TW201209113A - Contamination resistant coating composition with excellent durability - Google Patents

Abstract

Disclosed is a contamination resistant coating composition capable of forming a coating film, especially a coating film with medium or less gloss due to a matting agent, etc., having excellent retention properties with respect to contamination resistance against rainwater, etc. as well as corrosion resistance, in particular, a contamination resistant coating composition suitable for forming a top-coating film on a coated metal sheet. The coating composition comprises a specific organosilicate and/or a condensate component thereof in a resin binder containing a polyester resin component having a specific fatty acid modified polyester resin and a melamine resin component having a butyl etherified melamine resin.

Description

201209113 VI. Description of the Invention: [Description of the present invention relates to a composition of a pollution-resistant coating which can form a coating film which is excellent in maintaining weather resistance and the like against rainwater and the like. And the present invention particularly relates to a method for forming a coating composition suitable for coating a coating film on a coated metal sheet, a coating film excellent in rainwater stain resistance using the pollution-resistant coating composition, and A coating metal plate formed by forming a hardened coating film with a stain-resistant coating composition. C]1 Background Art Up to now, on exterior substrates (e.g., structures, displays, fences, utensils, machinery, etc.), exterior coatings having excellent weather resistance have been applied for the purpose of decoration or protection. Examples of the coating material used for the exterior use include a polyurethane resin coating material, a fluororesin coating material, an anthraquinone resin coating material, an acrylic resin coating material, and a polyester coating material, but the coating materials may be used. Exposure to the outside of the house will cause the surface of the coated object to be easily soiled due to the influence of dust, iron powder, rain (acid rain), sun light, etc., and will have the disadvantage of reducing the appearance of the film. In order to solve this problem, the present applicant has proposed an upper coating composition excellent in stain resistance, which is a coating composition (1) containing an organic solvent (which is a fluorine-containing resin and an amine-based resin). The binder is contained as a reaction-hardening organic resin or a coating composition containing an organic solvent (2) (which is a mixture of a fluororesin containing a radical and/or a hydroxyl-containing acrylic resin with a (block) 201209113 a cyanic acid vinegar compound cross-linking agent as a reaction-hardening organic resin), a coating composition obtained by blending a tetrakis-based phthalic acid ester and/or a condensate thereof, and characterized in that the surface of the coating film is treated with water after acid treatment The contact angle is 7 degrees or less (refer to Patent Document 1, International Publication WO 94/06870). However, in the case of the coating composition of Patent Document 1, when it is used outdoors, it is insufficient in the retention of the pollution of rain, streaks, dirt, rainwater, etc., and even in the initial stage, it is resistant to rain and the like. Not enough. In addition, as a coating composition for precoated steel sheets which is excellent in stain resistance, workability, and appearance of a coating film, it has a weight ratio of (A) a hydroxyl value of 5 to 300 and a number average molecular weight of ~2_0. A proposal of a thermosetting resin composition comprising an alcohol resin, (8) an amine resin, (C) an aerobic furnace, and a curing catalyst (D) (see Patent Document 2). However, when the thermosetting resin composition is obtained, the core of the (4) and long-term rain streak contamination is good when it is made into a glossy (four), but it is made into a forging surface (satin) by adding a matting agent or the like. luster. In the following), Wei Shimu's genus 'Cai (4)/// or so [Patent Document 丨] International Publication W094/06870 [Patent Document 2] Japanese Patent Special Open 忉 忉 号 公报 【 赛 赛 内容 内容 内容 内容 内容DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The present invention provides a pollution-resistant coating composition which can form a coating film which is excellent in retaining property against rain pollution and the like, and is particularly suitable for forming a coating composition. A stain-resistant coating composition of a coating film on a satin-coated metallic sheet. Means for Solving the Problems The inventors of the present invention have repeatedly studied the above problems in order to solve the above-mentioned problems, and as a result, have found that a polyester resin component (which contains a specific fatty acid-modified polystyrene resin) and a melamine resin component (which contains a butyl group) have been found. The resin binder of the etherified melamine tree includes a coating composition of a specific organic phthalate and/or a condensate component thereof, particularly in a coating film having a gloss of 60 or less gloss (about 60 or less). The present invention can be completed by forming a coating film excellent in retainability against rain or the like. That is, the present invention includes the following inventions: Item 1: A pollution-resistant coating composition comprising: '(A) a polyester resin containing 50 to 100% by mass of an average molecular weight of 5000 to 30000, a hydroxyl value of 5~ l 〇〇mgKOH/g, a fatty acid-modified polyester resin (A1) having an oil length of 3 to 30% as a solid component, and the fatty acid-modified polyester resin (A1) is reacted by the following (al) to (a3) And a. (al): a polybasic acid containing an alicyclic polybasic acid (al-Ι); (a2): an alcohol containing a trihydric or higher polyhydric alcohol (a2-l); and (a3): a fatty acid; In the reaction, the content of the alicyclic polybasic acid (al-1) in the polybasic acid (al) is in the range of 50 to 100 mol% based on the total amount of the polybasic acid (al); and the alcohol (a2) Based on the total amount, the content of the ternary or higher polyol 201209113 (a2-l) in the alcohol (a2) is in the range of 10 to 70 mol / 〇; (B) the melamine resin contains 50 to 100% by mass. a butyl etherified melamine resin (B1) as a solid component; and (C) an organic phthalic acid ester and/or a condensate thereof, represented by the following formula: General formula: (Rjn-SHOR2)^ [wherein, R1 Can also be epoxy or a substituted alkyl group having 1 to 18 carbon atoms or a phenyl group, R 2 is an alkyl group having 1 to 6 carbon atoms, and η is 0 or 1]; wherein, the total solid content of the (Α) component and the (Β) component The solid content of the component (C) is 0. 〗 〜 50% by mass. Item 2: The pollution-resistant coating composition according to the item 1, wherein, in the reaction for obtaining the fatty acid-modified polyester resin (Α1), the polybasic acid component is based on the total amount of the polybasic acid component (al) The total content of the alicyclic polybasic acid (al-1) in (al) is in the range of 85 to 100 mol%. Item 3: The pollution-resistant coating composition according to the first or second aspect, wherein the total content of the solid content of the polyester resin component (A) and the melamine resin component (B) is 50 to 90. The polyester resin component (A) having a mass % is a solid component, and contains 10 to 50% by mass of the melamine resin component (B) as a solid component. The pollution-resistant coating composition according to any one of the items 1 to 3, wherein at least one of the alicyclic polybasic acids (al-Ι) is selected from the group consisting of: 1 , 2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, M-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 3-methyl-1 , 2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid and 1,3,5-cyclohexanetricarboxylic acid An acid alicyclic polycarboxylic acid, an acid of the alicyclic polycarboxylic acid 201209113 - an anhydride and a lower alkyl ester of the alicyclic polycarboxylic acid. The pollution-resistant coating composition according to any one of the items 1 to 4, wherein the trivalent or higher polyhydric alcohol (a2-l) is at least one selected from the group consisting of: Glycerin, trimethylolethane, trihydroxydecylpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, neopentyltetraol, dipentaerythritol, sorbitol, and mannitol a trihydric or higher alcohol; a polylactone polyol compound in which a lactone compound is added to the trihydric or higher alcohol; and a hydroxyalkyltrimeric isocyanate. The pollution-resistant coating composition according to any one of the items 1 to 5, wherein the fatty acid (a3) is at least one selected from the group consisting of the following: Coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, pine oil fatty acid, 'soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor seed oil fatty acid, dehydration I Hemp seed oil fatty acid, sunflower oil fatty acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and linoleic acid. Item 7: The pollution-resistant coating composition according to any one of items 1 to 6, further comprising a matting agent (D). Item 8: The pollution-resistant coating composition according to Item 7, wherein the matting agent (D) is contained in an amount of 0.1 to 30% by mass based on the total solid content of the polyester resin (Α) and the melamine resin (Β). As a solid component. Item 9: A method of forming a coating film, comprising: a step of forming a primer coating film on a one-sided or two-sided side of a metal plate with a chrome-free primer coating; and 201209113 in the aforementioned formed bottom In at least one of the paint films, the step of forming the upper coat film is carried out by the composition of the pollution-resistant paint of the first application of the patent application. Item 10: A method of manufacturing a coated metal sheet, comprising: a step of forming a primer coating film on a one-sided or two-sided surface of a metal plate with a chrome-free primer coating; and forming the foregoing In at least one of the primer coating films, the step of forming the upper coating film is carried out by using the pollution-resistant coating composition of claim 1 of the patent application. Item 11: A coated metal sheet obtained by the method as recited in Item 9 or 10. Advantageous Effects of Invention The stain-resistant coating composition of the present invention contains a specific resin binder containing a polyester resin component containing a specific fatty acid-modified polyester resin and a melamine resin component containing a butyl etherified melamine resin. A coating composition of an organic phthalic acid ester and/or a condensate thereof, and the composition of the coating material, particularly in a coating film having a gloss below the satin surface (60° gloss of about 50 or less), can form a resistance to rainwater or the like. A coating film excellent in contamination retention. Further, since the specific fatty acid-modified polyester resin having a required component is an alicyclic polybasic acid in a polybasic acid component of 50 mol/min or more, the weather resistance and hydrolysis resistance are good, and the fatty acid modified portion is usually The adsorption of the pigment component used in the composition of the pollution-resistant coating is related. The coating film obtained by the composition of the antifouling coating of the present invention, in particular, when a coating film having a gloss of satin or less is formed, it is possible to form a coating film having excellent stain resistance with respect to rainwater or the like, although still It is unclear, but it is presumed that 201209113 is as follows: It is presumed that the amount of the base resin which is the composition of the pollution-resistant coating of the present invention is a fatty acid-modified polyester resin which is a polybasic acid component which has a good weather resistance and good hydrolysis property. Further, it also has an adsorption-removing portion of the pigment component, and thus also exhibits a deterioration suppressing effect on the pigment component. By using a matting agent or the like as a coating film having a gloss below the forging surface, since the surface shape has a convex and concave shape to make the water wet better than the glossy coating film, and the hydrolysis resistance is exposed to a more severe condition. In the case of the quaternary coating system, the deterioration of the surface of the coating (pulverization, etc.) is accelerated, and it is likely to become an appearance state with poor appearance. On the other hand, the coating film obtained by the composition of the pollution-resistant coating material of the present invention is presumed to have excellent hydrolysis resistance and can suppress deterioration of the pigment component, so that it can exhibit excellent appearance and pollution resistance compared to the conventional polyester coating system. Sexuality. C embodiment; j embossed paint composition for carrying out the invention The pollution-resistant paint composition of the present invention comprises the following polyester resin component (A), melamine resin component (B) and organic phthalate and/or Or a coating composition of the condensate component (C). (A) Polyester Resin Component In the coating composition of the present invention, the polyester resin component (A) is contained in an amount of 50 to 1% by mass based on the total amount of the solid content of the polyester resin component (A) 201209113 The fatty acid-modified polyester resin (A1) is referred to as a solid component. (A1) Fatty acid-modified polyester resin The essential component of the polyester resin component (A), that is, the fatty acid-modified polyester resin (A1), is composed of the following polybasic acid component (al), alcohol component (a2), and fatty acid (a3). ) The reaction is obtained. (al) a polybasic acid component in the reaction for obtaining the above-mentioned fatty acid-modified polyester resin (A1), the polybasic acid component (al) contains an alicyclic polybasic acid (al-oxime), and is a polybasic acid component (al) Based on the total amount, the total content of the alicyclic polybasic acid (al-1) in the polybasic acid component (al) is 50 to 100 mol%. Within the scope. The total content of the alicyclic polybasic acid (al-1) is preferably in the range of 70 to 100 mol%, and more preferably in the range of 85 to 100 mol%. The alicyclic polybasic acid (al-oxime) is generally a compound having one or more alicyclic structures (for example, 4 to 6 membered rings) and two or more carboxyl groups in one molecule, an acid anhydride of the compound, and the compound. And an esterified product, and examples thereof include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 4-cyclohexene-1. 2-dicarboxylic acid, 3-mercapto-1,2-cyclohexanedicarboxylic acid, 4-mercapto-1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid An alicyclic polycarboxylic acid such as 1,3,5-cyclohexanetricarboxylic acid; an anhydride of the alicyclic polycarboxylic acid; a lower-grade burnt ester of the alicyclic polyholeic acid (here, a lower alkyl group) For example, it is an alkyl group having a carbon number of about 1 to 5, etc.). Among them, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic anhydride, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid are preferably used. 4-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic anhydride. Among the above, from the viewpoint of hydrolysis resistance, 1,2-cyclohexanedicarboxylate

