Powder coatings

Abstract: A powder coating which is specifically useful for the coating of electric appliances, office appliance, and the like and gives coatings giving good stain resistance, comprise (a) a base resin having a reactive functional group, (b) a hardener having in its molecule two or more functional groups which are reactive with the functional group of the base resin, and (c) an acrylic resin derived from monomers containing 40 to 100% by weight of t-butyl acrylate and/or t-butyl methacrylate.

Description: The present invention relates to a powder coating which is excellent in stain resistance and more specifically, it concerns a powder coating which is characterized by containing a particular acrylic resin having, as an essential constituting unit, t-butyl acrylate and/or t-butyl methacrylate, which is excellent in stain resistance and is particularly useful for the coating of electric appliance, office appliance and the like. In the coating of electric appliance, office appliance and the like, powder coating has been widely used. In these areas, coating stain by magic ink and tobacco smoke has often caused serious troubles and there are always big demands to have a powder coating being excellent in stain resistance. In Japanese Patent Publication (unexamined) No. 16778/90, as a measure for improving stain resistance, there discloses a powder coating comprising a hydroxyl group containing polyester resin and blocked isocyanate hardener, added with an acrylic resin containing a particular amount of hydroxyl group and glycidyl group. This technique is, however, only effective for the powder coating based on hydroxyl containing polyester and blocked isocyanate hardener and no improvement in stain resistance can be expected with other type of powder coating. In Japanese Patent Publication (unexamined) No. 178361/90, there discloses a technique wherein particular acrylic resin microparticles defined by glass transition temperature and SP vale and having an average diameter of 0.001 to 10 microns are existed on the surfaces of the respective powder coating particles, thereby improving stain resistance of the formed coating. In this method, a high molecular weight acrylic resin is always locatized on the surface of the applied coating and therefore, this technique is very useful for all of polyester-, epoxy- and acryl- powder coatings and however, in the preparation of powder coating, there needs an additional step of combining acrylic resin microparticles with the mother powder coating, which always push-up manufacturing cost of the powder coating. It is, therefore, an object of the invention to provide a powder coating which is excellent in stain resistance, can be easily and economically obtained by following a conventional way, without changing any steps involved, and by using any combinations of base resin and hardener heretofore proposed. Summary of the invention According to the invention, the abovementioned object can be attained with a powder coating which is excellent in stain resistance, essentially consisting of (a) a base resin having a reactive functional group (b) a hardener having in its molecule 2 or more functional groups which are reactive with the functional group of the base resin, and (c) an acrylic resin, containing 40 to 100 % by weight of the total of the constituting monomers of t-butyl acrylate and/or t-butyl methacrylate. The required amount of the acrylic resin (c) may vary with the type of base resin (a) used. That is, if the base resin (a) is polyester resin or epoxy resin, it should be in a range of 1 to 20 % by weight of the base resin, and if the base resin (a) is acrylic resin, then the amount of said resin (c) should preferably be in a range of 1 to 80 % by weight of the base resin. Thus, in the present invention, any of the heretofore proposed polyester resin, epoxy resin and acrylic resin for powder coating may be satisfactorily used. More specifically, in the case of polyester resin powder coating, one may use a powder coating based on a carboxyl containing polyester resin having a number average molecular weight of 1,000 to 10,000, preferably 1,500 to 8,000, an acid value of 5 to 100 KOH mg/g, and a glass transition temperature of 20 to 100°C, preferably 30 to 80°C, and an epoxy compound or resin having in its molecule 2 or more glycidyl groups; or a hydroxy containing polyester resin having a number average molecular weight of 1,000 to 10,000, preferably 1,500 to 8,000, a hydroxyl value of 5 to 100 KOH mg/g, and a glass transition temperature of 20 to 100°C, preferably 30 to 80°C, and a compound having in its molecule 2 or more isocyanate groups. If the number average molecular weight of the polyester resin is less than 1,000, there is an undesirable decrease in film strength and if it exceeds over the upper limit of 10,000, it is unable to get a coating with the desired excellent appearance because of the deficient flowability of the coating. As to the other requirements of the polyester resin, if the acid value or hydroxyl value is less than 5, there is a tendency of decrease in film strength, and if it exceeds over 100, then the lowering in film flexibility and impact strength due to excessively enhanced hardening. If the glass transition temperature is less than 20°C, there is a great decrease in blocking resistance and if it exceeds over 100°C, a great loss in flowability of coating. However, these requirements are very common to the polyester base powder coating and hence, are not of specific to the present powder coating. As far as the abovementioned requirements are fulfilled, any of the known carboxyl and/or hydroxy bearing polyester resins may be satisfactorily used as a base resin in the present invention. In preparing such polyester resin, the following acids may be used as a polybasic acid component: terephthalic acid, isophthalic acid, phthalic acid, methyl phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyl tetrahydro-phthalic acid, hexahydro-phthalic acid, and their reactive derivatives as anhydride, halide, ester and the like. Examples of polyhydric alcohol used as an alcohol component are ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexane dimethanol, 1,4-cyclohexane diol, neopentyl glycol, isopentyl glycol, bishydroxyethyl terephthalate, hydrogenated bisphenol A, hydrogenated bisphenol A-alkyleneoxide addtion products, trimethylol ethane, trimethylol propane, glycerine, pentaerythrythol and the like. Such reactive material as polyfunctional compound having both acid and hydroxyl groups may also be used as a starting material. If required, fat or fatty acid may be introduced into the polyester resin through ester exchange reaction, addition reaction and the like. The polyester resin may be prepared by using known one-step or poly-steps reaction. Any one skilled in the art may be easily obtained the polyester resin which will fulfil the abovementioned requirements, i.e. the designed Tg value by the selection of the type and amounts of starting materials, and number average molecular weight and acid value by the selection of reaction conditions. As already stated, glycidyl bearing epoxy compound or resin and isocyanate bearing compound may be used as a hardener for the abovementioned polyester resin. Examples of such epoxy compound or resin are reaction product of phenol compound as bisphenol A, phenol novolac and the like and epichlorohydrin; glycidyl ethers obtained by the reaction of an alcohol as ethyleneglycol, propylene glycol, 1,4-butane diol, polyethylene glycol, polypropylene glycol, neopentyl glycol, glycerin and the like and epichlorohydrin; glycidyl esters obtained by the reaction of a carboxylic acid as succinic acid, adipic acid, sebacic acid, phthalic acid, terephthalic acid, hexahydrophthalic acid, trimellitic acid, and the like and epichlorohydrin; reaction product of a hydroxycarboxylic acid as p-oxybenzoic acid, β-oxy naphthoic acid, and the like and epichlorohydrin; triglycidyl isocyanurate and its derivatives. Examples of isocyanate bearing compound are 3-isocyanate methyl-3,5,5-trimethyl-cyclohexyl isocyanate, toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and their derivatives reacted with such alcohol as ethyleneglycol, prolpylene glycol, dipropylene glycol, butylene glycol, trimethylol propane, hexane triol, glycerin, sorbitol and the like; and urethodione containing polyisocyanates as urethodione diisocyanate, urethodione toluylene diisocyanate, urethodione hexamethylene diisocyanate and the like. They are usually employed in the form blocked with a blocking agent as ε-caprolactam, phenol, benzylalcohol, methyl ethyl ketoxime and the like. In this invention, the base resin and the hardener are, as in the conventional powder coating, used in a weight ratio so as to give the functional group ratio of carboxyl group of the polyester resin / glycidyl group of three epoxy compound or resin or hydroxy group of the polyester resin / isocyanate group of the polyisocyanate compound plus isocyanate group derived from the urethodione group of the urethodione bearing polyisocyanate through dissociation, if any, of 0.5 to 2.0 and preferably 0.5 to 1.5. In the case of epoxy powder coating, an epoxy resin having a number average molecular weight of 1,000 to 10,000 and having in its molecule 2 or more glycidyl groups is used in combination with dicyandiamide or organic acid hydrazide, hardener. Examples of epoxy resin having in its molecule 2 or more glycidyl groups are the reaction product of a phenol compound, as bisphenol A and its hydrogenated product, phenol novolac and the like, and epichlorohydrin; the reaction product of a cresol compound, as cresol novolac and the like, and epichlorohydrin and the like. Examples of organic acid hydrazides are adipic acid dihydrazide, sebacic acid dihydrazide,isophthalic acid dihydrazide and the like. The epoxy resin and the hardener are compounded in the functional group ratio of glycidyl of the epoxy resin / active hydrogen of the dicyandiamide or organic acid hydrazide of 0.5 to 2.0, preferably 0.5 to 1.5. This is because, if the ratio is less than 0.5, there is undesired decrease in film hardeness, and if it exceeds over 2.0, there results too excess hardening, resulting the decrease in flexibility, impact strength and the like. Typical exmples of acrylic powder coating are the powder based on an acrylic resin having in its molecule 2 or more glycidyl groups and having a number average molecular weight of 1,000 to 30,000 and a glass transition temperature of 20 to 120°C and a compound and/or resin having in its molecule 2 or more carboxyl groups; the powder based on an acrylic resin having in its molecule 2 or more carboxylic groups and having a number average molecular weight of 1,000 to 30,000, an acid value of 5 to 200 KOH mg/g and a glass transition temperature of 20 to 120°C and an epoxy resin and/or compound having in its molecule 2 or more glycidyl groups; and the powder based on an acrylic resin having in its molecule 2 or more hydroxyl groups and having a number average molecular weight of 1,000 to 30,000, a hydroxyl value of 5 to 200 KOH mg/g and a glass transition temperature of 20 to 120°C and a compound having in its molecule 2 or more isocyanate groups. In the present acrylic powder coating, the heretofore known glycidyl containing-, carboxyl containing- or hydroxyl containing- acrylic resins are satisfactorily used as a base resin. However, such resin should have a number average molecular weight of 1,000 to 30,000, preferably 1,500 to 8,000, and a glass transition temperature of 20 to 120°C and preferably 30 to 80°C. Furthermore, in the case of a glycidyl bearing acrylic resin, it should have 20 to 50 % by weight of glycidyl containing monomer in the total of its constituting monomers, in the case of carboxyl containing acrylic resin, its acid value should be in a range of 5 to 200 KOH mg/g and preferably 20 to 100 KOH mg/g, and in the case of hydroxyl containing acrylic resin, its hydroxyl value should be in a range of 5 to 200 KOH mg/g and preferably 20 to 100 KOH mg/g. This is because, if the number average molecular weight is less than 1,000, there is undesired deficient in film strength, whereas if it exceeds over 30,000, it is unable to obtain a good appearance coating because of insufficient flowability of the coating. If the glass transition temperature is less than 20°C, there is a marked decrease in blocking resistance, and if it exceeds over 120°C, there is a shortage in flowability of the coating. When the glycidyl containing monomer content is less than 20 % by weight, or if the acid value or hydroxyl value is less than 5, there is a marked loss in film strength, whereas if the glycidyl containing monomer content is more than 50 % by weight or is the acid value or hydroxyl value exceeds over 200, there results excessively increased hardening, resulting the decrease in flexibility, impact strength and other properties of the formed coating. As far as the abovementioned requirements are fulfilled, the acrylic resin may be prepared by using any known materials and known methods. Speaking of the starting materials for the acrylic resin, examples of glycidyl containing monomers are glycidyl acrylate, glycidyl methacrylate, methyl glycidyl acrylate, methyl glycidyl methacrylate, glycidyl ether of allyl alcohol, glycidyl ether of methallyl alcohol, methyl glycidyl ether of allyl alcohol, methyl glycidyl ether of methallyl alcohol, N-glycidyl acrylamide, vinyl sulfonic acid glycidyl and the like; examples of carboxyl containing monomers are acrylic acid, methacrylic acidant the like; and examples of hydroxy containing monomers are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxy propyl acrylate, hydroxy propyl methacrylate, hydroxy butyl acrylate, hydroxy butyl methacrylate, allyl alcohol, methallyl alcohol and the like. Other monomers to be co-polymerized with carboxy containing monomer or glycidyl containing monomer are acrylate or methacrylate, and other ethylenically unsaturated monomers. They are used each singularly or in the form of combination of two or more. Examples of such acrylate or methacrylate are methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, 2-ethyloctyl acrylate, dodecyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl mthacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, 2-ethyloctyl methacrylate, dodecyl methacrylate, lauryl methacrylate, benzyl methacrylate, phenyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and the like. Examples of other ethylenically unsaturated monomers are fumaric acid dialkyl esters as diethyl fumarate, dibutyl fumarate and the like; itaconic acid dialkyl esters as diethyl itaconate, dibutyl itaconate and the like; styrene, vinyl toluene, -methyl styrene, acrylonitrile, mathacrylonitrile, acrylamide, methacrylamide, methylol acrylamide, alkoxy methylol amide, vinyl oxazoline, vinyl acetate, vinyl propionate, lauryl vinyl ether and the like. Such fluorine containing monomers as 2,2,2trifluoro acrylate, 2,2,2-trifluoro methacrylate, 1,1,1,3,3,3hexafluoroisopropyl (meth) acrylate and the like, and such reactive silicones as 3-methacryloisooxypropyl dimethoxy methyl silane, 3-methacryloisooxypropyl dimethoxy methyl silane, 3-methacryloisooxypropyl trimethoxy silane and the like may also be used as a specific monomer as desired. Examples of a compound and/or resin having in its molecule 2 or more carboxyl groups used as a hardener are dibasic acids as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecane dicarboxylic acid, 1,20-eicosane dicarboxylic acid, succinic acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid phthalic acid, isphthalic acid, hexhydrophthaqlic acid, cyclohexene 1,2-dicarboxylic acid and the like; and polyvalent carboxylic acids as trimellitic acid, and the like. They may be polycarboxylic anhydrides as succinic anhydride, sebacic anhydride, phthalic anhydride, itaconic anhydride, trimellitic anhydride and the like, and may also be polyester resin having in its molecule 2 or more carboxyl groups and the like. Examples of an epoxy compound or resin having in its molecule 2 or more glycidyl groups or a compound having in its molecule 2 or more isocyanate groups are the hereinbefore stated members

Claims: A powder coating comprising: (a) a base resin having a reactive functional group; (b) a hardener having in its molecule two or more functional groups which are reactive with the functional group of the base resin; and (c) an acrylic resin, derived from monomers containing 40 to 100% by weight of t-butyl acrylate and/or t-butyl methacrylate. A powder coating according to claim 1, wherein the base resin (a) is a polyester having carboxyl and/or hydroxyl groups, the hardener (b) is a compound and/or a resin having in its molecule two or more glycidyl groups or isocyanate groups, and the acrylic resin (c) is present in an amount of from 1 to 20% by weight based on the weight of the base resin (a). A powder coating according to claim 1, wherein the base resin (a) is an epoxy resin having a glycidyl group, the hardener (b) is a compound having in its molecule two or more active hydrogen-containing groups, and the acrylic resin (c) is present in an amount of from 1 to 20% by weight based on the weight of the base resin (a). A powder coating according to claim 3, wherein the hardener (b) is dicyandiamide or an organic acid hydroxide. A powder coating according to claim 1, wherein the base resin (a) is an acrylic resin having an epoxy group, carboxyl group or hydroxyl group, the hardener (b) is a compound having in its molecule two or more carboxyl group, epoxy groups or isocyanate groups, and the acrylic resin (c) is present in an amount of from 1 to 80% by weight based on the weight of the base resin (a).

Inventors: TCHIMURA HIDEKI, TOYODA YUJI, TSUTSUI KOICHI, UENAKA AKIMITSU, UNENO TASABURO, TCHIMURA, HIDEKI, TOYODA, YUJI, TSUTSUI, KOICHI, UENAKA, AKIMITSU, UNENO, TASABURO
Applicants: NIPPON PAINT CO LTD, NIPPON PAINT CO., LTD.
Application year: 1992
Main classification: C09D167
IPC codes: C09D4, C08L67, C08G59, C09D133, C09D175, C09D5, C09D163, C08F299, C08L63, C08F290, C09D167