0230] (B) Paint Containing the Orange-Based Pigment Having an Average Major Axial Diameter of 0.1 to 1.0 μm


[0231] The paint containing the orange-based pigment according to the present invention has a storage stability (ΔE* value) of usually not more than 1.5, preferably not more than 1.2. When a coating film is produced by using the solvent-based paints, the gloss of the coating film is usually 75 to 110%, preferably 80 to 110%; and the heat resistance temperature of the coating film is usually not less than 240° C., preferably not less than 245° C. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%; and the alkali resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%. As to the hue of the coating film produced from the paint, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from more than 0 to +100; the b* value thereof is from more than 0 to +100; and the h value thereof is 30 to 60°.


[0232] The paint containing the orange-based pigment obtained by using as the core particles iron oxide hydroxide particles coated with the hydroxides and/or oxides of aluminum and/or silicon according to the present invention, has a storage stability (ΔE* value) of usually not more than 1.5, preferably not more than 1.2. When a coating film is produced by using the solvent-based paints, the gloss of the coating film is usually 80 to 115%, preferably 85 to 115%; and the heat resistance temperature of the coating film is usually not less than 245° C., preferably not less than 250° C. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%; and the alkali resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%. As to the hue of the coating film produced from the paint, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from more than 0 to +100; the b* value thereof is from more than 0 to +100; and the h value thereof is 30 to 60°.


[0233] The water-based paint containing the orange-based pigment according to the present invention, has a storage stability (ΔE* value) of usually not more than 1.5, preferably not more than 1.2. When a coating film is produced by using the water-based paints, the gloss of the coating film is usually 70 to 110%, preferably 75 to 110%; and the heat resistance temperature of the coating film is usually not less than 235° C., preferably not less than 240° C. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%; and the alkali resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%. As to the hue of the coating film produced from the water-based paint, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from more than 0 to +100; the b* value thereof is from more than 0 to +100; and the h value thereof is 30 to 60°.


[0234] The water-based paint containing the orange-based pigment obtained by using as the core particles iron oxide hydroxide particles coated with the hydroxides and/or oxides of aluminum and/or silicon according to the present invention, has a storage stability (ΔE* value) of usually not more than 1.5, preferably not more than 1.2. When a coating film is produced by using the water-based paints, the gloss of the coating film is usually 75 to 115%, preferably 80 to 115%; and the heat resistance temperature of the coating film is usually not less than 240° C., preferably not less than 245° C. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%; and the alkali resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%. As to the hue of the coating film produced from the water-based paint, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from more than 0 to +100; the b* value thereof is from more than 0 to +100; and the h value thereof is 30 to 60°.


[0235] (C) Paint Containing the Green-Based Fine Pigment Having an Average Major Axial Diameter of from 0.005 to Less Than 0.1 μm


[0236] The paint containing the green-based fine pigment according to the present invention has a storage stability (ΔE* value) of usually not more than 1.5, preferably not more than 1.3. When a coating film is produced by using the solvent-based paints, the gloss of the coating film is usually 75 to 110%, preferably 80 to 110%; and the heat resistance temperature of the coating film is usually not less than 220° C., preferably not less than 225° C. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof is usually not more than 12%, more preferably not more than 10%; and the alkali resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%. As to the hue of the coating film produced from the paint, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from −100 to less than 0; and the b* value thereof is −100 to +100; and the h value thereof is 120 to 240°. As to the transparency of the coating film, the linear absorption thereof is preferably not more than 0.05 μm−1.


[0237] The paint containing the green-based fine pigment obtained by using as the core particles iron oxide hydroxide particles coated with the hydroxides and/or oxides of aluminum and/or silicon according to the present invention, has a storage stability (ΔE* value) of usually not more than 1.5, preferably not more than 1.3. When a coating film is produced by using the solvent-based paints, the gloss of the coating film is usually 80 to 115%, preferably 85 to 115%; and the heat resistance temperature of the coating film is usually not less than 230° C., preferably not less than 235° C. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%; and the alkali resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%. As to the hue of the coating film produced from the paint, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from −100 to less than 0; the b* value thereof is − 100 to +100; and the h value thereof is 120 to 240°. As to the transparency of the coating film, the linear absorption thereof is preferably not more than 0.05 μm−1.


[0238] The water-based paint containing the green-based fine pigment according to the present invention, has a storage stability (ΔE* value) of usually not more than 1.5, preferably not more than 1.3. When a coating film is produced by using the water-based paints, the gloss of the coating film is usually 70 to 110%, preferably 75 to 110%; and the heat resistance temperature of the coating film is usually not less than 220° C., preferably not less than 225° C. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%; and the alkali resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%. As to the hue of the coating film produced from the water-based paint, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from −100 to less than 0; and the b* value thereof is −100 to +100. As to the transparency of the coating film, the linear absorption thereof is preferably not more than 0.05 μm−1.


[0239] The water-based paint containing the green-based fine pigment obtained by using as the core particles iron oxide hydroxide particles coated with the hydroxides and/or oxides of aluminum and/or silicon according to the present invention, has a storage stability (ΔE* value) of usually not more than 1.5, preferably not more than 1.3. When a coating film is produced by using the water-based paints, the gloss of the coating film is usually 75 to 115%, preferably 80 to 115%; and the heat resistance temperature of the coating film is usually not less than 230° C., preferably not less than 235° C. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%; and the alkali resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%. As to the hue of the coating film produced from the water-based paint, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from −100 to less than 0; and the b* value thereof is −100 to +100; and the h value thereof is 120 to 240°. As to the transparency of the coating film, the linear absorption thereof is preferably not more than 0.05 μm−1.


[0240] (D) Paint Containing the Orange-Based Fine Pigment Having an Average Major Axial Diameter of from 0.005 μm to Less Than 0.1 μm


[0241] The paint containing the orange-based fine pigment according to the present invention, has a storage stability (ΔE* value) of usually not more than 1.5, preferably not more than 1.3. When a coating film is produced by using the solvent-based paints, the gloss of the coating film is usually 75 to 110%, preferably 80 to 110%; and the heat resistance temperature of the coating film is usually not less than 220° C., preferably not less than 225° C. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%; and the alkali resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%. As to the hue of the coating film produced from the paint, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from more than 0 to +100; the b* value thereof is from more than 0 to +100; and the h value thereof is 30 to 60°. As to the transparency of the coating film, the linear absorption thereof is preferably not more than 0.05 μm−1.


[0242] The paint containing the orange-based fine pigment obtained by using as the core particles iron oxide hydroxide particles coated with the hydroxides and/or oxides of aluminum and/or silicon according to the present invention, has a storage stability (ΔE* value) of usually not more than 1.5, preferably not more than 1.3. When a coating film is produced by using the solvent-based paints, the gloss of the coating film is usually 80 to 115%, preferably 85 to 115%; and the heat resistance temperature of the coating film is usually not less than 230° C., preferably not less than 235° C. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%; and the alkali resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%. As to the hue of the coating film produced from the paint, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from more than 0 to +100; the b* value thereof is from more than 0 to +100; and the h value thereof is 30 to 60°. As to the transparency of the coating film, the linear absorption thereof is preferably not more than 0.05 μm−1.


[0243] The water-based paint containing the orange-based fine pigment according to the present invention, has a storage stability (ΔE* value) of usually not more than 1.5, preferably not more than 1.3. When a coating film is produced by using the water-based paints, the gloss of the coating film is usually 70 to 110%, preferably 75 to 110%; and the heat resistance temperature of the coating film is usually not less than 220° C., preferably not less than 225° C. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%; and the alkali resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%. As to the hue of the coating film produced from the water-based paint, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from more than to +100; the b* value thereof is from more than to +100; and the h value thereof is 30 to 60°. As to the transparency of the coating film, the linear absorption thereof is preferably not more than 0.05 μm−1.


[0244] The water-based paint containing the orange-based fine pigment obtained by using as the core particles iron oxide hydroxide particles coated with the hydroxides and/or oxides of aluminum and/or silicon according to the present invention, has a storage stability (ΔE* value) of usually not more than 1.5, preferably not more than 1.3. When a coating film is produced by using the water-based paints, the gloss of the coating film is usually 75 to 115%, preferably 80 to 115%; and the heat resistance temperature of the coating film is usually not less than 230° C., preferably not less than 235° C. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%; and the alkali resistance (ΔG value) thereof is usually not more than 12%, preferably not more than 10%. As to the hue of the coating film produced from the water-based paint, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from more than 0 to +100; the b* value thereof is from more than 0 to +100; and the h value thereof is 30 to 60°. As to the transparency of the coating film, the linear absorption thereof is preferably not more than 0.05 μm−1.


[0245] In the paint of the present invention, the lower limit of the amount of the green or orange-based pigment blended therein usually 0.5 part by weight, preferably 1.0 part by weight, more preferably 2.0 parts by weight based on 100 parts by weight of a paint base material; and the upper limit of the amount of the green or orange-based pigment blended therein is usually 100 parts by weight, preferably 80 parts by weight, more preferably 50 parts by weight based on 100 parts by weight of the paint base material.


[0246] The paint based material contains green or orange-based pigments, resins and solvents, and may optionally contain defoamers, extender pigments, dryers, surfactants, hardeners, auxiliaries and the like, if required.


[0247] As the resins contained in the paint base material, there may be exemplified those ordinarily used for solvent-based paints such as acrylic resins, alkyd resins, polyester resins, polyurethane resins, epoxy resins, phenol resins, melamine resins, amino resins or the like. Also, as the resins for water-based paints, there may be exemplified ordinarily used ones such as water-soluble alkyd resins, water-soluble melamine resins, water-soluble acrylic resins, water-soluble urethane emulsion resins or the like.


[0248] As the solvents for solvent-based paints, there may be exemplified those ordinarily used for solvent-based paints such as toluene, xylene, thinner, butyl acetate, methyl acetate, methyl isobutyl ketone, butyl cellosolve, ethyl cellosolve, butyl alcohol, aliphatic hydrocarbons and mixtures thereof.


[0249] Also, as the solvents for water-based paints, there may be exemplified water, butyl cellosolve, butyl alcohol or the like which are ordinarily used for water-based paints, or mixtures thereof.


[0250] As the defoamer, there may be used commercially available products such as NOPCO 8034 (tradename), SN DEFOAMER 477 (tradename), SN DEFOAMER 5013 (tradename), SN DEFOAMER 247 (tradename) or SN DEFOAMER 382 (tradename) (all produced by SUN NOPCO LTD.); ANTIFOAM 08 (tradename) or EMULGEN 903 (tradename) (both produced by KAO CO., LTD.); or the like.


[0251] Next, the rubber or resin composition colored with the pigment according to the present invention will be described.


[0252] (A) Resin Composition Containing the Green-Based Pigment Having an Average Major Axial Diameter of 0.1 to 1.0 μm


[0253] The resin composition colored with the green-based pigment according to the present invention has a dispersing condition of usually rank 4 or 5, preferably rank 5 when visually observed and evaluated by the method described hereinafter; and a heat resistance temperature of usually not less than 215° C., preferably not less than 220° C. As to the hue of the resin composition, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from −100 to less than 0; and the b* value thereof is −100 to +100; and the h value thereof is 120 to 240°.


[0254] The resin composition colored with the green-based pigment obtained by using as the core particles iron oxide hydroxide particles coated with the hydroxides and/or oxides of aluminum and/or silicon according to the present invention, has a dispersing condition of usually rank 4 or 5, preferably rank 5 when visually observed and evaluated by the method described hereinafter; and a heat resistance temperature of usually not less than 220° C., preferably not less than 225° C. As to the hue of the resin composition, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from −100 to less than 0; the b* value thereof is −100 to +100; and the h value thereof is 120 to 240°.


[0255] (B) Resin Composition Containing the Orange-Based Pigment Having an Average Major Axial Diameter of 0.1 to 1.0 μm


[0256] The resin composition colored with the orange-based pigment according to the present invention has a dispersing condition of usually rank 4 or 5, preferably rank 5 when visually observed and evaluated by the method described hereinafter; and a heat resistance temperature of usually not less than 215° C., preferably not less than 220° C. As to the hue of the resin composition, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from more than 0 to +100; the b* value thereof is from more than 0 to +100; and the h value thereof is 30 to 60° C.


[0257] The resin composition colored with the orange-based pigment obtained by using as the core particles iron oxide hydroxide particles coated with the hydroxides and/or oxides of aluminum and/or silicon according to the present invention, has a dispersing condition of usually rank 4 or 5, preferably rank 5 when visually observed and evaluated by the method described hereinafter; and a heat resistance temperature of usually not less than 220° C., preferably not less than 225° C. As to the hue of the resin composition, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from more than 0 to +100; the b* value thereof is from more than 0 to +100; and the h value thereof is 30 to 60° C.


[0258] (C) Resin Composition Containing the Green-Based Fine Pigment Having an Average Major Axial Diameter of from 0.005 μm to Less Than 0.1 μm


[0259] The resin composition colored with the green-based fine pigment according to the present invention has a dispersing condition of usually rank 4 or 5, preferably rank 5 when visually observed and evaluated by the method described hereinafter; and a heat resistance temperature of usually not less than 210° C., preferably not less than 215° C. As to the hue of the resin composition, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from −100 to less than 0; the b* value thereof is −100 to +100; and the h value thereof is 120 to 240°. As to the transparency of the resin composition, the linear absorption thereof is preferably not more than 0.05 μm−1.


[0260] The resin composition colored with the green-based fine pigment obtained by using as the core particles iron oxide hydroxide particles coated with the hydroxides and/or oxides of aluminum and/or silicon according to the present invention, has a dispersing condition of usually rank 4 or 5, preferably rank 5 when visually observed and evaluated by the method described hereinafter; and a heat resistance temperature of usually not less than 215° C., preferably not less than 220° C. As to the hue of the resin composition, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from −100 to less than 0; the b* value thereof is −100 to +100; and the h value thereof is 120 to 240°. As to the transparency of the resin composition, the linear absorption thereof is preferably not more than 0.05 μm−1.


[0261] (D) Resin Composition Containing the Orange-Based Fine Pigment Having an Average Major Axial Diameter of from 0.005 to Less Than 0.1 μm


[0262] The resin composition colored with the orange-based fine pigment according to the present invention has a dispersing condition of usually rank 4 or 5, preferably rank 5 when visually observed and evaluated by the method described hereinafter; and a heat resistance temperature of usually not less than 210° C., preferably not less than 215° C. As to the hue of the resin composition, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from more than 0 to +100; the b* value thereof is from more than 0 to +100: and the h value thereof is 30 to 60°. As to the transparency of the resin composition, the linear absorption thereof is preferably not more than 0.05 μm−1.


[0263] The resin composition colored with the orange-based fine pigment obtained by using as the core particles iron oxide hydroxide particles coated with the hydroxides and/or oxides of aluminum and/or silicon according to the present invention, has a dispersing condition of usually rank 4 or 5, preferably rank 5 when visually observed and evaluated by the method described hereinafter; and a heat resistance temperature of usually not less than 215° C., preferably not less than 220° C. As to the hue of the resin composition, it is preferred that the L* value thereof is 25 to 85; the a* value thereof is from more than 0 to +100; the b* value thereof is from more than 0 to +100; and the h value thereof is 30 to 60°. As to the transparency of the resin composition, the linear absorption thereof is preferably not more than 0.05 μm−1.


[0264] In the resin composition according to the present invention, the amount of the green or orange-based pigment blended is usually 0.01 to 200 parts by weight based on 100 parts by weight of the rubber or resins composition.


[0265] In the case where the green or orange-based pigment having a particle size of 0.1 to 1.0 μm is used:


[0266] In the rubber or resin composition of the present invention, the amount of the green or orange-based pigment blended is usually 0.5 to 200 parts by weight based on 100 parts by weight of the rubber or resin composition. In the consideration of good handling property of the resin composition, the amount of the green or orange-based pigment blended is preferably 1.0 to 150 parts by weight, more preferably 2.5 to 100 parts by weight based on 100 parts by weight of the rubber or resin composition.


[0267] In the case where the green or orange-based fine pigment having a particle size of from 0.005 μm to less than 0.1 μm is used:


[0268] In the rubber or resin composition according to the present invention, the amount of the green or orange-based fine pigment blended is usually 0.01 to 50 parts by weight based on 100 parts by weight of the rubber or resin composition. In the consideration of good handling property of the resin composition, the amount of the green or orange-based fine pigment blended is preferably 0.05 to 45 parts by weight, more preferably 0.1 to 40 parts by weight based on 100 parts by weight of the rubber or resin composition.


[0269] The based material of the rubber or resin composition according to the present invention contains green or orange-based fine pigments and known thermoplastic resins, and may optionally contain various additives such as lubricants, plasticizers, antioxidants, ultraviolet light absorbers or the like, if required.


[0270] As the rubber or resins of the composition, there may be exemplified natural rubbers, synthetic rubbers, thermoplastic resins (e.g., polyolefins such as polyethylenes, polypropylenes, polybutenes and polyisobutylenes, polyvinyl chlorides, styrene polymers and polyamides) or the like.


[0271] The amount of the additives added is not more than 50% by weight based on the total weight of the green or orange-based fine pigments and resins. When the amount of the additives added is more than 50% by weight, the obtained rubber or resin composition is deteriorated in moldability.


[0272] The resin composition according to the present invention may be produced by preliminarily intimately mixing a raw resin material and the green or orange-based fine pigment together and applying a strong shear force to the mixture by a kneader or an extruder to deaggregate agglomerates of the green or orange-based fine pigment and uniformly disperse the individual green or orange-based fine pigment particles in the resin. The thus produced resin composition may be formed into an appropriate shape according to the application thereof upon use.


[0273] Next, the process for producing the green or orange-based pigment according to the present invention, is described.


[0274] The green or orange-based pigment of the present invention can be produced by mixing iron oxide hydroxide particles with alkoxysilane compounds or polysiloxanes to coat the surfaces of the iron oxide hydroxide particles with the alkoxysilane compounds or polysiloxanes; and then mixing the iron oxide hydroxide particles coated with the alkoxysilane compounds or polysiloxanes, with an organic pigment.


[0275] The coating of the iron oxide hydroxide particles with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes, may be conducted (i) by mechanically mixing and stirring the iron oxide hydroxide particles together with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes; or (ii) by mechanically mixing and stirring both the components together while spraying the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes onto the iron oxide hydroxide particles. In these cases, substantially whole amount of the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes added can be applied onto the surfaces of the iron oxide hydroxide particles.


[0276] In addition, by conducting the above-mentioned mixing or stirring treatment (i) of the iron oxide hydroxide particles as core particles together with the alkoxysilane compounds, at least a part of the alkoxysilane compounds coated on the iron oxide hydroxide particles as core particles may be changed to the organosilane compounds. In this case, there is also no affection against the formation of the organic pigment coat thereon.


[0277] In order to uniformly coat the surfaces of the iron oxide hydroxide particles with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes, it is preferred that the iron oxide hydroxide particles s are preliminarily diaggregated by using a pulverizer.


[0278] As apparatus (a) for mixing and stirring treatment (i) of the core particles with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes to form the coating layer thereof, and as apparatus (b) for mixing and stirring treatment (ii) of the organic pigment with the core particles whose surfaces are coated with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes to form the organic pigment coat, there may be preferably used those apparatus capable of applying a shear force to the particles, more preferably those apparatuses capable of conducting the application of shear force, spaturate force and compressed force at the same time.


[0279] As such apparatuses, there may be exemplified wheel-type kneaders, ball-type kneaders, blade-type kneaders, roll-type kneaders or the like. Among them, wheel-type kneaders are preferred.


[0280] Specific examples of the wheel-type kneaders may include an edge runner (equal to a mix muller, a Simpson mill or a sand mill), a multi-mull, a Stotz mill, a wet pan mill, a Conner mill, a ring muller, or the like. Among them, an edge runner, a multi-mull, a Stotz mill, a wet pan mill and a ring muller are preferred, and an edge runner is more preferred.


[0281] Specific examples of the ball-type kneaders may include a vibrating mill or the like. Specific examples of the blade-type kneaders may include a Henschel mixer, a planetary mixer, a Nawter mixer or the like. Specific examples of the roll-type kneaders may include an extruder or the like.


[0282] In order to coat the surfaces of the core particles with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes as uniformly as possible, the conditions of the above mixing or stirring treatment may be appropriately controlled such that the linear load is usually 2 to 200 Kg/cm (19.6 to 1960 N/cm), preferably 10 to 150 Kg/cm (98 to 1470 N/cm), more preferably 15 to 100 Kg/cm (147 to 980 N/cm); and the treating time is usually 5 to 120 minutes, preferably 10 to 90 minutes. It is preferred to appropriately adjust the stirring speed in the range of usually 2 to 2,000 rpm, preferably 5 to 1,000 rpm, more preferably 10 to 800 rpm.


[0283] The amount of the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes added, is preferably 0.15 to 45 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles. When the amount of the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes or the terminal-modified polysiloxanes added is less than 0.15 part by weight, it may become difficult to adhere the organic pigment in such an amount enough to obtain the iron oxide hydroxide composite particles according to the present invention. On the other hand, when the amount of the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes or the terminal-modified polysiloxanes added is more than 45 parts by weight, since a sufficient amount of the organic pigment can be adhered on the surface of the coating layer, it is meaningless to add more than 45 parts by weight.


[0284] Next, the organic pigment are added to the iron oxide hydroxide particles coated with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes, and the resultant mixture is mixed and stirred to form the organic pigment coat on the surfaces of the coating layer composed of the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes or the terminal-modified polysiloxanes. The drying or heat-treatment may be conducted.


[0285] It is preferred that the organic pigment are added little by little and slowly, especially about 5 to 60 minutes.


[0286] In order to form organic pigment coat onto the coating layer composed of the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes as uniformly as possible, the conditions of the above mixing or stirring treatment can be appropriately controlled such that the linear load is usually 2 to 200 Kg/cm (19.6 to 1960 N/cm), preferably 10 to 150 Kg/cm (98 to 1470 N/cm), more preferably 15 to 100 Kg/cm (147 to 980 N/cm); and the treating time is usually 5 to 120 minutes, preferably 10 to 90 minutes. It is preferred to appropriately adjust the stirring speed in the range of usually 2 to 2,000 rpm, preferably 5 to 1,000 rpm, more preferably 10 to 800 rpm.


[0287] The preferable amount of the organic blue-based pigment added is 5 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles. When the amount of the organic blue-based pigment added is more than 30 parts by weight, the aimed green-based pigment of the present invention may not be obtained.


[0288] The preferable amount of the organic red-based pigment added is 1 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide particles. When the amount of the organic red-based pigment added is out of the above specified range, the aimed orange-based pigment of the present invention may not be obtained.


[0289] The heating temperature used in the drying and heating steps is usually 40 to 200° C., preferably 60 to 150° C. The treating time of these steps is usually from 10 minutes to 12 hours, preferably from 30 minutes to 3 hours.