S 10 201209113 'Excellent 1,2-cyclohexanedicarboxylic anhydride. The above alicyclic polybasic acid (al-oxime) may be used singly or in combination of two or more. In the reaction for obtaining the above fatty acid-modified polyester resin (A1), in addition to the alicyclic polybasic acid (al-Ι), an aromatic polybasic acid (al-2) and an aliphatic polybasic acid (a 1- 3) Comes as a polybasic acid component. The aromatic polybasic acid (al-2) is generally an aromatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aromatic compound, and an esterified product of the aromatic compound, and examples thereof include: An aromatic polycarboxylic acid such as citric acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, trimellitic acid or pyromellitic acid; An acid anhydride of a carboxylic acid; a lower alkyl ester of the aromatic polycarboxylic acid (herein, the lower alkyl group means, for example, an alkyl group having a carbon number of about 1 to 5). The above aromatic polybasic acid (al-2) may be used singly or in combination of two or more. The above aliphatic polybasic acid (al-3) is generally an aliphatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aliphatic compound, and an esterified product of the aliphatic compound. Specific examples thereof include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, eleven succinic acid, dodecanedioic acid, and thirteen burns. An aliphatic polybasic carboxylic acid such as a diacid, an 18th compound diacid or a citric acid; an acid anhydride of the aliphatic polycarboxylic acid; a lower alkyl ester of the aliphatic polycarboxylic acid (here, a lower alkyl group means, for example, carbon A number of 1 to 5 alkyl groups.) and so on. The above aliphatic polybasic acid may be used singly or in combination of two or more. The above aliphatic polybasic acid (al-3) is preferably a dicarboxylic acid having an alkyl chain 201209113 having a carbon number of 4 to 18. Examples of the dicarboxylic acid having an alkyl chain having 4 to 18 carbon atoms include adipic acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid. Tridecanedioic acid, octadecanedioic acid, and the like, and adipic acid is preferably used therein. (a2) Alcohol component In the above reaction for obtaining a fatty acid-modified polyester resin (A1), the alcohol component (a2) contains a trihydric or higher polyhydric alcohol (a2-l), and the total amount of the alcohol component (a2) is The total content of the trihydric or higher polyhydric alcohol (a2-l) in the alcohol component 〇2) is in the range of 10 to 70 mol%. The total content of the trihydric or higher polyhydric alcohols (a2-l) is preferably in the range of 20 to 65 mol%, more preferably in the range of 30 to 60 mol%. The above trihydric or higher polyhydric alcohol (a2-1) may, for example, be glycerin, trimethylsulfanylethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, neopentaerythritol a trihydric or higher alcohol such as an alcohol, dipentaerythritol, sorbitol or mannitol; or a polylactone polyol obtained by adding a lactone compound such as ε-caprolactone to the trihydric or higher alcohol a compound; ginsyl (hydroxyethyl) trimeric isocyanate such as ginseng (2-hydroxyethyl) tripolyisocyanate, ginic acid (2-hydroxypropyl) tripolyisocyanate or ginseng (2-hydroxybutyl) isocyanurate. Among them, from the viewpoint of high molecular weight of the fatty acid-modified polyester resin (Α1) and the reactivity of the reforming reaction with the fatty acid (a3), it is preferable to use trimethylolpropane. In the above reaction for obtaining the fatty acid-modified polyester resin (A1), in addition to the trihydric or higher polyhydric alcohol (a2-l), a diol (a2-2) and a monohydric alcohol (a2-3) may be used. Alcohol (a2) component.

