Title of Invention	"COATING COMPOSITION"
Abstract	A coating composition containing a base coating" composition (I)/ preferably metallic base coating composition comprising a cellulose derivative (A),  an acrylic resin (B)/ a polyester resin (C) and at least one organic solvent (D) selected from the group consisting of an ester organic solvent and a ketone organic solvent, and a diluent (II) comprising an aliphatic hydrocarbon organic solvent (E), the cellulose derivative (A) being contained in an amount of 5 to 75% by weight based on the weight of a total solid content of the components (A) , (B) and (C), the aliphatic hydrocarbon solvent (D) being contained in an amount of 5 to 90% by weight in the diluent (II

Title of Invention

"COATING COMPOSITION"

Abstract

A coating composition containing a base coating" composition (I)/ preferably metallic base coating composition comprising a cellulose derivative (A),  an acrylic resin (B)/ a polyester resin (C) and at least one organic solvent (D) selected from the group consisting of an ester organic solvent and a ketone organic solvent, and a diluent (II) comprising an aliphatic hydrocarbon organic solvent (E), the cellulose derivative (A) being contained in an amount of 5 to 75% by weight based on the weight of a total solid content of the components (A) , (B) and (C), the aliphatic hydrocarbon solvent (D) being contained in an amount of 5 to 90% by weight in the diluent (II

