Aqueous coating composition

Abstract: Disclosed is an aqueous coating composition which keeps in high nonvolatile contents during coating operation and capable of being effectively applied even under a relatively high humidity condition. The coating composition imparts high orientation of metallic pigment particles to the cured film. The aqueous coating composition of the present invention comprises a specific acryl polymer varnish (a) and a specific urethane oligomer dispersion.

Description: FIELD OF THE INVENTION The present invention relates to an aqueous coating composition which has good application properties and, when cured, had good surface appearance. In particularly, it relates to an aqueous metallic coating composition which, when coated and cured, has superior orientation of aluminum pigment. BACKGROUND OF THE INVENTION The paint layer of motorcars is generally composed of three layers, i.e. an undercoat layer, an intermediatecoat layer and an overcoat layer. The overcoat layer is formed by coating a metallic base paint containing a metallic pigment on an intermediatecoated plate and then coating a clear paint thereon without baking or curing the metallic base coating (i.e. by so-called "wet-on-wet" method), followed by baking or curing the metallic base coating and clear coating (i.e. by so-called "two coat one bake" method). The metallic base paint used in this method can exhibit excellent surface appearance in case where flake-like metallic pigment, such as aluminum pigment, is uniformly orientated therein. Japanese Kokai Publication 58-168664 discloses an aqueous paint which contains an aqueous polyurethane dispersant. However, a problem has occurred in surface appearance because the metallic pigment is not uniformly orientated. Japanese Kokai Publication 1-287183 discloses an aqueous metallic base paint which contains an acrylic emulsion, a urethane emulsion and a cross-linking agent. Since the paint is an aqueous dispersion, environmental pollution problems do not come about in comparison with solvent type paint, but a problem often occurs in orientation or a metallic pigment and a surface appearance is not always satisfactory. SUMMARY OF THE INVENTION The present inventors already proposed an aqueous metallic coating composition using an amide group-containing aqueous acrylic resin. An improvement has been made on the proposed coating composition and the present invention provides an aqueous coating composition which keeps in high nonvolatile contents during coating operation and capable of being effectively applied even under a relatively high humidity condition. Of course, the coating composition imparts high orientation of metallic pigment particles to the cured film. The aqueous coating composition of the present invention comprises; (a) an aqueous varnish of a film-forming polymer having a number average molecular weight of 6,000 to 50,000, prepared by copolymerizing 5 to 40 % by weight of amide group-containing ethylenic monomers, 3 to 15 % by weight of acidic group-containing ethylenic monomers, 10 to 40 % by weight of hydroxyl group-containing ethylenic monomers and the balance of the other ethylenic monomers, and a portion of the acid groups is neutralized, (b) an aqueous dispersion of a urethane oligomer in an aqueous medium containing a primary and/or secondary polyamine, prepared by reacting hydroxyl-terminated diol compounds having a molecular weight of 100 to 5,000, diisocyanate compounds and active-hydrogen containing hydrophilic compounds under isocyanate-rich conditions, followed by dispersing the reaction product in the aqueous medium; the polymer varnish (a) being present in an amount of 95 to 10 wt % (solid) and the oligomer dispersion being present in an amount of 5 to 90 wt % (solid) in the composition. DETAILED DESCRIPTION OF THE INVENTION The amide group-containing ethylenic monomers used for obtaining said film-forming polymer (a) according to the present invention are generally (meth)acrylamides. Examples of the (meth)acrylamides are acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-dibutylacrylamide, N, N-dibutylmethacrylamide, N, N-dioctylacrylamide, N, M-dioctylmethacrylamide, N-monobutylacrylamide, N-monobutylmethacrylamide, N-monooctylacrylamide, N-monooctylmethacrylamide and the like. Acrylamide or methacrylamide is preferably used. The acid groups of the acid group-containing ethylenic monomers include a carboxylic group and a sulfonic group. Carboxylic group-containing monomers include styrene derivatives (for example, 3-vinylsalicylic acid, 3-vinylacetylsalicylic acid and the like); and (meth)acrylic acid derivatives (for example, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid and the like). In