S 12 201209113 Monohydric alcohol (a2-2) may, for example, be trimethylene glycol, tetraethylene glycol, tri: ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol, dipropylene glycol, 1,4-butanediol , 1,3-butanol, 2,3-butanediol, hydrazine, 2-butanediol, 3-hydrazino-[, 2-butanediol, 2-butyl-2-ethyl-1,3- Propylene glycol, u pentanediol, pentanediol, pentylene glycol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3_methyl·4' 3_pentanediol, 3~mercapto-1,5-pentanediol, 2,2,4-trimethyl-1,3_pentanol, 1,6-hexanediol, anthracene, 5-hexyl Alcohol, 1,4-hexanediol, 2,5-hexanediol, neopentyl alcohol, 1,4-cyclohexane red methanol, tricyclo-weidi methanol, hydrogenated double-presence A, hydrogenated double-F An alcohol; a polylactone diol obtained by adding an internal vinegar compound to the diol; a acetal diol compound such as bis(hydroxyethyl)terephthalate; The epoxy compound adduct, polyethylene glycol, polypropylene glycol, and t-butanol are condensed into a diol compound. The 7L alcohol (a2-3) may, for example, be a monohydric alcohol such as methanol, ethanol, propanol, butanol, stearyl alcohol or 2-phenoxyethanol; propylene oxide, butylene oxide, and a synthetic hydrazine branch are saturated. An alcohol compound obtained by reacting a monoepoxy compound with an acid, such as a dehydrated fatty acid ester (trade name "Cardura E10", manufactured by HEXI〇N Specialty Chemicals Co., Ltd.). (a3) Fatty Acid In the above reaction for obtaining a fatty acid-modified polyester resin (A1), the fatty acid (a3) is a linear hydrocarbon of a linear hydrocarbon, and examples thereof include coconut oil fatty acid, cottonseed oil fatty acid, and hemp seed oil fatty acid. Fatty acid such as rice bran oil fatty acid, fish oil fatty acid, pine oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, hemp seed oil fatty acid, dehydrated dried hemp seed oil fatty acid, cole oil fatty acid; lauric acid , nutmeg acid, grazing 13 201209113 palmitic acid, stearic acid, oleic acid, linoleic acid, linoleic acid and so on. The above fatty acids may be used singly or in combination of two or more. In the above, 'from the viewpoint of weather resistance, it is preferable that the degree of unsaturation is low. Specifically, it is preferable that the male value is 20 or less, and particularly preferably 1 or less. The iodine value can be expressed as the number of indicators indicating the degree of unsaturation of the compound, and is expressed in grams of iodine absorbed by 100 g of the sample. The measurement system can be carried out in accordance with the specifications of JIS K 5421. From the viewpoint of the above unsaturation, the fatty acid (a3) is preferably a coconut oil fatty acid, lauric acid, myristic acid, palmitic acid or stearic acid, and particularly preferably a coconut oil fatty acid. The production of the fatty acid-modified polyester resin (A1) is not particularly limited and can be carried out in accordance with a usual method. For example, the polybasic acid component (al), the alcohol component (a2), and the fatty acid (a3) are reacted in a nitrogen gas stream at 50 to 25 ° C for 5 to 10 hours to carry out an esterification reaction. Or a method of transesterification. The modification by the fatty acid oxime 3) may be carried out at the same time as the esterification reaction or transesterification reaction with the polybasic acid component (al) and the alcohol component (a2), or after the esterification reaction or after the transesterification reaction. I will do it at a time. The polybasic acid component 〇1), the alcohol component (a2) and the fatty acid (a3) may be added at once or in portions. Further, the carboxyl group-containing fatty acid modified polyester resin may be esterified by using the above alcohol component (a2) after synthesizing the carboxyl group-containing fatty acid-modified polyester resin. Further, after the synthesis of the hydroxyl group-containing fatty acid-modified polyester resin is started, the acid anhydride is reacted, and the hydroxyl group-containing fatty acid-modified polyester resin is half-esterified. In order to promote the reaction in the above-mentioned vinegar or vinegar shift reaction, it is also possible to use the catalyst in 201209113. As the catalyst, known catalysts such as dibutyltin oxide, antimony trioxide, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutylphosphonium titanate, tetraisopropyl titanate or the like can be used. Further, the fatty acid-modified polyester resin (A1) may be modified with a monoepoxy compound after preparation of the resin or preparation of hydrazine. The monoepoxy compound can be preferably produced by using, for example, dehydrogalglycerol which synthesizes a highly branched saturated fatty acid (trade name "Cardura E10", manufactured by HEXION Specialty Chemicals Co., Ltd.). From the viewpoint of the processability of the obtained coating film, the fatty acid-modified polyester resin (A1) preferably has a number average molecular weight in the range of 5,000 to 30,000 and has a range of 7,000 to 25,000. The number average molecular weight is better' and is preferably more preferably a number average molecular weight in the range of 10,000 to 20,000. Further, from the viewpoint of the curability of the obtained coating film, the fatty acid-modified polyester resin (A1) is generally preferably in the range of from 5 to 100 mgKOH/g, and has from 10 to 90 mgKOH/ The value in the range of g is more preferable, and the hydroxyl value in the range of 40 to 80 mgKOH/g is more preferable. Further, from the viewpoint of the weather resistance of the obtained coating film, the fatty acid-modified polyester resin (A1) preferably has an oil length in the range of 3 to 30%, and has a range of 5 to 20%. The oil is better. Here, the oil length means the mass % of the fatty acid component (a3) with respect to the total amount of the polybasic acid component (al), the alcohol component (a2), and the fatty acid component (a3) of the constituent components. Moreover, the fatty acid-modified polyester resin (A1) has a glass transition temperature in the range of 0 to 50 ° C from the viewpoint of hardness, workability, and the like of the obtained coating film, and has a temperature of 10 to 40 ° C. The glass transition temperature within the range is preferred. 15 201209113 The number average molecular weight and the hydroxyl value adjustment of the fatty acid-modified polyester resin (A1) can be carried out, for example, by adjusting the carboxyl group in the polybasic acid component (al) and the fatty acid component (a3) and the aforementioned alcohol component. The method of the equivalent ratio of hydroxyl groups (COOH/OH) in (a2), or the method of adjusting the reaction time in the aforementioned esterification reaction or transesterification reaction, and the like. Further, the equivalent ratio (COOH/OH) of the carboxyl group in the polybasic acid component (al) to the hydroxyl group in the alcohol component (a2) is generally in the range of 0-5 to 0.98, and preferably in the range of 0-6 to 0.95. . Further, the number average molecular weight and the weight average molecular weight in the present specification are the number average molecular weight and the weight average molecular weight measured by a gel permeation chromatography instrument ("HLC8120GPC", manufactured by Tosoh Co., Ltd.), and standard polystyrene. The molecular weight of ethylene is derived from the benchmark conversion. In this measurement, "TSK-gel G4000HXL", "TSK-gel G3000HXL", "TSK-gel G2500HXLj, "TSK-gel G2000HXLJ (all are trade names, manufactured by Tosoh)) are used for the column. Root, and using the following measurement conditions: mobile phase tetrahydrofuran, measuring temperature 40 ° C, flow rate 1 mL / min, detector Rj. Also, in this specification, the glass transition temperature (Tg) is by differential thermal analysis (DSC) The polyester resin component (A), in addition to the fatty acid-modified polyester resin (A1), may contain a conventional oil-free polyester resin (A2) which is not modified with a usual fatty acid, and is an oil-free polyester. The resin (A2) is a polyester resin obtained by an esterification reaction or a transesterification reaction of a polybasic acid component (ai) and an alcohol component (a2) by a general method, and a polybasic acid component (al) and an alcohol component (a2). Can be used for the above fatty acid modification