Full Text	SPECIFICATION Title of the Invention: Coating Composition Field of the Invention: The present invention relates to a coating composition capable of forming a coating showing excellent properties in finish properties, drying properties, hardness, adhesion properties, etc., and substantially free of volatile organic compounds such as toluene/ xylene and the like, use of which is controlled due to influences on environment. Description of Background Art: In the art, an acrylic lacquer and acrylurethane coating composition are mainly used in the field of an automobile-repair coating composition from the standpoint of drying a coating film under the conditions of normal temperature drying or forced drying. In the case where a lacquer type coating composition is used in the above field, from the standpoint of drying properties of coating film, a coating composition containing, as a main vehicle component, a blend of a polyester resin with cellulose acetate butylate (hereinafter may be referred to as CAB), a blend of an acrylic resin with polyester resin and CAB, etc., has been used, resulting such problems that unsatisfactory compatibility between respective components may cause undesirable influences on finish properties, and that, in a metallic coating, phenomenon exhibiting a pigment orientation mottles in a pigment-containing coating film after coating (hereinafter may be referred to as mottling), and phenomenon exhibiting a pigment orientation mottles in a pigment-containing coating film after coating a clear coating composition onto the pigment-containing coating film, (hereinafter may be referred to as after-mottling) may reduce finish properties. For the purpose of solving the above problems, the present applicant proposed in the following patent references 1 and 2 a coating composition containing a CAB graft copolymer, polyester resin and acrylic resin in a specified mixing ratio. The use of the above coating composition makes it possible to improve compatibility between respective components, and to form a coating film showing good finish appearance without exhibiting mottling and after-mottling even in the metallic coating. However, the above coating composition is such that the coating composition and a diluting thinner for controlling a viscosity of the coating composition contain an organic solvent such as toluene, xylene and the like. Generally, a coating composition prepared by a coating composition producer has a viscosity too high to be subjected to coating as it is, so that the coating composition producer provides a distributor the coating composition along with a diluting thinner. A painter may buy the above coating composition and the diluting thinner from the distributor, and may formulate the above coating composition and the diluting thinner so as to be coated for the purpose of controlling a viscosity and coating workability as required. Recently, influences of the volatile organic compound on environment has produced problems, and the organic solvents usually used in the field of coating compositions/ for example, toluene, xylene, etc. are regulated as environmental pollutants, for example, under Pollutant Release and Transfer Register (hereinafter may referred to as PRTR), etc. Consequently, the coating compositions and diluting thinners containing the above organic solvents in a reduced amount or substantially free of the above organic solvents are highly demanded. In connection therewith, the following Patent Reference No. 3 discloses an automobile-repair coating composition comprising a specified (meth)acrylic copolymer, a polyisocyanate compound and an organic solvent in a specified amount, the organic solvent being an aliphatic or aromatic hydrocarbon solvent having a specified solubility parameter and a specified boiling point. However, the use of the above coating composition produces such problems that the use of the above coating composition as a clear coating composition onto a metallic coating film makes possible controlling development of after-mottling and providing a metallic finish with good appearance, whereas the use of the above coating composition as a base coating composition results unsatisfactory coating film properties in finish properties, drying properties and adhesion properties, and that the above coating composition contains organic solvents such as toluene/ xylene, etc. On the other hand, for the purpose of solving the above problems, for example, in the coating compositions such as base coat coating composition, clear coating composition as used in metallic coating in the art, removal of organic solvents such as toluene, xylene and the like from the coating composition or diluting thinner and replacement with an organic solvent dissolving the resin in the coating composition, for example, an ester organic solvent and the like may exhibit after-mottling, as well as phenomenon of mottling, and particularly may remarkably reduce finish properties due to redissolution of the coating film with the organic solvents replaced on forming a clear coating film onto the metallic coating film. Patent Reference 1: Japanese Patent Application Laid-Open Publication No. 2000-178500 Patent Reference 2: Japanese Patent Application Laid-Open Publication No. 2002-129090 Patent Reference 3: Japanese Patent Application Laid-Open Publication No. 256715/94 Summary of the Invention: An, object of the present invention is to provide a coating composition which is substantially free of the volatile organic compounds and shows good properties in coating workability and finish properties, and which is capable of forming a coating film showing good properties in water resistance, adhesion properties, etc. For the purpose of solving the above problems, the present inventors made intensive studies to find out that a specified coating composition containing a base coating composition (I) comprising a specified resin composition and a specified organic solvent, and a diluent (II) containing a specified amount of a specified organic solvent can solve the above problems, resulting in accomplishing the present invention. That is, the present invention relates to a coating composition containing a base coating composition (I) comprising a cellulose derivative (A), an acrylic resin (B), a polyester resin (C) and at least one organic solvent (D) selected from the group consisting of an ester organic solvent and a ketone organic solvent, and a diluent (II) comprising an aliphatic hydrocarbon organic solvent (E), the cellulose derivative (A) being contained in an amount of 5 to 75% by weight based on the weight of a total solid content of the components (A), (B) and (C), the aliphatic hydrocarbon solvent (D) being contained in an amount of 5 to 90% by weight in the diluent (II), the base coating composition (I) preferably being a metallic base coating composition, and a coating method by use of the coating composition. The present invention can provide the following particular effects. The present coating composition is substantially free of the volatile organic compounds under regulation so as to be harmless to environment and human body. The present coating composition shows good storage stability, because the base coating composition comprises specified resins and specified organic solvent and shows good compatibility between respective components. The present coating composition makes it possible to form a coating film showing good properties in finish properties, water resistance, adhesion properties, etc. under the conditions of normal temperature drying or forced drying, because mixing the base coating composition with the diluent containing a specified amount of the specified solvent results in that the coating composition on coating can have a specified solvent composition. The present coating composition makes it possible to control redissolution on forming a clear coating film onto the metallic coating film, and to form a coating film showing good finish properties without developing metallic pigment orientation mottling even in the case of a metallic coating, in which mottling and after-mottling may easily take place. Detailed Description of the Invention: The cellulose derivative (A) in the present invention is a compound containing a cellulose structural unit, and may include, for example, a cellulose esterified product obtained by esterifying the hydroxyl group in the cellulose with an acid such as fatty acid, nitric acid and the like, a copolymer (F) prepared by reacting a polymerizably unsaturated group-containing cellulose esterified product obtained by introducing a polymerizably unsaturated group into the cellulose esterified product with a polymerizably unsaturated monomer, and the like. The cellulose esterified product may include, for example, nitrocellulose, cellulose acetate butylate, cellulose acetate, cellulose acetate propionate and the like. Of these, cellulose acetate butylate is preferable. The cellulose acetate butylate may be prepared by butyl-esterifying a partially acetylated product, and is such that an acetyl group content is in the range of 1 to 30% by weight, and a butyl group content is in the range of 16 to 60% by weight, and specifically may include, for example, CAB-381-0.5, CAB-381-0.1, CAB-381-2.0, CAB-551-0.2 (Trade names, marketed by Eastman Chemical Company), and the like. The cellulose derivative (A) makes it possible to improve drying properties and adhesion properties of a resulting coating film, and, in the case where the coating composition of the present invention contains glitters such as aluminum powder, to improve orientation of glitters in the coating film. The cellulose acetate butylate has a number average molecular weight in the range of 15,000 to 100,000, particularly 20,000 to 35,000. A number average molecular weight within the above range makes it possible to control mottling and after-mottling while keeping good compatibility with acrylic resin and polyester resin, resulting in making it possible to form a coating film showing good finish properties. In the present specification/ the number average molecular weight is a value determined by converting a number average molecular weight measured by use of a permeation chromatograph (marketed by Tosoh Corporation under the trade name of HLC8120GPC) from a number average molecular weight of styrene as a standard. The above measuring was performed under the conditions of 4 columns: TSK gel G-4000HxL, TSK gel G-3000HxL, TSK gel G-2500HxL, TSK gel G-2000HxL (trade names, all marketed by Tosoh Corporation), mobile phase: tetrahydrofuran, measuring temperature: 40°C, flow rate/cc(ml)/min., and detector RI. The cellulose derivative (A) in the present invention may include the cellulose esterified product and a copolymer (F) prepared by reacting a polymerizably unsaturated group-containing cellulose esterified product obtained by introducing a polymerizably unsaturated group into the cellulose esterified product with a polymerizably unsaturated monomer. In the present invention, particularly a combined use of the cellulose esterified product with the copolymer (F) makes it possible to improve compatibility between respective resins contained in the base coating composition (I), and to improve finish properties of a resulting coating film. The copolymer (F) may be prepared, for example, by copolymerizing a polymerizably unsaturated group-containing cellulose esterified product obtained by reacting the cellulose esterified product and an Isocyanate group-containing polymerizably unsaturated monomer with a polymerizably unsaturated monomer. The polymerizably unsaturated monomer may include any polymer!zable monomers having an ethylenically unsaturated bond, for example, polymerizably unsaturated monomers containing straight-chain or branched chain C1-18 hydrocarbon groups such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl acrylate (marketed by Osaka Organic Chemical Industry Ltd.), and the like'; cycloalkyl group-containing polymerizably unsaturated monomers such as cyclohexyl (meth)acrylate, methyl cyclohexyl (meth)acrylate, t-butyl cyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, and the like; isobornyl group-containing polymerizably unsaturated monomers such as isobornyl (meth)acrylate and the like; adamantyl group-containing polymerizably unsaturated monomers such as adamantyl (meth)acrylate and the like; aromatic vinyl monomers such as styrene, a-methylstyrene, vinyltoluene and the like; phosphate group-containing polymerizably unsaturated monomers such as (2~ acryloyloxyethyl) acid phosphate, (2-methacryloyloxyethyl) acid phosphate, (2-acryloyloxypropyl) acid phosphate, (2- methacryloyloxypropyl) acid phosphate and the like; hydroxyl .group-containing (meth)acrylate, for example, C2-C8-hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and the like, allyl alcohol, e-caprolactone-modified products of the C2-C8 hydroxyalkyl (meth)acrylate, and the like; hydroxyl group-containing polymerizably unsaturated monomer such as (meth)acrylate having a hydroxyl group-terminating polyoxyethylene chain and the like; carboxyl group-containing polymerizably unsaturated monomer such as (meth)acrylate acid, maleic acid, crotonic acid, ß-carboxyethyl acrylate and the like; alkoxysilyl group-containing polymerizably unsaturated monomer such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, y-(meth)acryloyloxy-propyltrimethoxysilane, y-(meth)acryloyloxy-propyltriethoxysilane and the like; perfluoroalkyl (meth)acrylate such as perfluorobutylethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate and the like; a polymerizably unsaturated monomer having a fluorized alkyl group such as fluoroolefin and the like; epoxy group-containing polymerizably unsaturated monomer such as glycidyl (meth) acrylate, ß-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, 3,4- epoxycyclohexylpropyl (meth)acrylate, allylglycidyl ether and the like; polymerizably unsaturated monomer having a photopolymerizably functional group such as maleimide group and the like; 1,2,2,6,6-pentamethylpiperizyl (meth)acrylate, 1, 2,2,2,6, 6-tetramethylpiperizinyl (meth)acrylate and the like; a vinyl compound such as N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate, and the like; (meth)acrylonitrile and the like; amide group-containing polymerizably unsaturated monomer such as (meth)acrylamide, dimethylaminopropyl (meth)acrylamide and the like; amino group-containing polymerizably unsaturated monomer such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N-t-butylaminoethyl (meth)acrylate, an adduct of glycidyl (meth)acrylate with amines and the like; quaternary ammonium salt group-containing polymerizably unsaturated monomer such as 2-(methacryloyloxy) ethyltrimethylammonium chloride, 2-(methacryloyloxy)ethyltrimethylammonium bromide, methacryloylaminopropyltrimethylammonium chloride, methacryloyl aminopropyl trimethylammonium bromide, tetrabutylammonium (meth)acrylate, tetramethylammonium (meth)acrylate, trimethylbenzylammonium (meth)acrylate, 2-(methacryloyloxy)ethyltrimethylammonium dimethyl phosphate, and the like; (meth)acrylate having an alkoxy group-terminating polyoxyalkylene chain; sulfonate group-containing polymerizably unsaturated monomer such as 2-acrylamide-2-methylpropane sulfonic acid, allyl sulfonic acid, sodium styrene sulfonate, sulfoethyl methacrylate, sodium'or ammonium salt thereof, and the like; carbonyl group- containing polymerizably unsaturated monomer such as acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl styrol, C4-C7 vinylalkylketone, for example, vinylmethyl ketone, vinylethyl ketone, vinylbutyl ketone and the like; and the like. These may be used alone or in combination. The isocyanate group-containing polymerizably unsaturated monomer used for introducing the polymerizably unsaturated group into the cellulose esterified product may include, for example, an isocyanato group-containing vinyl monomer such as isocyanatoethyl acrylate, m-isopropenyl-a,a-dimethylbenzyl isocyanate and the like, adduct of diisocyanate with the above-mentioned hydroxyl group-containing polymerizably unsaturated monomer, and the like. The copolymerization reaction of the polymerizably unsaturated, group containing cellulose esterified product with the polymerizably unsaturated monomer may be carried out in the presence of a radical polymerization initiator such as organic perpoxides according to solution polymerization process, etc. In the preparation of the copolymer (F) , a mixing --weight ratio of polymerizably unsaturated monomer/cellulose esterified product may preferably be in the range of 5/95 to 95/5, preferably 10/90 to 90/10. Acrylic Resin (B) In the present invention, the acrylic resin (B) is a component used mainly as a film-forming component, also as a pigment-dispersing resin, and may include a resin obtained by copolymerizing polymerizably unsaturated monomers by use of a polymerization initiator in the presence of an organic solvent. The above polymerizably unsaturated may arbitrarily be selected from ones exemplified in the preparation of the copolymer (F) in the cellulose derivative (A) to be used. The acrylic resin (B) in the present invention is such that a copolymer obtained from polymerizably unsaturated monomers constituting the acrylic resin (B) has a glass transition temperature in the range of 0 to 80°C, preferably 5 to 75°C from the standpoints of adhesion properties and water-resistant adhesion properties of the resulting coating film. In the present specification, the glass transition temperature at absolute temperature is a value calculated from the following formula: (FORMULA REMOVED) respective monomers/ that is, weight of respective monomers/total weight of monomers * 100 (%), T1 T2 Tn represent glass transition temperatures at absolute temperature of homopolymers of respective monomers. The glass transition temperatures of homopolymers of respective monomers are values from Polymer Hand Book (4th Edition). Glass transition temperatures of homopolymers of monomers