[0290] When the obtained green or orange-based pigment is subjected to the above drying and heating steps, the alkoxysilane compounds used as the coating thereof are finally converted into organosilane compounds.


[0291] If required, prior to mixing and stirring with the alkoxysilane compounds or polysiloxanes, the iron oxide hydroxide particles may be preliminarily coated with at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon to form an intermediate coating layer thereon.


[0292] At least a part of the surface of the iron oxide hydroxide particles may be coated with at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon (hereinafter referred to merely as “hydroxides and/or oxides of aluminum and/or silicon”), if required, in advance of mixing and stirring with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes or the terminal-modified polysiloxanes.


[0293] The coating of the hydroxides and/or oxides of aluminum and/or silicon may be conducted by adding an aluminum compound, a silicon compound or both the compounds to a water suspension in which the iron oxide hydroxide particles are dispersed, followed by mixing and stirring, and further adjusting the pH value of the suspension, if required, thereby coating the surfaces of the iron oxide hydroxide particles with hydroxides and/or oxides of aluminum and/or silicon. The thus obtained iron oxide hydroxide particles coated with the hydroxides and/or oxides of aluminum and/or silicon are then filtered out, washed with water, dried and pulverized. Further, the iron oxide hydroxide particles coated with the hydroxides and/or oxides of aluminum and/or silicon may be subjected to post-treatments such as deaeration treatment and compaction treatment, if required.


[0294] As the aluminum compounds, there may be exemplified aluminum salts such as aluminum acetate, aluminum sulfate, aluminum chloride or aluminum nitrate, alkali aluminates such as sodium aluminate or the like.


[0295] The amount of the aluminum compound added is 0.01 to 20% by weight (calculated as Al) based on the weight of the iron oxide hydroxide particles. When the amount of the aluminum compound added is less than 0.01% by weight, it may be difficult to sufficiently coat the surfaces of the iron oxide hydroxide particles with hydroxides and/or oxides of aluminum, thereby failing to improve the effective reduction of the organic pigment desorption percentage. On the other hand, when the amount of the aluminum compound added is more than 20% by weight, the coating effect is saturated and, therefore, it is meaningless to add such an excess amount of the aluminum compound.


[0296] As the silicon compounds, there may be exemplified #3 water glass, sodium orthosilicate, sodium metasilicate or the like.


[0297] The amount of the silicon compound added is 0.01 to 20% by weight (calculated as SiO2) based on the weight of the iron oxide hydroxide particles. When the amount of the silicon compound added is less than 0.01% by weight, it may be difficult to sufficiently coat the surfaces of the iron oxide hydroxide particles with hydroxides and/or oxides of silicon, thereby failing to improve the effective reduction of the organic pigment desorption percentage. On the other hand, when the amount of the silicon compound added is more than 20% by weight, the coating effect is saturated and, therefore, it is meaningless to add such an excess amount of the silicon compound.


[0298] In the case where both the aluminum and silicon compounds are used in combination for the coating, the total amount of the aluminum and silicon compounds added is preferably 0.01 to 20% by weight (calculated as a sum of Al and SiO2) based on the weight of the iron oxide hydroxide particles.


[0299] The point of the present invention lies in the following. That is, the green or orange-based pigment obtained by coating the surfaces of iron oxide hydroxide particles having an average particle size of 0.1 to 1.0 μm with organosilicon compounds and then adhering an organic blue or red-based pigment onto the surface of coating composed of the organosilicon compounds, is a harmless green or orange-based pigment capable of exhibiting excellent chemical resistances, high hiding power and tinting strength, and improved heat resistance.


[0300] Another point of the present invention lies in the following. That is, the green or orange-based fine pigment obtained by coating the surfaces of iron oxide hydroxide particles having an average particle size of from 0.005 to less than 0.1 μm with organosilicon compounds and then adhering an organic blue or red-based pigment onto the surface of coating composed of the organosilicon compounds, is a harmless green or orange-based fine pigment capable of exhibiting excellent chemical resistances, excellent tinting strength and improved heat resistance.


[0301] The reason why the pigment exhibiting a green color can be obtained by the present invention, is considered as follows. That is, similarly to such a principle that a film exhibiting a green color is obtained by overlapping a blue film on a yellow film, when the iron oxide hydroxide particles having a yellow color is coated with the organic blue-based pigment having a low hiding power, the obtained composite particles can exhibit a green color.


[0302] Also, the reason why the pigment exhibiting an orange color can be obtained by the present invention, is considered as follows. That is, similarly to such a principle that a film exhibiting an orange color is obtained by overlapping a red film on a yellow film, when the iron oxide hydroxide particles having a yellow color is coated with the organic red-based pigment having a low hiding power, the obtained composite particles can exhibit an orange color.


[0303] The reason why the green or orange-based pigment of the present invention is excellent in chemical resistances, is considered as follows. That is, the iron oxide hydroxide particles as core particles themselves are excellent in chemical resistances. Further, by selecting the organic blue or red-based pigment to be adhered onto the particles from those pigments having excellent chemical resistances, the obtained green or orange-based pigment can also exhibit excellent chemical resistances as a whole.


[0304] The reason why the green or orange-based pigment of the present invention has excellent tinting strength, is considered as follows. That is, the organic blue or red-based pigment is strongly fixed onto the surfaces of the iron oxide hydroxide particles having excellent tinting strength through the coating layer composed of the organosilicon compounds to form composite particles. As a result, the obtained green or orange-based pigment can also exhibit an excellent tinting strength.


[0305] The reason why the green or orange-based pigment of the present invention has an excellent heat resistance, is considered as follows. That is, the iron oxide hydroxide particles which are inherently deteriorated in heat resistance, are coated with the organosilicon compounds having an excellent heat resistance. Further, the organic blue or red-based pigment having an excellent heat resistance is fixed onto the surface of the coating layer composed of the organosilicon compounds. As a result, the obtained green or orange-based pigment can be enhanced in heat resistance.


[0306] The organic green or orange-based pigment according to the present invention contains no harmful elements and compounds and, therefore, can show not only excellent hygiene and safety, but also is effective for environmental protection.


[0307] Also, the green or orange-based pigment having an average major axial diameter of 0.1 to 1.0 μm according to the present invention, has high tinting strength, and excellent heat resistance and chemical resistances, and are harmless.


[0308] In the paint and resin composition of the present invention, there is used the green or orange-based pigment which is not only excellent in heat resistance and chemical resistances but also harmless. Therefore, the paint and resin composition of the present invention is suitable as green or orange paints and resin compositions which are free from environmental pollution.


[0309] The green or orange-based fine pigment having an average major axial diameter of from 0.005 to less than 0.1 μm according to the present invention, is harmless and enhanced in chemical resistances and heat resistance. Further, by using such a green or orange-based fine pigment, it is possible to obtain paints and resin compositions having an excellent transparency. Therefore, the green or orange-based fine pigment of the present invention is suitable as coloring pigments for resins, paints and printing inks.


[0310] The paint and resin composition of the present invention are produced using the green or orange-based fine pigment which has excellent heat resistance and chemical resistances, and is harmless. Therefore, the paint and resin composition of the present invention are suitable as green or orange paints and resin compositions which are free from environmental pollution and have an excellent transparency.







EXAMPLES

[0311] The present invention is described in more detail by Examples and Comparative Examples, but the Examples are only illustrative and, therefore, not intended to limit the scope of the present invention.


[0312] Various properties were measured by the following methods.


[0313] (1) The average major axial diameter and average minor axial diameter of the particles were respectively expressed by average values (measured in a predetermined direction) of about 350 particles which were sampled from a micrograph obtained by magnifying an original electron micrograph by four times in each of the longitudinal and transverse directions.


[0314] (2) The aspect ratio of the particles was expressed by a ratio of average major axial diameter to average minor axial diameter thereof.


[0315] (3) The geometrical standard deviation of major axial diameters of the particles was expressed by values obtained by the following method. That is, the major axial diameters were measured from the above magnified electron micrograph. The actual major axial diameters and the number of the particles were obtained from the calculation on the basis of the measured values. On a logarithmic normal probability paper, the major axial diameters were plotted at regular intervals on the abscissa-axis and the accumulative number (under integration sieve) of particles belonging to each interval of the major axial diameters were plotted by percentage on the ordinate-axis by a statistical technique.


[0316] The major axial diameters corresponding to the number of particles of 50% and 84.13%, respectively, were read from the graph, and the geometrical standard deviation (under integration sieve) was measured from the following formula:


[0317] Geometrical standard deviation= {major axial diameter corresponding to 84.13% under integration sieve)/{major axial diameter (geometrical average diameter) corresponding to 50% under integration sieve}


[0318] The closer to 1 the geometrical standard deviation value, the more excellent the particle size distribution of the major axial diameters of the particles.


[0319] (4) The specific surface area was expressed by values measured by a BET method.


[0320] (5) The amounts of Al and Si which were present within iron oxide hydroxide particles or on the surfaces thereof; the amount of Al contained in the aluminum and iron oxide hydroxide composite of adhered onto the surfaces of the iron oxide hydroxide particles; and the amount of Si contained in the coating layer composed of organosilicon compounds, were measured by a fluorescent X-ray spectroscopy device “3063 M-type” (manufactured by RIGAKU DENKI KOGYO CO., LTD.) according to JIS K0119 “General rule of fluorescent X-ray analysis”.


[0321] Meanwhile, the amount of Si contained in oxides of silicon, hydroxides of silicon and organosilicon compounds coated on the surfaces of the iron oxide hydroxide particles, is expressed by the value obtained by subtracting the amount of Si measured prior to the respective treatment steps from that measured after the respective treatment steps.


[0322] (6) The amount (wt. %) of Fe contained in aluminum and iron oxide hydroxide composite which was coated on the surfaces of the iron oxide hydroxide particles, is expressed by the value obtained by the following method.


[0323] That is, 0.25 g of the iron oxide hydroxide particles was weighed and charged into a 100 ml conical flask, and then mixed with 33.3 ml of ion exchange water. The flask was placed in a water bath heated to 60° C., and the contents of the flask were stirred for 20 minutes by a magnetic stirrer, thereby obtaining a suspension.


[0324] Next, the suspension was mixed with 16.7 ml of a 12N-hydrochloric acid solution and further stirred for 20 minutes. As a result, a portion of the coat of aluminum and iron oxide hydroxide composite adhered on the surface of each iron oxide hydroxide particle which portion extends from an outer surface of the coat up to approximately a mid point of the distance between the outer surface of the coat and an outer surface of each iron oxide hydroxide particle, and has a substantially uniform composition, was dissolved out with the acid from the outermost surface of the coated particle toward the inside thereof (This fact was already confirmed by many experiments). Thereafter, the suspension containing components dissolved-out by the acid was subjected to suction filtration using a 0.1 μm-membrane filter. The amounts (ppm) of Al and Fe in the obtained filtrate were measured by an inductively-coupled plasma atomic emission spectrometer (SPS-4000 manufactured by Seiko Denshi Kogyo Co., Ltd.).


[0325] Further, the amount of Fe contained in the aluminum and iron oxide hydroxide composite was calculated from the weight percentage of Al to Fe obtained from the measured amounts of Al and Fe in the filtrate and the amount (% by weight) of Al in the aluminum and iron oxide hydroxide composite obtained by the above-mentioned fluorescent X-ray analysis, according to the following formula (i):


[0326] Amount of Fe (% by weight)=Amount of Al (% by weight)/Weight ratio of Al to Fe


[0327] (7) The amount of the organic pigment adhered on the iron oxide hydroxide composite particles was obtained by measuring the carbon content thereof using “HORIBA METAL CARBON/SULFUR ANALYZER EMIA-2200 MODEL” (manufactured by Horiba Seisakusho Co., Ltd.).


[0328] (8) The desorption percentage of the organic pigment adhered on the iron oxide hydroxide composite particles, is expressed by the value measured by the following method. The closer to 0% the desorption percentage of the organic pigment, the less the amount of the organic pigment desorbed from the surface of the iron oxide hydroxide composite particles.


[0329] Three grams of the iron oxide hydroxide composite particles and 40 ml of ethanol were placed in a precipitation tube, and subjected to ultrasonic dispersion for 20 minutes. The obtained dispersion was allowed to stand for 120 minutes, thereby separating the dispersion into the iron oxide hydroxide composite particles and the organic pigment desorbed therefrom due to the difference in precipitating speed therebetween. Subsequently, the iron oxide hydroxide composite particles were mixed again with 40 ml of ethanol, and subjected to ultrasonic dispersion for 20 minutes. The obtained dispersion was allowed to stand for 120 minutes, thereby separating the dispersion into the iron oxide hydroxide composite particles and the organic pigment. The thus separated iron oxide hydroxide composite particles were dried at 80° C. for one hour to measure the amount of the organic pigment desorbed therefrom. The desorption percentage (%) of the organic pigment is calculated according to the following formula:


[0330] Desorption percentage (%) of organic pigment ={(Wa-We)/Wa}×100


[0331] wherein Wa represents an amount of the organic pigment adhered onto the iron oxide hydroxide composite particles; and We represents an amount of the organic pigment adhered onto the iron oxide hydroxide composite particles after desorption test.


[0332] (9) The hue of each of the iron oxide hydroxide particles, the organic pigment and the green or orange-based pigment, were measured by the following method.


[0333] That is, 0.5 g of each sample and 0.5 ml of castor oil were intimately kneaded together by a Hoover's muller to form a paste. 4.5 g of clear lacquer was added to the obtained paste and was intimately mixed to form a paint. The paint was applied on a cast-coated paper by using a 150 μm (6-mil) applicator to produce a coating film piece (having a film thickness of about 30 μm). The thus obtained coating film piece was measured by a Multi-spectro-colour-meter MSC-IS-2D (manufactured by SUGA TESTING MACHINES MANUFACTURING CO., LTD.) to determine L*, a* and b* values thereof.


[0334] Meanwhile, the h value is expressed by the value calculated from the above measured a* and b* values according to the following formulae:


[0335] h=tan−1(b*/a*) (a*>0, b*≦0);


[0336] h=180+tan−1(b*/a*) (a*<0); and


[0337] h=360+tan−1(b*/a*) (a*>0, b*<0)


[0338] (10) The heat resistance of each of the iron oxide hydroxide particles, the organic pigment and the iron oxide hydroxide composite particles, was expressed by the temperature read out from a DSC chart obtained by subjecting a test sample to differential scanning calorimetry (DSC) using a thermal analyzing apparatus SSC-5000 (manufactured by SEIKO DENSHI KOGYO Co., Ltd.), which temperature was read at a crossing point of two tangential lines on two curves constituting the first one of two infection points which form a peak on the DSC chart.


[0339] (11-1) The tinting strengths of the green-based pigment were measured by the following method.


[0340] That is, a primary color enamel and a vehicle enamel prepared by the following methods were respectively applied on a cast-coated paper by using a 150 μm (6-mil) applicator to produce coating film pieces. The thus obtained coating film pieces were measured by a Multi-spectro-colour-meter MSC-IS-2D (manufactured by SUGA TESTING MACHINES MANUFACTURING CO., LTD.) to determine the L* values thereof. The difference between the measured L* values was expressed by ΔL*.


[0341] Based on the thus measured ΔL* value and the ΔLs* value obtained from chrome green (Comparative Example 6) as a reference sample, the tinting strength (%) was calculated according to the following formula:


[0342] Tinting strength (%)=100+{(ΔLs*−ΔL*)×10}


[0343] (11-2) The tinting strength of the orange-based pigment was measured by the following method.


[0344] That is, a primary color enamel and a vehicle enamel prepared by the following methods were respectively applied on a cast-coated paper by using a 150 μm (6-mil) applicator to produce coating film pieces. The thus obtained coating film pieces were measured by a Multi-spectro-colour-meter MSC-IS-2D (manufactured by SUGA TESTING MACHINES MANUFACTURING CO., LTD.) to determine the L* values thereof. The difference between the measured L* values was expressed by ΔL*.


[0345] Next, the organic red-based pigment and the iron oxide hydroxide particles were simply blended together at the same mixing ratio as used for the production of the orange-based pigment, thereby preparing a mixed pigment as a reference sample for the orange-based pigment. The thus prepared reference sample was used to produce coating film pieces of the primary color enamel and the vehicle enamel by the same method as used above, and then the obtained coating film pieces were measured by the same method as above to determine L* values of the respective coating film pieces. The difference between the measured L* values was expressed by ΔLs*.


[0346] Based on the thus obtained ΔL* and ΔLs* values for the orange-based pigment and the reference sample, respectively, the tinting strength (%) was calculated according to the following formula:


[0347] Tinting strength (%)=100+{(ΔLs* −ΔL*)×10}


[0348] Preparation of Primary Color Enamel


[0349] 10 g of the above sample, 16 g of amino alkyd resin and 6 g of a thinner were blended together. The obtained mixture was charged together with 90 g of 3 mmφ glass beads into a 140-ml glass bottle, and then mixed and dispersed together for 45 minutes using a paint shaker. Thereafter, 50 g of amino alkyd resin was added to the obtained dispersion, and further dispersed together for 5 minutes using a paint shaker, thereby preparing a primary color enamel.


[0350] Preparation of Vehicle Enamel


[0351] 12 g of the above-prepared primary color enamel and 40 g of AMIRAC WHITE (titanium dioxide-dispersed amino alkyd resin) were blended together, and then mixed and dispersed together for 15 minutes using a paint shaker, thereby preparing a vehicle enamel.


[0352] (12) The hiding power of the organic pigment and the green or orange-based pigment is expressed by the value measured by the criptometer method according to paragraph 8.2 of JIS K5101, using the above obtained primary color enamel.


[0353] (13) The acid resistance of the iron oxide hydroxide particles and the iron oxide hydroxide composite particles was measured by the following method.


[0354] That is, 10 g of sample particles were immersed in a 5% sulfuric acid solution for 10 minutes. Thereafter, the sample particles were taken out of the sulfuric acid solution, washed with water and then dried. The thus dried particles were used to form a coating film by the same method as described above. The L*, a* and b* values of the coating film were measured, and the acid resistance was expressed by the value of color difference ΔE* calculated according to the following formula:


[0355] ΔE* value=((ΔL*)2+(Δa*)2 +(Δb*)2)½


[0356] wherein ΔL* represents the difference between the L* values before and after immersing the sample particles in acid or alkali; Δa* represents the difference between the a* values before and after immersing the sample particles in acid or alkali; and Δb* represents the difference between the a* values before and after immersing the sample particles in acid or alkali.


[0357] The smaller the ΔE* value, the more excellent the acid resistance.


[0358] (14) The alkali resistance of the iron oxide hydroxide particles and the iron oxide hydroxide composite particles was measured by the following method.


[0359] That is, 10 g of sample particles were immersed in a 1% sodium hydroxide solution for 15 minutes. Thereafter, the sample particles were taken out of the sodium hydroxide solution, washed with water and then dried. The thus dried particles were used to form a coating film by the same method as described above. The L*, a* and b* values of the coating film were measured, and the alkali resistance was expressed by the value of color difference ΔE* calculated according to the following formula:


[0360] ΔE* value=((ΔL*)2 +(Δa*)2 +(Δb*)2)½


[0361] wherein ΔL* represents the difference between the L* values before and after immersing the sample particles in acid or alkali; Δa* represents the difference between the a* values before and after immersing the sample particles in acid or alkali; and Δb* represents the difference between the a* values before and after immersing the sample particles in acid or alkali.


[0362] The smaller the ΔE* value, the more excellent the alkali resistance.


[0363] (15) The hue of the coating film obtained by using the solvent-based paint or water-based paint containing the green or orange-based pigment was determined by the following method.


[0364] That is, the paint produced by the method described hereinafter, was respectively coated on a cold-rolled steel plate (0.8 mm×70 mm×150 mm: JIS G-3141) and then dried to form a coating film having a thickness of 150 μm thereon, thereby preparing a coating film test piece. Also, the hue of the resin composition colored with the green or orange-based pigment was determined using a colored resin plate prepared by the method described hereinafter. The L*, a* and b* values of the thus prepared coating film test piece and colored resin plate were measured by using a Multi-spectro-colour-meter MSC-IS-2D (manufactured by SUGA TESTING MACHINES MANUFACTURING CO., LTD.).


[0365] Meanwhile, the h value of the paint or resin composition was calculated from the measured a* and b* values according to the above-specified formula:


[0366] h=tan−1(b*/a*) (a*>0, b*≦0);


[0367] h=180+tan−1(b*/a*) (a*<0); and


[0368] h=360+tan−1(b*/a*) (a*>0, b*<0)


[0369] (16) The gloss of a coating film formed obtained by using the paint containing the green or orange-based pigment, was measured by irradiating light onto the above coating film test pieces at an incident angle of 60°, using a glossmeter UGV-5D (manufactured by SUGA TESTING MACHINES MANUFACTURING CO., LTD.).


[0370] The higher the gloss, the more excellent the dispersibility of the paint containing the green or orange-based pigment.


[0371] (17) The transparency of the solvent-based paint or water-based paint containing the green or orange-based fine pigment, was determined using a coating film having a thickness of 150 μm (6 mil) which was prepared by applying each paint prepared by the method described hereinafter onto a 100 μm-thick clear base film.


[0372] Also, the transparency of the rubber or resin composition was determined using a resin plate prepared by the method described hereinafter.


[0373] In order to determine the transparency of the paint or resin composition, the light transmittance of the coating film or the resin plate was measured by a self-recording photoelectric spectrophotometer “UV-2100” (manufactured by Shimadzu Seisakusho Co., Ltd.). Based on the measured light transmittance, the linear absorption thereof was calculated according to the following formula:


[0374] Linear absorption (μm−1)=ln(1/t)/FT


[0375] wherein t represents a light transmittance at λ= 900 nm; and FT is a thickness of the coating film or the resin plate used for the measurement.


[0376] The smaller the linear absorption, the higher the light transmittance of the paint or resin composition, i.e., the higher the transparency thereof.


[0377] (18-1) The heat resistance of a coating film formed from the solvent-based paint or water-based paint containing the green or orange-based pigment is determined as follows.


[0378] That is, the above prepared coating film test piece was placed in an electric furnace, and while varying the temperature of the electric furnace, heat-treated for 15 minutes at each temperature. The hues (L* value, a* value and b* value) of the coating film test piece before and after heat treatment at each temperature were respectively measured by a Multi-spectro-colour-meter MSC-IS-2D (manufactured by SUGA TESTING MACHINES MANUFACTURING CO., LTD.).


[0379] Based on the measured values before the heat treatment as standard values, the ΔE* value was calculated according to the below-mentioned formula. On the semi-logarithmic graph paper, the heating temperatures were plotted on the abscissa-axis, and the ΔE* values were plotted on the ordinate-axis. The temperature at which the ΔE* value was identical to just 1.5, was determined as the heat-resisting temperature of the coating film.