S 16 201209113 ' The ester resin (A1) is exemplified and manufactured in the same manner as the method exemplified above for the fatty acid-modified polyester resin (Al). In the present invention, the polyester resin component (A) is used. The total solid content, the solid content of the fatty acid-modified polyester resin (A1) is 50 to 1% by mass. In particular, from the viewpoint of the weather resistance and corrosion resistance of the obtained coating film, it is preferably in the range of 60 to 100% by mass, and more preferably in the range of 70 to 100% by mass. (B) Melamine Resin Component In the coating composition of the present invention, the melamine resin component (B) contains 50 to 1% by mass of the following butyl etherification relative to the total solid content of the melamine resin component (B). The melamine resin (B1) is used as a solid component. (B1) Butyl etherified melamine resin • Butyl etherified melamine resin, which is an addition reaction product of melamine and an aldehyde component such as furfural or trimeric furfural (may be either monomer or multi-body) A melamine resin in which a part or all of a hydroxymethyl group of a methylolated melamine resin is etherified with n-butanol or isobutanol. Here, in the butyl etherified melamine resin, a trimeric amine resin comprising a part or all of a hydroxymethyl group of a hydroxylated melamine resin which is etherified with n-butanol is carried out with isobutanol. Any one of a melamine resin obtained by etherification and a melamine resin obtained by etherification of n-butanol and isobutanol. The number average molecular weight of the butyl etherified melamine resin is preferably in the range of 800 to 8,000, and particularly in the range of 1,000 to 5,000, from the viewpoints of processability and stain resistance of the obtained coating film. good. As the butyl etherified melamine resin (B1), one type or a mixture of two or more types can be used. 17 201209113 Commercial products of butyl etherified melamine resin (B1) include, for example, Uvan 20SE and Uvan 225 (all of which are manufactured by Mitsui Chemicals Co., Ltd.), SUPER BECKAMINE J820-60, and SUPER BECKAMINE L-117. -60 ' SUPER BECKAMINE L-109-65, SUPER BECKAMINE 47-508-60, SUPER BECKAMINE Ll 18-60, SUPER BECKAMINE G821-60 (all of which are DIC products). The melamine resin component (B) may contain a melamine resin (melamine resin (B2)) other than the above butyl etherified melamine resin (B1). Specifically, for example, a part of the thiolated melamine resin which is an addition reaction product (may be a monomer or a multi-body) of melamine, a melamine, a trimerization or the like may be mentioned. All of the mercapto group is a trisamine resin obtained by etherification of one or more alcohols other than n-butanol and isobutanol, n-butanol and/or isobutanol, and A melamine resin obtained by etherifying one or more alcohols other than butanol and isobutanol. Examples of the alcohol other than n-butanol and isobutanol used in the etherification include monohydric alcohol, ethanol, n-propanol, isopropanol, 2-ethylbutanol, and 2-ethylhexanol. alcohol. Specific examples of the melamine resin (B2) include a melamine resin (methyl etherified melamine resin) which is etherified by methanol, and a melamine resin which is etherified by methanol and butanol (methyl/butyl mixed etherified melamine) Resin) and so on. Examples of the melamine resin which is etherified by methanol include, for example, Sumimal®-100, Sumimal M-40S, and Sumimal M-55 (all of which are manufactured by Sumitomo Chemical Co., Ltd., trade name), Cymel 300, and Cymel 303. Cymel 325, Cymel 327, Cymel 350, Cymel 370, Cymel 730, Cymel 736, s 18 201209113

Cymel 738 (all of which are manufactured by Japan CYTEC Industries Co., Ltd., trade name), Melan 522, and Melan 523 (all of which are manufactured by Hitachi Chemical Co., Ltd., trade name), NIKALAC MS17, NIKALAC MS15 'NIKALAC MS001 'NIKALAC MX430 'NIKALAC MX650 (any one is a chemical company, trade name), Resimene 740, Resimene 741, Resimene 747 (all of which are manufactured by Monsanto, trade name), etc. Ether etherified melamine resin. The melamine resin which is etherified by decyl alcohol and butanol can be exemplified by, for example:

Cymel 232, Cymel 235, Cymel 202, Cymel 238, Cymel 254, Cymel 266, Cymel 272, Cymel 1130, Cymel XV-514, Cymel XV805 (all of which are manufactured by CYTEC Industries Co., Ltd., trade name), Methyl/butyl mixed etherified melamine resin such as Sumimal M66B (manufactured by Sumitomo Chemical Co., Ltd., trade name), Resimene 753, and Resimene 755 (all of which are manufactured by Monsanto Co., Ltd.). In the present invention, the solid content of the butyl etherified melamine resin (B1) is 50 to 100% by mass based on the total solid content of the melamine resin component (B). In particular, from the viewpoint of the processability of the obtained coating film and the retention of the staining property, it is preferably in the range of 70 to 1% by mass, and is in the range of 80 to 100% by mass. Better in the range. The 'butyl etherified melamine resin (B1) is less polar than the oxime etherified melamine resin, sulfhydryl/butyl mixed melamine resin, and the compatibility with the matrix resin, that is, the polyester resin (A). good. Therefore, the coating film obtained from the pollution-resistant coating composition containing the butyl etherified melamine resin (B1) is excellent in crosslinking uniformity. 19 201209113 Further, the butyl etherified melamine resin (B1) is less likely to be localized toward the surface layer in the coating film than the methyl etherified melamine resin and the methyl/butyl mixed etherified melamine resin. Therefore, the coating film obtained from the pollution-resistant coating composition containing the butyl etherified melamine resin (B1) is also excellent in weather resistance. Moreover, in order to accelerate the hardening reaction of the polyester resin component (A) and the melamine resin component (B), a hardening catalyst may be used as needed. As the hardening catalyst for promoting the hardening reaction, a sulfonic acid compound or a sulfonic acid compound neutralizer can be generally used. The sulfonic acid compound may, for example, be p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalene acid or dinonylnaphthalene diacid. The neutralizing agent in the neutralizing agent of the acid compound may, for example, be a basic compound such as a primary amine, a secondary amine, a tertiary amine, ammonium, caustic soda or caustic potash. In the antimony coating composition of the present invention, the polyester resin component (A) and the melamine resin component (B) are based on the total solid content of the polyester resin component (A) and the melamine resin component (B). The solid content-containing ratio 'the polyester resin component (A) is 50 to 90% by mass. /. And the melamine resin component (B) is 10 to 50% by mass. In particular, the polyester resin component (A) is 6 〇 from the viewpoints of curability, stain resistance, mechanical strength, workability, solvent resistance, corrosion resistance, weather resistance, and the like of the obtained coating film. It is preferable that the 〇 mass% and the melamine resin component (B) are 2 〇 to 40% by mass. (C) Organic phthalic acid ester and/or its condensate component (C) of the present invention is an organic oxalate ester and/or its condensate represented by the following formula:

S 20 201209113 Formula: (Rin-SHOR2)^ [In the formula, R1 is an alkyl group having 1 to 18 carbon atoms or a phenyl group which may be substituted by an epoxy group or a fluorenyl group, and R2 is an alkyl group having 1 to 6 carbon atoms. And. ]. The component contained in the coating composition of the present invention is a user who is effective in imparting a hydrophilizing effect on the surface of the substrate after application, and from the viewpoint of the effect, the above organic phthalate is used. The condensate is better. Specific examples of R1 in the above formula include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl-n-octyl, 2-ethylhexyl , mercapto, fluorenyl, benzyl, dodecyl, tetradecyl, hexadecanyl, octadecyl, dehydroglyceryl, methyldehydroglyceryl (2-fluorenyl dehydroglyceryl), fluorenylmethyl , 2-fluorenylethyl, 2-mercaptopropyl, 3-mercaptopropyl, 4-hydrazinobutyl, phenyl, p-nonylphenyl and the like. Specific examples of the organic phthalic acid ester of the component (C) include tetrafunctional decane such as tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetraisopropoxy hydride, tetrabutoxy decane or tetraisobutoxy oxane. Mercapto trimethoxy decane, decyl triethoxy decane, methyl tripropoxy decane, decyl triisopropoxy decane, methyl tri-n-butoxy oxane, decyl triisobutane decane, phenyl trimethoxy decane , stupid triethoxy decane, phenyl tripropoxy decane, phenyl triisopropoxy decane, stupid tri-n-butoxy oxane, phenyl triisobutoxy oxane, hexyl trimethyl decyl hexyl triethoxy decane, laurel Trimethoxy decane, lauryl triethoxy decane, decyl trimethoxy decane, decyl trimethoxy decane, hydrazine methyl triethoxy decane, decyl triethoxy decane, propylene trimethoxy decane, hydrazine A trifunctional decane such as an internal triethoxyoxane. The condensate of the above-mentioned organic phthalic acid ester may, for example, be a condensate of one or a combination of two or more of a tetrafunctional or trifunctional decane, such as 21 201209113. The condensate of the organic phthalic acid ester can be produced by a general method, and commercially available products are, for example, MKC phthalate MS5, MS56, MS57, MS56S, MS56SB5, MS58B15, MS58B30, ES40, EMS31, BTS (any of the above) All are manufactured by Mitsubishi Chemical Co., Ltd., trade name), mercapto phthalate 51, ethyl phthalate 40, ethyl phthalate 40T, ethyl phthalate 48 (all of which are Colcoat ( Stock system, trade name), KR500, KR9218, X-41-1805, X-41-1810, X-41-1818, X-41-1053, X-4M〇56 (all of which are Shin-Etsu Chemical Industrial (share) system, trade name) and so on. Further, it is also possible to carry out partial hydrolysis condensation by condensing the organic phthalic acid esters singly or in combination of two or more kinds. The condensate of the organic phthalate is a branched or linear condensate, and the degree of condensation is 2 to 1 Torr, and preferably 2 to 20. In the coating composition of the present invention, the condensate of the organic phthalate or the organic phthalate of the component (C) may be used singly or in combination of two or more. The organic phthalic acid ester represented by the above formula and/or its condensate has an oxime group as an OR2 group and an alkoxy group having 2 to 6 carbon atoms, and a methoxy group/carbon number of 2 to 6 The amount ratio of the alkoxy groups is preferably in the range of 95/5 to 30/70 from the viewpoint of pot life after the coating is prepared. In the coating composition of the present invention, the solid content of the component (C) is 0.1 to 50% by mass based on the total solid content of the component (A) and the component (B), and is 0.5 to 30% by mass. Good, and more preferably 1 to 20% by mass. When the amount of the component (C) is within the above range, the effect of the bismuth component can be further exhibited, and the initial stain resistance and stain resistance can be maintained from the obtained coating film, and the obtained coating can be obtained. Mechanical strength and durability of the film

S 22 201209113 is also better for the face. In the coating composition of the present invention, in addition to the above (A) and (c), a hydrolysis accelerator, a coloring pigment, or a dioxygen microparticle may be contained, such as an acidic surfactant or a linoleic acid compound. Such as body pigments, organic tree 曰 曰 & & amp 机 机 机 机 机 机 & & & & & & & & & & & & & & & & & & & & & & & & & & 体 体 体 体 体 体 体 体 体 体 体 体 体A well-known material. The above-mentioned acidic surfactant or boric acid-based compound has a function of promoting the hydrolysis of the organic ingredient and/or its condensate component (c). An acidic interface, a hydrolysis accelerator such as a compound or a compound is used, and although θ is used to shorten the usable time of the coating composition of the present invention, it can be used from the viewpoint of improving the pollution property. The surfactants which are acid & can be, for example, polyoxyethylene filled with acid vinegar, burned base 8 碟 碟 碟 acid salt; for example, sodium lauryl sodium, dodecyl benzene senna, etc. g, different $ keco sodium granules, ca. oxalic acid, H benzene, acid salt, etc.; (iv) phenyl sulfosulfate (poly) oxyethylene sulfhydryl sulfonate, etc.; Performance &L soil number 0 acid is now a surfactant such as citrate. Examples of the rotten acid compound include, for example, trimethyl borate, triethyl borate, tributyl borate, and the like, and the like, and the total solid content of the (β) component and the (β) component. The solid content of the accelerator is preferably 3% by mass or less, and particularly preferably 0.5 to 2% by mass, more preferably more preferably 5% by mass. Examples of the above-mentioned extender pigment include: zirconia granules, talc, mica 23 201209113 powder, cerium oxide, and the like. The solid content of the extender pigment is preferably 0.1 to 20% by mass, and particularly preferably 0.5 to 15% by mass, particularly preferably 1%, based on the total of the solid components of the component (A) and the component (B). ~10% by mass is better. Further, in order to achieve the purpose of improving the gloss of the appearance of the obtained coating film by matting or satin, the coating composition of the present invention may contain a matting agent (D). The matting agent (D) is used in order to lower the gloss of the obtained coating film, and may be any of an organic matting agent and an inorganic matting agent. Further, these may be used singly or in combination of two or more. In the coating composition of the present invention, the coating film having an excellent appearance, such as matte or satin, which has a reduced gloss, is particularly excellent in the form of a coating film which is excellent in stain resistance and corrosion resistance. The organic matting agent may, for example, be an organic resin fine particle which is not completely melted by firing when the coating film is formed. The organic resin fine particles usually have an average particle diameter in the range of 3 to 80 / /m, and preferably in the range of 5 to 60 / / m, and are preferable from the viewpoints of the appearance of the coating film, the workability of the coating, and the like. The organic matting agent may, for example, be a fluororesin such as polyvinylidene fluoride or polytetrafluoroethylene, a polyamine, an acrylic resin, a polyamine phthalic acid, a resin, a sulphur resin, a polypropylene, and a resistant resin. Polyamide 11, nylon 12 and other polyamines. Examples of the inorganic matting agent include cerium oxide, mica, alumina, talc, clay, calcium carbonate, barium sulfate, and the like. These matting agents (D) may be used singly or in combination of two or more. The matting agent (D) has a solid content of 0.1 to 30% by mass, particularly preferably 0.5 to 20% by mass, based on the total of the solid components of the components (A) and (B).

S 24 201209113 The contaminated coating composition of the present invention can be produced by uniformly mixing the above (AHC) component and, if necessary, the other components described above. Preferably, it can be produced by mixing and dispersing a component with a portion of the resin component (A) and/or a pigment dispersant in advance, and mixing the paste with the residual component. The coating composition of the present invention may be used as a one-component type coating material, but it may be prepared by first separating the component (C), that is, the organic substance, and/or its condensate, from other components, and mixing them just before use. Two-component paint. From the standpoint of storage, etc., it is preferable to use a two-component paint. The method for forming a coating film using the pollution-resistant coating composition of the present invention may be exemplified by adjusting the coating composition to a desired viscosity by adding an organic solvent or the like as needed, using air blasting, electrostatic air spraying, and affinity coating. Machine, flow applicator, coating machine by immersion, bristles, coating rods, squeegees, etc., so that the coating thickness after drying is usually 〇5~30〇em, and becomes 5 ~5〇"m is preferred and is heated at a temperature of usually 8〇~3〇〇°C for 5 seconds~丨 hours to harden it. Further, in the above method, the coating method is preferably applied by a spray coating or a roll coater. In this specification, it is understood that coating = coating. Coating film forming method The coating film opening method of the present invention is characterized in that a chrome-free primer coating containing no chromium-containing anti-recording component is formed on one or both sides of a metal plate to form a bottom. At least one of the paint film and the primer coat film is formed by the step of forming the top coat film with the stain-resistant paint composition of the present invention. 25 201209113 In other words, the method for forming a coating film of the present invention is a coating film forming method comprising the steps of: forming a primer coating film on a one-sided or two-sided surface of a metal plate with a chrome-free primer coating; And the step of forming an overcoat film with the stain-resistant coating composition of the present invention on at least one of the formed primer coating films. Further, the present invention provides a method for producing a coated metal sheet comprising the steps of the method for forming a coating film, and a coated metal sheet obtained by the method for forming a coating film or the method for producing a coated metal sheet. The coating film forming method of the present invention can be used for precoat coating or post coating coating. Preferred examples of use include coating of the above-mentioned exterior substrate (for example, a building, a display, a fence, an appliance, a machine, etc.). Examples of the metal plate of the object to be coated in the method for forming a coating film of the present invention include cold-rolled steel sheets, hot-dip galvanized steel sheets, electric galvanized steel sheets, and alloy galvanized steel sheets (iron-zinc, aluminum-zinc, nickel-zinc, etc.). Alloy galvanized steel sheet), aluminum plate, stainless steel plate, copper plate, copper plated steel plate, tin plated steel plate, and the like. When it is applied to a metal, it is possible to directly coat the primer as long as the metal surface of the material to be coated is not contaminated with oil or the like, but it is preferable to improve the adhesion and corrosion resistance to the coating film. It is hoped that a well-known metal surface treatment can be applied. These well-known surface treatment methods can be listed as a phosphate surface treatment, a chromate surface treatment, a missurface treatment, and the like. In the present invention, a primer for forming a primer coating film can be formed on a metal plate, and from the viewpoint of environmental protection, it is characterized in that it does not contain a chromium-containing rust-preventing component.