not disclosed in the above Hand Book are determined as follows. Homopolymers from respective monomers having a weight average molecular weight of about 50,000 are prepared as respective samples, followed by charging the sample into a measuring cup in a differential scanning thermal analyzer DSC-50Q Type (trade name, marketed by Shimazu Corporation), sucking under vacuum to completely remove a solvent, measuring a change in quanty of heat in the range of -100°C to +100°C at a heating rate of 3°C/min., and taking a changing point of an initial base line on a low temperature side as the glass transition temperature. A preferable comonomer in the acrylic resin may include the above-mentioned hydroxyl group containing polymerizably unsaturated monomer. A mixing amount of the above monomer is in the range of 0.1 to 35% by weight, preferably 1 to 30% by weight based on the weight of the total polymerizably unsaturated monomers used in the preparation of the acrylic resin (B) from the standpoints of adhesion properties and water resistance of the resulting coating film. Copolymerization of the above coiaonomers makes it possible to improve adhesion properties of a coating film formed from a resulting coating composition, and to react with a curing agent contained in a clear coating composition. The acrylic resin (B) may preferably contain a carboxyl group-containing polymerizably unsaturated monomer as a comonomer from the standpoints of adhesion properties of the resulting coating film and pigment dispersibility. A mixing amount of the carboxyl group-containing polymerizably unsaturated monomer may be in the range of 0.05 to 10% by weight, preferably 0.07 to 5.0% by weight in a total polymerizably unsaturated monomers used in the preparation of acrylic resin (B). The acrylic resin (B) may preferably contain an amino group-containing polymerizably unsaturated monomer from the standpoints of pigment dispersibility and improvements in appearance, particularly gloss appearance of a multi-coating film formed by coating a clear coating composition onto a coating film formed from the coating composition of the present invention. A mixing amount of the amino group-containing polymerizably unsaturated monomer may be in the range of 0.1 to 60% by weight, preferably 0.5 to 50% by weight in total polymerizably unsaturated monomers used in the preparation of the acrylic resin (B). The polymerization initiator used in the preparation of the acrylic resin (B) of the present invention may include any known ones used in solution polymerization process, for example, organic peroxides such as benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide and the like; azo compounds such as azobisisobutylonitrile, azobis (2,4-dimethylvaleronitrile and the like, and the like. These may be used alone or in combination. A mixing amount of the polymerization initiator may be in the range of 0.1 to 10% by weight, preferably 0.2 to 8% by weight based on a total weight of total polymerizably unsaturated monomers used in the preparation of the acrylic resin (B). The acrylic resin (B) obtained as above in the present invention may have a weight average molecular weight in the range of 5,000 to 80,000/ preferably 6,000 to 70,000 from the standpoints of adhesion properties of the resulting coating film and pigment dispersibility. In the present specification, the weight average molecular weight is a value determined by converting a weight average molecular weight measured by use of a permeation chromatograph (marketed by Tosoh Corporation under the trade name of HLC3120GPC) from a weight average molecular weight of styrene as a standard. The above measuring was performed under the conditions of 4 columns: TSK gel G-4000HxL, TSK gel G-3000HL, TSK gel G-2500HxL, TSK gel G-2000HxL (trade names, all marketed by Tosoh Corporation), mobile phase: tetrahydrofuran, measuring temperature: 40°C, flow rate/cc(ml)/min., and detector RI. Polyester Resin (C) The polyester resin (C) in the present invention may include resins obtained by copolymerizing comonomers mainly containing a polybasic acid and a polyhydric alcohol according to the conventional process. The polybasic acid may include, for example, adipic acid, succinic acid, isophthalic acid, terephthalic acid, phthalic anhydride, maleic anhydride, maleic anhydride, trimellitic acid, hexahydrophthalic anhydride, sodium 5-sulfoisophthalate, and the like. The polyhydric alcohol may include, for example, ethylene glycol, propylene glycol, glycerin, trimethylol propane, neopentyl glycol, 1,6-hexanediol, pentaerithritol, sorbitol and the like, and optionally may include, as a comonomer, fatty acid such as dehydrated castor oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, tall oil fatty acid and the like, monobasic acid such as benzoic acid, fats and oils, and the like. The use of the polyester resin (C) in the coating composition of the present invention makes it possible to improve adhesion properties, particularly to promote penetration of a curing agent from a clear coating composition containing the curing agent, resulting in improving adhesion properties with a clear coating film. The polyester resin (C) has a weight average molecular weight in the range of 5,000 to 100,000, preferably 10,000 to 70, 000, and a hydroxy1 value in the range of 5 to 150 mgKOH/g, preferably 10 to 140 mgKOH/g from the standpoint of adhesion properties of the resulting coating film. The polyester resin (C) may have a glass transition temperature in the range of -70 to 0°C, preferably -65 to -5°C. The glass transition temperature of the polyester resin (c) is determined as such that a sample is charged into a measuring cup in a differential scanning thermal analyzer DSC-50Q Type (trade name, marketed by Shimazu Corporation), sucking under pressure to completely remove a solvent, measuring a change in quanty of heat in the range of -100°C to +100°c at a heating rate of 3°c/min., and taking a changing point of an initial base line on a low temperature side as the glass transition temperature. Organic Solvent (D) The organic solvent (D) in the present invention may include preferably an organic solvent not to exhibit an adverse effect on drying properties of the resulting coating film and a coating environment, and an organic solvent capable of dissolving the resins in the coating composition of the present invention, particularly the cellulose derivative (A), and capable of exhibiting good compatibility between respective resins, and may include, for example, at least one organic solvent selected from an ester organic solvent and a ketone organic solvent. The ester organic solvent in the organic solvent (D) may include, for example, ethyl acetate, butyl acetate, isobutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and the like. The ketone organic solvent may include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylisoamyl ketone, diisobutyl ketone, methylhexyl ketone, isophorone and the like. These may be used alone or in combination. The organic solvent (D) may preferably has a molecular weight in the range of 58 to 220, particularly 72 to 200. Particularly, the ester organic solvent is suitable for showing an effect to improve the storage stability of the base coating composition and compatibility with the following aliphatic hydrocarbon organic solvent. (E). The organic solvent (D) may be added at any state in the preparation of the base coating composition (I)/ and also may be added as a reactive solvent or diluting solvent in the preparation of the resin contained in the coating composition. Aliphatic hydrocarbon organic solvent (E) The aliphatic hydrocarbon organic solvent may include a compound having a high flash point and high boiling point and not exhibiting adverse effects on environment and human body, for example, straight chain alkane such as n-butane, n-hexane, n-heptane, n-pentane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane and the like; branched alkane such as 2-methylbutane, 2,2-dimethylpropane, 2-iaethylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2-methylhexane, 3-methylhexane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2,2,3-trimethylpentane, 2,2, 4-trimethylpentane, 3,4-diethylhexane, 2,6-dimethyloctane, 3,3-dimethyloctahe, 3,5-dimethyloctane, 4, 4-dimethyloctane, 3-ethyl-3-methylbutane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 2-methylundecane, 3-methylundecane, 2,2,4,6,6-pentamethylheptane and the like; cyclic alkane such as cyclopentane, t-decalin, cyclohexane, methylcyclohexane, ethylcyclohexane, 1,2-dimethyl cyclohexane, 1,3-dimethyl cyclohexane, 1,4-dimethyl cyclohexane, propyl cyclohexane, isopropyl cyclohexane, 1,2-methylethyl cyclohexaner 1,3-methylethyl cyclohexane, 1,4-methylethyl cyclohexane, 1,2,3-trimethyl cyclohexane, 1,2,4-trimethyl cyclohexane, 1,3,5-trimethyl cyclohexane and the like; and the like. These may be used alone or in combination. In the case where the coating composition of the present invention is a metallic coating composition containing a glitter, the organic solvent (E) may preferably include C5-12' particularly C6-10 alkane, particularly cyclic alkane, more particularly alkylcyclohexane from the standpoints of capable of controlling development of mottling of the resulting coating film and capable of remarkably improve finish properties. The alkylcyclohexane may include, for example, methylcyclohexane, ethylcyclohexane, 1,2-dimethyl cyclohexane, 1,3-dimethyl cyclohexane, 1,4-dimethyl cyclohexane, propylcyclohexane, isopropylcyclohexane, 1,2-methylethyl cyclohexane, 1,3-methylethyl cyclohexane, 1,4-methylethyl cyclohexane, 1,2,3-trimethyl cyclohexane, 1,2,4-trimethyl cyclohexane, 1,3,5-trimethyl cyclohexane and the like. The organic solvent (E) may preferably contained in the following diluent (II) in an amount of 5 to 90% by weight, preferably 10 to 80% by weight in the diluent (II) from the standpoint of a long period of storage stability of the base coating composition (I). The organic solvent (E) less than 5% by weight in the diluent (II) may produce irregularity in finish properties of a coating film formed by coating the coating composition obtained by mixing the diluent (II) with the base coating composition as in the present invention. On the other hand, when more than 90% by weight, an insufficient solubility of the diluent (II) with the base coating composition may reduce stability of the coating composition prepared by mixing the above two components for controlling viscosity and finish properties. Base Coating Composition (I) In the present invention, the base coating composition (I) contains, as essential components, components (A), (B), (C) and (D) . The cellulose derivative (A) is contained in an amount of 5 to 75% by weight, preferably 10 to 70% by weight in a total solid content weight of the components (A), (B) and (C). The component (A) less than 5% by weight may reduce drying properties of the coating film formed from the coating composition of the present invention. On the other hand, when more than 75% by weight, adhesion properties with a coating substrate and with a clear coating film may be reduced. The acrylic resin (B) is contained in an amount of 5 to 90% by weight, preferably 10 to 85% by weight, and the polyester resin (C) is contained in an amount of 5 to 45% by weight, preferably 10 to 40% by weight in the total solid content weight of the components (A), (B) and (C) respectively. The component (B) less than 5% by weight may reduce adhesion properties with the coating substrate and with the clear coating film. On the other hand, when more than 90% by weight, drying properties of the resulting coating film may be reduced. The component (C) less than 5% by weight may result insufficient permeability of a crosslinking component from a clear coating film. On the other hand, when more than 45% by weight, hardness of the coating film may be reduced. In the present invention, the base coating composition (I) may be either a color coating composition or a clear coating composition. Of these, the color coating composition, particularly a glitter-containing coating composition may exhibit the effect of the present invention to a maximum. A pigment to be used in the base coating composition may include any pigment used in the field of the coating composition without particular limitations, for example, glitter, color pigment, extender pigment and the like. The glitter may include, for example, metallic pigment such as aluminum powder, bronze powder, copper powder, tin powder, iron phosphate and the like; pearlescent pigment such as mica, metal oxide-coating mica powder, metal oxide-coating alumina -flake, metal oxide-coating silica flake, mica-shaped iron oxide, and the like. The color pigment may include, for example, a white pigment such as titanium oxide, and the like; a black pigment such as carbon black, acetylene black, lamp black, born black, graphite, black iron oxide, aniline black and the like; an yellow pigment such as yellow iron oxide, titanium yellow, monoazo yellow, condensation azo yellow, azomethine yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindolin, quinophthalone, benzidine yellow, permanent yellow and the like; an orange pigment such as permanent orange and the like; a red pigment such as red iron oxide, naphthol AS azo red, anthanthrone, anthraquinonyl red, perylene maroon, quinacridone red pigment, diketopyroropyrol, watchung red, permanent red and the like; a violet pigment such as cobalt violet, quinacridone violet, dioxazine violet and the like; a blue pigment such as cobalt blue, phthalocyanin blue, threne blue, and the like; a green pigment such as phthalocyanine green and the like; and the like. The extender pigment may include, for example, zinc powder, baryta powder, settling barium sulfate, barium carbonate, calcium carbonate, plaster, clay, silica, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, gloss white, mica powder and the like. A mixing amount of the pigment in the coating composition of the present invention may arbitrarily be determined depending on kind of the pigment, and may usually be in the range of 1 to 250% by weight, preferably 2 to 240% by weight based on a-resin solid content weight in the coating composition. For example, in the case of the glitter-containing coating composition, the glitter may be contained in an amount of 1 to 60% by weight, preferably 2 to 55% by weight based on the above. The base coating composition (I) may optionally contain additives for use in a coating composition in the art, for example/ thickening agent/ ultraviolet light absorber, photostabilizer, anti-oxidant, surface controlling agent, pigment dispersant, curing catalyst and the like, and may also contain the organic solvent (E) and other organic solvents within such a range as not to exhibit an adverse effect on the storage stability of the base coating composition (I) and on drying properties of the coating composition of the present invention. The other organic solvent may include ones other than the organic solvents (D) and (£), for example, aromatic hydrocarbon organic solvent such as toluene, xylene and the like; ether organic solvent such as dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono-tert-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol monoisopropyl ether and the like; and alcohol organic solvent such as methanol, isopropanol/ tert-butanol, secondary butanol, isobutanol, n-butanol, 2-ethylhexanol, n-octanol, benzyl alcohol and the like. These may be used in such an amount as not to exhibit adverse effect on coating film performances of a coating film formed from the coating composition of the present invention. Diluent (II) In the present invention, the diluent (II) is mixed with the base coating composition (I) for the purpose of controlling a coating composition viscosity for improving coating workability, and forming a coating film exhibiting little or no mottling or after mottling and showing good finish properties. The diluent (II) may contain the aliphatic hydrocarbon organic solvent in an amount of 5 to 90% by weight, preferably 10 to 80% by weight, the ester organic solvent in an amount of 8 to 85% by weight, preferably 10 to 80% by weight, the ketone organic solvent in an amount of 2 to 35% by weight, preferably 5 to 30% by weight, and other organic solvent in an amount of 0 to 30% by weight, preferably 0 to 25% by weight, for the purpose of improving a mixing stability of the diluent (II) with the resins contained in the base coating composition, particularly the cellulose derivative (A) and improving finish properties of the coating film formed from the coating composition of the present invention. The diluent (II) may optionally contain additives for use in a coating composition in the art, for example, thickening agent/ ultraviolet light absorber, photostabilizer, anti-oxidant, surface controlling agent, pigment dispersant, curing catalyst and the like. Coating Composition The coating composition of the present invention contains the base coating composition (II) and the diluent (II) and is such that, from the standpoints of coating workability and finish properties, the organic solvent (D) is in the range of 100 to 700 parts by weight, preferably 120 to 690 parts by weight, and the solvent (E) is in the range of 20 to 340 parts by weight, preferably 25 to 330 parts by weight per 100 parts by weight of the resin solid content in the base coating composition (I). In the present invention, from the standpoints of improving compatibility between resins contained in the coating composition of the present invention and from forming a coating film showing good finish properties, the aliphatic hydrocarbon organic solvent (E) may be in the range of 20 to 340 parts by weight, preferably 25 to 330 parts by weight, the ester organic solvent may be in the range of 90 to 590 parts by weight, preferably 100 to 580 parts by weight, and the ketone organic solvent may be in the range of 10 to 110 parts by weight, preferably 20 to 110 