addition, sulfonic group-containing ethylenic monomers include p-vinylbenzenesulfonic acid, 2-acrylamide-propanesulfonic acid and the like. The acid group-containing ethylenic monomers may be diesters, such as half esters, half amides and half thioesters. The monomers include half esters, half amides and half thioesters of maleic acid, fumaric acid and itaconic acid. Alcohols for forming the half esters have 1 to 12 carbon atoms and include methanol, ethanol, propanol, butanol, methyl cellosolve, ethyl cellosolve, dimethylamino ethanol, diethylamino ethanol, acetol, allyl alcohol, propargyl alcohol and the like. Preferred are butanol, dimethylamino ethanol, dimethylamino ethanol, acetol, allyl alcohol and propagyl alcohol. Mercaptanes for forming half thioesters have 1 to 12 carbon atoms and include ethyl mercaptane, propyl mercaptane, butyl mercaptane and the like. Amines for forming half amides have 1 to 12 carbon atoms and include ethylamine, diethylamine, butylamine, dibutylamine, cyclohexylamine, aniline, naphthylamine and the like. Among them, half thioesters have a little problem in odor and half esters and half amides are preferably used. Reactions, such as half esterification, half thioesterification and half amidization, are carried out at temperatures of room temperature to 120°C according to the usual methods and with tertiary amines as a catalyst under certain circumstances. The hydroxylic group-containing ethylenic monomers include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,4-dihydroxy-4'-vinyl benzophenone, N-(2-hydroxyethyl) acrylamide, N-(2-hydroxyethyl) methacrylamide and the like. The film-forming polymers according to the present invention are obtained by copolymerizing the above described monomers with other ethylenic monomers by the known methods. The other ethylenic monomers include styrene, alpha-methylstyrene, acrylic esters (e.g. methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate), methacrylic esters (e.g. methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate and p-butyl methacrylate) and the like. The amide group-containing ethylenic monomers used for the preparation of the film-forming polymers are used in a quantity of 5 to 40 % by weight, preferably 8 to 30 % by weight. If they are used in a quantity less than 5 % by weight, a disadvantage occurs in that flake-like metallic pigments have poor orientation and thus a surface appearance is poor while if they are used in a quantity exceeding 40 % by weight, the obtained film has poor water resistance. The acid group-containing ethylenic monomers are used in a quantity of 3 to 15 % by weight, preferably 5 to 13 % by weight. If they are used in a quantity less than 3 % by weight, an aqueous dispersibility is deteriorated while if they are used in a quantity exceeding 15 % by weight, the film is deteriorated in water resistance. The hydroxylic group-containing ethylenic monomers are used in a quantity of 10 to 40 % by weight, preferably 13 to 30 % by weight. If they are used in a quantity less than 10 % by weight, the film is deteriorated in curing ability while if they are used in a quantity exceeding 40 % by weight, the film is deteriorated in water resistance. The obtained polymers have a number average molecular weight of 6,000 to 50, 000, preferably 8,000 to 30,000. If it is less than 6,000, they are insufficient in operating ability and curing ability while if it exceeds 50, 000, a nonvolatile content during coating is excessively reduced and thus a workability is deteriorated. In addition, a molecular weight was measured by the GPC method. The hydroxyl-terminated diol compounds have a molecular weight of 100 to 5,000, which are used for the preparation of said aqueous dispersion (b) according to the present invention, are typically polyether diols or polyester diols. The compounds include polymers or copolymers of alkylene oxides (ethylene oxide, propylene oxide, methylene oxide and the like) and/or heterocyclic ethers (tetrahydrofuran and the like). Typical examples of the compounds are polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and polyoctamethylene ether glycol; polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, poly-3-methylpentyl adipate, polyethylene-butylene adipate and polyneopentyl-hexyl adipate; polylactone diol, for example polycarprolactone diol and poly-3-methylvalerolactone diol; polycarbonate diol; and mixtures thereof. Preferred is polycarbonate diol, in view of water resistance and adhesive properties of the cured film. The diisocyanate compounds used in the present invention include aliphatic diisocyanates, for example hexamethylene diisocyanate, 2, 2, 4-trimethylhexane diisocyanate and lysine diisocyanate; alicyclic