S 26 201209113 chrome-free primer coating. As long as the primer is a chrome-free primer coating material, a well-known primer used in the field of colored color steel plate coating, industrial mechanical coating, and metal parts coating can be suitably used. The chrome-free primer coating can be appropriately selected depending on the type of the material to be coated and the type of metal surface treatment. In particular, epoxy-based, polyester-based primer coatings and modified primer coatings thereof are preferred, and polyester-based primer coatings are preferred when processing properties are particularly required. The specific method of forming the primer coating film may, for example, be a method in which the primer coating material is applied, and then it is hardened by heating as needed. At this time, the primer coating can be applied by a coating method such as roll coating or spray coating to a thickness of 1 to 30 // m (preferably 2 to 20 // m). The coating method is carried out, and it is usually cured by heating at an ambient gas temperature of 80 to 300 ° C for 5 seconds to 1 hour. In the case of precoating, it is preferred to heat the material at a maximum temperature of 140 to 250 ° C for 15 seconds to 120 seconds to harden it. The layer structure of the primer coating film is not particularly limited, and may be, for example, one layer or a second layer in which a second primer coating film (middle coating film) is formed on the first primer coating film. When the primer coating film is formed into two layers, the first primer coating film can have a resist function, and the second primer coating film (the intermediate coating film) can have workability, peeling resistance, etc., and the second layer can be made. Paint films have different functions. Next, in the coating film forming method of the present invention, at least one of the primer coating films formed on one or both sides of the metal plate is formed with the pollution-resistant coating composition of the present invention. Apply the film on top. That is, the upper coating film is formed by overlapping at least one surface of the formed primer coating film. Here, 27 201209113 "At least above the primer coating" means: when a primer is formed on one side of the metal sheet - forming (four) on the one side of the primer (four); when in the metal When a primer coating film is formed on the other surface of the board, the primer coating film formed on the double-sided surface is formed on the primer coating film on one surface of the metal sheet, or is formed on the primer coating film formed on the double-sided surface of the metal sheet Above the primer coating on both sides. The specific method of forming the overcoat film may, for example, be a method in which the stain-resistant paint composition of the present invention is applied, and then it is cured by heating as needed. The coating method may be exemplified by curtain coating, roll coater coating, dipping coating, spraying, and the like. The film thickness is usually applied in such a manner that the dry paint is in the range of 5 to 50 / zm (preferably 8 to 25 #m). When the coating composition of the present invention is precoated, the coating method is not limited, but it is preferably coated by a curtain coating or a roll coater from the viewpoint of economy of precoated steel sheet coating. When applying to a roll coater, from the viewpoint of practicality, it is preferable to use a lower feed method by two rolls (so-called natural reverse coating, natural coating). . Alternatively, from the viewpoint of optimizing the uniformity of the coated surface, it is also possible to carry out the upper feed or the lower feed by the two parents. The curing condition of the overcoat film formed by the coating composition of the present invention is usually carried out at a maximum temperature of 12 〇 26 to 26 (r sec for 15 seconds to 30 minutes. Coating by coil coating or the like) In the precoating and coating field, it is usually carried out in the range of 15 to 90 seconds after the material reaches the maximum temperature of 16 〇 to 26 〇〇 C. The following examples are given by way of production examples and examples. The invention will be more specifically described.

S 28 201209113 The present invention is not limited by the following examples. In addition, any of the following, "parts" and "%" are based on quality standards. Production Example 1 of Polyester Resin The following raw materials were fed into a flask having a thermometer, a stirrer, a heating device, and a rectification column: 150.9 parts (0-98 moles) 38.9 parts (0.37 moles) 9.6 parts (0.06 moles) 77.8 parts (0_57 mol) 1,2-cyclohexanal succinic anhydride neopentyl glycol butyl ethyl propylene glycol trimethylolpropane scorpion oil fatty acid 44·1 part (0.21 mol) dibutyltin oxide (catalyst) ) 〇.〇3 copies. The temperature was then raised to 16 Torr while stirring the contents. 〇, and slowly heated from 160 ° C to 230 in 3 hours. (: 'and after continuing the reaction at 230 ° C for 30 minutes, the rectification column was replaced with a water separator, and in order to promote the removal of the condensation water produced as a by-product, 'addition of bisbenzene with respect to the total feed amount of 5% The reaction was further carried out at 230 ° C, and the heating was stopped when the acid value became 4 mg K 〇 H / g, and was diluted with Swazol 1500 (hydrocarbon solvent) to obtain a polyester resin having a solid content of 65 〇 / ( (A1-1) The obtained resin had a number average molecular weight of 15,000, a hydroxyl value (mg of potassium hydroxide required for neutralizing the resin lg), 75 mgKOH/g, an oil length of 14.7%, and a moth value of 5 > Production Example 2 to 13 The mixture was mixed as shown in the following Table 1, and the same procedure as in Production Example 1 was carried out to obtain a solution of each of the poly-resin resins (a1_2hAM3) of 29 201209113 solid component 65. The composition ratio of each component of the table was a molar ratio. The number average molecular weight, the menstrual value, the oil length and the enthalpy value of each resin are shown in Table 1. Further, the polyester resins (A1_7 (AM3) of Production Examples 7 to 13 are resins for the comparative examples. Table 1] Manufacturing Example No. 1 2 3 4 5 6 7 8 9 10 11 12 13 Polyester resin (A1-X) 1 2 3 4 5 6 7 8 9 10 11 12 13 1,2-ring 0.98 0.67 0.73 0.97 0.58 0.4 0.94 0.96 0.77 0.97 0.95 0.95 1) 13⁄4.3⁄4. 0.67 to the present dicarboxylic acid 0.3 m-formic acid 0.29 0.29 0.26 hexanoic acid 0.22 0.39 0.2 neopentyl fermentation 0.37 0.47 0.47 0. ΤΓΊ 0.55 0.47 0.4 0.4 0.65 0.3 0.55 0.35 0.85 1,t) 匕一醉0.2 0.05 butyl ethyl propylene dilute 0.06 0.1 0.1 0.1 0.1 0.2 0.25 0.1 0.1 dimethylolpropane 0.57 0.43 0.53 6.65 -― .. 0.35 0.07 0.73 0.3 0.4 0.1 0.7 0.35 0.65 Coconut oil fatty acid 0.21 0.13 '〇.21~ 0.13 0.15 0.2 0.16 0.02 0.65 Stearic acid 0.37 0.16 Number average molecule 3·15000 7000 5700 7400 5800 7000 7000 3800 7000 6500 8500 7500 4700 gauge laungKUH/g Oil length (%) Iodine value 75 14.7 5> 77 9.8 5> 83 15.5 5> 53 29.5 5> 77 5.7 5> 77 9.8 5> 46 11.2 5> 63 14.2 5> 4 11.9 5> 113 15.3 5> 85 1.6 5> 15 36.0 5> 47 0 5> Production and performance test of the pollution-resistant paint composition Examples 1 to 18 and Comparative Examples 1 to 1 Coating was carried out to prepare various stain-resistant paint compositions No. 1 to 28. The contaminated coating composition N〇i9 to 28 is a comparative coating composition. Κρ color 8620 primer (Kansai Paint) was pre-coated on the surface and inside of a 55%-thick zinc-coated steel plate (Galvalume steel plate) with a thickness of 〇35匪 applied by chemical conversion treatment. The vinegar primer for the steel plate is used to make the dry lining 5 μm, and the force is applied. If the material reaches the maximum temperature of 220 ° C and fired for 40 seconds ', a primer Wei steel plate is obtained. Coating stick