[0380] ΔE* value=((ΔL*)2 +(Δa*)2 +(Δb*)2)½


[0381] wherein ΔL* represents a difference between L* values of the coating film before and after the heat treatment; Δa* represents a difference between a* values of the coating film before and after the heat treatment; and Δb* represents a difference between b* values of the coating film before and after the heat treatment.


[0382] (18-2) The heat resistance of a coating film formed from the solvent-based paint or water-based paint containing the green or orange-based fine pigment is determined as follows.


[0383] That is, a paint prepared by the method described hereinafter was applied onto a transparent glass plate (0.8 mm (thickness)×70 mm (width)×150 mm (length)). The coated glass plate was placed in an electric furnace, and while varying the temperature of the electric furnace, heat-treated for 15 minutes at each temperature. The hues (L* value, a* value and b* value) of the coated glass plate on a standard white back plate before and after heat treatment at each temperature were respectively measured by a Multi-spectro-colour-meter MSC-IS-2D (manufactured by SUGA TESTING MACHINES MANUFACTURING CO., LTD.) according to JIS Z 8729.


[0384] Based on the measured values before the heat treatment as standard values, the ΔE* value was calculated according to the above-mentioned formula. On the semi-logarithmic graph paper, the heating temperatures were plotted on the abscissa-axis, and the ΔE* values were plotted on the ordinate-axis. The temperature at which the ΔE* value was identical to just 1.5, was determined as the heat-resisting temperature of the coating film.


[0385] ΔE* value=((ΔL*)2 +(Δa*)2 +(Δb*)2)½


[0386] wherein ΔL* represents a difference between L* values of the coating film before and after the heat treatment; Δa* represents a difference between a* values of the coating film before and after the heat treatment; and Δb* represents a difference between b* values of the coating film before and after the heat treatment.


[0387] (19) The heat resistance of a rubber or resin composition containing the green or orange-based pigment was determined as follow. That is, a resin plate prepared by the method described hereinafter was cut into 5 cm square, was placed in a hot press, and while varying the temperature of the hot press and applying a load of 98 MPa (1 ton/cm2) thereto, heat-treated for 10 minutes at each temperature. The hues (L* value, a* value and b* value) of the resin plate before and after heat treatment at each temperature were respectively measured. Based on the measured values before the heat treatment as standard values, the ΔE* value was calculated according to the above-mentioned formula. On the semi-logarithmic graph paper, the heating temperatures were plotted on the abscissa-axis, and the ΔE* values were plotted on the ordinate-axis. The temperature at which the ΔE* value was identical to just 1.5, was determined as the heat-resisting temperature of the resin composition.


[0388] ΔE* value =((ΔL*)2 + (Δa*)2 + (Δb*)2)½


[0389] wherein ΔL* represents a difference between L* values of the coating film before and after the heat treatment; Δa* represents a difference between a* values of the coating film before and after the heat treatment; and Δb* represents a difference between b* values of the coating film before and after the heat treatment.


[0390] (20-1) The storage stability of a paint containing the green or orange-based pigment was determined by the following method.


[0391] That is, the paint produced by dispersing a mill base prepared by blending the below-mentioned components together at the predetermined mixing ratio, for 90 minutes, was coated on a cold-rolled steel plate (0.8 mm×70 mm×150 mm: JIS G-3141) and then dried to form a coating film having a thickness of 150 μm thereon. The hue (L*, a* and b* values) of the thus obtained coating film was measured. Further, after the paint was allowed to stand at 25° C. for one week, the paint was applied onto a cold-rolled steel plate and then dried to form a coating film by the same method as described above. Then, the hue (L*, a* and b* values) of the obtained coating film were also measured. Based on the thus measured L*, a* and b* values, the ΔE* value was calculated according to the below-mentioned formula:


[0392] ΔE* value ((ΔL*)2 + (Δa*)2 + (Δb*)2)½


[0393] wherein ΔL* represents a difference between L* values of the compared coating films prepared from the respective paints before and after the keeping test; Δa* represents a difference between a* values of the compared coating films prepared from the respective paints before and after the keeping test; and Δb* represents a difference between b* values of the compared coating films prepared from the respective paints before and after the keeping test.


[0394] (20-2) The storage stability of a paint containing the green or orange-based fine pigment was determined as follows.


[0395] That is, the paint prepared by the method described hereinafter, was applied onto a clear base film and then dried to form a coating film having a thickness of 150 μm (6 mil) thereon. The L*, a* and b* values of the obtained coating film were measured. Further, after the paint was allowed to stand at 25° C. for one week, the paint was applied onto a clear base film and then dried to form a coating film by the same method as described above. Then, the L*, a* and b* values of the obtained coating film were also measured. Based on the thus measured L*, a* and b* values, the ΔE* value was calculated according to the below-mentioned formula:


[0396] ΔE* value=((ΔL*)2 + (Δa*)2 + (Δb*)2)½


[0397] wherein ΔL* represents a difference between L* values of the compared coating films prepared from the respective paints before and after the keeping test; Δa* represents a difference between a* values of the compared coating films prepared from the respective paints before and after the keeping test; and Δb* represents a difference between b* values of the compared coating films prepared from the respective paints before and after the keeping test.


[0398] (21) The acid resistance of a coating film was measured by the following method.


[0399] That is, the coated plate was prepared by the same method as used above for the evaluation of heat resistance. The gloss of the coated plate was measured. Then, the coated plate suspended by a thread was immersed by about 120 mm in depth into a 5 wt. % aqueous sulfuric acid solution filled in a 1,000-ml beaker, and was allowed to stand in the suspended condition at 25° C. for 24 hours.


[0400] Next, the coated plate was removed from the aqueous sulfuric acid solution and gently washed with flowing water. After water attached to the coated plate was removed by shaking, the gloss of the coated plate was measured at a central portion thereof. Based on the measured gloss values before and after the immersion, the change in gloss (ΔG value) was calculated, thereby evaluating the acid resistance of the coating film. The smaller the ΔG value, the more excellent the acid resistance of the coating film.


[0401] (22) The alkali resistance of a coating film was measured by the following method. That is, the coated plate was prepared by the same method as used above for the evaluation of heat resistance. The gloss of the coated plate was measured. Then, the coated plate suspended by a thread was immersed by about 120 mm in depth into a 1 wt. % aqueous sodium hydroxide solution filled in a 1,000-ml beaker, and was allowed to stand in the suspended condition at 25° C. for 24 hours.


[0402] Next, the coated plate was removed from the aqueous sodium hydroxide solution and gently washed with flowing water. After water attached to the coated plate was removed by shaking, the gloss of the coated plate was measured at a central portion thereof. Based on the measured gloss values before and after the immersion, the change in gloss (ΔG value) was calculated, thereby evaluating the alkali resistance of the coating film. The smaller the ΔG value, the more excellent the alkali resistance of the coating film.


[0403] (23) The viscosity at 25° C. of the paint prepared by the method described hereinafter, was measured at a shear rate (D) of 1.92 sec−1 by E-type viscometer (cone plate-type viscometer) EMD-R (manufactured by TOKYO KEIKI CO., LTD.).


[0404] (24) The dispersibility of the green or orange-based pigment in resin composition was evaluated by visually counting the number of undispersed aggregate particles on a surface of the colored resin plate produced by the method described hereinafter, and by classifying the results into the following five ranks. The 5th rank represents the most excellent dispersing condition.


[0405] Rank 1: not less than 50 undispersed aggregate particles per 1 cm2 were recognized;


[0406] Rank 2: 10 to 49 undispersed aggregate particles per 1 cm2 were recognized;


[0407] Rank 3: 5 to 9 undispersed aggregate particles per 1 cm2 were recognized;


[0408] Rank 4: 1 to 4 undispersed aggregate particles per 1 cm2 were recognized;


[0409] Rank 5: No undispersed aggregate particles were recognized.



Example 1


<Production of Green-Based Pigment>

[0410] 11.0 kg of goethite particles (particle shape: acicular shape; average major axial diameter: 0.40 μm; aspect ratio: 5.3:1; geometrical standard deviation value: 1.44; BET specific surface area value: 18.8 m2/g; L* value: 59.3; a* value: 16.5; b* value: 53.9; h value: 73.0°; heat resistance temperature: 198° C.), were charged into an edge runner “MPUV-2 Model” (tradename, manufactured by MATSUMOTO CHUZO TEKKOSHO CO., LTD.). Then, a methyltriethoxysilane solution prepared by mixing and diluting 220 g of methyltriethoxysilane (tradename: TSL8123, produced by GE Toshiba Silicone Co., Ltd.) with 200 ml of ethanol was added to the goethite particles while operating the edge runner. The resultant mixture was mixed and stirred at a linear load of 392 N/cm (40 Kg/cm) and a stirring speed of 22 rpm for 20 minutes.


[0411] Next, 825 g of an organic blue pigment A (kind: copper phthalocyanine blue; particle shape: granular shape; average major axial diameter: 0.06 μm; hiding power: 240 cm2/g; L* value: 17.7; a* value: 9.7; b* value: −23.4; h value: 292.5°; heat resistance temperature: 256° C.), were added to the above mixture for 10 minutes while operating the edge runner. Further, the obtained mixture was mixed and stirred at a linear load of 392 N/cm (40 Kg/cm) and a stirring speed of 22 rpm for 20 minutes to form a coating layer composed of the organic blue pigment A on the methyltriethoxysilane coat, thereby obtaining a green-based pigment. The obtained green-based pigment was heat-treated at 105° C. for 60 minutes by using a drier.


[0412] The obtained green-based pigment was acicular particles having an average major axial diameter of 0.40 μm, an aspect ratio of 5.3:1, a geometrical standard deviation value of 1.44, a BET specific surface area value of 20.1 m2/g, a L* value of 39.9, an a* value of −13.2, a b* value of 19.8, a h value of 123.7°, a tinting strength of 141% and a hiding power of 1,950 cm2/g. As to the chemical resistances of the green-based pigment, the acid resistance (ΔE* value) thereof was 0.99, and the alkali resistance (ΔE* value) thereof was 0.86. As to the heat resistance of the green-based pigment, the heat resistance temperature thereof was 227° C. The desorption percentage of the organic blue pigment from the green-based pigment was 7.0% by weight. The amount of a coating layer composed of organosilane compounds produced from methyltriethoxysilane was 0.29% by weight (calculated as Si). The amount of the coating layer composed of the organic blue pigment A was 4.61% by weight (calculated as C) (corresponding to 7.5 parts by weight based on 100 parts by weight of the goethite core particles).


[0413] As a result of the observation of electron micrograph, almost no organic blue pigment A liberated was recognized, so that it was confirmed that a substantially whole amount of the organic blue pigment A added was adhered on the coating layer composed of the organosilane compounds produced from methyltriethoxysilane.



Example 2


<Production of Solvent-Based Paint Containing Green-Based Pigment>

[0414] 10 g of the green-based pigment produced in Example 1, was blended with an amino alkyd resin and a thinner at the following weight ratio, and charged into a 140-ml glass bottle together with 90 g of 3 mmφ glass beads. Next, the obtained mixture was mixed and dispersed for 90 minutes by a paint shaker, thereby preparing a mill base.
1Composition of Mill Base:Green-based pigment12.2 parts by weightAmino alkyd resin (AMILAC No. 1026,19.5 parts by weightproduced by KANSAI PAINT CO., LTD.)Thinner 7.3 parts by weight


[0415] The above-prepared mill base was blended with an amino alkyd resin at the following weight ratio, and the obtained mixture was further mixed and dispersed for 15 minutes by a paint shaker, thereby obtaining a solvent-based paint containing the green-based pigment.
2Composition of paint:Mill base39.0 parts by weightAmino Alkyd resin (AMILAC No. 1026,61.0 parts by weightKANSAI PAINT CO., LTD.)


[0416] The thus obtained solvent-based paint showed a viscosity of 1,452 cP. As to the storage stability of the solvent-based paint, the ΔE* value thereof was 0.92.


[0417] Then, the solvent-based paint was applied onto a cold-rolled steel plate (0.8 mm×70 mm×150 mm; JIS G-3141) and then dried to form a coating film having a thickness of 150 μm thereon. The thus obtained coating film showed a gloss of 87% and a heat resistance temperature of 249° C. As to the hue of the coating film, the L* value thereof was 40.2; the a* value thereof was −12.4; the b* value thereof was 20.5; and the h value thereof was 121.2°. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof was 9.3%, and the alkali resistance (ΔG value) thereof was 7.9%.



Example 3


<Production of Water-Based Paint Containing Green-Based Pigment>

[0418] 7.62 g of the green-based pigment obtained in Example 1, was blended with a water-soluble alkyd resin at the following weight ratio, and charged into a 140-ml glass bottle together with 90 g of 3 mmφ glass beads. Next, the obtained mixture was mixed and dispersed for 90 minutes by a paint shaker, thereby preparing a mill base.
3Composition of Mill Base:Green-based pigment12.4 parts by weight Water-soluble alkyd resin9.0 parts by weight(tradename: “S-118”, produced by DAI-NIPPON INK KAGAKU KOGYO CO., LTD.)Defoamer (tradename: “NOPCO 8034”,produced by SUN NOPCO LTD.)0.1 parts by weightWater4.8 parts by weightButyl cellosolve4.1 parts by weight


[0419] The above-prepared mill base was blended with paint components at the following weight ratio, and the obtained mixture was further mixed and dispersed for 15 minutes by a paint shaker, thereby obtaining a water-soluble paint.
4Composition of paint:Mill base30.4 parts by weightWater-soluble alkyd resin46.2 parts by weight(tradename: S-118, produced by DAI-NIPPON INK KAGAKU KOGYO CO., LTD.)Water-soluble melamine resin12.6 parts by weight(tradename: S-695, produced by DAI-NIPPON INK KAGAKU KOGYO CO., LTD.)Defoamer (tradename: “NOPCO 8034”, 0.1 parts by weightproduced by SUN NOPCO LTD.)Water 9.1 parts by weightButyl cellosolve 1.6 parts by weight


[0420] The thus obtained water-based paint showed a viscosity of 2,118 cP. As to the storage stability of the water-based paint, the ΔE* value thereof was 1.00.


[0421] Then, the water-based paint was applied onto a cold-rolled steel plate (0.8 mm×70 mm×150 mm; JIS G-3141) and then dried to form a coating film having a thickness of 150 μm thereon. The thus obtained coating film showed a gloss of 82% and a heat resistance temperature of 247° C. As to the hue of the coating film, the L* value thereof was 40.7; the a* value thereof was −12.6; the b* value thereof was 20.9; and the h value thereof was 121.1°. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof was 9.6%, and the alkali resistance (ΔG value) thereof was 8.8%.



Example 4


<Production of Resin Composition>

[0422] 2.5 g of the green-based pigment obtained in Example 1, and 47. 5 g of a polyvinyl chloride resin 103EP8D (produced by NIPPON ZEON CO., LTD.) were weighed and charged into a 100 ml beaker, and intimately mixed together by a spatula, thereby obtaining mixed particles.


[0423] 0.5 g of calcium stearate was added to the mixed particles. The mixed particles were slowly supplied to hot rolls heated to 160° C. whose clearance was set to 0.2 mm, and continuously kneaded therebetween until a uniform resin composition was produced. The resin composition kneaded was separated from the hot rolls and used as a raw material for forming a colored resin plate.


[0424] Next, the thus-produced resin composition was interposed between a pair of surface-polished stainless steel plates, placed within a hot press heated to 180° C. and subjected to a pressure molding while applying a pressure of 1 ton/cm2 thereto, thereby obtaining a colored resin plate having a thickness of 1 mm. The thus-produced colored resin plate had a dispersing condition of rank 5 and a heat resistance temperature of 223° C. As to the hue of the resin plate, the L* value thereof was 42.2; the a* value thereof was −10.8; the b* value thereof was 17.9; and the h value thereof was 121.10.



Example 5


<Production of Orange-Based Pigment>

[0425] 11.0 kg of goethite particles (particle shape: acicular shape; average major axial diameter: 0.40 μm; aspect ratio: 5.3:1; geometrical standard deviation value: 1.44; BET specific surface area value: 18.8 m2/g; L* value: 59.3; a* value: 16.5; b* value: 53.9; h value: 73.0°; heat resistance temperature: 198° C.), were charged into an edge runner “MPUV-2 Model” (tradename, manufactured by MATSUMOTO CHUZO TEKKOSHO CO., LTD.). Then, a methyltriethoxysilane solution prepared by mixing and diluting 220 g of methyltriethoxysilane (tradename: TSL8123, produced by GE Toshiba Silicone Co., Ltd.) with 200 ml of ethanol was added to the goethite particles while operating the edge runner. The resultant mixture was mixed and stirred at a linear load of 392 N/cm (40 Kg/cm) and a stirring speed of 22 rpm for 20 minutes.


[0426] Next, 825 g of an organic red pigment D (kind: quinacridone red; particle shape: granular shape; average major axial diameter: 0.58 μm; hiding power: 480 cm2/g; heat resistance temperature: 488° C.; L* value: 37.0; a* value: 51.9; b* value: 20.6; h value: 21.6°), were added to the above mixture for 10 minutes while operating the edge runner. Further, the obtained mixture was mixed and stirred at a linear load of 392 N/cm (40 Kg/cm) and a stirring speed of 22 rpm for 20 minutes to form a coating layer composed of the organic red pigment D on the methyltriethoxysilane coat, thereby obtaining an orange-based pigment. The obtained orange-based pigment was heat-treated at 105° C. for 60 minutes by using a drier.


[0427] The obtained orange-based pigment was acicular particles having an average major axial diameter of 0.40 μm, an aspect ratio of 5.3:1, a geometrical standard deviation value of 1.44, a BET specific surface area value of 21.2 m2/g, a L* value of 46.3, an a* value of 37.1, a b* value of 42.6, a h value of 48.9°, a tinting strength of 137% and a hiding power of 1,970 cm2/g. As to the chemical resistances of the orange-based pigment, the acid resistance (ΔE* value) thereof was 0.97, and the alkali resistance (ΔE* value) thereof was 0.85. As to the heat resistance of the orange-based pigment, the heat resistance temperature thereof was 229° C. The desorption percentage of the organic red pigment from the orange-based pigment was 6.9%. The amount of a coating layer composed of organosilane compounds produced from methyltriethoxysilane was 0.30% by weight (calculated as Si). The amount of the coating layer composed of the organic red pigment D was 5.30% by weight (calculated as C) (corresponding to 7.5 parts by weight based on 100 parts by weight of the goethite core particles).


[0428] As a result of the observation of electron micrograph, almost no organic red pigment D liberated was recognized, so that it was confirmed that a substantially whole amount of the organic red pigment D added was adhered on the coating layer composed of the organosilane compounds produced from methyltriethoxysilane.



Example 6


<Production of Solvent-Based Paint Containing Orange-Based Pigment>

[0429] 10 g of the orange-based pigment produced in Example 5, was blended with an amino alkyd resin and a thinner at the following weight ratio, and charged into a 140-ml glass bottle together with 90 g of 3 mmφ glass beads. Next, the obtained mixture was mixed and dispersed for 90 minutes by a paint shaker, thereby preparing a mill base.
5Composition of Mill Base:Orange-based pigment12.2 parts by weightAmino alkyd resin (AMILAC No. 1026,19.5 parts by weightproduced by KANSAI PAINT CO., LTD.)Thinner 7.3 parts by weight


[0430] The above-prepared mill base was blended with an amino alkyd resin at the following weight ratio, and the obtained mixture was further mixed and dispersed for 15 minutes by a paint shaker, thereby obtaining a solvent-based paint containing the orange-based pigment.
6Composition of paint:Mill base39.0 parts by weightAmino alkyd resin (AMILAC No. 1026,61.0 parts by weightproduced by KANSAI PAINT CO., LTD.)


[0431] The thus obtained solvent-based paint showed a viscosity of 1,315 cP. As to the storage stability of the solvent-based paint, the ΔE* value thereof was 0.86.


[0432] Then, the solvent-based paint was applied onto a cold-rolled steel plate (0.8 mm×70 mm×150 mm; JIS G-3141) and then dried to form a coating film having a thickness of 150 μm thereon. The thus obtained coating film showed a gloss of 87% and a heat resistance temperature of 250° C. As to the hue of the coating film, the L* value thereof was 48.0; the a* value thereof was 36.5; the b* value thereof was 42.1; and the h value thereof was 49.1°. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof was 8.7%, and the alkali resistance (ΔG value) thereof was 7.7%.



Example 7


<Production of Water-Based Paint Containing Orange-Based Pigment>

[0433] 7.62 g of the orange-based pigment obtained in Example 5, was blended with a water-soluble alkyd resin and the like at the following weight ratio, and charged into a 140-ml glass bottle together with 90 g of 3 mmφ glass beads. Next, the obtained mixture was mixed and dispersed for 90 minutes by a paint shaker, thereby preparing a mill base.
7Composition of Mill Base:Orange-based pigment12.4 parts by weight Water-soluble alkyd resin9.0 parts by weight(tradename: “S-118”, produced by DAI-NIPPON INK KAGAKU KOGYO CO., LTD.)Defoamer (tradename: “NOPCO 8034”,0.1 parts by weightproduced by SUN NOPCO LTD.)Water4.8 parts by weightButyl cellosolve4.1 parts by weight


[0434] The above-prepared mill base was blended with paint components at the following weight ratio, and the obtained mixture was further mixed and dispersed for 15 minutes by a paint shaker, thereby obtaining a water-soluble paint.
8Composition of paint:Mill base30.4 parts by weightWater-soluble alkyd resin46.2 parts by weight(tradename: S-118, produced by DAI-NIPPON INK KAGAKU KOGYO CO., LTD.)Water-soluble melamine resin12.6 parts by weight(tradename: S-695, produced by DAI-NIPPON INK KAGAKU KOGYO CO., LTD.)Defoamer (tradename: “NOPCO 8034”, 0.1 parts by weightproduced by SUN NOPCO LTD.)Water 9.1 parts by weightButyl cellosolve 1.6 parts by weight


[0435] The thus obtained water-based paint showed a viscosity of 2,434 cP. As to the storage stability of the water-based paint, the ΔE* value thereof was 0.98.


[0436] Then, the water-based paint was applied onto a cold-rolled steel plate (0.8 mm×70 mm×150 mm; JIS G-3141) and then dried to form a coating film having a thickness of 150 μm thereon. The thus obtained coating film showed a gloss of 82% and a heat resistance temperature of 248° C. As to the hue of the coating film, the L* value thereof was 48.5; the a* value thereof was 36.7; the b* value thereof was 42.0; and the h value thereof was 48.9°. As to the chemical resistances of the coating film, the acid resistance (ΔG value) thereof was 9.4%, and the alkali resistance (ΔG value) thereof was 8.2%.



Example 8


<Production of Resin Composition>

[0437] 2.5 g of the orange-based pigment obtained in Example 5, and 47. 5 g of a polyvinyl chloride resin 103EP8D (produced by NIPPON ZEON CO., LTD.) were weighed and charged into a 100 ml beaker, and intimately mixed together by a spatula, thereby obtaining mixed particles.


[0438] 0.5 g of calcium stearate was added to the mixed particles. The mixed particles were slowly supplied to hot rolls heated to 160° C. whose clearance was set to 0.2 mm, and continuously kneaded therebetween until a uniform resin composition was produced. The resin composition kneaded was separated from the hot rolls and used as a raw material for forming a colored resin plate.


[0439] Next, the thus-produced resin composition was interposed between a pair of surface-polished stainless steel plates, placed within a hot press heated to 180° C. and subjected to a pressure molding while applying a pressure of 98 MPa (1 ton/cm2) thereto, thereby obtaining a colored resin plate having a thickness of 1 mm. The thus-produced colored resin plate had a dispersing condition of rank 5 and a heat resistance temperature of 224° C. As to the hue of the resin plate, the L* value thereof was 49.4; the a* value thereof was 36.2; the b* value thereof was 41.9; and the h value thereof was 49.20.



Example 9


<Production of Green-Based Fine Pigment>

[0440] 11.0 kg of goethite fine particles (particle shape: acicular shape; average major axial diameter: 0.0710 μm; average minor axial diameter: 0.0081 μm; aspect ratio: 8.8:1; geometrical standard deviation value: 1.38; BET specific surface area value: 159.8 m2/g; aluminum content: 0.83% by weight; L* value: 51.6; a* value: 31.4; b* value: 61.7; h value: 63.0°; acid resistance (ΔG value): 1.92; alkali resistance (ΔG value): 1.75; hiding power: 152 cm2/g; heat resistance temperature: 245° C.), were charged into an edge runner “MPUV-2 Model” (tradename, manufactured by MATSUMOTO CHUZO TEKKOSHO CO., LTD.). Then, a methyltriethoxysilane solution prepared by mixing and diluting 220 g of methyltriethoxysilane (tradename: TSL8123, produced by GE Toshiba Silicone Co., Ltd.) with 200 ml of ethanol was added to the goethite fine particles while operating the edge runner. The resultant mixture was mixed and stirred at a linear load of 392 N/cm (40 Kg/cm) and a stirring speed of 22 rpm for 20 minutes.


[0441] Next, 1,100 g of an organic blue pigment A (kind: copper phthalocyanine blue; particle shape: granular shape; average major axial diameter: 0.06 μm; hiding power: 240 cm2/g; L* value: 17.7; a* value: 9.7; b* value: −23.4; h value: 292.5°; heat resistance temperature: 256° C.), were added to the above mixture for 10 minutes while operating the edge runner. Further, the obtained mixture was mixed and stirred at a linear load of 392 N/cm (40 Kg/cm) and a stirring speed of 22 rpm for 20 minutes to form a coating layer composed of the organic blue pigment A on the methyltriethoxysilane coat. Then, the obtained particles were heat-treated at 105° C. for 60 minutes by using a dryer, thereby obtaining a green-based fine pigment.


[0442] The obtained green-based fine pigment was acicular particles having an average major axial diameter of 0.0722 μm, an average minor axial diameter of 0.0082 μm, an aspect ratio of 8.8:1, a geometrical standard deviation value of 1.33, a BET specific surface area value of 153.6 m2/g, a L* value of 31.6, an a* value of −8.7, a b* value of 0.3, a h value of 178.0°, a tinting strength of 123% and a hiding power of 159 cm2/g. As to the chemical resistances of the green-based fine pigment, the acid resistance (ΔE* value) thereof was 1.14, and the alkali resistance (ΔE* value) thereof was 1.06. As to the heat resistance of the green-based fine pigment, the heat resistance temperature thereof was 257° C. The desorption percentage of the organic blue pigment from the green-based fine pigment was 7.1%. The amount of a coating layer composed of organosilane compounds produced from methyltriethoxysilane was 0.30% by weight (calculated as Si). The amount of the coating layer composed of the organic blue pigment A was 5.99 % by weight (calculated as C) (corresponding to 10 parts by weight based on 100 parts by weight of the goethite core fine particles).


[0443] As a result of the observation of electron micrograph, almost no organic blue pigment A liberated was recognized. Therefore, it was confirmed that a substantially whole amount of the organic blue pigment A added was adhered on the coating layer composed of the organosilane compounds produced from methyltriethoxysilane.



Example 10


<Production of Solvent-Based Paint Containing Green-Based Fine Pigment>

[0444] 5 g of the green-based fine pigment produced in Example 9 was blended with the below-mentioned paint base materials at the following weight ratio in a 250-ml glass bottle. Next, the obtained mixture was mixed and dispersed together with 160 g of 3 mmφ glass beads for 120 minutes by a paint shaker, thereby preparing a solvent-based paint.
9Composition of Solvent-based Paint:Green-based fine pigment 9.9 parts by weightMelamine resin (tradename: SUPER-PEKKAMINE19.8 parts by weightJ-820-60, produced by DAI-NIPPON INKKAGAKU KOGYO CO., LTD.)Alkyd resin (tradename: BEKKOSOLE 1307-60EL,39.6 parts by weightproduced by DAI-NIPPON INK KAGAKUKOGYO CO., LTD.)Xylene29.7 parts by weightButanol 1.0 part by weight


[0445] The thus obtained solvent-based paint showed a viscosity of 1,676 cP. As to the storage stability of the solvent-based paint, the ΔE* value thereof was 0.87.


[0446] The solvent-based paint was applied onto a clear base film and then dried to form a coating film having a thickness of 150 μm (6 mil) thereon. The thus obtained coating film showed a gloss of 86.1%. As to the hue of the coating film, the L* value thereof was 32.3; the a* value thereof was −16.3; the b* value thereof was 2.0; and the h value thereof was 173.0°. The linear absorption of the coating film was 0.0184 μm−1.


[0447] Then, the solvent-based paint was applied onto a transparent glass plate (0.8 mm in thickness×70 mm in width× 150 mm in length) to form a coating film having a thickness of 150 μm (6 mil) thereon. As to the chemical resistances of the obtained coating film, the acid resistance (ΔG value) thereof was 8.2%, and the alkali resistance (ΔG value) thereof was 7.7%.


[0448] Then, the heat resistance of the coating film was determined as follows. That is, five coated plates were prepared using the solvent-based paint by the same method as described above. The respective coated plates were placed within Geer ovens heated to 210° C., 230° C., 250° C, 270° C. and 290° C., respectively, and heat-treated therein for 15 minutes. Thereafter, the coated plates were removed from the ovens to measure the hue values thereof. Based on the hue values before the heat treatment as standard values, the ΔE* value of each coated plate was measured. From the relationship between the heat-treating temperature and the ΔE* value, it was recognized that the temperature at which the ΔE* value was identical to just 1.5, was 269° C.



Example 11


<Production of Water-Based Paint Containing Green-Based Fine Pigment>

[0449] 5 g of the green-based fine pigment produced in Example 9 was blended with the below-mentioned paint base materials at the following weight ratio in a 250-ml glass bottle. Next, the obtained mixture was mixed and dispersed together with 160 g of 3 mmφ glass beads for 120 minutes by a paint shaker, thereby preparing a water-based paint.
10Composition of Water-based Paint:Green-based fine pigment10.1 parts by weightWater-soluble melamine resin (tradename: S-695, 9.3 parts by weightproduced by DAI-NIPPON INK KAGAKUKOGYO CO., LTD.)Water-soluble alkyd resin (tradename: S-118,40.7 parts by weightproduced by DAI-NIPPON INK KAGAKUKOGYO CO., LTD.)Defoamer (tradename: “NOPCO 8034”, 0.2 part by weightproduced by SUN NOPCO LTD.)Water28.2 parts by weightButyl cellosolve11.5 parts by weight


[0450] The thus obtained water-based paint showed a viscosity of 2,184 cP. As to the storage stability of the water-based paint, the ΔE* value thereof was 0.92.


[0451] The water-based paint was applied onto a clear base film and then dried to form a coating film having a thickness of 150 μm (6 mil) thereon. The thus obtained coating film showed a gloss of 82.3%. As to the hue of the coating film, the L* value thereof was 32.9; the a* value thereof was −16.2; the b* value thereof was 2.1; and the h value thereof was 172.6°. The linear absorption of the coating film was 0.0199 μm−1.


[0452] Then, the water-based paint was applied onto a transparent glass plate (0.8 mm in thickness×70 mm in width×150 mm in length) to form a coating film having a thickness of 150 μm (6 mil) thereon. As to the chemical resistances of the obtained coating film, the acid resistance (ΔG value) thereof was 8.7%, and the alkali resistance (ΔG value) thereof was 8.0%.


[0453] Then, the heat resistance of the coating film was determined as follows. That is, five coated plates were prepared using the water-based paint by the same method as described above. The respective coated plates were placed within Geer ovens heated to 210° C., 230° C., 250° C., 270° C. and 290° C., respectively, and heat-treated therein for 15 minutes. Thereafter, the coated plates were removed from the ovens to measure the hue values thereof. Based on the hue values before the heat treatment as standard values, the ΔE* value of each coated plate was measured. From the relationship between the heat-treating temperature and the ΔE* value, it was recognized that the temperature at which the ΔE* value was identical to just 1.5, was 264° C.



Example 12


<Production of Resin Composition>

[0454] 0.5 g of the green-based fine pigment obtained in Example 9, and 49. 5 g of a polyvinyl chloride resin 103EP8D (produced by NIPPON ZEON CO., LTD.) were weighed and charged into a 100 ml beaker, and intimately mixed together by a spatula, thereby obtaining mixed particles.


[0455] 1.0 g of calcium stearate was added to the mixed particles. The mixed particles were slowly supplied to hot rolls heated to 160° C. whose clearance was set to 0.2 mm, and continuously kneaded therebetween until a uniform resin composition was produced. The resin composition kneaded was separated from the hot rolls and used as a raw material for forming a colored resin plate.


[0456] Next, the thus-produced resin composition was interposed between a pair of surface-polished stainless steel plates, placed within a hot press heated to 180° C. and subjected to a pressure molding while applying a pressure of 98 MPa (1 ton/cm2) thereto, thereby obtaining a colored resin plate having a thickness of 1 mm. As to the hue of the resin plate, the L* value thereof was 32.4; the a* value thereof was −12.6; the b* value thereof was 2.4; and the h value thereof was 169.2°. The thus-produced colored resin plate had a dispersing condition of rank 5 and a linear absorption of 0.0192 μm−1.


[0457] Then, the heat resistance of the resin composition was determined as follows. That is, five colored resin plates were prepared using the resin composition and cut into 5 cm square to prepare 5 test specimens. The respective test specimens were placed within hot presses heated to 185° C., 200° C., 215° C., 230° C. and 245° C., respectively, and heat-treated therein for 10 minutes while applying a pressure of 98 MPa (1 ton/cm2) thereto. Thereafter, the resin plates were removed from the presses to measure the hue values thereof. Based on the hue values before the heat treatment as standard values, the ΔE* value of each resin plate was measured. From the relationship between the heat-treating temperature and the ΔE* value, it was recognized that the temperature at which the ΔE* value was identical to just 1.5, was 231° C.



Example 13


<Production of Orange-Based Fine Pigment>

[0458] 11.0 kg of goethite fine particles (particle shape: acicular shape; average major axial diameter: 0.0710 μm; average minor axial diameter: 0.0081 μm; aspect ratio: 8.8:1; geometrical standard deviation value: 1.38; BET specific surface area value: 159.8 m2/g; aluminum content: 0.83% by weight; L* value: 51.6; a* value: 31.4; b* value: 61.7; h value: 63.0°; acid resistance: 1.92; alkali resistance: 1.75; hiding power: 152 cm2/g; heat resistance temperature: 245° C.), were charged into an edge runner “MPUV-2 Model” (tradename, manufactured by MATSUMOTO CHUZO TEKKOSHO CO., LTD.). Then, a methyltriethoxysilane solution prepared by mixing and diluting 220 g of methyltriethoxysilane (tradename: TSL8123, produced by GE Toshiba Silicone Co., Ltd.) with 200 ml of ethanol was added to the goethite fine particles while operating the edge runner. The resultant mixture was mixed and stirred at a linear load of 441 N/cm (45 Kg/cm) and a stirring speed of 22 rpm for 30 minutes.


[0459] Next, 1,100 g of an organic red pigment D (kind: quinacridone red; particle shape: granular shape; average major axial diameter: 0.58 μm; hiding power: 480 cm2/g; L* value: 37.0; a* value: 51.9; b* value: 20.6; h value: 21.6°; heat resistance temperature: 488° C.), was added to the above mixture for 10 minutes while operating the edge runner. Further, the obtained mixture was mixed and stirred at a linear load of 441 N/cm (45 Kg/cm) and a stirring speed of 22 rpm for 30 minutes to form a coating layer composed of the organic red pigment A on the methyltriethoxysilane coat. Then, the obtained particles were heat-treated at 105° C. for 60 minutes by using a dryer, thereby obtaining orange-based fine pigment.


[0460] The obtained orange-based fine pigment was acicular particles having an average major axial diameter of 0.0720 μm, an average minor axial diameter of 0.0084 μm, an aspect ratio of 8.6:1, a geometrical standard deviation value of 1.38, a BET specific surface area value of 162.1 m2/g, a L* value of 35.2, an a* value of 49.8, a b* value of 40.2, a h value of 38.9°, a tinting strength of 129% and a hiding power of 161 cm2/g. As to the chemical resistances of the orange-based fine pigment, the acid resistance (ΔE* value) thereof was 1.09, and the alkali resistance (ΔE* value) thereof was 1.04. As to the heat resistance of the orange-based fine pigment, the heat resistance temperature thereof was 254° C. The desorption percentage of the organic red pigment from the orange-based fine pigment was 7.0%. The amount of a coating layer composed of organosilane compounds produced from methyltriethoxysilane was 0.30% by weight (calculated as Si). The amount of the coating layer composed of the organic red pigment D was 6.89% by weight (calculated as C) (corresponding to 10 parts by weight based on 100 parts by weight of the goethite core fine particles).


[0461] As a result of the observation of electron micrograph, almost no organic red pigment D liberated was recognized. Therefore, it was confirmed that a substantially whole amount of the organic red pigment D added was adhered on the coating layer composed of the organosilane compounds produced from methyltriethoxysilane.



Example 14


<Production of Solvent-Based Paint Containing Orange-Based Fine Pigment>

[0462] 5 g of the orange-based fine pigment produced in Example 13 was blended with the below-mentioned paint base materials at the following weight ratio in a 250-ml glass bottle. Next, the obtained mixture was mixed and dispersed together with 160 g of 3 mmφ glass beads for 120 minutes by a paint shaker, thereby preparing a solvent-based paint.
11Composition of Solvent-based Paint:Orange-based fine pigment 9.9 parts by weightMelamine resin (tradename: SUPER-PEKK-19.8 parts by weightAMINE J-820-60, produced by DAI-NIPPONINK KAGAKU KOGYO CO., LTD.)Alkyd resin (tradename: BEKKOSOLE39.6 parts by weight1307-60EL, produced by DAI-NIPPONINK KAGAKU KOGYO CO., LTD.)Xylene29.7 parts by weightButanol 1.0 parts by weight


[0463] The thus obtained solvent-based paint showed a viscosity of 3,119 cP. As to the storage stability of the solvent-based paint, the ΔE* value thereof was 0.95.


[0464] The solvent-based paint was applied onto a clear base film and then dried to form a coating film having a thickness of 150 μm (6 mil) thereon. The thus obtained coating film showed a gloss of 82.2%. As to the hue of the coating film, the L* value thereof was 36.0; the a* value thereof was 49.5; the b* value thereof was 40.6; and the h value thereof 39.4°. The linear absorption of the coating film was 0.0202 μm−1.


[0465] Then, the solvent-based paint was applied onto a transparent glass plate (0.8 mm in thickness×70 mm in width×150 mm in length) to form a coating film having a thickness of 150 μm (6 mil) thereon. As to the chemical resistances of the obtained coating film, the acid resistance (ΔG value) thereof was 8.5%, and the alkali resistance (ΔG value) thereof was 8.0%.


[0466] Then, the heat resistance of the coating film was determined as follows. That is, five coated plates were prepared using the solvent-based paint by the same method as described above. The respective coated plates were placed within Geer ovens heated to 210° C., 230° C., 250° C., 270° C. and 290° C., respectively, and heat-treated therein for 15 minutes. Thereafter, the coated plates were removed from the ovens to measure the hue values thereof. Based on the hue values before the heat treatment as standard values, the ΔE* value of each coated plate was measured. From the relationship between the heat-treating temperature and the ΔE* value, it was recognized that the temperature at which the ΔE* value was identical to just 1.5, was 259° C.



Example 15


<Production of Water-Based Paint Containing Orange-Based Fine Pigment>

[0467] 5 g of the orange-based fine pigment produced in Example 13 was blended with the below-mentioned paint base materials at the following weight ratio in a 250-ml glass bottle. Next, the obtained mixture was mixed and dispersed together with 160 g of 3 mmφ glass beads for 120 minutes by a paint shaker, thereby preparing a water-based paint.
12Composition of Water-based Paint:Orange-based fine pigment10.1 parts by weightWater-soluble melamine resin (tradename: 9.3 parts by weightS-695, produced by DAI-NIPPONINK KAGAKU KOGYO CO., LTD.)Water-soluble alkyd resin (tradename:40.7 parts by weightS-118, produced by DAI-NIPPONINK KAGAKU KOGYO CO., LTD.)Defoamer (tradename: 0.2 parts by weight“NOPCO 8034”, producedby SUN NOPCO LTD.)Water28.2 parts by weightButyl cellosolve11.5 parts by weight


[0468] The thus obtained water-based paint showed a viscosity of 3,209 cP. As to the storage stability of the water-based paint, the ΔE* value thereof was 0.92.


[0469] The water-based paint was applied onto a clear base film and then dried to form a coating film having a thickness of 150 μm (6 mil) thereon. The thus obtained coating film showed a gloss of 78.8%. As to the hue of the coating film, the L* value thereof was 36.1; the a* value thereof was 49.4; the b* value thereof was 40.2; and the h value thereof was 39.1°. The linear absorption of the coating film was 0.0215 μm−1.


[0470] Then, the water-based paint was applied onto a transparent glass plate (0.8 mm in thickness×70 mm in width×150 mm in length) to form a coating film having a thickness of 150 μm (6 mil) thereon. As to the chemical resistances of the obtained coating film, the acid resistance (ΔG value) thereof was 8.7%, and the alkali resistance (ΔG value) thereof was 8.1%.


[0471] Then, the heat resistance of the coating film was determined as follows. That is, five coated plates were prepared using the water-based paint by the same method as described above. The respective coated plates were placed within Geer ovens heated to 210° C., 230° C., 250° C., 270° C. and 290° C., respectively, and heat-treated therein for 15 minutes. Thereafter, the coated plates were removed from the ovens to measure the hue values thereof. Based on the hue values before the heat treatment as standard values, the ΔE* value of each coated plate was measured. From the relationship between the heat-treating temperature and the ΔE* value, it was recognized that the temperature at which the ΔE* value was identical to just 1.5, was 256° C.



Example 16


<Production of Resin Composition>

[0472] 0.5 g of the orange-based fine pigment obtained in Example 13, and 49. 5 g of a polyvinyl chloride resin 103EP8D (produced by NIPPON ZEON CO., LTD.) were weighed and charged into a 100 ml beaker, and intimately mixed together by a spatula, thereby obtaining mixed particles.


[0473] 1.0 g of calcium stearate was added to the mixed particles. The mixed particles were slowly supplied to hot rolls heated to 160° C. whose clearance was set to 0.2 mm, and continuously kneaded therebetween until a uniform resin composition was produced. The resin composition kneaded was separated from the hot rolls and used as a raw material for forming a colored resin plate.


[0474] Next, the thus-produced resin composition was interposed between a pair of surface-polished stainless steel plates, placed within a hot press heated to 180° C. and subjected to a pressure molding while applying a pressure of 98 MPa (1 ton/cm2) thereto, thereby obtaining a colored resin plate having a thickness of 1 mm. As to the hue of the resin plate, the L* value thereof was 36.2; the a* value thereof was 49.9; the b* value thereof was 40.6; and the h value thereof was 39.1°. The thus-produced colored resin plate had a dispersing condition of rank 5 and a linear absorption of 0.0211 μm−1.


[0475] Then, the heat resistance of the resin composition was determined as follows. That is, five colored resin plates were prepared from the resin composition and cut into 5 cm square to prepare 5 test specimens. The respective test specimens were placed within hot presses heated to 185° C., 200° C., 215° C., 230° C. and 245° C., respectively, and heat-treated therein for 10 minutes while applying a pressure of 98 MPa (1 ton/cm2) thereto. Thereafter, the resin plates were removed from the presses to measure the hue values thereof. Based on the hue values before the heat treatment as standard values, the ΔE* value of each resin plate was measured. From the relationship between the heat-treating temperature and the ΔE* value, it was recognized that the temperature at which the ΔE* value was identical to just 1.5, was 229° C.



Core Particles 1 to 4

[0476] As core particles, iron oxide hydroxide particles having properties shown in Table 1 were prepared.



Core Particles 5

[0477]

20
kg of acicular goethite particles (core particles 1) and 150 liters of water were mixed together, thereby obtaining a slurry containing the acicular goethite particles. The pH value of the obtained re-dispersed slurry containing the acicular goethite particles was adjusted to 10.5 using an aqueous sodium hydroxide solution, and then the concentration of the solid content in the slurry was adjusted to 98 g/liter by adding water thereto. After 150 liters of the slurry was heated to 60° C., 2,722 ml of a 1.0 mol/liter sodium aluminate solution (corresponding to 0.5% by weight (calculated as Al) based on the weight of the acicular goethite particles) was added to the slurry. After allowing the obtained slurry to stand for 30 minutes, the pH value of the obtained slurry was adjusted to 7.5 by adding acetic acid thereto. Further, after allowing the obtained slurry to stand for 30 minutes, the slurry was subjected to filtration, washing with water, drying and pulverization, thereby obtaining the acicular goethite particles whose surfaces were coated with hydroxides of aluminum.


[0478] The production condition are shown in Table 2, and various properties of the obtained surface-treated acicular goethite particles are shown in Table 3.



Core Particles 6 to 8

[0479] The same procedure as defined above for the production of the core particles 5, was conducted except that the respective iron oxide hydroxide particles (core particles 2 to 4) were used instead of the core particles 1, and kinds and amounts of coating materials to be adhered thereon were changed variously, thereby obtaining surface-coated iron oxide hydroxide particles.


[0480] The production condition are shown in Table 2, and various properties of the obtained surface-treated iron oxide hydroxide particles are shown in Table 3.



Core Particles 9 to 12

[0481] As core particles, iron oxide hydroxide fine particles having properties shown in Table 4 were prepared.



Core particles 13

[0482]

20
kg of acicular goethite fine particles (core particles 9) and 150 liters of water were mixed together, thereby obtaining a slurry containing the acicular goethite fine particles. The pH value of the obtained re-dispersed slurry containing the acicular goethite fine particles was adjusted to 10.5 using an aqueous sodium hydroxide solution, and then the concentration of the solid content in the slurry was adjusted to 98 g/liter by adding water thereto. After 150 liters of the slurry was heated to 60° C., 5,444 ml of a 5.0 mol/liter sodium aluminate solution (corresponding to 5% by weight (calculated as Al) based on the weight of the acicular goethite fine particles) was added to the slurry. After allowing the obtained slurry to stand for 30 minutes, the pH value of the obtained slurry was adjusted to 7.5 by adding acetic acid thereto. Further, after allowing the obtained slurry to stand for 30 minutes, the slurry was subjected to filtration, washing with water, drying and pulverization, thereby obtaining the acicular goethite fine particles whose surfaces were coated with hydroxides of aluminum.


[0483] The production condition are shown in Table 5, and various properties of the obtained surface-treated acicular goethite fine particles are shown in Table 6.



Core Particles 14 to 16

[0484] The same procedure as defined above for the production of the core particles 13, was conducted except that the respective iron oxide hydroxide particles (core particles 10 to 12) were used instead to the core particles 9, and kinds and amounts of coating materials to be adhered were changed variously, thereby obtaining surface-coated iron oxide hydroxide fine particles.


[0485] The production condition are shown in Table 5, and various properties of the obtained surface-treated iron oxide hydroxide fine particles are shown in Table 6.


[0486] Meanwhile, in “Kind of coating material” of the “surface-treating step” as described in Tables, “A” represents hydroxides of aluminum, and “S” represents oxides of silicon.



Organic Blue Pigments A to C

[0487] The organic blue pigments having properties shown in Table 7 were prepared.



Organic Red Pigments D and E

[0488] The organic red pigments having properties shown in Table 7 were prepared.



Examples 17 to 24 and Comparative Examples 1 to 5

[0489] The same procedure as defined in Example 1 was conducted except that kinds of the core particles, kinds and amounts of alkoxysilane compounds, polysiloxanes or silicon compounds added in the coating step, linear loads and times used for the edge runner treatment in the above coating step, kinds and amounts of organic blue pigments added in the organic blue pigment-adhering step, and linear loads and times used for the edge runner treatment in the above adhering step, were changed variously, thereby obtaining green-based pigments.


[0490] The production conditions are shown in Table 8, and various properties of the obtained green-based pigments are shown in Table 9.



Comparative Examples 6 to 8

[0491] In these Comparative Examples, chrome green (Comparative Example 6), chromium oxide (Comparative Example 7) and phthalocyanine green (Comparative Example 8) were used solely. The results are shown in Table 9.



Examples 25 to 32 and Comparative Examples 9 to 16

[0492] The same procedure as defined in Example 2 was conducted except that kinds of green-based pigments were changed variously, thereby obtaining solvent-based paints.


[0493] Various properties of the obtained solvent-based paints and coating films are shown in Table 10.



Examples 33 to 40 and Comparative Examples 17 to 24

[0494] The same procedure as defined in Example 3 was conducted except that kinds of green-based pigments were changed variously, thereby obtaining water-based paints.


[0495] Various properties of the obtained water-based paints and coating films are shown in Table 11.



Examples 41 to 48 and Comparative Examples 25 to 32

[0496] The same procedure as defined in Example 4 was conducted except that kinds of green-based pigments were changed variously, thereby obtaining resin compositions.


[0497] The production conditions and various properties of the obtained resin compositions are shown in Table 12.



Examples 49 to 56 and Comparative Examples 33 to 37

[0498] The same procedure as defined in Example 5 was conducted except that kinds of the core particles, kinds and amounts of alkoxysilane compounds, polysiloxanes or silicon compounds added in the coating step, linear loads and times used for the edge runner treatment in the above coating step, kinds and amounts of organic red pigments added in the organic red pigment-adhering step, and linear loads and times used for the edge runner treatment in the above adhering step, were changed variously, thereby obtaining orange-based pigments.


[0499] The production conditions are shown in Table 13, and various properties of the obtained orange-based pigments are shown in Table 14.



Examples 57 to 64 and Comparative Examples 38 to 42

[0500] The same procedure as defined in Example 6 was conducted except that kinds of orange-based pigments were changed variously, thereby obtaining solvent-based paints.


[0501] Various properties of the obtained solvent-based paints and coating films are shown in Table 15.



Examples 65 to 72 and Comparative Examples 43 to 47

[0502] The same procedure as defined in Example 7 was conducted except that kinds of orange-based pigments were changed variously, thereby obtaining water-based paints.


[0503] Various properties of the obtained water-based paints and coating films are shown in Table 16.



Examples 73 to 80 and Comparative Examples 48 to 52

[0504] The same procedure as defined in Example 8 was conducted except that kinds of orange-based pigments were changed variously, thereby obtaining resin compositions.


[0505] The production conditions and various properties of the obtained resin compositions are shown in Table 17.



Examples 81 to 88 and Comparative Examples 53 to 57

[0506] The same procedure as defined in Example 9 was conducted except that kinds of the core particles, kinds and amounts of alkoxysilane compounds, polysiloxanes or silicon compounds added in the coating step, linear loads and times used for the edge runner treatment in the above coating step, kinds and amounts of organic blue pigments added in the organic blue pigment-adhering step, and linear loads and times used for the edge runner treatment in the above adhering step, were changed variously, thereby obtaining green-based fine pigments.


[0507] The production conditions are shown in Table 18, and various properties of the obtained green-based fine pigments are shown in Table 19.



Examples 89 to 96 and Comparative Examples 58 to 62

[0508] The same procedure as defined in Example 10 was conducted except that kinds of green-based fine pigments were changed variously, thereby obtaining solvent-based paints.


[0509] Various properties of the obtained solvent-based paints and coating films are shown in Table 20.



Examples 97 to 104 and Comparative Examples 63 to 67

[0510] The same procedure as defined in Example 11 was conducted except that kinds of green-based fine pigments were changed variously, thereby obtaining water-based paints.


[0511] Various properties of the obtained water-based paints and coating films are shown in Table 21.



Examples 105 to 112 and Comparative Examples 68 to 72

[0512] The same procedure as defined in Example 12 was conducted except that kinds of green-based fine pigments were changed variously, thereby obtaining resin compositions.


[0513] The production conditions and various properties of the obtained resin compositions are shown in Table 22.



Examples 113 to 120 and Comparative Examples 73 to 77

[0514] The same procedure as defined in Example 13 was conducted except that kinds of the core particles, kinds and amounts of alkoxysilane compounds, polysiloxanes or silicon compounds added in the coating step, linear loads and times used for the edge runner treatment in the above coating step, kinds and amounts of organic red pigments added in the organic red pigment-adhering step, and linear loads and times used for the edge runner treatment in the above adhering step, were changed variously, thereby obtaining orange-based fine pigments.


[0515] The production conditions are shown in Table 23, and various properties of the obtained orange-based fine pigments are shown in Table 24.



Examples 121 to 128 and Comparative Examples 78 to 82

[0516] The same procedure as defined in Example 14 was conducted except that kinds of orange-based fine pigments were changed variously, thereby obtaining solvent-based paints.


[0517] Various properties of the obtained solvent-based paints and coating films are shown in Table 25.



Examples 129 to 136 and Comparative Examples 83 to 87

[0518] The same procedure as defined in Example 15 was conducted except that kinds of orange-based fine pigments were changed variously, thereby obtaining water-based paints.


[0519] Various properties of the obtained water-based paints and coating films are shown in Table 26.



Examples 137 to 144 and Comparative Examples 88 to 92

[0520] The same procedure as defined in Example 16 was conducted except that kinds of orange-based fine pigments were changed variously, thereby obtaining resin compositions.


[0521] The production conditions and various properties of the obtained resin compositions are shown in Table 27.
13TABLE 1Properties of iron oxidehydroxide particlesKind of ironAverageoxidemajor axialCorehydroxideParticlediameterparticlesparticlesshape(μm)CoreGoethiteAcicular0.43particles 1CoreGoethiteAcicular0.38particles 2CoreGoethiteAcicular0.40particles 3CoreLepidocrociteRectangular0.20particles 4Properties of iron oxide hydroxideparticlesGeometricalBETAlstandardspecificcontentAspectdeviationsurfacewithinCoreratiovaluearea valueparticlesparticles(−)(−)(m2/g)(wt. %)Core5.8:11.4516.8particles 1Core6.1:11.3922.3particles 2Core5.6:11.4119.82.36particles 3Core4.6:11.4171.2particles 4Properties of iron oxide hydroxideparticlesHueHeatL*a*b*hresistanceCorevaluevaluevaluevaluetemperatureparticles(−)(−)(−)(°)(° C.)Core61.215.354.874.4202particles 1Core58.617.152.171.8195particles 2Core60.614.955.074.8250particles 3Core54.820.437.661.5193particles 4


[0522]

14








TABLE 2














Surface-treating step



Kind of
Additives













Core
core

Calculated
Amount



particles
particles
Kind
as
(wt. %)







Core
Core
Sodium
A;
0.5



particles 5
particles 1
aluminate



Core
Core
Water
SiO2
0.2



particles 6
particles 2
glass #3



Core
Core
Aluminum
Al
1.0



particles 7
particles 3
sulfate



Core
Core
Aluminum
Al
0.5



particles 8
particles 4
sulfate





Water
SiO2
1.5





glass #3













Surface-treating step



Coating material












Core

Calculated
Amount



particles
Kind
as
(wt. %)







Core
A
Al
0.49



particles 5



Core
S
SiO2
0.18



particles 6



Core
A
Al
0.97



particles 7



Core
A
Al
0.48



particles 8
S
SiO2
1.45











[0523]

15







TABLE 3













Properties of surface-treated iron oxide



hydroxide particles














Average major




Core
Particle
axial diameter
Aspect ratio



particles
shape
(μm)
(−)







Core
Acicular
0.43
5.8:1



particles 5



Core
Acicular
0.38
6.1:1



particles 6



Core
Acicular
0.40
5.6:1



particles 7



Core
Rectangular
0.21
4.6:1



particles 8













Properties of surface-treated iron oxide



hydroxide particles













Geometrical
BET specific
Al content




standard
surface area
within



Core
deviation value
value
particles



particles
(−)
(m2/g)
(wt. %)







Core
1.45
17.0




particles 5



Core
1.40
22.5




particles 6



Core
1.41
19.5
2.34



particles 7



Core
1.42
70.8




particles 8













Properties of surface-treated iron oxide



hydroxide particles










Hue
Heat















L*
a*
b*
h
resistance



Core
value
value
value
value
temperature



particles
(−)
(−)
(−)
(°)
(° C.)







Core
61.3
15.1
54.7
74.6
221



particles 5



Core
58.7
17.2
52.3
71.8
208



particles 6



Core
60.4
15.0
55.2
74.8
260



particles 7



Core
55.0
20.2
37.5
61.7
208



particles 8











[0524]

16








TABLE 4













Kind of iron
Properties of iron oxide



oxide
hydroxide fine particles













hydroxide

Average



Core
fine
Particle
diameter



particles
particles
shape
(μm)







Core
Goethite
Acicular
0.0813



particles 9



Core
Goethite
Spindle-
0.0571



particles 10

shaped



Core
Goethite
Acicular
0.0763



particles 11



Core
Lepidocrocite
Rectangular
0.0900



particles 12













Properties of iron oxide hydroxide fine



particles













Average

Geometrical




minor axial
Aspect
standard



Core
diameter
ratio
deviation value



particles
(μm)
(−)
(−)







Core
0.0095
8.6:1
1.41



particles 9



Core
0.0093
6.1:1
1.35



particles 10



Core
0.0118
6.5:1
1.36



particles 11



Core
0.0179
5.0:1
1.40



particles 12













Properties of iron oxide hydroxide fine



particles













Al content within




BET specific
particles



Core
surface area
(calculated as Al)



particles
value (m2/g)
(wt. %)







Core
148.9




particles 9



Core
192.1
2.56



particles 10



Core
149.2
1.87



particles 11



Core
100.4




particles 12













Properties of iron oxide hydroxide fine



particles



Composite oxide hydroxide












Coating amount
Coating amount




of Al
of Fe



Core
(calculated as Al)
(calculated as Fe)



particles
(wt. %)
(wt. %)







Core





particles 9



Core





particles 10



Core
1.31
11.0



particles 11



Core





particles 12













Properties of iron oxide hydroxide fine



particles










Hue
















L*
a*
b*
h
Hiding



Core
value
value
value
value
power



particles
(−)
(−)
(−)
(°)
(cm2/g)







Core
50.1
29.4
54.2
61.5
171



particles 9



Core
52.6
29.6
57.0
65.6
144



particles 10



Core
54.3
27.3
58.9
65.1
158



particles 11



Core
48.4
33.6
59.4
60.5
209



particles 12













Properties of iron oxide hydroxide fine



particles










Chemical resistance














Acid
Alkali
Heat




resistance
resistance
resistance



Core
ΔE* value
ΔE* value
temperature



particles
(−)
(−)
(° C.)







Core
2.05
1.83
192



particles 9



Core
1.96
1.72
246



particles 10



Core
1.77
1.67
270



particles 11



Core
2.24
2.11
189



particles 12











[0525]

17








TABLE 5














Surface-treating step



Kind of
Additives











Core
core

Calculated
Amount


particles
particles
Kind
as
(wt. %)





Core
Core
Sodium
Al
5.0


particles 13
particles 9
aluminate


Core
Core
Water
SiO2
2.0


particles 14
particles 10
glass #3


Core
Core
Sodium
Al
1.0


particles 15
particles 11
aluminate




Water
SiO2
0.5




glass #3


Core
Core
Aluminum
Al
2.0


particles 16
particles 12
sulfate












Surface-treating step



Coating material












Core

Calculated
Amount



particles
Kind
as
(wt. %)







Core
A
Al
4.75



particles 13



Core
S
SiO2
1.96



particles 14



Core
A
Al
0.98



particles 15
S
SiO2
0.49



Core
A
Al
1.96



particles 16











[0526]

18







TABLE 6













Properties of surface-treated iron



oxide hydroxide fine particles













Average
Average





major axial
minor axial
Aspect



Core
diameter
diameter
ratio



particles
(μm)
(μm)
(−)







Core
0.0816
0.0098
8.3:1



particles 13



Core
0.0572
0.0094
6.1:1



particles 14



Core
0.0765
0.0120
6.4:1



particles 15



Core
0.0901
0.0180
5.0:1



particles 16













Properties of surface-treated iron oxide



hydroxide fine particles















Al content*1




Geometrical

within




standard

particles




deviation
BET specific
(calculated



Core
value
surface area
as Al)



particles
(−)
value (m2/g)
(wt. %)







Core
1.42
154.2




particles 13



Core
1.35
186.6
2.56



particles 14



Core
1.37
152.9
1.87



particles 15



Core
1.41
109.1




particles 16













Properties of surface-treated iron



oxide hydroxide fine particles



Composite oxide hydroxide












Coating amount
Coating amount




of Al*1
of Fe*1



Core
(calculated as Al)
(calculated as Fe)



particles
(wt. %)
(wt. %)







Core





particles 13



Core





particles 14



Core
1.13
0.64



particles 15



Core





particles 16













Properties of surface-treated iron oxide



hydroxide fine particles










Hue
















L*
a*
b*
h
Hiding



Core
value
value
value
value
power



particles
(−)
(−)
(−)
(°)
(cm2/g)







Core
51.1
29.1
54.3
61.8
166



particles 13



Core
53.8
29.3
57.6
63.0
140



particles 14



Core
55.2
26.1
58.1
65.8
152



particles 15



Core
49.3
34.0
60.2
60.5
207



particles 16













Properties of surface-treated iron oxide



hydroxide fine particles










Chemical resistances














Acid
Alkali





resistance
resistance
Heat



Core
ΔE* value
ΔE* value
resistance



particles
(−)
(−)
(° C.)







Core
1.98
1.80
222



particles 13



Core
1.92
1.71
253



particles 14



Core
1.73
1.65
274



particles 15



Core
2.18
2.05
208



particles 16








*1: Coating amount on core particles








[0527]

19








TABLE 7













Organic
Properties of organic pigment



pigment
Kind







Organic blue
Copper phthalocyanine blue



pigment A
(C. I. Pigment Blue 15:1)



Organic blue
Copper phthalocyanine blue



pigment B
(C. I. Pigment Blue 15:4)



Organic blue
Copper phthalocyanine blue



pigment C
(C. I. Pigment Blue 15:2)



Organic red
Quinacridone red



pigment D



Organic red
Quinacridone red



pigment E













Properties of organic pigment














Average






particle
Hiding



Organic

size
power



pigment
Particle shape
(μm)
(cm2/g)







Organic blue
Granular
0.06
240



pigment A



Organic blue
Granular
0.08
272



pigment B



Organic blue
Granular
0.10
301



pigment C



Organic red
Granular
0.58
480



pigment D



Organic red
Granular
0.50
220



pigment E













Properties of organic pigment










Hue
Heat













L*
a*
b*
h
resistance


Organic
value
value
value
value
temperature


pigment
(−)
(−)
(−)
(°)
(° C.)





Organic blue
17.7
9.7
−23.4
292.5
256


pigment A


Organic blue
17.3
11.6
−26.5
293.6
273


pigment B


Organic blue
16.9
12.1
−28.8
292.8
266


pigment C


Organic red
37.0
51.9
20.6
21.6
488


pigment D


Organic red
28.3
58.0
20.6
19.5
319


pigment E










[0528]

20







TABLE 8













Production of green-based



pigment



Coating step with



alkoxysilane,



polysiloxane or silicon



compound



Additives













Amount


Examples


added


and


(part


Comparative
Kind of core

by


Examples
particles
Kind
weight)





Example 17
Core particles 1
Methyl
2.0




triethoxysilane


Example 18
Core particles 2
Methyl
0.5




trimethoxysilane


Example 19
Core particles 3
Phenyl
2.0




triethoxysilane


Example 20
Core particles 4
Methyl hydrogen
1.0




polysiloxane


Example 21
Core particles 5
Methyl
1.0




triethoxysilane


Example 22
Core particles 6
BYK-080
1.0


Example 23
Core particles 7
Isobutyl
2.0




trimethoxysilane


Example 24
Core particles 8
TSF4770
1.5


Comparative
Core particles 1




Example 1


Comparative
Core particles 1
Methyl
1.0


Example 2

triethoxysilane


Comparative
Core particles 1
Methyl
1.0


Example 3

triethoxysilane


Comparative
Core particles 1
Methyl
0.005


Example 4

triethoxysilane


Comparative
Core particles 1
γ-aminopropyl
1.0


Example 5

triethoxysilane












Production of green-based pigment



Coating step with alkoxysilane,



polysiloxane or silicon compound









Examples

Coating amount


and
Edge runner treatment
(calculated as










Comparative
Linear load
Time
Si)











Examples
(N/cm)
(Kg/cm)
(min.)
(wt. %)





Example 17
392
40
15
0.30


Example 18
294
30
20
0.10


Example 19
392
40
20
0.26


Example 20
588
60
20
0.42


Example 21
490
50
15
0.15


Example 22
441
45
15
0.17


Example 23
392
40
20
0.30


Example 24
294
30
30
0.34


Comparative






Example 1


Comparative
392
40
20
0.15


Example 2


Comparative
392
40
20
0.15


Example 3


Comparative
392
40
20
7 × 10−4


Example 4


Comparative
392
40
20
0.13


Example 5














Production of green-based pigment



Examples
Adhesion step with organic blue pigment



and
Organic blue pigment











Comparative

Amount adhered



Examples
Kind
(part by weight)







Example 17
A
10.0



Example 18
A
7.5



Example 19
A
20.0



Example 20
A
5.0



Example 21
A
7.5



Example 22
B
15.0



Example 23
B
10.0



Example 24
B
25.0



Comparative
A
10.0



Example 1



Comparative
A
1.0



Example 2



Comparative
A
35.0



Example 3



Comparative
A
10.0



Example 4



Comparative
A
10.0



Example 5













Production of green-based pigment



Adhesion step with organic blue pigment









Examples

Amount adhered


and
Edge runner treatment
(calculated as










Comparative
Linear load
Time
C)











Examples
(N/cm)
(Kg/cm)
(min.)
(wt. %)





Example 17
392
40
20
6.03


Example 18
294
30
30
4.61


Example 19
294
30
20
11.07


Example 20
392
40
20
3.14


Example 21
490
50
15
4.62


Example 22
441
45
20
8.65


Example 23
294
30
20
6.04


Example 24
588
60
30
13.30


Comparative
392
40
20
6.02


Example 1


Comparative
392
40
20
0.63


Example 2


Comparative
392
40
20
17.26


Example 3


Comparative
392
40
20
6.02


Example 4


Comparative
392
40
20
6.03


Example 5










[0529]

21







TABLE 9













Properties of green-based pigment











Examples and
Average major axial




comparative
diameter
Aspect ratio



Examples
(μm)
(−)







Example 17
0.43
5.8:1



Example 18
0.38
6.1:1



Example 19
0.41
5.6:1



Example 20
0.20
4.6:1



Example 21
0.43
5.8:1



Example 22
0.38
6.1:1



Example 23
0.40
5.6:1



Example 24
0.21
4.6:1



Comparative
0.43
5.8:1



Example 1



Comparative
0.43
5.8:1



Example 2



Comparative
0.43
5.8:1



Example 3



Comparative
0.43
5.8:1



Example 4



Comparative
0.43
5.8:1



Example 5



Comparative
0.20




Example 6



Comparative
0.21




Example 7



Comparative
0.60




Example 8













Properties of green-based pigment













Geometrical






standard
BET specific
Al content



Example and
deviation
surface area
within



Comparative
value
value
particles



Examples
(−)
(m2/g)
(wt. %)







Example 17
1.45
18.3




Example 18
1.39
24.6




Example 19
1.41
22.1
1.94



Example 20
1.41
73.6




Example 21
1.45
19.1




Example 22
1.39
25.9




Example 23
1.41
20.2
2.09



Example 24
1.41
76.5




Comparative

26.8




Example 1



Comparative
1.45
17.9




Example 2



Comparative

29.3




Example 3



Comparative

26.3




Example 4



Comparative

25.8




Example 5



Comparative
1.89
10.5




Example 6



Comparative
2.32
68.2




Example 7



Comparative
1.76
2.1




Example 8













Properties of green-based pigment


Example and
Hue











Comparative
*L value
a* value
b* value
h value


Example
(−)
(−)
(−)
(°)





Example 17
35.5
−16.1
12.4
142.4


Example 18
38.8
−12.6
18.2
124.7


Example 19
28.5
−20.1
0.9
177.4


Example 20
36.1
−16.4
−1.2
184.2


Example 21
38.5
−12.3
18.0
124.3


Example 22
31.5
−19.6
4.7
166.5


Example 23
35.0
−16.6
12.8
142.4


Example 24
27.9
−14.8
−10.3
214.8


Comparative
30.5
−19.6
7.4
159.3


Example 1


Comparative
51.2
5.7
43.5
82.5


Example 2


Comparative
21.3
−18.6
−6.3
198.7


Example 3


Comparative
30.3
−19.1
7.6
158.3


Example 4


Comparative
31.0
−19.8
7.6
159.0


Example 5


Comparative
39.5
−20.0
22.1
132.1


Example 6


Comparative
11.3
−24.8
25.6
134.1


Example 7


Comparative
38.5
−19.1
20.8
132.6


Example 8












Properties of green-based pigment









Chemical resistance














Acid
Alkali


Examples and
Tinting
Hiding
resistance
resistance


Comparative
strength
power
ΔE* value
ΔE* value


Examples
(%)
(cm2/g)
(−)
(−)





Example 17
134
1,920
0.93
0.78


Example 18
140
1,960
1.02
0.89


Example 19
125
1,830
0.83
0.71


Example 20
151
2,030
1.37
1.22


Example 21
143
1,950
0.74
0.61


Example 22
121
1,850
0.66
0.52


Example 23
138
1,970
0.79
0.67


Example 24
126
1,820
0.51
0.45


Comparative
4
1,730
2.16
2.01


Example 1


Comparative
186
1,950
1.88
1.75


Example 2


Comparative
7
1,680
0.76
0.68


Example 3


Comparative
5
1,730
2.05
1.93


Example 4


Comparative
5
1,740
2.04
1.92


Example 5


Comparative
100
1,180
2.58
2.13


Example 6


Comparative
98
420
1.89
2.15


Example 7


Comparative
78
680
1.16
1.88


Example 8












Properties of green-based pigment













Desorption



Example and
Heat resistance
percentage of



Comparative
temperature
organic pigment



Examples
(° C.)
(%)







Example 17
231
7.4



Example 18
225
7.1



Example 19
268
8.8



Example 20
220
6.5



Example 21
249
3.4



Example 22
240
4.3



Example 23
275
3.8



Example 24
246
4.6



Comparative
203
68.4



Example 1



Comparative
206
6.3



Example 2



Comparative
234
24.6



Example 3



Comparative
204
54.8



Example 4



Comparative
205
50.3



Example 5



Comparative
211




Example 6
211




Comparative
228




Example 7



Comparative
256




Example 8











[0530]

22








TABLE 10













Production




of paint
Properties of paint












Example and
Kind of

Storage



Comparative
green-based
Viscosity
stability



Examples
pigment
(cP)
(−)







Example 25
Example 17
1,280
0.76



Example 26
Example 18
1,357
0.91



Example 27
Example 19
1,408
0.85



Example 28
Example 20
1,408
0.98



Example 29
Example 21
1,562
0.64



Example 30
Example 22
1,178
0.58



Example 31
Example 23
1,280
0.45



Example 32
Example 24
1,433
0.51



Comparative
Comparative
2,560
2.13



Example 9
Example 1



Comparative
Comparative
1,408
1.53



Example 10
Example 2



Comparative
Comparative
3,884
2.56



Example 11
Example 3



Comparative
Comparative
1,562
2.01



Example 12
Example 4



Comparative
Comparative
3,072
1.99



Example 13
Example 5



Comparative
Comparative
2,560
2.71



Example 14
Example 6



Comparative
Comparative
2,432
2.13



Example 15
Example 7



Comparative
Comparative
640
1.86



Example 16
Example 8













Properties of coating film










Heat-
Chemical resistances













resistance
Acid
Alkali


Examples and
60°
temperature
resistance
resistance


Comparative
gloss
of coating
ΔG value
ΔG value


Examples
(%)
film (° C.)
(%)
(%)





Example 25
86
253
8.1
7.0


Example 26
88
248
9.3
8.0


Example 27
90
270
7.8
6.6


Example 28
85
244
10.8
10.1


Example 29
91
263
6.5
5.6


Example 30
89
256
5.1
4.2


Example 31
93
276
5.4
4.5


Example 32
94
261
4.6
3.1


Comparative
68
213
16.8
14.8


Example 9


Comparative
83
220
14.8
13.9


Example 10


Comparative
56
255
7.7
6.7


Example 11


Comparative
68
215
15.9
14.3


Exmple 12


Comparative
71
216
15.5
14.1


Example 13


Comparative
73
236
31.6
28.3


Example 14


Comparative
69
253
21.8
16.9


Example 15


Comparative
51
266
11.6
10.2


Example 16












Properties of coating film


Examples and
Hue











Comparative
L* value
a* value
b* value
h value


Examples
(−)
(−)
(−)
(°)





Example 25
37.1
−16.3
12.5
142.5


Example 26
39.9
−11.3
18.6
121.3


Example 27
29.6
−19.8
1.1
176.6


Example 28
37.4
−16.1
−0.6
182.1


Example 29
39.9
−12.0
17.6
124.3


Example 30
32.6
−19.3
4.9
165.8


Example 31
36.6
−15.6
12.6
141.1


Example 32
28.7
−14.3
−10.0
215.0


Comparative
31.4
−19.0
7.5
158.5


Example 9


Comparative
51.7
5.9
43.9
82.3


Example 10


Comparative
22.4
−18.1
−6.1
198.6


Example 11


Comparative
31.5
−18.9
7.7
157.8


Example 12


Comparative
32.0
−19.1
7.8
157.8


Example 13


Comparative
41.0
−19.3
21.6
131.8


Example 14


Comparative
12.6
−24.6
133.5


Example 15


Comparative
40.0
−18.3
21.6
130.3


Example 16










[0531]

23








TABLE 11













Production




of water-



based paint
Properties of paint










Examples and
Kind of

Storage


Comparative
green-based
Viscosity
stability


Examples
pigment
(cP)
(−)





Example 33
Example 17
2,048
0.83


Example 34
Example 18
2,176
1.02


Example 35
Example 19
2,560
0.98


Example 36
Example 20
2,253
1.06


Example 37
Example 21
2,432
0.76


Example 38
Example 22
1,920
0.68


Example 39
Example 23
1,896
0.50


Example 40
Example 24
1,997
0.56


Comparative
Comparative
2,688
2.69


Example 17
Example 1


Comparative
Comparative
2,944
1.62


Example 18
Example 2


Comparative
Comparative
4,813
3.13


Example 19
Example 3


Comparative
Comparative
3,276
2.56


Example 20
Example 4


Comparative
Comparative
3,226
2.57


Example 21
Example 5


Comparative
Comparative
4,044
3.16


Example 22
Example 6


Comparative
Comparative
5,069
2.32


Example 23
Example 7


Comparative
Comparative
1,920
2.46


Example 24
Example 8












Properties of coating film


Example and
Hue











Comparative
L* value
a* value
b* value
h value


Examples
(−)
(−)
(−)
(°)





Example 33
37.6
−16.3
12.6
142.3


Example 34
39.8
−11.8
17.3
124.3


Example 35
29.7
−20.1
1.2
176.6


Example 36
37.1
−16.6
−1.1
183.8


Example 37
40.2
−11.8
17.9
123.4


Example 38
32.3
−19.5
4.4
167.3


Example 39
37.0
−15.2
12.2
141.2


Example 40
28.4
−15.0
−9.6
212.6


Comparative
31.1
−19.1
7.7
158.0


Example 17


Comparative
52.0
5.6
44.1
82.8


Example 18


Comparative
22.3
−18.0
−5.8
197.9


Example 19


Comparative
31.1
−19.0
7.8
157.7


Example 20


Comparative
31.7
−19.4
7.9
157.8


Example 21


Comparative
40.6
−19.0
22.8
129.8


Example 22


Comparative
12.5
−25.3
27.3
132.8


Example 23


Comparative
39.6
−19.6
23.6
129.7


Example 24












Properties of coating film










Heat-
Chemical resistance













resistance
Acid
Alkali


Examples and
60°
temperature
resistance
resistance


Comparative
gloss
of coating
ΔG value
ΔG value


Examples
(%)
film (° C.)
(%)
(%)





Example 33
82
251
8.9
7.5


Example 34
83
246
9.7
8.9


Example 35
83
266
8.0
7.1


Example 26
81
238
11.5
10.6


Example 37
85
257
7.3
6.0


Example 38
86
246
6.0
4.9


Example 39
88
271
6.3
5.2


Example 40
87
252
5.2
4.4


Comparative
61
208
18.0
15.8


Example 17


Comparative
78
218
15.7
14.3


Example 18


Comparative
50
249
8.9
7.6


Example 19


Comparative
62
210
17.1
16.8


Example 20


Comparative
66
211
16.3
16.5


Example 21


Comparative
68
226
32.2
30.8


Example 22


Comparative
63
246
22.6
17.8


Example 23


Comparative
53
253
12.7
11.0


Example 24










[0532]

24








TABLE 12














Production of resin composition



Examples and
Green-based pigment











Comparative

Amount



Examples
Kind
(part by weight)







Example 41
Example 17
1.0



Example 42
Example 18
1.0



Example 43
Example 19
1.0



Example 44
Example 20
1.0



Example 45
Example 21
1.0



Example 46
Example 22
1.0



Example 47
Example 23
1.0



Example 48
Example 24
1.0



Comparative
Comparative
1.0



Example 25
Example 1



Comparative
Comparative
1.0



Example 26
Example 2



Comparative
Comparative
1.0



Example 27
Example 3



Comparative
Comparative
1.0



Example 28
Example 4



Comparative
Comparative
1.0



Example 29
Example 5



Comparative
Comparative
1.0



Example 30
Example 6



Comparative
Comparative
1.0



Example 31
Example 7



Comparative
Comparative
1.0



Example 32
Example 8













Production of resin composition



Resin











Example and

Amount



Comparative

(part by



Examples
Kind
weight)







Example 41
Polyvinyl chloride resin
99.0



Example 42
Polyvinyl chloride resin
99.0



Example 43
Polyvinyl chloride resin
99.0



Example 44
Polyvinyl chloride resin
99.0



Example 45
Polyvinyl chloride resin
99.0



Example 46
Polyvinyl chloride resin
99.0



Example 47
Polyvinyl chloride resin
99.0



Example 48
Polyvinyl chloride resin
99.0



Comparative
Polyvinyl chloride resin
99.0



Example 25



Comparative
Polyvinyl chloride resin
99.0



Example 26



Comparative
Polyvinyl chloride resin
99.0



Example 27



Comparative
Polyvinyl chloride resin
99.0



Example 28



Comparative
Polyvinyl chloride resin
99.0



Example 29



Comparative
Polyvinyl chloride resin
99.0



Example 30



Comparative
Polyvinyl chloride resin
99.0



Example 31



Comparative
Polyvinyl chloride resin
99.0



Example 32













Production of resin composition










Additives













Examples and

Amount
Kneading



Comparative

(part by
temperature



Examples
Kind
weight)
(° C.)







Example 41
Calcium Stearate
2.0
160



Example 42
Calcium Stearate
2.0
160



Example 43
Calcium Stearate
2.0
160



Example 44
Calcium Stearate
2.0
160



Example 45
Calcium Stearate
2.0
160



Example 46
Calcium Stearate
2.0
160



Example 47
Calcium Stearate
2.0
160



Example 48
Calcium Stearate
2.0
160



Comparative
Calcium Stearate
2.0
160



Example 25



Comparative
Calcium Stearate
2.0
160



Example 26



Comparative
Calcium Stearate
2.0
160



Example 27



Comparative
Calcium Stearate
2.0
160



Example 28



Comparative
Calcium Stearate
2.0
160



Example 29



Comparative
Calcium Stearate
2.0
160



Example 30



Comparative
Calcium Stearate
2.0
160



Example 31



Comparative
Calcium Stearate
2.0
160



Example 32













Properties of resin composition













Heat-resistance



Examples and
Dispersion
temperature of



Comparative
condition
resin composition



Examples
(−)
(° C.)







Example 41
5
224



Example 42
5
223



Example 43
5
232



Example 44
4
218



Example 45
5
230



Example 46
5
226



Example 47
5
239



Example 49
5
229



Comparative
2
190



Example 25



Comparative
3
200



Example 26



Comparative
2
233



Example 27



Comparative
3
192



Example 28



Comparative
2
196



Example 29



Comparative
3
218



Example 30



Comparative
3
210



Example 31



Comparative
3
228



Example 32













Properties of coating film


Examples and
Hue











Comparative
L* value
a* value
b* value
h value


Examples
(−)
(−)
(−)
(°)





Example 41
39.8
−14.6
12.9
138.8


Example 42
41.3
−9.8
16.9
120.3


Example 43
31.5
−18.4
1.4
175.6


Example 44
38.5
−15.3
−0.8
183.0


Example 45
41.9
−10.8
18.1
120.8


Example 46
34.0
−17.6
4.7
165.0


Example 47
38.9
−14.4
12.5
139.0


Example 48
30.1
−13.6
−9.0
213.5


Comparative
32.0
−17.4
8.1
155.0


Example 25


Comparative
53.6
7.3
44.6
80.7


Example 26


Comparative
23.9
−16.2
−5.2
197.8


Example 27


Comparative
32.8
−17.3
8.1
154.9


Example 28


Comparative
33.6
−17.5
8.2
154.9


Example 29


Comparative
42.4
−17.8
23.0
127.7


Example 30


Comparative
13.8
−23.9
27.6
130.9


Example 31


Comparative
41.1
−18.6
24.0
127.8


Example 32










[0533]

25







TABLE 13













Production of orange-



based pigment



Coating step with



alkoxysilane,



polysiloxane or silicon



compound



Additives













Amount


Examples


added


and


(part


Comparative
Kind of core

by


Examples
particles
Kind
weight





Example 49
Core particles 1
Methyl
1.0




triethoxysilane


Example 50
Core particles 2
Methyl
3.0




triethoxysilane


Example 51
Core particles 3
Phenyl
2.0




triethoxysilane


Example 52
Core particles 4
Methyl hydrogen
1.0




polysiloxane


Example 53
Core particles 5
Methyl
1.0




triethoxysilane


Example 54
Core particles 6
BYK-080
2.0


Example 55
Core particles 7
Isobutyl
1.0




trimethoxysilane


Example 56
Core particles 8
TSF4770
1.0


Comparative
Core particles 1




Example 33


Comparative
Core particles 1
Methyl
1.0


Example 34

triethoxysilane


Comparative
Core particles 1
Methyl
1.0


Example 35

triethoxysilane


Comparative
Core particles 1
Methyl
0.005


Example 36

triethoxysilane


COmparative
Core particles 1
γ-aminopropyl
1.0


Example 37

triethoxysilane












Production of orange-based pigment



Coating step with alkoxysilane,



polysiloxane or silicon compound









Example

Coating amount


and
Edge runner treatment
(calculated as










Comparative
Linear load
Time
Si)











Examples
(N/cm)
(Kg/cm)
(min.)
(wt. %)





Example 49
588
60
20
0.15


Example 50
294
30
30
0.59


Example 51
441
45
30
0.27


Example 52
588
60
20
0.44


Example 53
294
30
30
0.15


Example 54
392
40
30
0.36


Example 55
588
60
30
0.15


Example 56
392
40
20
0.34


Comparative






Example 33


Comparative
392
40
20
0.15


Example 34


Comparative
392
40
20
0.15


Example 35


Comparative
392
40
20
7 × 10−4


Example 36


Comparative
392
40
20
0.13


Example 37














Production of orange-based pigment



Examples
Adhesion step with organic red pigment



and
Organic red pigment











Comparative

Amount adhered



Examples
Kind
(part by weight)







Example 49
D
10.0



Example 50
E
20.0



Example 51
D
15.0



Example 52
E
20.0



Example 53
D
10.0



Example 54
E
7.5



Example 55
D
10.0



Example 56
E
20.0



Comparative
D
10.0



Example 33



Comparative
D
100.0



Example 34



Comparative
D
0.5



Example 35



Comparative
D
10.0



Example 36



Comparative
D
10.0



Example 37













Production of orange-based pigment



Adhesion step with organic red pigment









Examples

Amount adhered


and
Edge runner treatment
(calculated as










Comparative
Linear load
Time
C)











Examples
(N/cm)
(Kg/cm)
(min.)
(wt. %)





Example 41
392
40
20
6.95


Example 50
588
60
20
12.78


Example 51
294
30
30
9.99


Example 52
588
60
20
12.80


Example 53
441
45
30
6.96


Example 54
392
40
30
5.33


Example 55
588
60
20
6.93


Example 56
588
60
20
12.77


Comparative
392
40
20
6.92


Example 33


Comparative
392
40
20
38.26


Example 34


Comparative
392
40
20
0.35


Example 35


Comparative
392
40
20
6.95


Example 36


Comparative
392
40
20
6.94


Example 37










[0534]

26







TABLE 14













Properties of orange-based pigment











Example and
Average major axial




Comparative
diameter
Aspect ratio



Examples
(μm)
(−)







Example 49
0.43
5.8:1



Example 50
0.39
6.1:1



Example 51
0.40
5.6:1



Example 52
0.20
4.6:1



Example 53
0.43
5.8:1



Example 54
0.38
6.1:1



Example 55
0.40
5.6:1



Example 56
0.21
4.6:1



Comparative
0.43
5.8:1



Example 33



Comparative
0.43
5.8:1



Example 34



Comparative
0.43
5.8:1



Example 35



Comparative
0.43
5.8:1



Example 36



Comparative
0.43
5.8:1



Example 37













Properties of oragne-based pigment













Geometrical






standard

Al content



Examples and
deviation
BET specific
within



Comparative
value
surface area
particles



Examples
(−)
value (m2/g)
(wt. %)







Example 49
1.45
21.3




Example 50
1.39
23.2




Example 51
1.41
21.6
2.00



Example 52
1.41
71.6




Example 53
1.45
21.8




Example 54
1.39
24.5




Example 55
1.41
23.8
2.09



Example 56
1.42
72.6




Comparative

28.6




Example 33



Comparative

34.0




Example 34



Comparative
1.45
16.3




Example 35



Comparative

26.8




Example 36



Comparative

24.6




Example 37











[0535]

27








TABLE 15













Production
Properties of paint













of paint

Storage



Examples and
Kind of

stability



Comparative
orange-based
Viscosity
ΔE* value



Examples
pigment
(cP)
(−)







Example 57
Example 49
1,280
0.81



Example 59
Example 50
1,196
0.92



Example 59
Example 51
982
0.88



Example 60
Example 52
1,442
0.90



Example 61
Example 53
1,386
0.60



Example 62
Example 54
1,272
0.49



Example 63
Example 55
1,071
0.55



Example 64
Example 56
1,121
0.65



Comparative
Comparative
2,560
2.16



Example 38
Example 33



Comparative
Comparative
2,883
2,93



Example 39
Example 34



Comparative
Comparative
982
1.62



Example 40
Example 35



Comparative
Comparative
3,160
2.09



Example 41
Example 36



Comparative
Comparative
2,830
2.06



Example 42
Example 37













Properties of coating film










Heat-




resistance
Chemical resistance













temperature
Acid
Alkali


Examples and
60°
of coating
resistance
resistance


Comparative
gloss
film
ΔG value
ΔG value


Examples
(%)
(° C.)
(%)
(%)





Example 57
87
250
8.3
7.1


Example 58
86
252
7.8
6.9


Example 59
89
271
8.1
7.1


Example 60
85
248
10.4
10.0


Example 61
92
262
6.5
5.2


Example 62
93
253
6.6
5.4


Example 63
95
282
5.9
4.3


Example 64
90
257
7.7
7.0


Comparative
66
214
16.3
14.9


Example 38


Comparative
53
256
14.2
13.3


Example 39


Comparative
77
211
15.6
14.0


Example 40


Comparative
67
213
16.0
14.9


Example 41


Comparative
69
215
15.8
14.5


Example 42












Properties of coating film


Examples and
Hue











Comparative
L* value
a* value
b* value
h value


Examples
(−)
(−)
(−)
(°)





Example 57
47.6
37.6
38.4
45.6


Example 58
41.7
46.6
35.1
37.0


Example 59
42.3
46.9
38.0
39.0


Example 60
37.4
49.1
34.6
35.2


Example 61
48.1
40.3
36.2
41.9


Example 62
49.2
35.5
44.6
51.5


Example 63
43.6
39.2
40.9
46.2


Example 64
49.3
49.8
33.0
33.5


Comparative
47.5
37.0
40.2
47.4


Example 38


Comparative
41.2
51.1
26.8
27.7


Example 39


Comparative
54.6
20.6
45.7
65.7


Example 40


Comparative
48.9
39.3
39.9
45.4


Example 41


Comparative
48.4
36.6
40.4
47.8


Example 42










[0536]

28








TABLE 16













Production




of water-
Properties of paint













based paint

Storage



Examples and
Kind of

stability



Comparative
orange-based
Viscosity
ΔE* value



Examples
pigment
(cP)
(−)







Example 65
Example 49
2,560
0.92



Example 66
Example 50
2,283
1.01



Example 67
Example 51
2,762
0.96



Example 68
Example 52
2,836
1.00



Example 69
Example 53
2,401
0.71



Example 70
Example 54
2,320
0.59



Example 71
Example 55
2,532
0.64



Example 72
Example 56
2,689
0.77



Comparative
Comparative
3,882
2.62



Example 43
Example 33



Comparative
Comparative
4,156
3.36



Example 44
Example 34



Comparative
Comparative
2,160
1.74



Example 45
Example 35



Comparative
Comparative
4,442
2.47



Example 46
Example 36



Comparative
Comparative
3,716
2.43



Example 47
Example 37













Properties of coating film










Heat-




resistance
Chemical resistances













temperature
Acid
Alklai


Examples and
60°
of coating
resistance
resistance


Comparative
gloss
film
ΔG value
ΔG value


Example
(%)
(° C.)
(%)
(%)





Example 65
84
246
8.9
8.2


Example 66
81
251
8.2
7.6


Example 67
85
268
8.6
7.8


Example 68
81
245
10.9
10.5


Example 69
87
259
6.8
5.7


Example 70
89
250
7.0
5.9


Example 71
90
280
6.3
5.0


Example 72
85
254
8.1
7.7


Comparative
60
211
17.5
15.6


Example 43


Comparative
47
252
15.5
15.0


Example 44


Comparative
71
207
16.4
14.8


Example 45


Comparative
62
210
16.8
15.6


Example 46


Comparative
63
212
17.2
15.3


Example 47












Properties of coating film


Examples and
Hue











Comparative
L* value
a* value
b* value
h value


Examples
(−)
(−)
(−)
(°)





Example 65
47.7
37.5
38.0
45.4


Example 66
41.9
46.8
35.4
37.1


Example 67
42.0
46.6
38.3
39.4


Example 68
37.6
49.2
34.5
35.0


Example 69
47.8
40.6
36.0
41.6


Example 70
49.1
35.7
44.8
51.4


Example 71
43.3
39.5
41.1
46.1


Example 72
49.0
50.0
32.9
33.3


Comparative
47.2
37.3
40.3
47.2


Example 43


Comparative
41.6
51.4
26.5
27.3


Example 44


Comparative
55.0
20.9
45.8
65.5


Example 45


Comparative
48.3
39.1
39.7
45.4


Example 46


Comparative
48.1
36.8
40.2
47.5


Example 47










[0537]

29








TABLE 17














Production of resin




composition



Examples and
Orange-based pigment











Comparative

Amount



Examples
Kind
(part by weight)







Example 73
Example 49
1.0



Example 74
Example 50
1.0



Example 75
Example 51
1.0



Example 76
Example 52
1.0



Example 77
Example 53
1.0



Example 78
Example 54
1.0



Example 79
Example 55
1.0



Example 80
Example 56
1.0



Comparative
Comparative
1.0



Example 48
Example 33



Comparative
Comparative
1.0



Example 49
Example 34



Comparative
Comparative
1.0



Example 50
Example 35



Comparative
Comparative
1.0



Example 51
Example 36



Comparative
Comparative
1.0



Example 52
Example 37













Production of resin composition



Resin











Examples and

Amount



Comparative

(part by



Examples
Kind
weight)







Example 73
Polyvinyl chloride resin
99.0



Example 74
Polyvinyl chloride resin
99.0



Example 75
Polyvinyl chloride resin
99.0



Example 76
Polyvinyl chloride resin
99.0



Example 77
Polyvinyl chloride resin
99.0



Example 78
Polyvinyl chloride resin
99.0



Example 79
Polyvinyl chloride resin
99.0



Example 80
Polyvinyl chloride resin
99.0



Comparative
Polyvinyl chloride resin
99.0



Example 48



Comparative
Polyvinyl chloride resin
99.0



Example 49



Comparative
Polyvinyl chloride resin
99.0



Example 50



Comparative
Polyvinyl chloride resin
99.0



Example 51



Comparative
Polyvinyl chloride resin
99.0



Example 52













Production of resin composition










Additives













Examples and

Amount
Kneading



Comparative

(part by
temperature



Examples
Kind
weight)
(° C.)







Example 73
Calcium stearate
2.0
160



Example 74
Calcium stearate
2.0
160



Example 75
Calcium stearate
2.0
160



Example 76
Calcium stearate
2.0
160



Example 77
Calcium stearate
2.0
160



Example 78
Calcium stearate
2.0
160



Example 79
Calcium stearate
2.0
160



Example 80
Calcium stearate
2.0
160



Comparative
Calcium stearate
2.0
160



Example 48



Comparative
Calcium stearate
2.0
160



Example 49



Comparative
Calcium stearate
2.0
160



Example 50



Comparative
Calcium stearate
2.0
160



Example 51



Comparative
Calcium stearate
2.0
160



Example 52













Properties of resin composition













Heat-resistance



Examples and
Dispersion
temperatures of



Comparative
condition
resin composition



Examples
(−)
(° C.)







Example 73
5
226



Example 74
5
229



Example 75
5
232



Example 76
5
223



Example 77
5
231



Example 78
5
226



Example 79
5
238



Example 80
5
230



Comparative
2
192



Example 48



Comparative
2
224



Example 49



Comparative
3
193



Example 50



Comparative
2
195



Example 51



Comparative
2
196



Example 52













Properties of resin composition


Examples and
Hue











Comparative
L* value
a* value
b* value
h value


Examples
(−)
(−)
(−)
(°)





Example 73
49.7
36.3
38.3
46.5


Example 74
43.8
45.3
35.0
37.7


Example 75
43.9
44.9
38.1
40.3


Example 76
39.5
47.8
34.7
36.0


Example 77
49.6
38.6
35.9
42.9


Example 78
51.0
34.1
44.5
52.5


Example 79
45.1
38.2
41.3
47.2


Example 80
50.7
48.2
32.8
34.2


Comparative
49.2
35.6
40.0
48.3


Example 48


Comparative
43.3
50.0
26.1
27.6


Example 49


Comparative
56.4
19.4
45.4
66.9


Example 50


Comparative
50.0
37.3
39.9
46.9


Example 51


Comparative
49.9
34.9
40.2
49.0


Example 52










[0538]

30







TABLE 18













Production of green-based



fine pigment



Coating step with



alkoxysilane,



polysiloxane or silicon



compound



Additives















Amount



Examples


added



and


(part



Comparative
Kind of core

by



Examples
particles
Kind
weight)







Example 81
Core particles 9
Methyl
1.0





triethoxysilane



Example 82
Core particles 10
Methyl
0.5





trimethoxysil-





ane



Example 83
Core particles 11
Phenyl
2.0





triethoxysilane



Example 84
Core particles 12
Methyl hydro-
1.0





gen polysilox-





ane



Example 85
Core particles 13
Methyl
2.0





triethoxysilane



Example 86
Core particles 14
Methyl
1.0





triethoxysilane



Example 87
Core particles 15
Methyl
1.5





triethoxysilane



Example 88
Core particles 16
Methyl
3.0





triethoxysilane



Comparative
Core particles 9





Example 53



Comparative
Core particles 9
Methyl
1.0



Example 54

triethoxysilane



Comparative
Core particles 9
Methyl
0.005



Example 55

triethoxysilane



Comparative
Core particles 9
Methyl
1.0



Example 56

triethoxysilane



Comparative
Core particles 9
γ-aminopropyl
1.0



Example 57

triethoxysilane













Production of green-based fine pigment



Coating step with alkoxysilane,



polysiloxane or silicon compound









Examples

Coating amount


and
Edge runner treatment
(calculated as










Comparative
Linear load
Time
Si)











Examples
(N/cm)
(Kg/cm)
(min.)
(wt. %)





Example 81
392
40
30
0.15


Example 82
588
60
20
0.10


Example 83
490
50
20
0.26


Example 84
294
30
30
0.42


Example 85
588
60
20
0.30


Example 86
441
45
20
0.15


Example 87
735
75
20
0.23


Example 88
441
45
30
0.45


Comparative






Example 53


Comparative
588
60
20
0.15


Example 54


Comparative
588
60
20
6 × 10−4


Example 55


Comparative
588
60
20
0.15


Example 56


Comparative
588
60
20
0.12


Example 57














Production of green-based fine pigment



Examples
Adhesion step with organic blue pigment



and
Organic blue pigment











Comparative

Amount adhered



Examples
Kind
(part by weight)







Example 81
A
10.0



Example 82
B
7.5



Example 83
C
15.0



Example 84
A
20.0



Example 85
A
15.0



Example 86
A
12.0



Example 87
A
7.5



Example 88
A
10.0



Comparative
A
10.0



Example 53



Comparative





Example 54



Comparative
A
10.0



Example 55



Comparative
A
1.0



Example 56



Comparative
A
10.0



Example 57











[0539]

31







TABLE 19













Properties of green-based fine pigment













Average
Average




Examples and
major axial
minor axial
Aspect



Comparative
diameter
diameter
ratio



Examples
(μm)
(μm)
(−)







Example 81
0.0825
0.0100
8.3:1



Example 82
0.0580
0.0097
6.0:1



Example 83
0.0777
0.0125
6.2:1



Example 84
0.0918
0.0188
4.9:1



Example 85
0.0831
0.0102
8.1:1



Example 86
0.0585
0.0101
5.8:1



Example 87
0.0777
0.0125
6.2:1



Example 88
0.0910
0.0185
4.9:1



Comparative
0.0814
0.0096
8.5:1



Example 53



Comparative
0.0813
0.0096
8.5:1



Example 54



Comparative
0.0815
0.0097
8.4:1



Example 55



Comparative
0.0816
0.0097
8.4:1



Example 56



Comparative
0.0815
0.0097
8.4:1



Example 57













Properties of green-based fine pigment













Geometrical






standard

Al content*1



Examples and
deviation
BET specific
within



Comparative
value
surface area
particles



Examples
(−)
value (m2/g)
(wt. %)







Example 81
1.41
142.2




Example 82
1.36
189.6
2.56



Example 83
1.37
143.8
1.87



Example 84
1.41
96.0




Example 85
1.42
148.1




Example 86
1.36
180.5
2.56



Example 87
1.37
149.6
1.87



Example 88
1.41
106.2




Comparative

164.7




Example 53



Comparative
1.41
149.2




Example 54



Comparative

160.1




Example 55



Comparative
1.41
147.6




Example 56



Comparative

161.3




Example 57













Properties of green-based fine pigment



Composite oxide hydroxide












Coating amount
Coating amount



Examples and
of Al*1
of Fe*1



Comparative
(calculated as Al)
(calculated as Fe)



Examples
(wt. %)
(wt. %)







Example 81





Example 82





Example 83
1.13
0.64



Example 84





Example 85





Example 86





Example 87
1.13
0.64



Example 88





Comparative





Example 53



Comparative





Example 54



Comparative





Example 55



Comparative





Example 56



Comparative





Example 57













Properties of green-based fine pigment


Examples and
Hue











Comparative
L* value
a* value
b* value
h value


Examples
(−)
(−)
(−)
(°)





Example 81
31.9
−14.2
3.8
165.0


Example 82
33.2
−11.2
5.2
155.1


Example 83
28.6
−16.8
0.6
178.0


Example 84
26.5
−16.9
−1.1
183.7


Example 85
30.1
−14.2
−1.9
187.6


Example 86
31.2
−18.2
0.4
178.7


Example 87
35.3
−10.8
6.6
148.6


Example 88
27.4
−12.0
9.1
142.8


Comparative
30.9
−9.3
4.6
153.7


Example 53


Comparative
50.2
29.8
54.0
61.1


Example 54


Comparative
31.2
−8.3
4.1
153.7


Example 55


Comparative
31.4
10.5
30.4
70.9


Example 56


Comparative
30.3
−8.0
4.4
151.2


Example 57












Properties of green-based fine pigment









Chemical resistances
















Acid
Alkali



Examples and
Tinting
Hiding
resistance
resistance



Comparative
strength
power
ΔE* value
ΔE* value



Examples
(%)
(cm2/g)
(−)
(−)







Example 81
133
177
1.26
1.12



Example 82
126
152
1.05
1.00



Example 83
142
176
0.98
0.91



Example 84
148
215
1.23
1.02



Example 85
146
175
1.14
1.03



Example 86
140
150
1.01
0.95



Example 87
131
158
0.95
0.87



Example 88
134
211
1.23
0.97



Comparative
110
208
2.04
1.83



Example 53



Comparative
104
172
2.00
1.81



Example 54



Comparative
112
203
2,04
1.81



Example 55



Comparative
108
172
1.97
1.78



Example 56



Comparative
111
202
1.99
1.80



Example 57













Properties of green-based fine pigment













Desorption



Examples and
Heat resistance
percentage of



Comparative
temperature
organic pigment



Examples
(° C.)
(%)







Example 81
223
6.8



Example 82
259
6.1



Example 83
283
7.6



Example 84
229
8.1



Example 85
243
4.7



Example 86
267
4.6



Example 87
284
2.9



Example 88
239
3.4



Comparative
193
68.3



Example 53



Comparative
197




Example 54



Comparative
194
49.3



Example 55



Comparative
197
5.7



Example 56



Comparative
198
46.6



Example 57








*1: Coating amount on core particles








[0540]

32








TABLE 20













Production
Properties of paint










of paint
Storage












Examples and
Kind of

stability



Comparative
green-based
Viscosity
ΔE* value



Examples
fine pigment
(cP)
(−)







Example 89
Example 81
 1,690
0.93



Example 90
Example 82
 1,741
0.88



Example 91
Example 83
 1,997
0.77



Example 92
Example 84
 1,796
0.93



Example 93
Example 85
 2,124
0.61



Example 94
Example 86
 1,920
0.52



Example 95
Example 87
 2,560
0.47



Example 96
Example 88
 2,051
0.64



Comparative
Comparative
10,240
2.24



Example 58
Example 53



Comparative
Comparative
 2,560
1.58



Example 59
Example 54



Comparative
Comparative
 8,960
2.03



Example 60
Example 55



Comparative
Comparative
 2,816
1.52



Example 61
Example 56



Comparative
Comparative
 6,656
2.00



Example 62
Example 57













Properties of coating film









Hue














Examples and
60°
L*
a*
b*
h



Comparative
gloss
value
value
value
value



Examples
(%)
(−)
(−)
(−)
(°)







Example 89
81.6
33.3
−20.2
4.8
166.6



Example 90
85.3
35.4
−17.6
6.0
161.2



Example 91
88.2
30.1
−22.4
1.6
175.9



Example 92
81.3
27.5
−22.9
−0.8
182.0



Example 93
86.7
32.2
−21.5
−1.1
182.9



Example 94
88.1
33.8
−24.1
1.3
176.9



Example 95
91.6
36.4
−16.9
2.5
171.6



Example 96
85.4
29.6
−20.1
10.1
153.3



Comparative
65.2
32.8
−10.1
6.6
146.8



Example 58



Comparative
79.8
54.3
28.6
62.3
65.3



Example 59



Comparative
68.9
33.9
−11.6
5.9
153.0



Example 60



Comparative
80.4
40.3
28.4
40.1
54.7



Example 61



Comparative
68.5
31.1
−12.4
6.1
153.8



Example 62













Properties of coating film



Chemical resistances











Examples and
Acid resistsnce
Alkali resistance



Comparative
ΔG value
ΔG value



Examples
(−)
(−)







Example 89
8.4
7.6



Example 90
8.0
7.1



Example 91
7.6
6.8



Example 92
9.1
8.7



Example 93
6.7
5.5



Example 94
6.4
5.2



Example 95
4.3
3.9



Example 96
6.0
5.6



Comparative
14.9
13.2



Example 58



Comparative
13.1
12.6



Example 59



Comparative
14.4
12.4



Example 60



Comparative
12.8
12.1



Example 61



Comparative
14.5
12.4



Example 62













Properties of coating film











Examples and
Heat resistance
Transparency



Comparative
temperature
(linear absorption)



Examples
(° C.)
(μm−1)







Example 89
241
0.0296



Example 90
265
0.0182



Example 91
285
0.0262



Example 92
247
0.0360



Example 93
258
0.0251



Example 94
274
0.0177



Example 95
286
0.0194



Example 96
252
0.0312



Comparative
213
0.0892



Example 58



Comparative
215
0.0532



Example 59



Comparative
214
0.0823



Example 60



Comparative
219
0.0666



Example 61



Comparative
215
0.0834



Example 62











[0541]

33








TABLE 21













Production




of water-
Properties of paint










based paint
Storage












Examples and
Kind of

stability



Comparative
green-based
Viscosity
ΔE* value



Examples
fine pigment
(cP)
(−)







Example 97
Example 81
 2,867
1.00



Example 98
Example 82
 3,482
0.96



Example 99
Example 83
 3,200
0.87



Example 100
Example 84
 3,294
1.04



Example 101
Example 85
 3,123
0.71



Example 102
Example 86
 2,944
0.61



Example 103
Example 87
 2,816
0.55



Example 104
Example 88
 2,731
0.72



Comparative
Comparative
11,385
2.38



Example 63
Example 53



Comparative
Comparative
 3,482
1.69



Example 64
Example 54



Comparative
Comparative
12,800
2.26



Example 65
Example 55



Comparative
Comparative
 3,123
1.65



Example 66
Example 56



Comparative
Comparative
 6,400
2.21



Example 67
Example 57













Properties of coating film









Hue














Examples and
60°
L*
a*
b*
h



Comparative
gloss
value
value
value
value



Examples
(%)
(−)
(−)
(−)
(°)







Example 97
77.8
33.5
−20.0
4.2
168.1



Example 98
80.6
35.7
−17.5
5.6
162.3



Example 99
83.2
30.6
−22.2
1.0
177.4



Example 100
76.5
27.9
−22.7
−0.9
182.3



Example 101
82.9
33.2
−21.4
−1.2
183.2



Example 102
84.0
34.2
−24.0
1.4
176.7



Example 103
87.4
36.9
−16.7
2.6
171.2



Example 104
81.1
29.7
−20.4
10.0
153.9



Comparative
60.1
33.1
−10.0
6.5
147.0



Example 63



Comparative
73.2
55.3
28.3
62.9
65.8



Example 64



Comparative
63.6
34.4
−11.5
6.1
152.1



Example 65



Comparative
74.2
40.8
27.9
41.4
56.0



Example 66



Comparative
62.3
31.7
−12.1
6.3
152.5



Example 67













Properties of coating film



Chemical resistance











Examples and
Acid resistance
Alkali resistance



Comparative
ΔG value
ΔG value



Examples
(−)
(−)







Example 97
8.6
8.1



Example 98
8.9
7.4



Example 99
8.0
7.2



Example 100
9.4
9.0



Example 101
7.1
5.9



Example 102
6.9
5.7



Example 103
5.0
4.3



Example 104
6.7
6.1



Comparative
15.7
14.1



Example 63



Comparative
14.0
13.5



Example 64



Comparative
15.5
13.4



Example 65



Comparative
13.9
13.0



Example 66



Comparative
15.2
13.3



Example 67













Properties of coating film











Examples and
Heat resistance
Transparency



Comparative
temperature
(linear absorption)



Examples
(° C.)
(μm−1)







Example 97
240
0.0314



Example 98
262
0.0201



Example 99
284
0.0285



Example 100
245
0.0380



Example 101
253
0.0262



Example 102
271
0.0189



Example 103
285
0.0211



Example 104
251
0.0331



Comparative
207
0.0951



Example 63



Comparative
210
0.0560



Example 64



Comparative
208
0.0853



Example 65



Comparative
214
0.0696



Example 66



Comparative
210
0.0854



Example 67











[0542]

34









TABLE 22














Production of





resin composition
Properties of resin



Examples and
Kind of green-
composition



Comparative
based fine
Dispersion condition



Examples
pigment
(−)







Example 105
Example 81
4



Example 106
Example 82
5



Example 107
Example 83
5



Example 108
Example 84
4



Example 109
Example 85
5



Example 110
Example 86
5



Example 111
Example 87
5



Example 112
Example 88
5



Comparative
Comparative
2



Example 68
Example 53



Comparative
Comparative
3



Example 69
Example 54



Comparative
Comparative
2



Example 70
Example 55



Comparative
Comparative
2



Example 71
Example 56



Comparative
Comparative
2



Example 72
Example 57













Properties of resin composition


Examples and
Hue











Comparative
L* value
a* value
b* value
h value


Examples
(−)
(−)
(−)
(°)





Example 105
33.2
−17.2
6.6
159.0


Example 106
34.1
−15.6
7.1
155.5


Example 107
29.8
−18.6
3.2
170.2


Example 108
27.9
−19.5
0.7
177.9


Example 109
32.0
−19.8
−1.4
184.0


Example 110
32.3
−21.6
2.6
173.1


Example 111
36.3
−14.2
8.9
147.9


Example 112
29.7
−15.1
10.8
144.4


Comparative
32.8
−13.6
6.6
154.1


Example 68


Comparative
52.3
27.0
57.3
64.8


Example 69


Comparative
33.2
−12.2
6.3
152.7


Example 70


Comparative
34.3
6.6
34.2
79.1


Example 71


Comparative
32.1
−12.8
6.6
152.7


Example 72












Properties of resin composition











Examples and
Heat resistance
Transparency



Comparative
temperature
(linear absorption)



Examples
(° C.)
(μm−1)







Example 105
225
0.0312



Example 106
234
0.0199



Example 107
238
0.0274



Example 108
227
0.0368



Example 109
231
0.0261



Example 110
235
0.0183



Example 111
240
0.0200



Example 112
231
0.0320



Comparative
195
0.0919



Example 68



Comparative
200
0.0550



Example 69



Comparative
197
0.0851



Example 70



Comparative
202
0.0688



Example 71



Comparative
198
0.0857



Example 72











[0543]

35







TABLE 23













Production of orange-



based fine pigment



Coating step with



alkoxysilane,



polysiloxane or silicon



compound



Additives















Amount



Examples


added



and


(part



Comparative
Kind of core

by



Examples
particles
Kind
weight)







Example 113
Core particles 9
Methyl
2.0





triethopxysilane



Example 114
Core particles 10
Methyl
1.0





trimethoxysilane



Example 115
Core particles 11
Phenyl
1.5





triethoxysilane



Example 116
Core particles 12
Methyl hydrogen
1.0





polysiloxane



Example 117
Core particles 13
Methyl
2.0





triethoxysilane



Example 118
Core particles 14
Methyl
1.0





triethoxysilane



Example 119
Core particles 15
Methyl
1.5





triethoxysilane



Example 120
Core particles 16
Methyl
2.0





triethoxysilane



Comparative
Core particles 9





Example 73



Comparative
Core particles 9
Methyl
1.0



Example 74



Comparative
Core particles 9
Methyl
0.005



Example 75



Comparative
Core particles 9
Methyl
1.0



Example 76

triethoxysilane



Comparative
Core particles 9
γ-aminopropyl
1.0



Example 77

triethoxysilane













Production of orange-based fine pigment



Coating step with alkoxysilane,



polysiloxane or silicon compound











Coating amount


Examples and
Edge runner treatment
(calculated as










Comparative
Linear load
Time
Si)











Examples
(N/cm)
(Kg/cm)
(min.)
(wt. %)





Example 113
588
60
20
0.30


Example 114
588
60
20
0.19


Example 115
441
45
30
0.20


Example 116
588
60
20
0.44


Example 117
294
30
30
0.30


Example 118
588
60
20
0.15


Example 119
441
45
30
0.23


Example 120
588
60
20
0.30


Comparative






Example 73


Comparative
588
60
20
0.15


Example 74


Comparative
588
60
20
6 × 10−4


Example 75


Comparative
588
60
20
0.15


Example 76


Comparative
588
60
20
0.12


Example 77














Production of orange-based fine pigment




Adhesion step with organic red pigment



Examples and
Organic red pigment











Comparative

Amount adhered



Examples
Kind
(part by weight)







Example 113
D
10.0



Example 114
E
15.0



Example 115
D
20.0



Example 116
E
15.0



Example 117
D
10.0



Example 118
E
5.0



Example 119
D
10.0



Example 120
E
25.0



Comparative
D
10.0



Example 73



Comparative
D
100.0



Example 74



Comparative
D
10.0



Example 75



Comparative
D
0.5



Example 76



Comparative
D
10.0



Example 77













Production of orange-based fine pigment



Adhesion step with organic red pigment











Amount adhered


Examples and
Linear runner treatment
(calculated as










Comparative
Linear load
Time
C)











Examples
(N/cm)
(Kg/cm)
(min.)
(wt. %)





Example 113
588
60
20
6.93


Example 114
294
30
30
10.00


Example 115
441
45
30
12.77


Example 116
294
30
30
9.98


Example 117
588
60
20
6.91


Example 118
294
30
30
3.62


Example 119
441
45
20
6.94


Example 120
588
60
20
15.33


Comparative
588
60
20
6.92


Example 73


Comparative
588
60
20
38.31


Example 74


Comparative
588
60
20
6.90


Example 75


Comparative
588
60
20
0.34


Example 76


Comparative
588
60
20
6.91


Example 77










[0544]

36







TABLE 24













Properties of orange-based fine pigment













Average
Average




Examples and
major axial
minor axial
Aspect



Comparative
diameter
diameter
ratio



Examples
(μm)
(μm)
(−)







Example 113
0.0824
0.0098
8.4:1



Example 114
0.0585
0.0100
5.9:1



Example 115
0.0783
0.0127
6.2:1



Example 116
0.0913
0.0186
4.9:1



Example 117
0.0829
0.0102
8.1:1



Example 118
0.0579
0.0097
6.0:1



Example 119
0.0777
0.0125
6.2:1



Example 120
0.0919
0.0193
4.8:1



Comparative
0.0815
0.0096
8.5:1



Example 73



Comparative
0.0849
0.0107
7.9:1



Example 74



Comparative
0.0816
0.0097
8.4:1



Example 75



Comparative
0.0814
0.0096
8.5:1



Example 76



Comparative
0.0817
0.0097
8.4:1



Example 77













Properties of orange-based fine pigment













Geometrical






standard
BET specific
Al content*1



Examples and
deviation
surface area
within



Comparative
value
value
particles



Examples
(−)
(m2/g)
(wt. %)







Example 113
1.41
151.2




Example 114
1.35
190.6
2.56



Example 115
1.36
150.6
1.87



Example 116
1.41
100.6




Example 117
1.41
152.6




Example 118
1.35
184.3
2.56



Example 119
1.37
152.1
1.87



Example 120
1.42
111.1




Comparative

135.8




Example 73



Comparative

146.8




Example 74



Comparative

140.4




Example 75



Comparative
1.41
141.2




Example 76



Comparative

146.6




Example 77













Properties of orange-based fine pigment



Composite oxide hydroxide












Coating amount
Coating amount



Examples and
of Al*1
of Fe*1



Comparative
(calculated as Al)
(calculated as Fe)



Examples
(wt. %)
(wt. %)







Example 113





Example 114





Example 115
1.13
0.64



Example 116





Example 117





Example 118





Example 119
1.13
0.64



Example 120





Comparative





Example 73



Comparative





Example 74



Comparative





Example 75



Comparative





Example 76



Comparative





Example 77













Properties of orange-based fine pigment


Example and
Hue











Comparative
L* value
a* value
b* value
h value


Examples
(−)
(−)
(−)
(°)





Example 113
34.6
49.1
38.0
37.7


Example 114
35.1
49.4
36.8
36.7


Example 115
34.4
49.3
33.7
34.4


Example 116
32.1
50.1
35.5
35.3


Example 117
35.6
49.2
37.6
37.4


Example 118
43.2
40.6
42.4
46.2


Example 119
38.9
48.4
38.9
38.8


Example 120
31.0
50.9
31.1
31.4


Comparative
35.1
46.7
40.6
41.0


Example 73


Comparative
28.3
51.2
23.4
24.6


Example 74


Comparative
34.9
47.2
39.9
40.2


Example 75


Comparative
46.2
32.9
51.4
57.4


Example 76


Comparative
34.8
47.3
39.7
40.0


Example 77












Properties of orange-based fine pigment









Chemical resistance














Acid
Alkali


Examples and
Tinting
Hiding
resistance
resistance


Comparative
strength
power
ΔE* value
ΔE* value


Examples
(%)
(cm2/g)
(−)
(−)





Example 113
128
180
1.27
1.18


Example 114
132
152
1.08
1.00


Example 115
136
172
0.99
0.96


Example 116
126
223
1.29
1.21


Example 117
131
176
1.16
1.09


Example 118
130
145
1.06
0.98


Example 119
134
161
0.94
0.91


Example 120
133
224
1.21
1.13


Comparative
100
197
2.04
1.81


Example 73


Comparative
116
266
1.74
1.66


Example 74


Comparative
102
190
2.00
1.76


Example 75


Comparative
106
174
1.82
1.71


Example 76


Comparative
104
189
1.99
1.74


Example 77












Properties of orange-based fine pigment













Desorption



Examples and
Heat resistance
percentage of



Comparative
temperature
organic pigment



Examples
(° C.)
(%)







Example 113
224
7.1



Example 114
253
8.3



Example 115
276
9.2



Example 116
226
8.7



Example 117
238
3.9



Example 118
267
2.2



Example 119
281
2.6



Example 120
230
4.8



Comparative
194
69.4



Example 73



Comparative
231
60.1



Example 74



Comparative
197
57.2



Example 75



Comparative
200
6.8



Example 76



Comparative
199
56.6



Example 77








*1: Coating amount on core particles








[0545]

37








TABLE 25













Production
Properties of paint










of paint
Storage












Examples and
Kind of

stability



Comparative
orange-based
Viscosity
ΔE* value



Examples
fine pigment
(cP)
(−)







Example 121
Example 113
 3,580
0.96



Example 122
Example 114
 3,180
0.92



Example 123
Example 115
 2,863
0.81



Example 124
Example 116
 3,265
0.99



Example 125
Example 117
 3,384
0.93



Example 126
Example 118
 3,062
0.90



Example 127
Example 119
 3,056
0.77



Example 128
Example 120
 2,786
0.97



Comparative
Comparative
12,560
2.34



Example 78
Example 73



Comparative
Comparative
 3,183
1.60



Example 79
Example 74



Comparative
Comparative
 2,965
2.30



Example 80
Example 75



Comparative
Comparative
 2,872
1.65



Example 81
Example 76



Comparative
Comparative
 3,682
2.28



Example 82
Example 77













Properties of coating film









Hue














Examples and
60°
L*
a*
b*
h



Comparative
gloss
value
value
value
value



Examples
(%)
(−)
(−)
(−)
(°)







Example 121
81.7
35.8
48.3
38.0
38.2



Example 122
86.1
36.4
48.5
36.6
37.0



Example 123
88.9
36.3
48.6
33.8
34.8



Example 124
81.2
33.6
49.3
35.7
35.9



Example 125
87.0
36.8
48.6
37.6
37.7



Example 126
88.8
44.1
39.8
42.3
46.7



Example 127
92.3
40.3
47.7
39.1
39.3



Example 128
85.7
32.3
50.1
30.9
31.7



Comparative
64.6
36.6
45.3
40.2
41.6



Example 78



Comparative
58.5
29.9
50.2
23.5
25.1



Example 79



Comparative
68.0
36.3
46.3
39.4
40.4



Example 80



Comparative
80.3
47.6
31.8
51.1
58.1



Example 81



Comparative
68.9
36.1
46.3
39.2
40.3



Example 82













Properties of coating film



Chemical resistances











Examples and
Acid resistance
Alkali resistance



Comparative
ΔG value
ΔG value



Examples
(−)
(−)







Example 121
8.9
8.1



Example 122
8.4
7.6



Example 123
7.7
6.8



Example 124
9.2
8.4



Example 125
8.5
7.8



Example 126
8.2
7.1



Example 127
5.1
4.6



Example 128
8.7
7.9



Comparative
15.1
14.7



Example 78



Comparative
12.6
12.1



Example 79



Comparative
14.7
14.2



Example 80



Comparative
13.4
13.6



Example 81



Comparative
14.7
14.0



Example 82













Properties of coating film











Examples and
Heat resistance
Transparency



Comparative
temperature
(linear absorption)



Examples
(° C.)
(μm−1)







Example 121
243
0.0300



Example 122
261
0.0186



Example 123
281
0.0260



Example 124
246
0.0362



Example 125
254
0.0261



Example 126
273
0.0170



Example 127
283
0.0199



Example 128
248
0.0332



Comparative
208
0.0872



Example 78



Comparative
246
0.1032



Example 79



Comparative
215
0.0828



Example 80



Comparative
216
0.0296



Example 81



Comparative
217
0.0816



Example 82











[0546]

38








TABLE 26













Production




of water-
Properties of paint










based paint
Storage












Examples and
Kind of

Stability



Comparative
orange-based
Viscosity
ΔE* value



Examples
fine pigment
(cP)
(−)







Example 129
Example 113
 3,670
1.03



Example 130
Example 114
 3,281
0.98



Example 131
Example 115
 3,659
0.88



Example 132
Example 116
 3,263
1.05



Example 133
Example 117
 3,486
1.00



Example 134
Example 118
 3,365
0.96



Example 135
Example 119
 4,163
0.81



Example 136
Example 120
 3,887
1.04



Comparative
Comparative
11,197
2.45



Example 83
Example 73



Comparative
Comparative
 3,663
1.69



Example 84
Example 74



Comparative
Comparative
 2,816
2.41



Example 85
Example 75



Comparative
Comparative
 3,162
1.72



Example 86
Example 76



Comparative
Comparative
 3,386
2.38



Example 87
Example 77













Properties of coating film









Hue














Examples and
60°
L*
a*
b*
h



Comparative
gloss
value
value
value
value



Examples
(%)
(−)
(−)
(−)
(°)







Example 129
77.5
35.9
48.8
38.3
38.1



Example 130
81.4
36.6
48.2
36.6
37.2



Example 131
84.2
36.2
48.5
33.8
34.9



Example 132
76.9
33.5
49.6
35.8
35.8



Example 133
81.8
36.6
48.9
37.9
37.8



Example 134
83.9
43.9
39.8
42.0
46.5



Example 135
87.5
40.6
48.0
39.3
39.3



Example 136
81.3
32.6
50.1
31.0
31.7



Comparative
60.1
36.8
45.8
40.4
41.4



Example 83



Comparative
53.4
29.8
50.3
23.7
25.2



Example 84



Comparative
63.0
36.3
46.6
39.6
40.4



Example 85



Comparative
75.8
47.1
32.2
51.6
58.0



Example 86



Comparative
64.0
36.3
46.6
39.3
40.1



Example 87













Properties of coating film



Chemical resistances











Examples and
Acid resistance
Alkali resistance



Comparative
ΔG value
ΔG value



Examples
(−)
(−)







Example 129
9.2
8.3



Example 130
8.6
7.5



Example 131
8.0
7.0



Example 132
9.6
8.7



Example 133
8.7
8.1



Example 134
8.3
7.3



Example 135
5.4
5.0



Example 136
8.7
8.2



Comparative
15.6
15.0



Example 83



COmparative
12.9
12.4



Example 84



Comparative
15.1
14.6



Example 85



Comparative
13.5
13.9



Example 86



Comparative
14.9
14.4



Example 87













Properties of coating film











Examples and
Heat resistance
Transparency



Comparative
temperature
(linear absorption)



Examples
(° C.)
(μm−1)







Example 129
240
0.0319



Example 130
259
0.0204



Example 131
278
0.0280



Example 132
243
0.0377



Example 133
250
0.0282



Example 134
271
0.0188



Example 135
279
0.0216



Example 136
244
0.0353



Comparative
204
0.0893



Example 83



Comparative
240
0.1051



Example 84



Comparative
211
0.0849



Example 85



Comparative
214
0.0314



Example 86



Comparative
212
0.0833



Example 87











[0547]

39









TABLE 27














Production of





resin composition
Properties of resin



Examples and
Kind of orange-
composition



Comparative
based fine
Dispersion condition



Examples
pigment
(−)







Example 137
Example 113
4



Example 138
Example 114
5



Example 139
Example 115
5



Example 140
Example 116
5



Example 141
Example 117
5



Example 142
Example 118
5



Example 143
Example 119
5



Example 144
Example 120
5



Comparative
Comparative
2



Example 88
Example 73



Comparative
Comparative
3



Example 89
Example 74



Comparative
Comparative
2



Example 90
Example 75



Comparative
Comparative
3



Example 91
Example 76



Comparative
Comparative
2



Example 92
Example 77













Properties of resin composition


Examples and
Hue











Comparative
L* value
a* value
b* value
h value


Examples
(−)
(−)
(−)
(°)





Example 137
35.8
49.5
38.7
38.0


Example 138
36.1
48.9
37.5
37.5


Example 139
36.6
49.6
35.0
35.2


Example 140
33.8
50.6
36.8
36.0


Example 141
36.9
49.9
39.2
38.2


Example 142
44.0
40.7
43.8
47.1


Example 143
40.5
49.1
40.3
39.4


Example 144
32.9
51.6
32.2
32.0


Comparative
36.9
46.5
41.6
41.8


Example 88


Comparative
29.9
51.5
24.6
25.5


Example 89


Comparative
36.1
47.9
41.0
40.6


Example 90


Comparative
47.2
32.6
52.6
58.2


Example 91


Comparative
36.5
48.0
40.2
39.9


Example 92












Properties of resin composition











Examples and
Heat resistance
Transparency



Comparative
temperature
(linear absorption)



Examples
(° C.)
(μm−1)







Example 137
223
0.0318



Example 138
231
0.0203



Example 139
236
0.0284



Example 140
228
0.0356



Example 141
235
0.0273



Example 142
237
0.0180



Example 143
239
0.0212



Example 144
225
0.0352



Comparative
195
0.0889



Example 88



Comparative
201
0.1045



Example 89



Comparative
197
0.0842



Example 90



Comparative
199
0.0310



Example 91



Comparative
198
0.0828



Example 92











Claims
  • 1. Iron oxide hydroxide composite particles having an average particle diameter of 0.005 to 1.0 μm, comprising: iron oxide hydroxide particles as core particles, a coating formed on surface of said iron oxide hydroxide particles, comprising at least one organosilicon compound selected from the group consisting of: (1) organosilane compounds obtainable from alkoxysilane compounds, and (2) polysiloxanes or modified polysiloxanes, and an organic pigment coat formed on said coating layer comprising said organosilicon compound, in an amount of from 1 to 30 parts by weight based on 100 parts by weight of said iron oxide hydroxide particles.
  • 2. Iron oxide hydroxide composite particles according to claim 1, wherein said iron oxide hydroxide particles are particles having a coat which is formed on at least a part of the surface of said iron oxide hydroxide particles and which comprises at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon in an amount of 0.01 to 20% by weight, calculated as Al or SiO2, based on the total weight of the iron oxide hydroxide particles coated.
  • 3. Iron oxide hydroxide composite particles according to claim 1, wherein said modified polysiloxanes are compounds selected from the group consisting of: (A) polysiloxanes modified with at least one compound selected from the group consisting of polyethers, polyesters and epoxy compounds, and (B) polysiloxanes whose molecular terminal is modified with at least one group selected from the group consisting of carboxylic acid groups, alcohol groups and a hydroxyl group.
  • 4. Iron oxide hydroxide composite particles according to claim 1, wherein said alkoxysilane compound is represented by the general formula (I):
  • 5. Iron oxide hydroxide composite particles according to claim 4, wherein said alkoxysilane compound is methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane or decyltrimethoxysilane.
  • 6. Iron oxide hydroxide composite particles according to claim 1, wherein said polysiloxanes are represented by the general formula (II): 6
  • 7. Iron oxide hydroxide composite particles according to claim 6, wherein said polysiloxanes are compounds having methyl hydrogen siloxane units.
  • 8. Iron oxide hydroxide composite particles according to claim 3, wherein said polysiloxanes modified with at least one compound selected from the group consisting of polyethers, polyesters and epoxy compounds are represented by the general formula (III), (IV) or (V): 7
  • 9. Iron oxide hydroxide composite particles according to claim 3, wherein said polysiloxanes whose molecular terminal is modified with at least one group selected from the group consisting of carboxylic acid groups, alcohol groups and a hydroxyl group are represented by the general formula (VI): 10
  • 10. Iron oxide hydroxide composite particles according to claim 1, wherein the amount of said coating organosilicon compounds is 0.02 to 5.0% by weight, calculated as Si, based on the total weight of the organosilicon compounds and said iron oxide hydroxide particles.
  • 11. Iron oxide hydroxide composite particles according to claim 1, wherein said organic pigment is organic blue-based pigment or organic red-based pigment.
  • 12. Iron oxide hydroxide composite particles according to claim 1, wherein said iron oxide hydroxide composite particles have an aspect ratio (average major axis diameter/average minor axis diameter) of 2.0:1 to 20.0:1.
  • 13. Iron oxide hydroxide composite particles according to claim 1, wherein said iron oxide hydroxide composite particles have a BET specific surface area value of 6 to 300 m2/g.
  • 14. Iron oxide hydroxide composite particles according to claim 1, wherein said iron oxide hydroxide composite particles have a geometrical standard deviation of major axis diameter of 1.01 to 2.0.
  • 15. Iron oxide hydroxide composite particles according to claim 1, which have an average particle diameter of from 0.005 to less than 0.1 μm, comprise: iron oxide hydroxide particles as core particles, a coating formed on surface of said iron oxide hydroxide particles, comprising at least one organosilicon compound selected from the group consisting of: (1) organosilane compounds obtainable from alkoxysilane compounds, and (2) polysiloxanes or modified polysiloxanes, and an organic blue-based pigment coat formed on said coating layer comprising said organosilicon compound, in an amount of from 5 to 30 parts by weight based on 100 parts by weight of said iron oxide hydroxide particles.
  • 16. Iron oxide hydroxide composite particles according to claim 15, wherein said iron oxide hydroxide particles are particles having a coat which is formed on at least a part of the surface of said iron oxide hydroxide particles and which comprises at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon in an amount of 0.01 to 20% by weight, calculated as Al or SiO2, based on the total weight of the iron oxide hydroxide particles coated.
  • 17. Iron oxide hydroxide composite particles according to claim 15, wherein said organic blue-based pigment is a phthalocyanine-based pigment and an alkali blue pigment.
  • 18. Iron oxide hydroxide composite particles according to claim 1, which have an average particle diameter of from 0.005 to less than 0.1 μm, comprise: iron oxide hydroxide particles as core particles, a coating formed on surface of said iron oxide hydroxide particles, comprising at least one organosilicon compound selected from the group consisting of: (1) organosilane compounds obtainable from alkoxysilane compounds, and (2) polysiloxanes or modified polysiloxanes, and an organic red-based pigment coat formed on said coating layer comprising said organosilicon compound, in an amount of from 1 to 30 parts by weight based on 100 parts by weight of said iron oxide hydroxide particles.
  • 19. Iron oxide hydroxide composite particles according to claim 18, wherein said iron oxide hydroxide particles are particles having a coat which is formed on at least a part of the surface of said iron oxide hydroxide particles and which comprises at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon in an amount of 0.01 to 20% by weight, calculated as Al or SiO2, based on the total weight of the iron oxide hydroxide particles coated.
  • 20. Iron oxide hydroxide composite particles according to claim 18, wherein said organic red-based pigment is quinacridone-based pigment, azo-based pigment, condensed azo-based pigment and perylene-based pigment.
  • 21. Iron oxide hydroxide composite particles according to claim 1, which have an average particle diameter of from 0.1 to 1.0 μm, comprises: iron oxide hydroxide particles as core particles, a coating formed on surface of said iron oxide hydroxide particles, comprising at least one organosilicon compound selected from the group consisting of: (1) organosilane compounds obtainable from alkoxysilane compounds, and (2) polysiloxanes or modified polysiloxanes, and an organic blue-based pigment coat formed on said coating layer comprising said organosilicon compound, in an amount of from 5 to 30 parts by weight based on 100 parts by weight of said iron oxide hydroxide particles.
  • 22. Iron oxide hydroxide composite particles according to claim 21, wherein said iron oxide hydroxide particles are particles having a coat which is formed on at least a part of the surface of said iron oxide hydroxide particles and which comprises at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon in an amount of 0.01 to 20% by weight, calculated as Al or SiO2, based on the total weight of the iron oxide hydroxide particles coated.
  • 23. Iron oxide hydroxide composite particles according to claim 21, wherein organic blue-based pigment is a phthalocyanine-based pigment and an alkali blue pigment.
  • 24. Iron oxide hydroxide composite particles according to claim 1, which have an average particle diameter of from 0.1 to 1.0 μm, and comprise: iron oxide hydroxide particles as core particles, a coating formed on surface of said iron oxide hydroxide particles, comprising at least one organosilicon compound selected from the group consisting of: (1) organosilane compounds obtainable from alkoxysilane compounds, and (2) polysiloxanes or modified polysiloxanes, and an organic red-based pigment coat formed on said coating layer comprising said organosilicon compound, in an amount of from 1 to 30 parts by weight based on 100 parts by weight of said iron oxide hydroxide particles.
  • 25. Iron oxide hydroxide composite particles according to claim 24, wherein said iron oxide hydroxide particles are particles having a coat which is formed on at least a part of the surface of said iron oxide hydroxide particles and which comprises at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon in an amount of 0.01 to 20% by weight, calculated as Al or SiO2, based on the total weight of the iron oxide hydroxide particles coated.
  • 26. Iron oxide hydroxide composite particles according to claim 24, wherein said organic red-based pigment is quinacridone-based pigment, azo-based pigment, condensed azo-based pigment and perylene-based pigment.
  • 27. A pigment comprising the iron oxide hydroxide composite particles as defined in claim 1.
  • 28. A green-based pigment comprising the iron oxide hydroxide composite particles as defined in claim 15 or 21.
  • 29. A orange-based pigment comprising the iron oxide hydroxide composite particles as defined in claim 18 or 24.
  • 30. A paint comprising: said pigment defined in claim 27; and a paint base material.
  • 31. A paint according to claim 30, wherein the amount of said pigment is 0.5 to 100 parts by weight based on 100 parts by weight of said paint base material.
  • 32. A rubber or resin composition comprising: said pigment defined in claim 27; and a base material for rubber or resin composition.
  • 33. A rubber or resin composition according to claim 32, wherein the amount of said pigment is 0.01 to 200 parts by weight based on 100 parts by weight of said base material for rubber or resin composition.
  • 34. A process for producing said iron oxide hydroxide composite particles defined in claim 1, which process comprises: mixing as core particles iron oxide hydroxide particles having an average particle diameter of 0.005 to 1.0 μm together with at least one compound selected from the group consisting of: (1) alkoxysilane compounds, and (2) polysiloxanes or modified polysiloxanes, by using an apparatus capable of applying a shear force to the core particles, thereby coating the surface of said iron oxide hydroxide particle with the said compounds; mixing the obtained iron oxide hydroxide particles coated with the said compounds and an organic pigment in an amount of 1 to 30 parts by weight based on 100 parts by weight of the core particles by using an apparatus capable of applying a shear force to the core particles, thereby forming an organic pigment coat on the surface of a coating layer comprising the organosilicon compounds.
  • 35. A process for producing black iron oxide hydroxide composite particles according to claim 34, wherein said iron oxide hydroxide particles as core particles are coated with at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon.
Priority Claims (4)
Number Date Country Kind
11-351915 Dec 1999 JP
2000-280265 Sep 2000 JP
2000-333786 Oct 2000 JP
2000-350232 Nov 2000 JP