diisocyanates having 4 to 18 carbon atoms, for example 1, 4-cyclohexane diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5-trimethylcyclohexane (isophoron diisocyanate), 4, 4'-dicyclohexylmethane diisocyanate, methylcyclohexylene diisocyanate and isopropylidenecyclohexyl-4, 4'-diisocyanate; modified compounds of the diisocyanates; and mixtures thereof. Preferred are hexamethylene diisocyanate, isophoron diisocyanate. The active-hydrogen containing hydrophilic compounds are compounds which have at least one active hydrogen (e.g. a hydroxyl group) in a molecule and having a hydrophilic group (e.g. a carboxylic group) and includes dimethylolacetic acid, dimethylolpropionc acid, dimethylolbutyric acid and the like. Preferred are dimethylolpropionic acid. In case of the preparation of the hydrophilic group-containing oligomers according to the present invention, a reaction is conducted under isocyanate-rich conditions, for example at NCO/OH equivalent ratio within a range of 1.1 to 1.9. The reaction easily occurs by mixing all compounds. The reaction may be conducted in a solvent if necessary. The obtained hydrophilic group-containing oligomers are dispersed in an aqueous medium which contains the primary and/or secondary polyamine. In this dispersing process, the hydrophilic group in the hydrophilic group-containing oligomers is neutralized. Examples of the polyamines are (ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, isophoronediamine, propane-2,2-cyclohexylamine, N,N-dimethyl-o-phenylenediamine, N,N'-dimethyl-o-phenylenediamine, N,N'-di-p-tolyl-m-phenylenediamine, p-aminodiphenylamine, hydradine, substituted hydradine (e.g. dimethylhydradine and 1,6-hexamethylenebis-hydradine), N-beta-aminoethylethanolamine and the like. The aqueous coating composition of the present invention can be used for any type coating usages, but usually is used for a thermosettig aqueous coating composition in combination with a curing agent. The curing agent is generally a melamine resin. The melamine resin is preferably a water-soluble melamine resin, including Cymel-303 available from Mitsui Toatsu Chemicals Inc. and Sumimal N-W available from Sumitomo Chemical Co. Ltd. and the like but it is not specially limited by them. Also a water-insoluble melamine resin can be used. The melamine resin is used in a quantity of 5 to 60 % by weight based on the film-forming polymer (a) (as measured in solid content). If the melamine resin is used in an excessive small quantity, curing ability is insufficient, while, if it is used in an excessive large quantity, the cured film is too hard and thus fragile. The aqueous coating composition of the present invention may usually contain metallic pigments (for example aluminum pigments, bronze pigments, mica, gold pigments and silver pigments). The metallic pigments are added in a quantity of 2 to 100 parts by weight based on 100 parts by weight (solid) of the aqueous coating composition. In addition, various kinds of additives (for example an ultraviolet inhibitor, an anti-foamant and a surface-regulating agent) and usual inorganic pigments may be added in the aqueous coating composition according to the present invention. The aqueous metallic coating composition of the present invention is remarkably superior in orientation of metal flakes and superior in surface appearance of the obtained film. In addition, nonvolatile contents are high during coating operation and the aqueous metallic paint is superior in also applicability. EXAMPLES The present invention will be below described in more detail with reference to the preferred Examples. However, the present invention is not limited by these Examples. Production of film-forming polymer (a) Production Example 1 Ethylene glycol monobutyl ether of 76 parts by weight was charged in a reaction vessel having a capacity of 1 liter, equipped with with a stirrer, a temperature regulator and a condenser, and then 61 parts by weight of a monomer solution, which comprised 15 parts by weight of styrene, 63 parts by weight of methyl methacrylate, 48 parts by weight of 2-hydroxydiethyl methacrylate, 117 parts by weight of n-butyl acrylate, 27 parts by weight of methacrylic acid, 30 parts by weight of acrylamide and 3 parts by weight of azobisisobutylonitrile, was added thereto and heated to 120°C with stirring. Then, the remaining 245 parts by weight of the monomer solution was added for 3 hours and the resulting mixture was stirred for 1 hour. Further, 28 parts by weight of dimethylethanolamine and 200 parts by weight of deionized water were added to the resulting mixture to obtain an acrylic resin varnish having nonvolatile content of 50 %, and the acrylic resin had a number average molecular weight of 12,000. This