S 30 201209113 Each stain-resistant coating (four) obtained as described above is applied to the surface of the primer-coated steel sheet so that the dry thickness becomes about _5_, and heating is performed to bring the material to the highest temperature to become 2 3 G t was fired for 5 seconds to obtain each coated steel sheet. The following performance tests were performed on each of the obtained coated steel sheets. The test results are shown together in Tables 2 and 3. Further, the amounts of the respective components in Tables 2 and 3 are the masses of the solid components. Further, when the coating of the stain-resistant coating composition is applied, the dispersion of the white pigment, i.e., titanium dioxide, is carried out. Further, a mixed solvent of cyclohexanone/Swazol 1500 (Maruzin's (3⁄4), aromatic petroleum-based high-boiling solvent) = 60/40 (mass ratio) is used for the viscosity adjustment of the coating composition. When painting, adjust the viscosity of the coating composition to about 100 seconds with Ford Cup #4 (25. 〇. 31 201209113 [Table 2]

Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Pollution-resistant coating composition No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 A Polyester resin ( A1-1) 75 60 75 75 75 75 75 75 75 75 75 75 75 Composition Polyester Resin (A1-2) 75 Polyester Resin (A1-3) 75 Polyester Resin (A1-4) 75 Polyester Resin (AI) -5) 75 Polyester Resin (AI-6) 75 Polyester Resin (AI-7) Polyester Resin (A1-8) Polyester Resin (A1-9) Polyester Resin (A1-10) Polyester Resin (A1 -I 1) Polyester Resin (A1-12) Polyester Resin (A1-13) 20 Uvan B 20SE-60 (ti 1) 25 25 25 25 25 25 20 20 15 25 25 25 25 25 25 25 Super beckamine Ingredient J820 -60 (t main 2) 25 Super beckamine L-l18-60 (Note 3) 25 Cymel 303 (ti 4) 5 Sumidur BL3175 (Note 5) 10 C MS56S (Note 6) 5 5 5 5 5 5 5 5 5 5 5 0.2 40 5 5 5 Composition MS58B30 (ti 7) 5 X-41-1805 (ti 8) 5 D Composition Syloid 161W (Note 9) 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 0 20 Other Nacure 5225 (Note 10) 1 Formate Component TK-1 (Note II) 0,2 Trimethyl borate Titanium Dioxide 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 60°Gloss 35 35 40 33 37 40 35 33 30 35 35 30 33 35 27 37 75 15 Performance Processability AAAAAAAAAAAAAAAAAA Test Pollution Resistance SSSSAASAASAAAASSAA Rain Resistance Resistant Results Λ Λ SAAAAAAASAAAASSAS Promotion of AAAAAAAAAASAASAASA General Assessment SSSSAASAASSAASSSSS s 32 201209113 [Table 3]

Comparative Example 1 ? 4 S 6 7 8 9 10 and 「 "Contaminated Coating Composition No. 19 20 ? 1 22 23 24 25 26 27 28 A Composition Polyester Resin iAUl," 75 75 75 Polyester Resin Polyester Resin Polyester Resin (Α1-4, polyester resin, polyester resin, ΑΙ.Μ: 3⁄4Cool resin ί A丨.7, 75 聚睡树脂 ί A 1- R, 75 polyester resin Αΐ _ lt; η 75 m si resin (Ai-in 75 polyester resin (Ai-m 75 poly Si resin ί A 1. 1 0, 75 saponin resin (A丨.1*^ 40 B component Uvan 20SE-60 main)) 25 25 25 25 25 25 25 25 25 Super beckamine J820-60 (Note 2, Super beckamine Ll 18-60 (Note 3, Cymel 303 (Note 4) 25 Sumidur BL3175 (t main 5, C component MS56S (Note 6, 5 5 S 5 5 S 5 5 0 60 MS58B30 (Note h X-41-1805 (Note 8) D component Syloid 161W (Note 9) 3 3 3 3 3 3 3 3 3 3 Other components Nacure 5225 (Note 10, Formate TK-1 (Note 11, Trimethyl borate __ Titanium dioxide 80 80 80 80 80 80 80 80 80 80 Performance test results 60° gloss ~ 35 33 36 35 14 ” 30 40 76 27 Processability ABACBABAAC Pollution resistance ^ ABAAABAAC s Rain resistance _ BBRBBBBBC s Promotion of weather resistance CBRAABABSB Total evaluation CBBCBBBB c C Further, 'Table 2 and Table 3 (Note 1) ~ (Note ii) are as follows. (Note l) Uvan 20SE-60: manufactured by Mitsui Chemicals Co., Ltd., butyl etherified melamine resin, and having a weight average molecular weight of about 4,000.

(Note 2) SUPER BECKAMINE J820-60: The product name "SUpER BECKAMINEJ-820-60", manufactured by DIC Co., Ltd., is a tributylamine resin solution. 33 201209113 (Note 3) SUPER BECKAMINE L-118-60 : The product name "SUPER BECKAMINE L-118-60", manufactured by DIC (stock), n-butyl etherified melamine resin solution. (Note 4) Cymel 303: A low molecular weight methyl etherified melamine resin manufactured by CYTEC Industries Co., Ltd. The content of urethane (meth) is more than 60% by weight. (Note 5) Sumidur BL3175: a methyl ethyl ketone oxime block compound of hexamethylene diisocyanate manufactured by Bayer Urethane Co., Ltd., manufactured by Bayer Urethane Co., Ltd. (Note 6) MS56S: Mitsubishi Chemical Co., Ltd., trade name "MKC phthalate MS56S", condensate of tetraoxan oxane, thiol esterified phthalate. (Note 7) MS58B30: Mitsubishi Chemical Co., Ltd., trade name "MKC phthalate MS58B30", condensate of tetraalkoxy decane, thiol/butyl mixed esterified phthalate, ratio of methyl/butyl number It is 70/30. (Note 8) X-41-1805: manufactured by Shin-Etsu Chemical Co., Ltd., trade name, mercaptoalkyl group containing a condensate of trialkoxysilane, the carbon number of mercaptoalkyl group is 18 or less, and the carbon number of alkoxy group It is 6 or less. (Note 9) Syloid 161W: manufactured by GRACE GMBH, trade name, organically processed cerium oxide micropowder, oil absorption 170ml/100g. (Note 10) Nacure 5225: an isopropanol solution of a secondary amine neutralized product of dodecylbenzenesulfonic acid, manufactured by King Industries, USA. The degree of neutralization of dodecylbenzenesulfonic acid/amine is about 1.1 (mole ratio). The active ingredient was about 33% by weight, and among them, dodecylbenzenesulfonic acid/amine (mass ratio) was about 8/25. The amount of the lanthanide in Table 2 is the mass fraction of the solid component of dodecylbenzenesulfonic acid.