parts by weight. Preparation of the coating composition may be performed, for example, by mixing with agitation the base coating composition (I) and the diluent (II) just before coating, in the present specification, the above mixing may be performed, for example, 3 hours before coating at the earliest. A mixing ratio of the diluent (II) to the base coating composition (I) to accomplish the above solvent compositions may be such that a mixing amount of the diluent (II) may be in the range of 20 to 250% by weight, preferably 30 to 200% by weight based on the weight of the base coating composition (I). A coating composition type of the coating composition in the present invention may not be particularly limited, but may preferably be two-pack type composition comprising the base coating composition (I) and the diluent (II). The coating composition of the present invention may optionally contain a curing agent such as polyisocyanate curing agent, blocked polyisocyanate curing agent/ melamine curing agent and the like. In the case where the coating composition contain the curing agent, depending on the kind of the curing agent, the coating composition type of the coating composition may arbitrarily be selected from three-pack type composition comprising the base coating composition (1), the diluent (II) and the curing agent, two-pack type composition comprising a mixture of the base coating composition (I) with the curing agent as one-pack composition and the diluent (II), and two-pack type composition comprising a mixture of the diluent (II) with the curing agent as one-pack composition and the base coating composition (I). Coating The present invention provides a coating method which comprises coating the coating composition of the present invention onto a coating substrate. The coating substrate may include a substrate known in the art, and a coating film formed onto the substrate. The substrate may not particularly be limited, and may include, for example, a metal such as iron, aluminum and the like; an organic substrate such as plastics and the like; an inorganic substrate such as concrete, wood and the like; and the like. The coating film formed onto the substrate may not particularly be limited, and may include, for example, a multi-layer coating film comprising a base coating film formed from a color base coating composition and a clear coating film as used in an automobile body, vehicles such as trains, etc. The base coating film may be combined with an under layer such as a primer coating film, electrodeposition coating film, intercoat coating film and the like. The base coating film formed from the color base coating composition generally represents a coating film formed from a coating composition containing a color pigment and/or glitter as coated for the purpose of imparting beautiful appearance on the coating substrate. The top clear coating film generally represents a top layer coating film capable forming a clear coating film. The electrodeposition coating film formed from a coating composition used in electrodeposition coating. The intercoat coating film generally represents a coating film formed between an undercoat coating film such as primer coating film and electrodeposition coating film, and a topcoat coating film such as base coating film and top clear coating film. A coating method of coating the coating composition of the present invention may not particularly limited, and may include, for example, spray coating, electrostatic coating, brushing, roller coating and the like. A drying method may include heat drying, forced drying, and normal temperature drying. In the present specification, the normal temperature drying is performed under a drying condition of a temperature lower than 40°C- The forced drying is performed under a drying condition of a temperature at 40°C or higher and lower than 80°C. The heat drying is performed under a drying condition of a temperature of 80°c or higher. The present invention provides a coating method which comprises coating the coating composition of the present invention onto a coating substrate to form a coating film, followed by coating a clear coating composition thereonto. The coating film formed from the coating composition of the present invention may be cured and dried prior to coating the clear coating composition, or may be uncured to form an uncured coating film, followed by coating a clear coating composition thereonto to form an uncured clear coating film, and drying both coating films. The clear coating composition used in the present invention may include any ones known in the art without particular limitations, for,example, a curable coating composition containing a base resin such as acrylic resin containing a crosslinkable functional group such as hydroxyl group and a fluorocarbon resin, and a curing agent such as blocked polyisocyanate, polyisocyanate, melamine resin and the like; a lacquer coating composition containing, as a main component, a cellulose acetate butylate-modified acrylic resin; and the like. The clear coating composition may optionally contain additives used in a coating composition known in the art, for example, pigments, cellulose derivatives, additive resins, ultraviolet light absorber, photostabilizer, surface controlling agent, curing catalyst and the like. Of these, in the case where a clear coating composition containing a polyisocyanate curing agent is used, a part of the polyisocyanate curing agent in the clear coating film may penetrate into the coating film from the coating composition of the present invention, resulting in that in the case where the coating film from the coating composition of the present invention contains hydroxyl group, the reaction of the penetrating polyisocyanate curing agent with the hydroxyl group makes it possible to make unnecessary use of a curing agent in the coating composition or to reduce an amount of a curing agent used therein, and to improve adhesion properties between the coating film from the coating composition of the present invention and the clear coating film. A coating method of coating the clear coating composition may include, for example, spray coating, electrostatic coating, brushing, roller coating and the like. A drying method may include heat drying, forced drying and normal temperature drying. Example The present invention is explained more in detail by the following Examples, in which "part" represents "part by weight", and "%" represents "% by weight". Preparation of Polyester Resin Solution Preparation Example 1 A 4-liter reactor equipped with a heating device, thermometer, stirrer, fractionating column and water separator-fitted reflux condenser was charged with the following components, followed by heating up to 160°C, and heating from 160°C to 230°C over 3 hours. hexahydro phthalic anhydride 29.7. parts adipic acid 25.4 parts neopentyl glycol 5.3 parts 1,6-hexane diol 39.6 parts Thereafter, the temperature of 230°c was kept for one hour, followed by distilling off the resulting condensation water (7.4 parts) by use of a fractionating column, adding 5 parts of xylene, refluxing" xylene and condensation water to remove the water by use of the water separator. Measuring of an acid value was started 2 hours after the addition of xylene, followed by vacuuming when the acid value became 2 or less to almost completely distill off xylene, cooling down to 120°C, diluting with butyl acetate so as to be a non-volatile matter content of 70%, and obtaining a polyester resin butyl acetate solution. The resulting resin had a weight average molecular weight of 20,000, a hydroxyl value of 32 mgKOH/g and a glass transition temperature of -52°C. Preparation of Acrylic Resin Solution Preparation Example 2 A 4-liter reactor equipped with a thermometer, stirrer, reflux condenser and pump for use in dropping was charged with 68 parts of butyl acetate, followed by heating up to 110°C with agitation, and dropping a mixed solution of the following monomer mixture and polymerization initiator at a constant speed over about 3 hours at 110°C. isobutyl methacrylate • 59.75 parts methyl methacrylate 10 parts isostearyl acrylate 10 parts (marketed by Osaka Organic Chemical Industry Ltd.) 2-hydroxyethyl acrylate 19 parts diitiethylaminoethyl methacrylate 1 part methacrylic acid 0.25 part azobis(2, 4-dimethylvaleronitrile) 0.2 part After the completion of dropping, the temperature at 110"C was kept for one hour with agitation, followed by dropping a solution prepared by dissolving 0.5 part of azobisdimethylvaleronitrile as an additional catalyst in 14 parts of butyl acetate at a constant speed over one hour, keeping at 110°c for one hour to complete the reaction. The acrylic resin solution obtained above had a non-volatile matter of 55.0%, and was a uniform transparent solution. The resulting resin had a weight average molecular weight of 50,000, hydroxy! value of 92 mgKOH/g, and glass transition temperature of 57"C. Preparation of CAB Graft Acrylic Resin Solution Preparation Example 3 A 4-liter reactor equipped with a thermometer, stirrer, reflux condenser and dropping funnel was charged with the following components, followed by heating under nitrogen atmosphere up to 110°c over about 4 hours. butyl acetate 600 parts CAB-381-0.5 (Note 1) 200 parts Heating up to 110°C was followed by completely dissolving CAB-381-0.5 (Mote 1), stopping heating, distilling off 133 parts of butyl acetate under vacuum, charging into the reactor 11.1 parts of 90% butyl acetate solution of an equimolar addition reaction product of isophoron diisocyanate with 2-hydroxyethyl acrylate, 0.02 part of p-t-butylcatechol as a polymerization inhibitor, and 0.02 part of dibutyltindilaurate as an urethani2ation catalyst, while the temperature within the reactor being kept at 87 °c, aging at 87°c for 7 hours under dry air to obtain an unsaturated group-containing cellulose acetate butylate solution, heating up to 115°C, dropping the following mixed solution of the polyroerizably unsaturated monomer and polymerization initiator over 2 hours. butyl acetate 130 parts methyl methacrylate 58.2 parts t-butylperoxy-2-ethylhexanoate 2 parts Completion of dropping was followed by dropping a mixed solution of 0.5 part of t-butylperoxy-2-ethylhexanoate and 20 parts of butylacetate over one hour/ and aging at 115°C for one hour under nitrogen atmosphere to obtain CAB-graft acrylic resin solution having a non-volatile matter of 30%. (Note 1) CAB-381-0.5: trade name, marketed by Eastman Chemical Company, cellulose acetate butylate, butyl group content 38%, number average molecular weight 300,000. Preparation of Base Coating Composition Preparation Examples 4-8 A reactor was charged with Aluminum Paste MC-606 (trade name, marketed by Asahi Kasei Metals Ltd., aluminum paste, aluminum powder/mineral spirit/C9 aromatic hydrocarbon organic solvent « 60/19.5/19.5, weight ratio, amine 1%) and 55% acrylic resin solution obtained in Preparation Example 2 according to the formulations shown in Table 1, followed by dispersing with agitation, adding 25% CAB551-0.2 solution (Note 2), 70% polyester resin solution obtained in Preparation Example 1, and 30% CAB graft acrylic resin solution according to the formulations shown in Table 1, adding butylacetate according to the formulation shown in Table 1, and stirring with a disper for about 20 minutes to obtain metallic base coating compositions (1-1) to (1-5). (TABLE REMOVED) (Note 2) 25% CAB551-0.2 solution; CAB551-0.2 (trade name, marketed by Eastman Chemical Company, cellulose acetate butylate, butyl group content 55%, number average molecular weight 30,000) was dissolved in butyl acetate to prepare a solution having a solid content of 25%. Preparation of Diluents Preparation Examples 9-26 Respective solvents were mixed according to the formulations shown in Table 2, followed by stirring with a disper for about 10 minutes to prepare diluents (II-l) to (TABLE REMOVED) Preparation of Coating Composition Example 1 A mixture of 100 parts of metallic coating composition (l-l) and 100 parts of diluent (II-l) was stirred to obtain a coating composition. Examples 2-16 and Comparative Examples 1-9 Example 1 was duplicated except that respective coating compositions were prepared according to respective formulations shown in Table 3. (TABLE REMOVED) Coating • KAR PRIMER-SURFACER GRAY (trade name, marketed by Kansai Paint Co., Ltd., lacquer primer surfacer) was coated onto a tinplate so as to be a dry film thickness of 40 um, followed by drying at 20°C for 30 minutes, sanding with a #400 water-resistant sandpaper, coating thereonto respective coating compositions obtained in Examples and Comparative Examples so as to be a dry film thickness of 30 urn by spray coating, drying at 20°C for 10 minutes, coating thereonto a clear coating composition (Note 3) by spray coating so as to be a dry film thickness of 40 urn, and drying at 20°C for 24 hours to obtain test panels. Respective test panels before or after coating the clear coating composition were subjected to the following performance tests. Test results are shown in Table 3. (Note 3) Clear coating composition: A mixture of 100 parts by weight of Retan PG Multi-Clear HX (Q) Base (trade name, marketed by Kansai Paint Co., Ltd., clear coating composition containing hydroxyl group-containing acrylic resin) and 50 parts by weight of Retan PG Multi-Clear HX Standard Curing agent (trade name, marketed by Kansai Paint Co., Ltd., hexamethylene diisocyanate curing agent) was diluted with the diluent (II-l) to a viscosity of 13 to 14 sec. (Ford Cup #4/25°C) to obtain the clear coating composition. (1) Drying Properties Above coating compositions were coated onto a glass plate so as to be a coating film thickness of 100 nm by use of a docter blade in a thermohygrostatic room under the conditions of a temperature of 20°C and humidity of 75%, followed by measuring a time required to be tack-free. Evaluation was made as follows. ®: drying time, less than 10 minutes, O: drying time, 10 minutes or more but less than 12 minutes, A: 12 minutes or more but less than 15 minutes, X: 15 minutes or more. (2) Mottling Pigment orientation mottling in the coating film of the test panel prior to coating the clear coating composition was visually examined. Test result was evaluated as follows. ©: no mottling developed, O: little mottling developed, but practicable, A; little mottling developed, X: mottling remarkably developed. (3) After-Mottling Pigment orientation mottling in the coating film of the test panel prepared after coating the clear coating composition and drying was visually examined. Test result was evaluated as follows. ®: no mottling developed, O: little mottling developed, but practicable, A: little mottling developed, X: mottling remarkably developed. (4) Adhesion Properties A test panel prepared by coating a clear coating composition, followed by drying was subjected to adhesion properties test as follows. On a diagonal line, cross cuts reaching a substrate of the test panel were formed by use of a knife, followed by subjecting to separation test with an adhesive tape. Test results were evaluated as follows. O: No separation, A: little separation, X: considerable separation. (5) PRTR regulated pollutant content Contents of toluene and xylene in respective coating compositions obtained in Examples and Comparative Examples were determined, and evaluation was made as follows. O: PRTR regulated pollutant content, less than 1%, X: PRTR regulated pollutant content, 1% or more. What is claimed is: 1. A coating composition containing a base coating composition (I) comprising a cellulose derivative (A), an acrylic resin (B), a polyester resin (C) and at least one organic solvent (D) selected from the group consisting of an ester organic solvent and a ketone organic solvent, and a diluent (II) comprising an aliphatic hydrocarbon organic solvent (E), the cellulose derivative (A) being contained in an amount of 5 to 75% by weight based on the weight of a total solid content of the components (A)/ (B) and (C), the aliphatic hydrocarbon solvent (E) being contained in an amount of 5 to 90% by weight in the diluent (II). 2. A coating composition as claimed in claim 1, wherein the base coating composition (I) is a metallic base coating composition. 3. A coating composition as claimed in claim 1 or 2, wherein the cellulose derivative (A) is cellulose acetate butylate. 4. A coating composition as claimed in any one of claims 1 to 3, wherein the cellulose derivative (A) includes a cellulose-esterified product and a copolymer (F) prepared by reacting a polymerizably unsaturated group-containing cellulose-esterified product obtained by introducing a polymerizably unsaturated group into the cellulose-esterified product with a polymerizably unsaturated monomer. 5. A coating composition as claimed in any one of claims 1 to 4, wherein the organic solvent (E) is alkylcyclohexane. 6. A coating composition as claimed in any one of claims 1 to 5, wherein the organic solvent (D) is contained in the range of 10 to 95% by weight in the diluent (II). 7. A coating composition as claimed in any one of claims 1 to 6, wherein the organic solvent (D) is contained in the range of 100 to 700 parts by weight, and the organic solvent (E) is contained in the range of 20 to 340 parts by weight based on 100 parts by weight of a resin solid content in the base coating composition (I) respectively. 8. A coating composition as claimed in any one of claims 1 to 7, wherein a mixing amount of the diluent (II) is in the range of 20 to 250% by weight based on the weight of the base coating composition (I). 9. A coating method which comprises coating a coating composition as claimed in any one of claims 1 to 8 onto a coating substrate. 10. A coating method which comprises coating a coating composition as claimed in any one of claims 1 to 8 onto a coating substrate to form a coating film, followed by coating a clear coating composition thereonto. 11. A coated product obtained by the coating method claimed in claim 9 or 10. as

Full Text

SPECIFICATION
Title of the Invention:
Coating Composition
Field of the Invention:
The present invention relates to a coating composition capable of forming a coating showing excellent properties in finish properties, drying properties, hardness, adhesion properties, etc., and substantially free of volatile organic compounds such as toluene/ xylene and the like, use of which is controlled due to influences on environment. Description of Background Art:
In the art, an acrylic lacquer and acrylurethane coating composition are mainly used in the field of an automobile-repair coating composition from the standpoint of drying a coating film under the conditions of normal temperature drying or forced drying.
In the case where a lacquer type coating composition is used in the above field, from the standpoint of drying properties of coating film, a coating composition containing, as a main vehicle component, a blend of a polyester resin with cellulose acetate butylate (hereinafter may be referred to as CAB), a blend of an acrylic resin with polyester resin and CAB, etc., has been used, resulting such problems that unsatisfactory compatibility between respective components may cause undesirable influences on finish properties, and that, in a metallic coating, phenomenon exhibiting a pigment
orientation mottles in a pigment-containing coating film after coating (hereinafter may be referred to as mottling), and phenomenon exhibiting a pigment orientation mottles in a pigment-containing coating film after coating a clear coating composition onto the pigment-containing coating film, (hereinafter may be referred to as after-mottling) may reduce finish properties.
For the purpose of solving the above problems, the present applicant proposed in the following patent references 1 and 2 a coating composition containing a CAB graft copolymer, polyester resin and acrylic resin in a specified mixing ratio. The use of the above coating composition makes it possible to improve compatibility between respective components, and to form a coating film showing good finish appearance without exhibiting mottling and after-mottling even in the metallic coating. However, the above coating composition is such that the coating composition and a diluting thinner for controlling a viscosity of the coating composition contain an organic solvent such as toluene, xylene and the like.
Generally, a coating composition prepared by a coating composition producer has a viscosity too high to be subjected to coating as it is, so that the coating composition producer provides a distributor the coating composition along with a diluting thinner. A painter may buy the above coating composition and the diluting thinner from the distributor, and may formulate the above coating composition and the
diluting thinner so as to be coated for the purpose of controlling a viscosity and coating workability as required.
Recently, influences of the volatile organic compound on environment has produced problems, and the organic solvents usually used in the field of coating compositions/ for example, toluene, xylene, etc. are regulated as environmental pollutants, for example, under Pollutant Release and Transfer Register (hereinafter may referred to as PRTR), etc. Consequently, the coating compositions and diluting thinners containing the above organic solvents in a reduced amount or substantially free of the above organic solvents are highly demanded.
In connection therewith, the following Patent Reference No. 3 discloses an automobile-repair coating composition comprising a specified (meth)acrylic copolymer, a polyisocyanate compound and an organic solvent in a specified amount, the organic solvent being an aliphatic or aromatic hydrocarbon solvent having a specified solubility parameter and a specified boiling point.
However, the use of the above coating composition produces such problems that the use of the above coating composition as a clear coating composition onto a metallic coating film makes possible controlling development of after-mottling and providing a metallic finish with good appearance, whereas the use of the above coating composition as a base coating composition results unsatisfactory coating film properties in finish properties, drying properties and
adhesion properties, and that the above coating composition contains organic solvents such as toluene/ xylene, etc.
On the other hand, for the purpose of solving the above problems, for example, in the coating compositions such as base coat coating composition, clear coating composition as used in metallic coating in the art, removal of organic solvents such as toluene, xylene and the like from the coating composition or diluting thinner and replacement with an organic solvent dissolving the resin in the coating composition, for example, an ester organic solvent and the like may exhibit after-mottling, as well as phenomenon of mottling, and particularly may remarkably reduce finish properties due to redissolution of the coating film with the organic solvents replaced on forming a clear coating film onto the metallic coating film.
Patent Reference 1: Japanese Patent Application Laid-Open
Publication No. 2000-178500
Patent Reference 2: Japanese Patent Application Laid-Open
Publication No. 2002-129090
Patent Reference 3: Japanese Patent Application Laid-Open
Publication No. 256715/94 Summary of the Invention:
An, object of the present invention is to provide a coating composition which is substantially free of the volatile organic compounds and shows good properties in coating workability and finish properties, and which is capable of forming a coating film showing good properties in
water resistance, adhesion properties, etc.
For the purpose of solving the above problems, the present inventors made intensive studies to find out that a specified coating composition containing a base coating composition (I) comprising a specified resin composition and a specified organic solvent, and a diluent (II) containing a specified amount of a specified organic solvent can solve the above problems, resulting in accomplishing the present invention.
That is, the present invention relates to a coating composition containing a base coating composition (I) comprising a cellulose derivative (A), an acrylic resin (B), a polyester resin (C) and at least one organic solvent (D) selected from the group consisting of an ester organic solvent and a ketone organic solvent, and a diluent (II) comprising an aliphatic hydrocarbon organic solvent (E), the cellulose derivative (A) being contained in an amount of 5 to 75% by weight based on the weight of a total solid content of the components (A), (B) and (C), the aliphatic hydrocarbon solvent (D) being contained in an amount of 5 to 90% by weight in the diluent (II), the base coating composition (I) preferably being a metallic base coating composition, and a coating method by use of the coating composition.
The present invention can provide the following particular effects.
The present coating composition is substantially free of the volatile organic compounds under regulation so as to
be harmless to environment and human body.
The present coating composition shows good storage stability, because the base coating composition comprises specified resins and specified organic solvent and shows good compatibility between respective components.
The present coating composition makes it possible to form a coating film showing good properties in finish properties, water resistance, adhesion properties, etc. under the conditions of normal temperature drying or forced drying, because mixing the base coating composition with the diluent containing a specified amount of the specified solvent results in that the coating composition on coating can have a specified solvent composition.
The present coating composition makes it possible to control redissolution on forming a clear coating film onto the metallic coating film, and to form a coating film showing good finish properties without developing metallic pigment orientation mottling even in the case of a metallic coating, in which mottling and after-mottling may easily take place. Detailed Description of the Invention:
The cellulose derivative (A) in the present invention is a compound containing a cellulose structural unit, and may include, for example, a cellulose esterified product obtained by esterifying the hydroxyl group in the cellulose with an acid such as fatty acid, nitric acid and the like, a copolymer (F) prepared by reacting a polymerizably unsaturated group-containing cellulose esterified product
obtained by introducing a polymerizably unsaturated group into the cellulose esterified product with a polymerizably unsaturated monomer, and the like.
The cellulose esterified product may include, for example, nitrocellulose, cellulose acetate butylate, cellulose acetate, cellulose acetate propionate and the like. Of these, cellulose acetate butylate is preferable.
The cellulose acetate butylate may be prepared by butyl-esterifying a partially acetylated product, and is such that an acetyl group content is in the range of 1 to 30% by weight, and a butyl group content is in the range of 16 to 60% by weight, and specifically may include, for example, CAB-381-0.5, CAB-381-0.1, CAB-381-2.0, CAB-551-0.2 (Trade names, marketed by Eastman Chemical Company), and the like.
The cellulose derivative (A) makes it possible to improve drying properties and adhesion properties of a resulting coating film, and, in the case where the coating composition of the present invention contains glitters such as aluminum powder, to improve orientation of glitters in the coating film.
The cellulose acetate butylate has a number average molecular weight in the range of 15,000 to 100,000, particularly 20,000 to 35,000. A number average molecular weight within the above range makes it possible to control mottling and after-mottling while keeping good compatibility with acrylic resin and polyester resin, resulting in making it possible to form a coating film showing good finish
properties.
In the present specification/ the number average molecular weight is a value determined by converting a number average molecular weight measured by use of a permeation chromatograph (marketed by Tosoh Corporation under the trade name of HLC8120GPC) from a number average molecular weight of styrene as a standard. The above measuring was performed under the conditions of 4 columns: TSK gel G-4000HxL, TSK gel G-3000HxL, TSK gel G-2500HxL, TSK gel G-2000HxL (trade names, all marketed by Tosoh Corporation), mobile phase: tetrahydrofuran, measuring temperature: 40°C, flow rate/cc(ml)/min., and detector RI.
The cellulose derivative (A) in the present invention may include the cellulose esterified product and a copolymer (F) prepared by reacting a polymerizably unsaturated group-containing cellulose esterified product obtained by introducing a polymerizably unsaturated group into the cellulose esterified product with a polymerizably unsaturated monomer.
In the present invention, particularly a combined use of the cellulose esterified product with the copolymer (F) makes it possible to improve compatibility between respective resins contained in the base coating composition (I), and to improve finish properties of a resulting coating film.
The copolymer (F) may be prepared, for example, by copolymerizing a polymerizably unsaturated group-containing cellulose esterified product obtained by reacting the
cellulose esterified product and an Isocyanate group-containing polymerizably unsaturated monomer with a polymerizably unsaturated monomer.
The polymerizably unsaturated monomer may include any polymer!zable monomers having an ethylenically unsaturated bond, for example, polymerizably unsaturated monomers containing straight-chain or branched chain C1-18 hydrocarbon groups such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl acrylate (marketed by Osaka Organic Chemical Industry Ltd.), and the like'; cycloalkyl group-containing polymerizably unsaturated monomers such as cyclohexyl (meth)acrylate, methyl cyclohexyl (meth)acrylate, t-butyl cyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, and the like; isobornyl group-containing polymerizably unsaturated monomers such as isobornyl (meth)acrylate and the like; adamantyl group-containing polymerizably unsaturated monomers such as adamantyl (meth)acrylate and the like; aromatic vinyl monomers such as styrene, a-methylstyrene, vinyltoluene and the like; phosphate group-containing polymerizably unsaturated monomers such as (2~ acryloyloxyethyl) acid phosphate, (2-methacryloyloxyethyl) acid phosphate, (2-acryloyloxypropyl) acid phosphate, (2-
methacryloyloxypropyl) acid phosphate and the like; hydroxyl .group-containing (meth)acrylate, for example, C2-C8-hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and the like, allyl alcohol, e-caprolactone-modified products of the C2-C8 hydroxyalkyl (meth)acrylate, and the like; hydroxyl group-containing polymerizably unsaturated monomer such as (meth)acrylate having a hydroxyl group-terminating polyoxyethylene chain and the like; carboxyl group-containing polymerizably unsaturated monomer such as (meth)acrylate acid, maleic acid, crotonic acid, ß-carboxyethyl acrylate and the like; alkoxysilyl group-containing polymerizably unsaturated monomer such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, y-(meth)acryloyloxy-propyltrimethoxysilane, y-(meth)acryloyloxy-propyltriethoxysilane and the like; perfluoroalkyl
(meth)acrylate such as perfluorobutylethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate and the like; a polymerizably unsaturated monomer having a fluorized alkyl group such as fluoroolefin and the like; epoxy group-containing polymerizably unsaturated monomer such as glycidyl
(meth) acrylate, ß-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, 3,4-
epoxycyclohexylpropyl (meth)acrylate, allylglycidyl ether and the like; polymerizably unsaturated monomer having a
photopolymerizably functional group such as maleimide group and the like; 1,2,2,6,6-pentamethylpiperizyl (meth)acrylate, 1, 2,2,2,6, 6-tetramethylpiperizinyl (meth)acrylate and the like; a vinyl compound such as N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate, and the like; (meth)acrylonitrile and the like; amide group-containing polymerizably unsaturated monomer such as (meth)acrylamide, dimethylaminopropyl (meth)acrylamide and the like; amino group-containing polymerizably unsaturated monomer such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N-t-butylaminoethyl (meth)acrylate, an adduct of glycidyl (meth)acrylate with amines and the like; quaternary ammonium salt group-containing polymerizably unsaturated monomer such as 2-(methacryloyloxy) ethyltrimethylammonium chloride, 2-(methacryloyloxy)ethyltrimethylammonium bromide, methacryloylaminopropyltrimethylammonium chloride, methacryloyl aminopropyl trimethylammonium bromide, tetrabutylammonium (meth)acrylate, tetramethylammonium (meth)acrylate, trimethylbenzylammonium (meth)acrylate, 2-(methacryloyloxy)ethyltrimethylammonium dimethyl phosphate, and the like; (meth)acrylate having an alkoxy group-terminating polyoxyalkylene chain; sulfonate group-containing polymerizably unsaturated monomer such as 2-acrylamide-2-methylpropane sulfonic acid, allyl sulfonic acid, sodium styrene sulfonate, sulfoethyl methacrylate, sodium'or ammonium salt thereof, and the like; carbonyl group-
containing polymerizably unsaturated monomer such as acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl styrol, C4-C7 vinylalkylketone, for example, vinylmethyl ketone, vinylethyl ketone, vinylbutyl ketone and the like; and the like. These may be used alone or in combination.
The isocyanate group-containing polymerizably unsaturated monomer used for introducing the polymerizably unsaturated group into the cellulose esterified product may include, for example, an isocyanato group-containing vinyl monomer such as isocyanatoethyl acrylate, m-isopropenyl-a,a-dimethylbenzyl isocyanate and the like, adduct of diisocyanate with the above-mentioned hydroxyl group-containing polymerizably unsaturated monomer, and the like.
The copolymerization reaction of the polymerizably unsaturated, group containing cellulose esterified product with the polymerizably unsaturated monomer may be carried out in the presence of a radical polymerization initiator such as organic perpoxides according to solution polymerization process, etc.
In the preparation of the copolymer (F) , a mixing --weight ratio of polymerizably unsaturated monomer/cellulose esterified product may preferably be in the range of 5/95 to 95/5, preferably 10/90 to 90/10. Acrylic Resin (B)
In the present invention, the acrylic resin (B) is a component used mainly as a film-forming component, also as a
pigment-dispersing resin, and may include a resin obtained by copolymerizing polymerizably unsaturated monomers by use of a polymerization initiator in the presence of an organic solvent.
The above polymerizably unsaturated may arbitrarily be selected from ones exemplified in the preparation of the copolymer (F) in the cellulose derivative (A) to be used.
The acrylic resin (B) in the present invention is such that a copolymer obtained from polymerizably unsaturated monomers constituting the acrylic resin (B) has a glass transition temperature in the range of 0 to 80°C, preferably 5 to 75°C from the standpoints of adhesion properties and water-resistant adhesion properties of the resulting coating film.
In the present specification, the glass transition temperature at absolute temperature is a value calculated from the following formula:
(FORMULA REMOVED)

respective monomers/ that is, weight of respective
monomers/total weight of monomers * 100 (%), T1 T2 Tn
represent glass transition temperatures at absolute temperature of homopolymers of respective monomers. The glass transition temperatures of homopolymers of respective monomers are values from Polymer Hand Book (4th Edition). Glass transition temperatures of homopolymers of monomers not disclosed in the above Hand Book are determined as follows.
Homopolymers from respective monomers having a weight average molecular weight of about 50,000 are prepared as respective samples, followed by charging the sample into a measuring cup in a differential scanning thermal analyzer DSC-50Q Type (trade name, marketed by Shimazu Corporation), sucking under vacuum to completely remove a solvent, measuring a change in quanty of heat in the range of -100°C to +100°C at a heating rate of 3°C/min., and taking a changing point of an initial base line on a low temperature side as the glass transition temperature.
A preferable comonomer in the acrylic resin may include the above-mentioned hydroxyl group containing polymerizably unsaturated monomer. A mixing amount of the above monomer is in the range of 0.1 to 35% by weight, preferably 1 to 30% by weight based on the weight of the total polymerizably unsaturated monomers used in the preparation of the acrylic resin (B) from the standpoints of adhesion properties and water resistance of the resulting coating film. Copolymerization of the above coiaonomers makes it possible to improve adhesion properties of a coating film formed from a resulting coating composition, and to react with a curing agent contained in a clear coating composition.
The acrylic resin (B) may preferably contain a carboxyl group-containing polymerizably unsaturated monomer as a comonomer from the standpoints of adhesion properties of the resulting coating film and pigment dispersibility. A mixing amount of the carboxyl group-containing polymerizably
unsaturated monomer may be in the range of 0.05 to 10% by weight, preferably 0.07 to 5.0% by weight in a total polymerizably unsaturated monomers used in the preparation of acrylic resin (B).
The acrylic resin (B) may preferably contain an amino group-containing polymerizably unsaturated monomer from the standpoints of pigment dispersibility and improvements in appearance, particularly gloss appearance of a multi-coating film formed by coating a clear coating composition onto a coating film formed from the coating composition of the present invention. A mixing amount of the amino group-containing polymerizably unsaturated monomer may be in the range of 0.1 to 60% by weight, preferably 0.5 to 50% by weight in total polymerizably unsaturated monomers used in the preparation of the acrylic resin (B).
The polymerization initiator used in the preparation of the acrylic resin (B) of the present invention may include any known ones used in solution polymerization process, for example, organic peroxides such as benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide and the like; azo compounds such as azobisisobutylonitrile, azobis (2,4-dimethylvaleronitrile and the like, and the like. These may be used alone or in combination.
A mixing amount of the polymerization initiator may be in the range of 0.1 to 10% by weight, preferably 0.2 to 8% by weight based on a total weight of total polymerizably unsaturated monomers used in the preparation of the acrylic
resin (B).
The acrylic resin (B) obtained as above in the present invention may have a weight average molecular weight in the range of 5,000 to 80,000/ preferably 6,000 to 70,000 from the standpoints of adhesion properties of the resulting coating film and pigment dispersibility.
In the present specification, the weight average molecular weight is a value determined by converting a weight average molecular weight measured by use of a permeation chromatograph (marketed by Tosoh Corporation under the trade name of HLC3120GPC) from a weight average molecular weight of styrene as a standard. The above measuring was performed under the conditions of 4 columns: TSK gel G-4000HxL, TSK gel G-3000H*L, TSK gel G-2500HxL, TSK gel G-2000HxL (trade names, all marketed by Tosoh Corporation), mobile phase: tetrahydrofuran, measuring temperature: 40°C, flow rate/cc(ml)/min., and detector RI. Polyester Resin (C)
The polyester resin (C) in the present invention may include resins obtained by copolymerizing comonomers mainly containing a polybasic acid and a polyhydric alcohol according to the conventional process. The polybasic acid may include, for example, adipic acid, succinic acid, isophthalic acid, terephthalic acid, phthalic anhydride, maleic anhydride, maleic anhydride, trimellitic acid, hexahydrophthalic anhydride, sodium 5-sulfoisophthalate, and the like. The polyhydric alcohol may include, for example,
ethylene glycol, propylene glycol, glycerin, trimethylol propane, neopentyl glycol, 1,6-hexanediol, pentaerithritol, sorbitol and the like, and optionally may include, as a comonomer, fatty acid such as dehydrated castor oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, tall oil fatty acid and the like, monobasic acid such as benzoic acid, fats and oils, and the like.
The use of the polyester resin (C) in the coating composition of the present invention makes it possible to improve adhesion properties, particularly to promote penetration of a curing agent from a clear coating composition containing the curing agent, resulting in improving adhesion properties with a clear coating film.
The polyester resin (C) has a weight average molecular weight in the range of 5,000 to 100,000, preferably 10,000 to 70, 000, and a hydroxy1 value in the range of 5 to 150 mgKOH/g, preferably 10 to 140 mgKOH/g from the standpoint of adhesion properties of the resulting coating film.
The polyester resin (C) may have a glass transition temperature in the range of -70 to 0°C, preferably -65 to -5°C. The glass transition temperature of the polyester resin (c) is determined as such that a sample is charged into a measuring cup in a differential scanning thermal analyzer DSC-50Q Type (trade name, marketed by Shimazu Corporation), sucking under pressure to completely remove a solvent, measuring a change in quanty of heat in the range of -100°C to +100°c at a heating rate of 3°c/min., and taking a
changing point of an initial base line on a low temperature side as the glass transition temperature. Organic Solvent (D)
The organic solvent (D) in the present invention may include preferably an organic solvent not to exhibit an adverse effect on drying properties of the resulting coating film and a coating environment, and an organic solvent capable of dissolving the resins in the coating composition of the present invention, particularly the cellulose derivative (A), and capable of exhibiting good compatibility between respective resins, and may include, for example, at least one organic solvent selected from an ester organic solvent and a ketone organic solvent.
The ester organic solvent in the organic solvent (D) may include, for example, ethyl acetate, butyl acetate, isobutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and the like. The ketone organic solvent may include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylisoamyl ketone, diisobutyl ketone, methylhexyl ketone, isophorone and the like. These may be used alone or in combination.
The organic solvent (D) may preferably has a molecular weight in the range of 58 to 220, particularly 72 to 200. Particularly, the ester organic solvent is suitable for
showing an effect to improve the storage stability of the base coating composition and compatibility with the following aliphatic hydrocarbon organic solvent. (E).
The organic solvent (D) may be added at any state in the preparation of the base coating composition (I)/ and also may be added as a reactive solvent or diluting solvent in the preparation of the resin contained in the coating composition. Aliphatic hydrocarbon organic solvent (E)
The aliphatic hydrocarbon organic solvent may include a compound having a high flash point and high boiling point and not exhibiting adverse effects on environment and human body, for example, straight chain alkane such as n-butane, n-hexane, n-heptane, n-pentane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane and the like; branched alkane such as 2-methylbutane, 2,2-dimethylpropane, 2-iaethylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2-methylhexane, 3-methylhexane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2,2,3-trimethylpentane, 2,2, 4-trimethylpentane, 3,4-diethylhexane, 2,6-dimethyloctane, 3,3-dimethyloctahe, 3,5-dimethyloctane, 4, 4-dimethyloctane, 3-ethyl-3-methylbutane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 2-methylundecane, 3-methylundecane, 2,2,4,6,6-pentamethylheptane and the like; cyclic alkane such as cyclopentane, t-decalin, cyclohexane, methylcyclohexane, ethylcyclohexane, 1,2-dimethyl cyclohexane, 1,3-dimethyl cyclohexane, 1,4-dimethyl cyclohexane, propyl
cyclohexane, isopropyl cyclohexane, 1,2-methylethyl cyclohexaner 1,3-methylethyl cyclohexane, 1,4-methylethyl cyclohexane, 1,2,3-trimethyl cyclohexane, 1,2,4-trimethyl cyclohexane, 1,3,5-trimethyl cyclohexane and the like; and the like. These may be used alone or in combination.
In the case where the coating composition of the present invention is a metallic coating composition containing a glitter, the organic solvent (E) may preferably include C5-12' particularly C6-10 alkane, particularly cyclic alkane, more particularly alkylcyclohexane from the standpoints of capable of controlling development of mottling of the resulting coating film and capable of remarkably improve finish properties.
The alkylcyclohexane may include, for example, methylcyclohexane, ethylcyclohexane, 1,2-dimethyl cyclohexane, 1,3-dimethyl cyclohexane, 1,4-dimethyl cyclohexane, propylcyclohexane, isopropylcyclohexane, 1,2-methylethyl cyclohexane, 1,3-methylethyl cyclohexane, 1,4-methylethyl cyclohexane, 1,2,3-trimethyl cyclohexane, 1,2,4-trimethyl cyclohexane, 1,3,5-trimethyl cyclohexane and the like.
The organic solvent (E) may preferably contained in the following diluent (II) in an amount of 5 to 90% by weight, preferably 10 to 80% by weight in the diluent (II) from the standpoint of a long period of storage stability of the base coating composition (I). The organic solvent (E) less than 5% by weight in the diluent (II) may produce irregularity in finish properties of a coating film formed by coating the
coating composition obtained by mixing the diluent (II) with the base coating composition as in the present invention. On the other hand, when more than 90% by weight, an insufficient solubility of the diluent (II) with the base coating composition may reduce stability of the coating composition prepared by mixing the above two components for controlling viscosity and finish properties. Base Coating Composition (I)
In the present invention, the base coating composition
(I) contains, as essential components, components (A), (B),
(C) and (D) . The cellulose derivative (A) is contained in an amount of 5 to 75% by weight, preferably 10 to 70% by weight in a total solid content weight of the components (A), (B) and (C).
The component (A) less than 5% by weight may reduce drying properties of the coating film formed from the coating composition of the present invention. On the other hand, when more than 75% by weight, adhesion properties with a coating substrate and with a clear coating film may be
reduced.
The acrylic resin (B) is contained in an amount of 5 to
90% by weight, preferably 10 to 85% by weight, and the polyester resin (C) is contained in an amount of 5 to 45% by
weight, preferably 10 to 40% by weight in the total solid
content weight of the components (A), (B) and (C)
respectively.
The component (B) less than 5% by weight may reduce
adhesion properties with the coating substrate and with the clear coating film. On the other hand, when more than 90% by weight, drying properties of the resulting coating film may be reduced. The component (C) less than 5% by weight may result insufficient permeability of a crosslinking component from a clear coating film. On the other hand, when more than 45% by weight, hardness of the coating film may be reduced.
In the present invention, the base coating composition (I) may be either a color coating composition or a clear coating composition. Of these, the color coating composition, particularly a glitter-containing coating composition may exhibit the effect of the present invention to a maximum.
A pigment to be used in the base coating composition may include any pigment used in the field of the coating composition without particular limitations, for example, glitter, color pigment, extender pigment and the like. The glitter may include, for example, metallic pigment such as aluminum powder, bronze powder, copper powder, tin powder, iron phosphate and the like; pearlescent pigment such as mica, metal oxide-coating mica powder, metal oxide-coating alumina -flake, metal oxide-coating silica flake, mica-shaped iron oxide, and the like. The color pigment may include, for example, a white pigment such as titanium oxide, and the like; a black pigment such as carbon black, acetylene black, lamp black, born black, graphite, black iron oxide, aniline black and the like; an yellow pigment such as yellow iron oxide, titanium yellow, monoazo yellow, condensation azo
yellow, azomethine yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindolin, quinophthalone, benzidine yellow, permanent yellow and the like; an orange pigment such as permanent orange and the like; a red pigment such as red iron oxide, naphthol AS azo red, anthanthrone, anthraquinonyl red, perylene maroon, quinacridone red pigment, diketopyroropyrol, watchung red, permanent red and the like; a violet pigment such as cobalt violet, quinacridone violet, dioxazine violet and the like; a blue pigment such as cobalt blue, phthalocyanin blue, threne blue, and the like; a green pigment such as phthalocyanine green and the like; and the like. The extender pigment may include, for example, zinc powder, baryta powder, settling barium sulfate, barium carbonate, calcium carbonate, plaster, clay, silica, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, gloss white, mica powder and the like.
A mixing amount of the pigment in the coating composition of the present invention may arbitrarily be determined depending on kind of the pigment, and may usually be in the range of 1 to 250% by weight, preferably 2 to 240% by weight based on a-resin solid content weight in the coating composition. For example, in the case of the glitter-containing coating composition, the glitter may be contained in an amount of 1 to 60% by weight, preferably 2 to 55% by weight based on the above.
The base coating composition (I) may optionally contain additives for use in a coating composition in the art, for
example/ thickening agent/ ultraviolet light absorber, photostabilizer, anti-oxidant, surface controlling agent, pigment dispersant, curing catalyst and the like, and may also contain the organic solvent (E) and other organic solvents within such a range as not to exhibit an adverse effect on the storage stability of the base coating composition (I) and on drying properties of the coating composition of the present invention.
The other organic solvent may include ones other than the organic solvents (D) and (£), for example, aromatic hydrocarbon organic solvent such as toluene, xylene and the like; ether organic solvent such as dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono-tert-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol monoisopropyl ether and the like; and alcohol organic solvent such as methanol,
isopropanol/ tert-butanol, secondary butanol, isobutanol, n-butanol, 2-ethylhexanol, n-octanol, benzyl alcohol and the like. These may be used in such an amount as not to exhibit adverse effect on coating film performances of a coating film formed from the coating composition of the present invention. Diluent (II)
In the present invention, the diluent (II) is mixed with the base coating composition (I) for the purpose of controlling a coating composition viscosity for improving coating workability, and forming a coating film exhibiting little or no mottling or after mottling and showing good finish properties.
The diluent (II) may contain the aliphatic hydrocarbon organic solvent in an amount of 5 to 90% by weight, preferably 10 to 80% by weight, the ester organic solvent in an amount of 8 to 85% by weight, preferably 10 to 80% by weight, the ketone organic solvent in an amount of 2 to 35% by weight, preferably 5 to 30% by weight, and other organic solvent in an amount of 0 to 30% by weight, preferably 0 to 25% by weight, for the purpose of improving a mixing stability of the diluent (II) with the resins contained in the base coating composition, particularly the cellulose derivative (A) and improving finish properties of the coating film formed from the coating composition of the present invention.
The diluent (II) may optionally contain additives for use in a coating composition in the art, for example,
thickening agent/ ultraviolet light absorber, photostabilizer, anti-oxidant, surface controlling agent, pigment dispersant, curing catalyst and the like. Coating Composition
The coating composition of the present invention contains the base coating composition (II) and the diluent (II) and is such that, from the standpoints of coating workability and finish properties, the organic solvent (D) is in the range of 100 to 700 parts by weight, preferably 120 to 690 parts by weight, and the solvent (E) is in the range of 20 to 340 parts by weight, preferably 25 to 330 parts by weight per 100 parts by weight of the resin solid content in the base coating composition (I).
In the present invention, from the standpoints of improving compatibility between resins contained in the coating composition of the present invention and from forming a coating film showing good finish properties, the aliphatic hydrocarbon organic solvent (E) may be in the range of 20 to 340 parts by weight, preferably 25 to 330 parts by weight, the ester organic solvent may be in the range of 90 to 590 parts by weight, preferably 100 to 580 parts by weight, and the ketone organic solvent may be in the range of 10 to 110 parts by weight, preferably 20 to 110 parts by weight.
Preparation of the coating composition may be performed, for example, by mixing with agitation the base coating composition (I) and the diluent (II) just before coating, in the present specification, the above mixing may be performed,
for example, 3 hours before coating at the earliest.
A mixing ratio of the diluent (II) to the base coating composition (I) to accomplish the above solvent compositions may be such that a mixing amount of the diluent (II) may be in the range of 20 to 250% by weight, preferably 30 to 200% by weight based on the weight of the base coating composition (I).
A coating composition type of the coating composition in the present invention may not be particularly limited, but may preferably be two-pack type composition comprising the base coating composition (I) and the diluent (II). The coating composition of the present invention may optionally contain a curing agent such as polyisocyanate curing agent, blocked polyisocyanate curing agent/ melamine curing agent and the like. In the case where the coating composition contain the curing agent, depending on the kind of the curing agent, the coating composition type of the coating composition may arbitrarily be selected from three-pack type composition comprising the base coating composition (1), the diluent (II) and the curing agent, two-pack type composition comprising a mixture of the base coating composition (I) with the curing agent as one-pack composition and the diluent (II), and two-pack type composition comprising a mixture of the diluent (II) with the curing agent as one-pack composition and the base coating composition (I). Coating
The present invention provides a coating method which
comprises coating the coating composition of the present invention onto a coating substrate.
The coating substrate may include a substrate known in the art, and a coating film formed onto the substrate. The substrate may not particularly be limited, and may include, for example, a metal such as iron, aluminum and the like; an organic substrate such as plastics and the like; an inorganic substrate such as concrete, wood and the like; and the like. The coating film formed onto the substrate may not particularly be limited, and may include, for example, a multi-layer coating film comprising a base coating film formed from a color base coating composition and a clear coating film as used in an automobile body, vehicles such as trains, etc. The base coating film may be combined with an under layer such as a primer coating film, electrodeposition coating film, intercoat coating film and the like.
The base coating film formed from the color base coating composition generally represents a coating film formed from a coating composition containing a color pigment and/or glitter as coated for the purpose of imparting beautiful appearance on the coating substrate. The top clear coating film generally represents a top layer coating film capable forming a clear coating film. The electrodeposition coating film formed from a coating composition used in electrodeposition coating. The intercoat coating film generally represents a coating film formed between an undercoat coating film such as primer coating film and
electrodeposition coating film, and a topcoat coating film such as base coating film and top clear coating film.
A coating method of coating the coating composition of the present invention may not particularly limited, and may include, for example, spray coating, electrostatic coating, brushing, roller coating and the like. A drying method may include heat drying, forced drying, and normal temperature drying. In the present specification, the normal temperature drying is performed under a drying condition of a temperature lower than 40°C- The forced drying is performed under a drying condition of a temperature at 40°C or higher and lower than 80°C. The heat drying is performed under a drying condition of a temperature of 80°c or higher.
The present invention provides a coating method which comprises coating the coating composition of the present invention onto a coating substrate to form a coating film, followed by coating a clear coating composition thereonto.
The coating film formed from the coating composition of the present invention may be cured and dried prior to coating the clear coating composition, or may be uncured to form an uncured coating film, followed by coating a clear coating composition thereonto to form an uncured clear coating film, and drying both coating films.
The clear coating composition used in the present invention may include any ones known in the art without particular limitations, for,example, a curable coating composition containing a base resin such as acrylic resin
containing a crosslinkable functional group such as hydroxyl group and a fluorocarbon resin, and a curing agent such as blocked polyisocyanate, polyisocyanate, melamine resin and the like; a lacquer coating composition containing, as a main component, a cellulose acetate butylate-modified acrylic resin; and the like. The clear coating composition may optionally contain additives used in a coating composition known in the art, for example, pigments, cellulose derivatives, additive resins, ultraviolet light absorber, photostabilizer, surface controlling agent, curing catalyst and the like. Of these, in the case where a clear coating composition containing a polyisocyanate curing agent is used, a part of the polyisocyanate curing agent in the clear coating film may penetrate into the coating film from the coating composition of the present invention, resulting in that in the case where the coating film from the coating composition of the present invention contains hydroxyl group, the reaction of the penetrating polyisocyanate curing agent with the hydroxyl group makes it possible to make unnecessary use of a curing agent in the coating composition or to reduce an amount of a curing agent used therein, and to improve adhesion properties between the coating film from the coating composition of the present invention and the clear coating film.
A coating method of coating the clear coating composition may include, for example, spray coating, electrostatic coating, brushing, roller coating and the like.
A drying method may include heat drying, forced drying and
normal temperature drying.
Example
The present invention is explained more in detail by the following Examples, in which "part" represents "part by weight", and "%" represents "% by weight". Preparation of Polyester Resin Solution Preparation Example 1
A 4-liter reactor equipped with a heating device, thermometer, stirrer, fractionating column and water separator-fitted reflux condenser was charged with the following components, followed by heating up to 160°C, and heating from 160°C to 230°C over 3 hours.
hexahydro phthalic anhydride 29.7. parts
adipic acid 25.4 parts
neopentyl glycol 5.3 parts
1,6-hexane diol 39.6 parts
Thereafter, the temperature of 230°c was kept for one hour, followed by distilling off the resulting condensation water (7.4 parts) by use of a fractionating column, adding 5 parts of xylene, refluxing" xylene and condensation water to remove the water by use of the water separator. Measuring of an acid value was started 2 hours after the addition of xylene, followed by vacuuming when the acid value became 2 or less to almost completely distill off xylene, cooling down to 120°C, diluting with butyl acetate so as to be a non-volatile matter content of 70%, and obtaining a polyester resin butyl
acetate solution. The resulting resin had a weight average molecular weight of 20,000, a hydroxyl value of 32 mgKOH/g and a glass transition temperature of -52°C. Preparation of Acrylic Resin Solution Preparation Example 2
A 4-liter reactor equipped with a thermometer, stirrer, reflux condenser and pump for use in dropping was charged with 68 parts of butyl acetate, followed by heating up to 110°C with agitation, and dropping a mixed solution of the following monomer mixture and polymerization initiator at a constant speed over about 3 hours at 110°C.
isobutyl methacrylate • 59.75 parts
methyl methacrylate 10 parts
isostearyl acrylate 10 parts
(marketed by Osaka Organic Chemical Industry Ltd.)
2-hydroxyethyl acrylate 19 parts
diitiethylaminoethyl methacrylate 1 part
methacrylic acid 0.25 part
azobis(2, 4-dimethylvaleronitrile) 0.2 part
After the completion of dropping, the temperature at 110"C was kept for one hour with agitation, followed by dropping a solution prepared by dissolving 0.5 part of azobisdimethylvaleronitrile as an additional catalyst in 14 parts of butyl acetate at a constant speed over one hour, keeping at 110°c for one hour to complete the reaction. The acrylic resin solution obtained above had a non-volatile
matter of 55.0%, and was a uniform transparent solution. The resulting resin had a weight average molecular weight of 50,000, hydroxy! value of 92 mgKOH/g, and glass transition temperature of 57"C.
Preparation of CAB Graft Acrylic Resin Solution Preparation Example 3
A 4-liter reactor equipped with a thermometer, stirrer, reflux condenser and dropping funnel was charged with the following components, followed by heating under nitrogen atmosphere up to 110°c over about 4 hours.
butyl acetate 600 parts
CAB-381-0.5 (Note 1) 200 parts
Heating up to 110°C was followed by completely dissolving CAB-381-0.5 (Mote 1), stopping heating, distilling off 133 parts of butyl acetate under vacuum, charging into the reactor 11.1 parts of 90% butyl acetate solution of an equimolar addition reaction product of isophoron diisocyanate with 2-hydroxyethyl acrylate, 0.02 part of p-t-butylcatechol as a polymerization inhibitor, and 0.02 part of dibutyltindilaurate as an urethani2ation catalyst, while the temperature within the reactor being kept at 87 °c, aging at 87°c for 7 hours under dry air to obtain an unsaturated group-containing cellulose acetate butylate solution, heating up to 115°C, dropping the following mixed solution of the polyroerizably unsaturated monomer and polymerization initiator over 2 hours.
butyl acetate 130 parts
methyl methacrylate 58.2 parts
t-butylperoxy-2-ethylhexanoate 2 parts
Completion of dropping was followed by dropping a mixed solution of 0.5 part of t-butylperoxy-2-ethylhexanoate and 20 parts of butylacetate over one hour/ and aging at 115°C for one hour under nitrogen atmosphere to obtain CAB-graft acrylic resin solution having a non-volatile matter of 30%. (Note 1) CAB-381-0.5: trade name, marketed by Eastman
Chemical Company, cellulose acetate butylate, butyl group content 38%, number average molecular weight 300,000. Preparation of Base Coating Composition Preparation Examples 4-8
A reactor was charged with Aluminum Paste MC-606 (trade name, marketed by Asahi Kasei Metals Ltd., aluminum paste, aluminum powder/mineral spirit/C9 aromatic hydrocarbon organic solvent « 60/19.5/19.5, weight ratio, amine 1%) and 55% acrylic resin solution obtained in Preparation Example 2 according to the formulations shown in Table 1, followed by dispersing with agitation, adding 25% CAB551-0.2 solution (Note 2), 70% polyester resin solution obtained in Preparation Example 1, and 30% CAB graft acrylic resin solution according to the formulations shown in Table 1, adding butylacetate according to the formulation shown in Table 1, and stirring with a disper for about 20 minutes to obtain metallic base coating compositions (1-1) to (1-5).
(TABLE REMOVED)

(Note 2) 25% CAB551-0.2 solution; CAB551-0.2 (trade name, marketed by Eastman Chemical Company, cellulose acetate butylate, butyl group content 55%, number average molecular weight 30,000) was dissolved in butyl acetate to prepare a solution having a solid content of 25%.
Preparation of Diluents
Preparation Examples 9-26
Respective solvents were mixed according to the
formulations shown in Table 2, followed by stirring with a
disper for about 10 minutes to prepare diluents (II-l) to
(TABLE REMOVED)

Preparation of Coating Composition Example 1
A mixture of 100 parts of metallic coating composition (l-l) and 100 parts of diluent (II-l) was stirred to obtain a coating composition. Examples 2-16 and Comparative Examples 1-9
Example 1 was duplicated except that respective coating compositions were prepared according to respective formulations shown in Table 3.
(TABLE REMOVED)

Coating
• KAR PRIMER-SURFACER GRAY (trade name, marketed by Kansai Paint Co., Ltd., lacquer primer surfacer) was coated onto a tinplate so as to be a dry film thickness of 40 um, followed by drying at 20°C for 30 minutes, sanding with a #400 water-resistant sandpaper, coating thereonto respective coating compositions obtained in Examples and Comparative Examples so as to be a dry film thickness of 30 urn by spray coating, drying at 20°C for 10 minutes, coating thereonto a clear coating composition (Note 3) by spray coating so as to be a dry film thickness of 40 urn, and drying at 20°C for 24 hours to obtain test panels. Respective test panels before or after coating the clear coating composition were subjected to the following performance tests. Test results are shown in Table 3. (Note 3) Clear coating composition:
A mixture of 100 parts by weight of Retan PG Multi-Clear HX (Q) Base (trade name, marketed by Kansai Paint Co., Ltd., clear coating composition containing hydroxyl group-containing acrylic resin) and 50 parts by weight of Retan PG Multi-Clear HX Standard Curing agent (trade name, marketed by Kansai Paint Co., Ltd., hexamethylene diisocyanate curing agent) was diluted with the diluent (II-l) to a viscosity of 13 to 14 sec. (Ford Cup #4/25°C) to obtain the clear coating composition. (*1) Drying Properties
Above coating compositions were coated onto a glass
plate so as to be a coating film thickness of 100 nm by use of a docter blade in a thermohygrostatic room under the conditions of a temperature of 20°C and humidity of 75%, followed by measuring a time required to be tack-free. Evaluation was made as follows. ®: drying time, less than 10 minutes, O: drying time, 10 minutes or more but less than 12 minutes, A: 12 minutes or more but less than 15 minutes, X: 15 minutes or more. (*2) Mottling
Pigment orientation mottling in the coating film of the test panel prior to coating the clear coating composition was visually examined. Test result was evaluated as follows. ©: no mottling developed, O: little mottling developed, but practicable, A; little mottling developed, X: mottling remarkably developed. (*3) After-Mottling
Pigment orientation mottling in the coating film of the test panel prepared after coating the clear coating composition and drying was visually examined. Test result was evaluated as follows. ®: no mottling developed, O: little mottling developed, but practicable, A: little mottling developed, X: mottling remarkably developed. (*4) Adhesion Properties
A test panel prepared by coating a clear coating composition, followed by drying was subjected to adhesion properties test as follows. On a diagonal line, cross cuts reaching a substrate of the test panel were formed by use of
a knife, followed by subjecting to separation test with an
adhesive tape. Test results were evaluated as follows. O:
No separation, A: little separation, X: considerable
separation.
(*5) PRTR regulated pollutant content
Contents of toluene and xylene in respective coating compositions obtained in Examples and Comparative Examples were determined, and evaluation was made as follows. O: PRTR regulated pollutant content, less than 1%, X: PRTR regulated pollutant content, 1% or more.

What is claimed is:
1. A coating composition containing a base coating composition (I) comprising a cellulose derivative (A), an acrylic resin (B), a polyester resin (C) and at least one organic solvent (D) selected from the group consisting of an ester organic solvent and a ketone organic solvent, and a diluent (II) comprising an aliphatic hydrocarbon organic solvent (E), the cellulose derivative (A) being contained in an amount of 5 to 75% by weight based on the weight of a total solid content of the components (A)/ (B) and (C), the aliphatic hydrocarbon solvent (E) being contained in an amount of 5 to 90% by weight in the diluent (II).
2. A coating composition as claimed in claim 1, wherein the base coating composition (I) is a metallic base coating composition.
3. A coating composition as claimed in claim 1 or 2, wherein the cellulose derivative (A) is cellulose acetate butylate.
4. A coating composition as claimed in any one of claims 1 to 3, wherein the cellulose derivative (A) includes a cellulose-esterified product and a copolymer (F) prepared by reacting a polymerizably unsaturated group-containing cellulose-esterified product obtained by introducing a polymerizably unsaturated group into the cellulose-esterified
product with a polymerizably unsaturated monomer.
5. A coating composition as claimed in any one of claims 1 to 4, wherein the organic solvent (E) is alkylcyclohexane.
6. A coating composition as claimed in any one of claims 1 to 5, wherein the organic solvent (D) is contained in the range of 10 to 95% by weight in the diluent (II).
7. A coating composition as claimed in any one of claims 1 to 6, wherein the organic solvent (D) is contained in the range of 100 to 700 parts by weight, and the organic solvent (E) is contained in the range of 20 to 340 parts by weight based on 100 parts by weight of a resin solid content in the base coating composition (I) respectively.
8. A coating composition as claimed in any one of claims 1 to 7, wherein a mixing amount of the diluent (II) is in the range of 20 to 250% by weight based on the weight of the base coating composition (I).
9. A coating method which comprises coating a coating composition as claimed in any one of claims 1 to 8 onto a coating substrate.
10. A coating method which comprises coating a coating
composition as claimed in any one of claims 1 to 8 onto a
coating substrate to form a coating film, followed by coating a clear coating composition thereonto.

11. A coated product obtained by the coating method claimed in claim 9 or 10.
as

Documents:

2877-del-2005-1-Abstract-(12-11-2012).pdf

2877-del-2005-1-Correspondence Others-(12-11-2012).pdf

2877-del-2005-1-Form-2-(12-11-2012).pdf

2877-del-2005-abstract.pdf

2877-del-2005-Claims-(12-11-2012).pdf

2877-del-2005-claims.pdf

2877-del-2005-Correspondence Others-(02-04-2012).pdf

2877-del-2005-Correspondence Others-(12-11-2012).pdf

2877-del-2005-Correspondence-Others-(16-01-2013).pdf

2877-del-2005-correspondence-others.pdf

2877-del-2005-description (complete).pdf

2877-del-2005-form-1.pdf

2877-del-2005-Form-13-(12-11-2012).pdf

2877-del-2005-form-18.pdf

2877-del-2005-form-2.pdf

2877-del-2005-Form-3-(02-04-2012).pdf

2877-del-2005-form-3.pdf

2877-del-2005-form-5.pdf

2877-del-2005-GPA-(02-04-2012).pdf

2877-del-2005-gpa.pdf

2877-del-2005-Petition-137-(12-11-2012).pdf

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Patent Number

256169

Indian Patent Application Number

2877/DEL/2005

PG Journal Number

20/2013

Publication Date

17-May-2013

Grant Date

10-May-2013

Date of Filing

27-Oct-2005

Name of Patentee

KANSAI PAINT CO.,LTD

Applicant Address

33-1, KANZAKI-CHO, AMAGASAKI-SHI, HYOGO-KEN, 661-0964, JAPAN

Inventors:

#	Inventor's Name	Inventor's Address
1	KATAOKA YASUYUKI	C/O KANSAI PAINT CO.,LTD. OF 17-1, HIGASHIYAWATA 4-CHOME, HIRATSUKA-SHI, KANAGAWA-KEN, 254-0016, JAPAN
2	KAWAGUCHI YOHICHI	C/O KANSAI PAINT CO.,LTD. OF 17-1, HIGASHIYAWATA 4-CHOME, HIRATSUKA-SHI, KANAGAWA-KEN, 254-0016, JAPAN
3	HIGUCHI KAZUNOBU	C/O KANSAI PAINT CO.,LTD. OF 17-1, HIGASHIYAWATA 4-CHOME, HIRATSUKA-SHI, KANAGAWA-KEN, 254-0016, JAPAN
4	TAKAHASHI TERUTAKA	C/O KANSAI PAINT CO.,LTD. OF 17-1, HIGASHIYAWATA 4-CHOME, HIRATSUKA-SHI, KANAGAWA-KEN, 254-0016, JAPAN

PCT International Classification Number

C09D 101/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2005-308944	2005-10-24	Japan
2	2004-316120	2004-10-29	Japan