resin is characterized in that its OH value is 70 and its acid value is 58. Production Example 2 A 3 liter reaction vessel, equipped with a nitrogen gas introducing tube, a temperature controller, a dropping funnel, a stirrer and a decanter, was charged with 500 parts by weight of 2-ethoxy propanol, and heated to 100 °C. A solution of 50 parts by weight of styrene, 50 parts by weight of methyl methacrylate, 200 parts by weight of 2-hydroxyethyl methacrylate, 120 parts by weight of 2-ethylhexyl methacrylate, 380 parts by weight of butyl acrylate, a solution of 100 parts by weight of monobutyl maleate and 300 parts by weight of methanol, 100 parts by weight of acrylamide and 30 parts by weight of azobisisobutylonitrile was added thereto through the dropping funnel. The addition was conducted for 3 hours with removing methanol with the decanter at 100 °C. The resulting mixture was stirred for further 30 minutes and then a solution comprising 50 parts by weight of butyl acetate and 3 parts by weight of t-butylperoxy-2-ethylhexanoate was added dropwise to it for 0.5 hours. Subsequently, the resulting mixture was held at 100°C for further 1.5 hours to distill off 300 parts by weight of methanol, followed by distilling off 200 parts by weight of the solvent under a reduced pressure. Further, 100 g of dimethylethanolamine and 570 g of deionized water were added to the resulting solution to obtain a transparent and viscous acrylic resin water-solubilized varnish having a nonvolatile content of 50 % and a number average molecular weight of 10,000. Production of urethane-containing aqueous dispersion (b) Production Example 3 Synthesis of hydrophilic group-containing oligomers A 5 liter reaction vessel, equipped with a thermometer, a stirrer, a condenser and a dropping funnel, was charged with 40.2 parts by weight of dimethylolpropionic acid, 30 parts by weight of triethylamine and 312 parts by weight of N-methylpyrrolidone and heated to 90 °C to be dissolved. Then, 290 parts by weight of isophorone diisocyanate and 700 parts by weight of polypropylene glycol (having a molecular weight of 1,000) were added to the resulting solution and stirred for 10 minutes, followed by adding 1.03 parts by weight of dibutyltin dilaurate. Subsequently, the resulting mixture was heated to 95 °C to react 1 hour. Preparation of aqueous dispersion A 5 liter reaction vessel, equipped with a thermometer, a stirrer, a condenser and a dropping funnel, was charged with 1,750 parts by weight of deionized water and 9.2 parts by weight of hydrazine hydrate and then the above obtained solution of urethane prepolymer was added with stirring. Subsequently, the resulting mixture was stirred for 30 minutes. The obtained composition was cloudy and stable aqueous dispersion, and had an acid value of 16.2 and a nonvolatile content of 33 %. Production Example 4 Synthesis of hydrophilic group-containing oligomers The same reaction vessel as Production Example 3 was charged with 40.2 parts by weight of dimethylolpropionic acid, 30 parts by weight of triethylamine and 402 parts by weight of N-methylpyrrolidone and heated to 90 °C to be dissolved. Then, 290 parts by weight of isophorone diisocyanate and 600 parts by weight of polypropylene glycol (having a molecular weight of 2,000) were added to the resulting solution and stirred for 10 minutes, followed by adding 1.3 parts by weight of dibutyltin dilaurate. Subsequently, the resulting mixture was heated to 95 °C to react 1 hour. Preparation of aqueous dispersion The same reaction vessel as Production Example 3 was charged with 2,293 parts by weight of deionized water and 11.5 parts by weight of hydrazine hydrate and then the above obtained solution of urethane prepolymer was added with stirring. Subsequently, the resulting mixture was stirred for 30 minutes. The obtained composition was cloudy and stable aqueous dispersion, and had an acid value of 12.5 and a nonvolatile content of 33 %. Production Example 5 A hydrophilic oligomer was prepared as generally described in Production Example 3, with the exception that polycarbonate diol having a number average molecular weight of 1,000 (available from Daicel Chemical Co., Ltd. as PLACCEL CD-211PL) was employed instead of polypropylene glycol. An aqueous dispersion also was also prepared as generally described in Production Example 3 to obtain urethan polymer dispersion having a nonvolatile content of 33 % and an acid value of 16.0. Preparation of clear paint Production Example 6 A clear paint gas prepared by mixing the following ingredients in a stainless vessel. Production Example 7 A clear paint was prepared by mixing the following ingredients in a stainless vessel. Ingredients Parts by weight Varnish 100 Desmodule N-75 16.7 Production Example 8 A clear paint was prepared by mixing the following ingredients in a stainless vessel and diluting with a thinner of butyl acetate/xylene = 1/1. Production Example 9 A clear paint was prepared by mixing the following ingredients in a stainless vessel and diluting with a thinner of butyl acetate/xylene = 1/1. Ingredients Parts by weight (g) Compound having carboxylic anhydride ⁵ 130 Oxazolidine compound 13 Compound having an alkoxysilyl ⁷ 65 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate 7 Tinubin 900 1.5 Irukanox 1010 1.0 Production Example 10 A one liter reaction vessel, equipped with a stirrer, a temperature controller and a condenser, was charged with 40 parts by weight of ethoxy propanol. To the content, 121.7 parts by weight of a monomer solution, which contained 4 parts by weight of sytrene, 35.96 parts by weight of n-butyl acrylate, 18.45 parts by weight of ethylhexyl methacrylate, 13.92 parts by weight of 2-hydroxyethyl methacrylate, 7.67 parts by weight of methacrylic acid, 40 parts by weight of a solution of 20 parts by weight of ethoxyl propanol and 20 parts by weight of acidphosphoxy(oxypropylene) monomethacryalte, and 1.7 parts by weight of azobisisobutylonitrile, was added dropwise for 3 hours and then mixed for another one hour. The resultant acryl resin had an acid value of 105, OH value of 60, a number average molecular weight of 6,000 and a nonvolatile content of 63 %. Preparation of aqueous coating composition Example 1 Fifteen parts by weight of an aluminum pigment paste (65 % aluminum content available from Toyo Aluminum Co., Ltd. as Alpaste 7160N) was uniformly mixed with 30 parts by weight of Cymel 303 (methoxylated methylol melamine available from Mitsui Toatsu Chemicals Inc.), with which 2 parts by weight of isostearyl acidphosphate (available from Sakai Chemical Co., Ltd. as Phophorex A-180L) was mixed to obtain an aluminum pigment solution. It is mixed with 112 parts by weight of the film-forming polymer of Production Example 1 and then mixed with 43 parts by weight of the urethane emulsion of Production Example 3 to obtain an aqueous metallic paint. Examples 2 and 3 Aqueous metallic paints were obtained from the respective ingredients shown in Table 1 in the same manner as in Example 1. Examples 4, 5 and 6 Cymel 303 (methoxy methylol melamine made by Mitsui Toatsu KK) of 30 parts by weight was added to an aluminum pigment paste (Alpaste 7160 N containing metallic aluminum in a quantity of 65 % made by Toyo Aluminum KK) of 15 parts by weight and the acrylic varnish obtained according to Production Example 10 of 4 parts by weight was added to the resulting mixture followed by uniformly mixing the resulting mixture. Subsequently, isostearil acid phosphate (Phosrex A-180L made by Sakai Kagaku KK) of 2 parts by weight was added to the resulting uniform mixture followed by uniformly mixing the resulting mixture to obtain an aluminum pigment solution. Then, aqueous metallic paints were obtained from the respective ingredients shown in Table 1 in the same manner as in Example 1. Comparative Example 1 Production of the Resin for the Aqueous Metallic Paint An aqueous metallic paint was produced in the same manner as in Production Example 1 excepting that 45 parts by weight of styrene was used and acrylic amide was not used. Preparation of the Comparative Aqueous Metallic Paint An aqueous metallic paint was prepared in the same manner as in Example 1 excepting that the above described resin was used in place of the film-forming polymer produced according to Production Example 1. Comparative Example 2 An aqueous metallic paint was produced by uniformly dispersing the aluminum pigment solution in the film-forming polymer obtained according to Production Example 1 of 140 parts by weight in the same manner as in Example 1. Evaluation of coatings Tests 1 to 10 A polished mild steel plate was subjected to a degrease and chemical treatment, and then coated with an electrodeposition paint in an intermediate coating line to obtain an intermediate coated steel panel. It was then coated with the aqueous metallic paint as shown in Table 2, and then coated with the clear paint as shown in Table 2. The metallic paint was spray-coated at 23 °C and relative humidity of 85 % so as to obtain a 20 micron layer, and the clear paint was also spray-coated at the same condition so as to obtain a 30 micron layer. The metallic paint was coated two stages with one minute interval and then preheated at 80 °C for 5 minutes. Then, the clear paint was coated one stage and subjected to a setting for 7 minutes. The coated panel was baked at 140 °C for 30 minutes and subjected to evaluations of adhesive properties and water resistance.

Claims: An aqueous coating composition comprising; (a) an aqueous varnish of a film-forming polymer having a number average molecular weight of 6,000 to 50,000, prepared by copolymerizing 5 to 40 % by weight of amide group-containing ethylenic monomers, 3 to 15 % by weight of acidic group-containing ethylenic monomers, 10 to 40 % by weight of hydroxyl group-containing ethylenic monomers and the balance of the other ethylenic monomers, and a portion of the acid groups is neutralized, (b) an aqueous dispersion of a urethane oligomer in an aqueous medium containing a primary and/or secondary polyamine, prepared by reacting hydroxyl-terminated diol compounds having a molecular weight of 100 to 5,000, diisocyanate compounds and active-hydrogen containing hydrophilic compounds under isocyanate-rich conditions, followed by dispersing the reaction product in the aqueous medium; said polymer varnish (a) being present in an amount of 95 to 10 wt % (solid) and the oligomer dispersion being present in an amount of 5 to 90 wt % (solid) in said composition. The aqueous coating composition according to Claim 1 wherein said amide group-containing ethylenic monomers are (meth)acrylamides. The aqueous coating composition according to claim 1 or 2 wherein said acid group-containing ethylenic monomers are selected from salicylic acid derivatives, (meth)acrylic acid, p-vinylbenzenesulfonic acid, 2-acrylamide-propane-sulfonic acid, half esters, half amides and half thioesters. The aqueous coating composition according to any one of the claims 1 to 3 wherein said hydroxylic group-containing ethylenic monomers are selected from 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methycrylate, 2-hydroxypropyl methacrylate, 2,4-dihydroxy-4'-vinyl benzophenone, N-(2-hydroxyethyl) acrylamide and N-(2-hydroxyethyl) methacryl-amide. The aqueous coating composition according to any one of the claims 1 to 4 wherein said hydroxyl-terminated diol compounds are polyether diols or polyester diols. The aqueous coating composition according to any one of the claims 1 to 5 wherein said hydroxyl-terminated diol compounds comprise polycarbonate diols. The aqueous coating composition according to any one of the claims 1 to 6 wherein said diisocyanate compounds are selected from aliphatic diisocyanates or alicyclic diisocyanates having 4 to 18 carbon atoms. The aqueous coating composition according to any one of the claims 1 to 7 wherein said active-hydrogen containing hydrophilic compounds are selected from dimethylolacetic acid, dimethylolpropionic acid and dimethylolbutyric acid. The aqueous coating composition according to any one of the claims 1 to 8 wherein said isocyanate-rich conditions are within the range of NCO/OH equivalent ratio of 1.1 to 1.9. The aqueous coating composition according to any one of the claims 1 to 9 further comprising a metallic pigment and a curing agent. The aqueous coating composition according to claim 10 wherein said metallic pigment is aluminium pigment and said curing agent is melamine resin.

Inventors: KONISHI SAKUICHI, KUWAJIMA TERUAKI, UMEDA SHINICHIRO, KONISHI, SAKUICHI, KUWAJIMA, TERUAKI, UMEDA, SHINICHIRO
Applicants: NIPPON PAINT CO LTD, NIPPON PAINT CO., LTD.
Application year: 1991
Main classification: C09D175
IPC codes: C08G18, C09D5, C09J151, C09D133, C09D175, C08L75