S 34 201209113 (Note ll) Formate ΤΚ-1: a hardening catalyst for an organotin solution manufactured by Takeda Pharmaceutical Co., Ltd., and a dissociation catalyst for a blocked polyisocyanate compound. The performance tests in Tables 2 and 3 were carried out in accordance with the following methods and evaluation criteria. 60° gloss: The 60-degree specular reflectance is measured in accordance with the 60-degree specular gloss specified in JIS Κ-5400 7.6 (1990). Workability: In the room of 20 C, the test plate was bent 18 degrees as the outer side, and the number of turns in which the bent portion did not break was indicated. The number of turns means that when the inside of the bent portion is not sandwiched by anything, it is 0Τ when it is bent at 18 degrees, and will be taken as π when one of the plates of the same thickness as the test plate is sandwiched; The film time is 2 Τ; the 3 pieces are taken as 3 Τ; the 4 pieces are taken as 4 □; the 5 pieces are taken as 5 Τ, and the 6 pieces are taken as 6 Τ. The results of the following determinations were made: A: When cracking was performed at 4 ,, it was almost impossible to confirm cracking; B: Although significant cracking was observed in 4T bending, it was almost impossible to confirm cracking in 6-bending bending; C: Significant cracking was confirmed in the 6T bending process. Outdoor exposure test: The outdoor exposure s test piece (1 〇〇 x 30 〇 mm) is placed on the north side of the coating film on the north side of the model, and in Kanazawa-cho, Kanazaki-cho, Kanazawa-machi The exposure test was carried out on the house, and the pollution resistance and the rain-stained streaky pollution (rain-striped stain) were evaluated on the basis of the following criteria. The stain resistance is obtained by multi-light source splitting based on JIS Z8370 and using a Suga test machine. The 201209113 colorimeter MSC-5N measures the color difference (ΔΕ) before and after exposure. Rain-resistant strips are stained by visual inspection. For pollution: It is evaluated by ΔΕ before and after the outdoor exposure test by the following criteria: S: ΔΕ is less than 2, A: ΔΕ is above 2 and less than 3, B: ΔΕ is above 3 and less than 5, C: △ E is 5 or more. Rain-resistant streaking pollution: The rain streaks after the outdoor exposure test were evaluated by the following criteria: S: no traces of rain streaks, A: few traces of rain streaks were observed, B: a considerable amount of rain streaks were observed, C : Deeply traces of rain streaks. Promotion of weather resistance: According to the pulverization of the coated plate after the 7-cycle (161 hours) test of hydrogen peroxide, the following criteria were evaluated: S: no generation of powdering was observed, A: small amount of powdering was observed. Or, whitening of a small amount of coating film was observed, B: whitening was observed, dullness was observed, powdering was slightly generated, and C: significant powdering was observed. Total evaluation: In the composition of the pollution-resistant paint, the processability of the coated material, the stain resistance of the obtained coating film, the pollution resistance to rain stripe, and the promotion of weather resistance

S 36 201209113 The high system is very important. Therefore, the total assessment is performed by the following criteria. s : Processability, pollution resistance, rain-resistant streak pollution and promotion of weather resistance are all S or A, and at least one is S; A: processability, pollution resistance, rain-resistant streaking pollution and promotion of weather resistance All evaluations are A; B: Processability, pollution resistance, rain-resistant streak pollution and promotion of weather resistance are all S, A or B, and at least one is B; C: scratch resistance, initial adhesion and weather resistance At least one of the assessments of sex is C. I: Simple description of the figure 3 (none) [Explanation of main component symbols] (none) 37

Claims (1)

201209113 VII 1. Patent application scope: A pollution-resistant coating composition comprising: (A) a polyester resin containing 50 to 100 mass average molecular weight of 5000 to 30000, a hydroxyl value of 5 to 100 mgKOH/g, and an oil length of 3 The fatty acid-modified polyester resin (A1) of 〜30°/° is used as a solid component, and the fatty acid-modified polyester resin (A1) is obtained by the following reaction of (al) to Q3): (al): contains fat a polybasic acid of a cyclo-type polybasic acid (al-Ι); (a2): an alcohol containing a trihydric or higher polyhydric alcohol (a2-l); and (a3): a fatty acid; and in the reaction, a polybasic acid (al) The total amount of the alicyclic polybasic acid (ai-i) in the polybasic acid (al) is in the range of 5 〇 to 100 mol%; and based on the total amount of the alcohol (a2), the alcohol ( The content of the trihydric or higher polyhydric alcohol (a2-l) in a2) is in the range of 1 〇 to 70 mol%; (B) the melamine resin contains 50 to 1 〇〇 mass. /. a butyl etherified melamine resin (B1) as a solid component; and (C) an organic phthalic acid ester and/or a condensate thereof, which is represented by the following formula: General formula: (i^VSHOR2)^ [wherein, R1 An alkyl group or a phenyl group of a carbon number which may be substituted by an epoxy group or a fluorenyl group, an alkyl group having a carbon number of R2, and a hydrazine or q; and a component (A) and (B) The total solid content is based on the reference, and the solid content of the component (C) is (u 〜5 〇 mass 0 / 〇. S 38 201209113 2. The pollution-resistant coating composition of claim 1 of the patent scope, wherein In the reaction of the fatty acid-modified polyester resin (A1), the total content of the alicyclic polybasic acid (al-Ι) in the polybasic acid component (al) is based on the total amount of the polybasic acid component (al). In the range of ~100 mol%. 3. The composition of the anti-fouling coating according to the first paragraph of the patent application, which contains 50~ based on the total solid content of the polyester resin component (A) and the melamine resin component (B). 90% by mass of the polyester resin component (A) as a solid component, and contains 10 to 50% by mass of the melamine resin component (B) as a solid 4. The composition of the pollution-resistant coating of claim 1, wherein the alicyclic polybasic acid (al-Ι) is selected from the group consisting of 1,2-cyclohexanedicarboxylic acid, 1,3-ring Hexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 3-mercapto-1,2-cyclohexanedicarboxylic acid, 4-methyl Alicyclic-1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, and alicyclic polycarboxylic acid of 1,3,5-cyclohexanetricarboxylic acid, the alicyclic group At least one acid of the group consisting of an acid anhydride of a polycarboxylic acid and a lower alkyl ester of the alicyclic polycarboxylic acid. 5. A composition of a pollution-resistant paint according to item 1 of the patent application, wherein a ternary or higher component The alcohol (a2-l) is selected from the group consisting of: glycerin, trishydroxycarbonyl, triterpene, diglycerin, triglycerin, 1,2,6-hexanetriol, neopentyl alcohol, dixin a trihydric or higher alcohol of pentaerythritol, sorbitol, and mannitol; a polylactone polyol compound obtained by adding an internal vinegar compound to the trihydric or higher alcohol; and a hydroxyalkyl group trimer At least one substance in the group consisting of isocyanates. 39 201209113 6. If applying The pollution-resistant coating composition of the first aspect of the patent, wherein the fatty acid (a3) is selected from the group consisting of coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, pine oil fatty acid, soybean oil fatty acid. Flaxseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor seed oil fatty acid, dehydrated castor seed oil fatty acid, sunflower oil fatty acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linseed oil a monocarboxylic acid of at least one linear hydrocarbon in the group consisting of acid and linoleic acid. 7. If the composition of the pollution-resistant coating of claim 1 is included, it further contains a matting agent (D). 8. The stain-resistant coating composition according to claim 7 of the patent application, which comprises 0.1 to 30% by mass of a matting agent (D) as a total solid content of the polyester resin (A) and the melamine resin (B). Solid content. 9. A method of forming a coating film, comprising the steps of: forming a primer coating film on a one-sided or two-sided side of a metal plate with a chrome-free primer coating; and forming the primer in the foregoing In at least one of the coating films, the step of forming an overcoat film is carried out by using the stain-resistant coating composition of claim 1 of the patent application. 10. A method of manufacturing a coated metal sheet, comprising: a step of forming a primer coating film on a one-sided or two-sided side of a metal plate with a chrome-free primer coating; and forming the foregoing In at least one of the primer coating films, the step of forming the upper coating film S 40 201209113 is carried out by the pollution-resistant coating composition of claim 1 of the patent application. 11. A coated metal sheet obtained by the method of claim 9 or 10. 41 201209113 IV. Designation of representative drawings: (1) The representative representative of the case is: (No). (2) A brief description of the symbol of the representative figure: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: