Kit for three-component coating composition, three-component coating composition and method for coating inside a mold

Abstract

The present invention aims to provide a kit for a three-component paint composition that has a low VOC content, can shorten the process of cleaning the painting equipment when multiple colors are used, and can form a coating film that has excellent hardness and adhesion and suppresses color unevenness. The present invention relates to a kit for a three-liquid coating composition comprising (A) (a1) a base agent containing an isocyanate-reactive group-containing compound, (B) (b1) a curing agent containing a polyisocyanate compound, and (C) (c1) a pigment paste containing an isocyanate-reactive group-containing compound and (c2) a pigment, the kit comprising ... and (c2) a pigment paste containing a pigment, the kit comprising a three-liquid coating composition comprising (A) (a1) a base agent containing an isoc A ) is in the range of 20 to 1800 mPa s, and the viscosity (V B ) is in the range of 20 to 1800 mPa·s, and the viscosity (V C ) is in the range of 20 to 1800 mPa·s.

Description

[Technical field]

[0001] The present invention relates to a kit for a three-component coating composition, a three-component coating composition, and an in-mold coating method using the kit or the three-component coating composition. [Background technology]

[0002] Conventionally, in order to impart excellent appearance and performance to a substrate surface, a coating composition has been applied to the substrate surface, and the wet coating film formed is cured to form a coating film. In recent years, from the viewpoint of reducing the environmental load, there has been a demand for reducing volatile organic compounds (VOCs) in the coating composition and reducing the air conditioning energy required during painting.

[0003] Furthermore, in recent years, in various technical fields, there has been a demand for coating film performance such as high coating film hardness and high adhesion between the coating film and the substrate, as well as suppression of color unevenness.

[0004] Furthermore, when using a multi-color coating composition, there is a problem in that the time required for cleaning the coating equipment is required when changing the coating color.

[0005] Patent Document 1 discloses a two-component coating material composition comprising a paint base component A and a curing component B, in which the paint base component A comprises: i. one or more polyols A1 selected from the group of polyols containing an ester group, and having a hydroxyl value of 300 to 500 mgKOH / g and a hydroxyl group functionality of more than 2; ii. a polyol having a general formula (I): R 1 that does not contain an ether group or an ester group; 1 -(OH) p (In the formula, R 1 is a p-valent branched, cyclic or linear, saturated or unsaturated aliphatic hydrocarbon radical having 5 to 18 carbon atoms, and the radical R 1 optionally containing one or more tertiary amino groups, and p is 2 to 6), iii. one or more aliphatic polyols A2 of the general formula (II): R 2 -(C=O) r -O-(AO) s -R 3(In the formula, R 2 is a saturated or unsaturated aliphatic hydrocarbon radical having 6 to 30 carbon atoms, R 3 is H, the radical PO(OH)2, or a radical of an optionally partially phosphorylated mono- or disaccharide or a radical of an optionally partially phosphorylated alditol, AO represents one or more alkylene oxide radicals selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide, r is 0 or 1, and s is 0 to 30), iv. one or more crosslinking catalysts A4 selected from the group of organotin compounds, v. any one or more polyamines A5 having at least two secondary amino groups and an amine value of 120 to 280 mg KOH / g, and ix. any one or more additives A9 selected from the group consisting of wetting agents and / or dispersants, rheological aids and flow control agents, and the curing component B comprises i. one or more polyisocyanates B1 having an average of 2.4 to 5 NCO groups, and the two-component coating material composition comprises, based on the total weight of the two-component coating material composition, D2369 (2015) describes two-component coating material compositions, which have a solids content of at least 96% by weight and are characterized in that the molar ratio of NCO groups in the curing component B to the acidic hydrogen atoms of hydroxyl groups, primary amino groups and secondary amino groups in the paint base component A is from 1:1.15 to 1:0.95, allow damage-free release from normally metallic mold surfaces without the use of external mold release agents and meanwhile ensure very good adhesion to the substrate and can be recoated with further coating films, such as, for example, base coats and clear coats, forming surfaces of very good quality without costly and inconvenient cleaning and / or polishing steps. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Special Publication No. 2020-528103 Summary of the Invention [Problem to be solved by the invention]

[0007] The technique described in Patent Document 1 has a low VOC content in the resulting two-component coating composition, but has the problem that, when multiple colors are produced, the time and effort required for cleaning the coating equipment is required.

[0008] The present invention aims to provide a kit for a three-component paint composition that has a low VOC content, can shorten the process of cleaning the painting equipment when multiple colors are used, and can form a coating film that has excellent hardness and adhesion and suppresses color unevenness. [Means for solving the problem]

[0009] As a result of intensive research conducted by the present inventors in order to achieve the above object, the present inventors have discovered a kit for a three-liquid type coating composition comprising a base agent (A) containing an isocyanate-reactive group-containing compound (a1), a curing agent (B) containing a polyisocyanate compound (b1), and a pigment paste (C) containing an isocyanate-reactive group-containing compound (c1) and a pigment (c2), the kit comprising a base agent (A) and a curing agent (B) containing a polyisocyanate compound (b1), the curing agent (B) containing a polyisocyanate compound (b1), and a pigment paste (C) containing an isocyanate-reactive group-containing compound (c1) and a pigment (c2), -1 , viscosity at 65℃ (V A ) is in the range of 20 to 1800 mPa s, and the shear rate of the curing agent (B) is -1 , viscosity at 65℃ (V B ) is in the range of 20 to 1800 mPa s, and the shear rate of the pigment paste (C) is 100 sec -1 , viscosity at 65℃ (V C It has been found that the above object can be achieved by using a kit in which the viscosity is in the range of 20 to 1800 mPa·s.

[0010] That is, the present invention provides the following <1> ~ <7> This is regarding.

[0011] <1> A kit for a three-liquid coating composition comprising (A) (a1) a base agent containing an isocyanate-reactive group-containing compound, (B) (b1) a curing agent containing a polyisocyanate compound, and (C) (c1) a pigment paste containing an isocyanate-reactive group-containing compound and (c2) a pigment, the kit comprising: -1 , viscosity at 65℃ (V A ) is in the range of 20 to 1800 mPa s, and the shear rate of the curing agent (B) is -1 , viscosity at 65℃ (V B ) is in the range of 20 to 1800 mPa s, and the shear rate of the pigment paste (C) is 100 sec -1 , viscosity at 65℃ (V C ) is within the range of 20 to 1800 mPa·s, kit. <2> The solid content is 95% by mass or more. <1> The three-component coating composition according to claim 1. <3> The solid content concentration of the pigment paste (C) is within the range of 85 to 98 mass%. <1> or <2> The kit according to claim 1, <4> The isocyanate-reactive group-containing compound (c1) includes an isocyanate-reactive group-containing compound having a number average molecular weight in the range of 250 to 2500. <1> ~ <3> 2. The kit according to claim 1 , <5> The content of the pigment (c2) is within the range of 1.0 to 65 mass% based on the total amount of the pigment paste (C). <1> ~ <4> 2. The kit according to claim 1 , <6> The above (V A ), the above (V B ) and the above (V C ) is expressed by the following formula (1) and formula (2): 0.4≦(V B ) / (V A )≦2.5 Equation (1) 0.3≦(V C ) / (V A )≦3.0 Equation (2) Fulfilling <1> ~ <5> 2. The kit according to claim 1 , <7> A three-liquid coating composition comprising a base agent (A) containing an isocyanate-reactive group-containing compound (a1), a curing agent (B) containing a polyisocyanate compound (b1), and a pigment paste (C) containing an isocyanate-reactive group-containing compound (c1) and a pigment (c2), wherein the base agent (A) is heated at a shear rate of 100 sec -1 , viscosity at 65℃ (V A ) is in the range of 20 to 1800 mPa s, and the shear rate of the curing agent (B) is -1 , viscosity at 65℃ (V B ) is in the range of 20 to 1800 mPa s, and the shear rate of the pigment paste (C) is 100 sec -1 , viscosity at 65℃ (V C ) is in the range of 20 to 1800 mPa·s. <8> In an in-mold coating method comprising the steps of injecting an in-mold coating paint composition between a molded substrate and an inner wall of a mold, curing the in-mold coating paint composition, and then removing the coated molded article from the mold, the in-mold coating paint composition being <1> ~ <6> A three-component paint composition formed from the kit according to any one of the preceding claims, or <7> The three-component coating composition according to any one of claims 1 to 5, Effect of the Invention

[0012] According to the present invention, it is possible to provide a kit for a three-component paint composition which has a low VOC content, can shorten the process of cleaning the painting equipment when multiple colors are used, and can form a coating film which has excellent hardness and adhesion and suppresses color unevenness. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention will be described in detail below, however, these are examples of preferred embodiments and the present invention is not limited to the contents thereof.

[0014] [Kit for three-liquid type paint composition, and three-liquid type paint composition] The kit for a three-liquid type coating composition according to the present invention (hereinafter, sometimes simply referred to as "kit") is a kit comprising a base agent (A) containing an isocyanate-reactive group-containing compound (a1), a curing agent (B) containing a polyisocyanate compound (b1), and a pigment paste (C) containing an isocyanate-reactive group-containing compound (c1) and a pigment (c2), -1 , viscosity at 65℃ (V A ) is in the range of 20 to 1800 mPa s, and the shear rate of the curing agent (B) is -1 , viscosity at 65℃ (V B ) is in the range of 20 to 1800 mPa s, and the shear rate of the pigment paste (C) is 100 sec -1 , viscosity at 65℃ (V C ) is in the range of 20 to 1800 mPa s. The three-liquid coating composition according to the present invention can be formed by mixing the base agent (A), the curing agent (B) and the pigment paste (C).

[0015] In addition, the viscosity (V A ), viscosity (V B ) and viscosity (V C The method for measuring the above-mentioned value will be described in the Examples.

[0016] The reasons why the kit of the present invention can form a three-component paint composition that has a low VOC content, can shorten the process of cleaning the painting equipment when multiple colors are produced, and can form a coating film that is excellent in hardness and adhesion and suppresses color unevenness are presumed to be as follows.

[0017] When a two-liquid paint composition containing a pigment-containing base agent and a curing agent is multi-colored, when changing colors, the base agent tank and piping must be washed, or a number of base agent tanks must be prepared for each color, and only the piping must be washed. Since tanks of base agents that are used in large quantities often have a large capacity, when the base agent tank and piping are washed, the labor required to wash the large capacity base agent tank is large, and when multiple base agent tanks are prepared, the size of the base agent tanks places a large burden on the painting site.

[0018] When a three-liquid paint composition containing a base agent (A), a hardener (B), and a pigment paste (C) is made into multiple colors, when changing colors, the pigment paste (C) tank and piping are washed, or a pigment paste (C) tank is prepared for each color and only the piping is washed. Since the volume of the pigment paste (C) tank, which is used in small amounts, is often small, when the pigment paste (C) tank and piping are washed, the labor required to wash the pigment paste (C) tank with a small volume is small, and when multiple pigment paste (C) tanks are prepared, the pigment paste (C) tanks are small, so the burden on the painting site is small.

[0019] However, although a three-component paint composition can shorten the process of cleaning the painting equipment when changing colors when multiple colors are produced, it has been found that when a paint composition with a low VOC content is used as a three-component paint composition, color unevenness is likely to occur and hardness and adhesion are likely to decrease.

[0020] When the above-mentioned coating composition with low VOC content is used as a three-component coating composition, color unevenness is likely to occur and hardness and adhesion are likely to decrease. It is presumed that this is because it is difficult to adjust the viscosity of the coating composition with low VOC content using a solvent, making it difficult to mix the three components of the base agent (A), hardener (B) and pigment paste (C).

[0021] As a result of extensive research, the present inventors have found that the shear rate of the main component (A) is 100 sec -1 , viscosity at 65℃ (V A ) is in the range of 20 to 1800 mPa s, and the shear rate of the curing agent (B) is -1 , viscosity at 65℃ (V B ) is in the range of 20 to 1800 mPa s, and the shear rate of the pigment paste (C) is 100 sec -1 , viscosity at 65℃ (V C ) in the range of 20 to 1,800 mPa s, it was found that even with the above-mentioned three-component paint composition having a low VOC content, a coating film having excellent hardness and adhesion and suppressed color unevenness can be formed.

[0022] In the kit according to the present invention, even the three-component paint composition with a low VOC content suppresses color unevenness and has excellent hardness and adhesion. This is presumably because the three components of the base resin (A), hardener (B), and pigment paste (C) are easily mixed, allowing the entire coating film to harden uniformly.

[0023] The solid content concentration of the three-component paint composition formed from the kit according to the present invention or the three-component paint composition according to the present disclosure is preferably 95% by mass or more, more preferably 96% by mass or more, and even more preferably 97% by mass or more, from the viewpoints of reducing the VOC content in the resulting paint composition and preventing the hardness and color unevenness of the coating film formed. The upper limit of the solid content concentration is 100% by mass.

[0024] In this specification, the term "solid content" refers to non-volatile components such as resins, curing agents, and pigments remaining after drying for 30 minutes at 80° C. The solid content can be determined, for example, by weighing a sample into a heat-resistant container such as an aluminum foil cup, spreading the sample on the bottom surface of the container, drying for 30 minutes at 80° C., and weighing the mass of the components remaining after drying.

[0025] In addition, in this specification, "solid content concentration" means the mass ratio of the solid content in the composition. Therefore, the solid content concentration of the composition can be calculated by, for example, weighing 1.0 g of the composition into a heat-resistant container such as an aluminum foil cup, spreading the composition on the bottom of the container, drying at 80°C for 30 minutes, weighing the mass of the components remaining in the composition after drying, and calculating the mass ratio of the components remaining after drying to the total mass of the composition before drying.

[0026] The base material (A) is subjected to a shear rate of 100 sec -1 , viscosity at 65℃ (V A ), the curing agent (B) is subjected to a shear rate of 100 sec -1 , viscosity at 65℃ (V B ) and the pigment paste (C), at a shear rate of 100 sec -1 , viscosity at 65℃ (VC ) is determined based on the following formula (1) and formula (2) from the viewpoint of hardness, adhesion, color unevenness, etc. of the coating film to be formed: 0.1≦(V B ) / (V A )≦7.1 0.2≦(V C ) / (V A )≦5.6 It is preferable that the following is satisfied.

[0027] The base material (A) is subjected to a shear rate of 100 sec -1 , viscosity at 65℃ (V A ), the curing agent (B) is subjected to a shear rate of 100 sec -1 , viscosity at 65℃ (V B ) and the pigment paste (C), at a shear rate of 100 sec -1 , viscosity at 65℃ (V C ) is determined based on the following formula (1) and formula (2) from the viewpoint of hardness, adhesion, color unevenness, etc. of the coating film to be formed: 0.4≦(V B ) / (V A )≦2.5 Equation (1) 0.3≦(V C ) / (V A )≦3.0 Equation (2) It is more preferable that the following conditions are satisfied:

[0028] The base material (A) is subjected to a shear rate of 100 sec -1 , viscosity at 65℃ (V A ) and the curing agent (B), at a shear rate of 100 sec -1 , viscosity at 65℃ (V B ) is determined from the viewpoint of the hardness and adhesion of the coating film formed, 0.4≦(V B ) / (V A )≦2.0 is more preferable, 0.4≦(V B ) / (V A )≦1.5 is more preferable.

[0029] The base material (A) is subjected to a shear rate of 100 sec -1, viscosity at 65℃ (V A ) and pigment paste (C), at a shear rate of 100 sec -1 , viscosity at 65℃ (V C ) from the viewpoint of uneven color of the coating film formed, 0.3≦(V C ) / (V A )≦2.5 is more preferable, 0.4≦(V C ) / (V A It is more preferable that the relationship be satisfied.

[0030] [Main ingredient (A)] The main component (A) contains an isocyanate-reactive group-containing compound (a1). [Isocyanate-reactive group-containing compound (a1)] The isocyanate-reactive group-containing compound (a1) is a compound having at least one isocyanate-reactive group in one molecule.

[0031] The isocyanate-reactive group is not particularly limited as long as it is a group that is reactive to an isocyanate group. Examples of the isocyanate-reactive group include a hydroxyl group, an amino group, and a thiol group, and from the viewpoint of the hardness, adhesion, and color unevenness of the coating film formed, it is preferable to include at least one selected from a hydroxyl group and an amino group, and more preferably to include a hydroxyl group.

[0032] Therefore, examples of the isocyanate-reactive group-containing compound (a1) include a hydroxyl group-containing compound (a11), an amino group-containing compound (a12), a thiol group-containing compound (a13), etc., and from the viewpoints of the hardness, adhesion, and color unevenness of the coating film to be formed, it is preferable to contain at least one compound selected from the hydroxyl group-containing compound (a11) and the amino group-containing compound (a12), and it is more preferable to contain the hydroxyl group-containing compound (a11).

[0033] From the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed, the isocyanate-reactive group-containing compound (a1) preferably contains an isocyanate-reactive group-containing compound having a number average molecular weight in the range of 250 to 2500, more preferably contains an isocyanate-reactive group-containing compound having a number average molecular weight in the range of 300 to 1800, and even more preferably contains an isocyanate-reactive group-containing compound having a number average molecular weight in the range of 300 to 1500.

[0034] [Hydroxyl-containing compound (a11)] The hydroxyl-containing compound (a11) is a compound having at least one hydroxyl group in one molecule. Examples of the hydroxyl-containing compound (a11) include hydroxyl-containing oligomers and hydroxyl-containing polymers, such as hydroxyl-containing polyester resins, hydroxyl-containing polycaprolactone resins, hydroxyl-containing polyether resins, hydroxyl-containing polycarbonate resins, hydroxyl-containing acrylic resins, hydroxyl-containing polyurethane resins, hydroxyl-containing epoxy resins, and hydroxyl-containing alkyd resins. Among them, from the viewpoints of reducing the VOC content in the resulting coating composition, and the hardness, adhesion, and color unevenness of the coating film formed, it is preferable to include at least one resin selected from hydroxyl-containing polyester resins, hydroxyl-containing polycaprolactone resins, and hydroxyl-containing polyether resins, and more preferably to include at least one resin selected from hydroxyl-containing polyester resins and hydroxyl-containing polycaprolactone resins. Each of these can be used alone or in combination of two or more.

[0035] The above hydroxyl-containing polyester resin can usually be produced by an esterification reaction or transesterification reaction between an acid component and an alcohol component.

[0036] The acid component may be a compound that is commonly used as a polycarboxylic acid in the production of the hydroxyl group-containing polyester resin, such as an aliphatic polybasic acid, an alicyclic polybasic acid, or an aromatic polybasic acid.

[0037] The above-mentioned aliphatic polybasic acid is generally an aliphatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aliphatic compound, and an esterification product of the aliphatic compound. Examples of the aliphatic polybasic acid include aliphatic polybasic carboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane diacid, dodecane diacid, brassylic acid, octadecanedioic acid, citric acid, and butanetetracarboxylic acid; anhydrides of the aliphatic polybasic carboxylic acids; and lower alkyl esters of the aliphatic polybasic carboxylic acids having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. The above-mentioned aliphatic polybasic acids can be used alone or in combination of two or more kinds.

[0038] The alicyclic polybasic acid is generally a compound having one or more alicyclic structures and two or more carboxyl groups in one molecule, an acid anhydride of the compound, and an esterification product of the compound. The alicyclic structure can be mainly a 4- to 6-membered ring structure. Examples of the alicyclic polybasic acid include alicyclic polycarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-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; anhydrides of the alicyclic polybasic acid; and lower alkyl esters of the alicyclic polybasic carboxylic acids having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. The above alicyclic polybasic acids can be used alone or in combination of two or more kinds.

[0039] The aromatic polybasic acid is generally an aromatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aromatic compound, and an esterification product of the aromatic compound. Examples of the aromatic polybasic acid include aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, trimellitic acid, and pyromellitic acid; anhydrides of the aromatic polybasic carboxylic acids; and lower alkyl esters of the aromatic polybasic carboxylic acids having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. The aromatic polybasic acids can be used alone or in combination of two or more kinds.

[0040] In addition, acid components other than the above-mentioned aliphatic polybasic acids, alicyclic polybasic acids, and aromatic polybasic acids can also be used. Such acid components are not particularly limited, and examples thereof include fatty acids such as coconut oil fatty acid, cottonseed oil fatty acid, hempseed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, and safflower oil fatty acid; monocarboxylic acids such as isononanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexanoic acid, and 10-phenyloctadecanoic acid; and hydroxycarboxylic acids such as lactic acid, 3-hydroxybutanoic acid, and 3-hydroxy-4-ethoxybenzoic acid. These acid components can be used alone or in combination of two or more.

[0041] As the alcohol component, a polyhydric alcohol having two or more hydroxyl groups in one molecule can be suitably used. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,2-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-pentanediol, 1 ,5-Pentanediol, 1,4-Pentanediol, 2,4-Pentanediol, 2,3-Dimethyltrimethylene glycol, Tetramethylene glycol, 3-Methyl-4,3-pentanediol, 3-Methyl-1,5-pentanediol, 2,2,4-Trimethyl-1,3-pentanediol, 1,6-Hexanediol, 1,5-Hexanediol, 1,4-Hexanediol, 2,5-Hexanediol, Neopentyl glycol, 1,4-Cyclohexanedimethanol, Tricyclohexane dihydric alcohols such as candimethanol, hydroxypivalic acid neopentyl glycol ester, hydrogenated bisphenol A, hydrogenated bisphenol F, and dimethylolpropionic acid; polylactone diols obtained by adding lactone compounds such as ε-caprolactone to these dihydric alcohols; ester diol compounds such as bis(hydroxyethyl)terephthalate; polyether diol compounds such as alkylene oxide adducts of bisphenol A, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; trihydric or higher alcohols such as glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tris(2-hydroxyethyl)isocyanuric acid, sorbitol, and mannitol; polylactone polyol compounds obtained by adding lactone compounds such as ε-caprolactone to these trihydric or higher alcohols; and fatty acid esters of glycerin.

[0042] In addition, alcohol components other than the above polyhydric alcohols can also be used. Such alcohol components are not particularly limited, and examples thereof include monoalcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, isobutyl alcohol, pentyl alcohol, 2-ethylhexyl alcohol, stearyl alcohol, benzyl alcohol, phenethyl alcohol, and 2-phenoxyethanol; and alcohol compounds obtained by reacting monoepoxy compounds such as propylene oxide, butylene oxide, and "Cardura E10P" (trade name, manufactured by Hexion, glycidyl ester of synthetic highly branched saturated fatty acid) with an acid.

[0043] The method for producing the hydroxyl-containing polyester resin is not particularly limited and can be carried out according to a conventional method. For example, the hydroxyl-containing polyester polyol resin can be produced by heating the acid component and the alcohol component in a nitrogen stream at about 150 to 250°C for about 5 to 10 hours to carry out an esterification reaction or an ester exchange reaction between the acid component and the alcohol component.

[0044] When the acid component and the alcohol component are subjected to an esterification reaction or an ester exchange reaction, these components may be added to a reaction vessel at once, or one or both may be added in several portions. Alternatively, the hydroxyl-containing polyester resin may be first synthesized, and then the resulting hydroxyl-containing polyester resin may be reacted with an acid anhydride to half-esterify the resulting hydroxyl-containing polyester resin to obtain a carboxyl- and hydroxyl-containing polyester resin. Alternatively, the carboxyl-containing polyester resin may be first synthesized, and then the alcohol component may be added to produce the hydroxyl-containing polyester resin.

[0045] In the above-mentioned esterification or transesterification reaction, a catalyst known per se, such as dibutyltin oxide, antimony trioxide, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, or tetraisopropyl titanate, can be used as a catalyst for promoting the reaction.

[0046] The hydroxyl-containing polyester resin may be modified with a fatty acid, a monoepoxy compound, a polyisocyanate compound, or the like during or after the production of the resin. Examples of the fatty acids include coconut oil fatty acids, cottonseed oil fatty acids, hempseed oil fatty acids, rice bran oil fatty acids, fish oil fatty acids, tall oil fatty acids, soybean oil fatty acids, linseed oil fatty acids, tung oil fatty acids, rapeseed oil fatty acids, castor oil fatty acids, dehydrated castor oil fatty acids, safflower oil fatty acids, and the like. An example of the monoepoxy compound that can be suitably used is "Cardura E10P" (trade name, manufactured by Hexion, glycidyl ester of synthetic highly branched saturated fatty acid).

[0047] Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as lysine diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; alicyclic diisocyanate compounds such as hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,3-(isocyanatomethyl)cyclohexane, and 1,4-(isocyanatomethyl)cyclohexane; Examples of the organic polyisocyanate include aromatic diisocyanate compounds such as isocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, and diphenylmethane diisocyanate; organic polyisocyanates themselves, such as trivalent or higher polyisocyanates, such as lysine triisocyanate and 4-(isocyanatomethyl)octamethylene diisocyanate; adducts of these organic polyisocyanates with polyhydric alcohols, low molecular weight polyester resins, water, and the like; cyclized polymers of these organic polyisocyanates (for example, isocyanurates), biuret adducts, and allophanate adducts. These polyisocyanate compounds can be used alone or in combination of two or more.

[0048] The hydroxyl value of the hydroxyl-containing polyester resin is preferably within a range of 50 to 800 mgKOH / g, more preferably within a range of 100 to 700 mgKOH / g, and even more preferably within a range of 300 to 600 mgKOH / g, from the viewpoints of the hardness and adhesion of the coating film to be formed.

[0049] The number average molecular weight of the hydroxyl group-containing polyester resin is preferably within the range of 250 to 2500, more preferably within the range of 300 to 1800, and even more preferably within the range of 350 to 1500, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film formed. The glass transition temperature (Tg) of the hydroxyl-containing polyester resin is preferably within the range of -80 to 10°C, more preferably within the range of -70 to 5°C, and even more preferably within the range of -60 to 0°C, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film formed. In this specification, the number average molecular weight and the weight average molecular weight are values ​​obtained by converting the retention time (retention volume) measured using a gel permeation chromatograph (GPC) into the molecular weight of polystyrene using the retention time (retention volume) of a standard polystyrene with a known molecular weight measured under the same conditions. Specifically, the gel permeation chromatograph uses "HLC-8120GPC" (trade name, manufactured by Tosoh Corporation), four columns in total, "TSKgel G4000HXL", "TSKgel G3000HXL", "TSKgel G2500HXL" and "TSKgel G2000HXL" (trade names, all manufactured by Tosoh Corporation), a differential refractometer is used as the detector, and the measurements can be performed under the following conditions: mobile phase: tetrahydrofuran, measurement temperature: 40°C, flow rate: 1mL / min.

[0050] The glass transition temperature can be measured, for example, by using a differential scanning calorimeter "DSC-50Q type" (manufactured by Shimadzu Corporation, product name), placing a sample in a measuring cup, and completely removing the solvent by vacuum suction, and then measuring the change in heat quantity in the range of -100°C to 150°C at a heating rate of 3°C / min, and taking the first change point in the baseline on the low temperature side as the static glass transition temperature.

[0051] When the hydroxyl-containing compound (a11) contains a hydroxyl-containing polyester resin, the content of the hydroxyl-containing polyester resin is preferably within the range of 50 to 100 mass %, more preferably within the range of 60 to 95 mass %, and even more preferably within the range of 70 to 90 mass %, based on the total solid content of the hydroxyl-containing compound (a11), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed.

[0052] The hydroxyl group-containing polycaprolactone resin can be obtained, for example, by ring-opening polymerization of ε-caprolactone using a dihydric to tetrahydric polyhydric alcohol as an initiator. Examples of the dihydric or higher polyhydric alcohol include polyhydric alcohol compounds obtained by reacting ethylene glycol, glycerin, trimethylolethane, trimethylolpropane, diglycerin, ditrimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, tris(2-hydroxyethyl)isocyanuric acid, and dimethylolalkanoic acid with a monoepoxy compound (for example, "Cardura E10P; glycidyl ester of synthetic highly branched saturated fatty acid" manufactured by HEXION Specialty Chemicals). These can be used alone or in combination of two or more. As the hydroxyl group-containing polycaprolactone resin, commercially available products can be used. Commercially available products include, for example, "Placcel 205", "Placcel 205H", "Placcel L205AL", "Placcel 205U", "Placcel 208", "Placcel 210", "Placcel 210N", "Placcel 210CP", "Placcel 212", "Placcel L212AL", "Placcel 220", "Placcel 220N", "Placcel 220CPB", "Placcel 220CPT", "Placcel 220UA", "Placcel 220NP1", "Placcel L220AL", "Placcel 220EB", "Placcel 230", "Placcel 230N", "Placcel 240", "Placcel 303", "Placcel 305", "Placcel 308", "Placcel 309", "Placcel 312", "Placcel 320", "Placcel L320AL", and "Placcel 410" (all trade names, manufactured by Daicel Corporation), "TONE Examples of such caps include "Capa 2043", "Capa 2101", "Capa 2201", "Capa 2205", "Capa 2209", "Capa 2201A", "Capa 2203A", "Capa 7201A", "Capa 7203", "Capa 3031", "Capa 3050J", "Capa 3091", and "Capa 4101" (all of which are product names manufactured by Ingevity).

[0053] The hydroxyl value of the hydroxyl-containing polycaprolactone resin is preferably within the range of 50 to 900 mgKOH / g, more preferably within the range of 100 to 750 mgKOH / g, and even more preferably within the range of 130 to 600 mgKOH / g, from the viewpoints of the hardness and adhesion of the coating film to be formed.

[0054] The number average molecular weight of the hydroxyl group-containing polycaprolactone resin is preferably within the range of 250 to 2500, more preferably within the range of 280 to 1500, and even more preferably within the range of 300 to 1000, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film formed. When the hydroxyl-containing compound (a11) contains the above-mentioned hydroxyl-containing polycaprolactone resin, the content of the hydroxyl-containing polycaprolactone resin is preferably within the range of 5 to 100 mass %, more preferably within the range of 10 to 75 mass %, and even more preferably within the range of 10 to 50 mass %, based on the total solid content of the hydroxyl-containing compound (a11), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed.

[0055] The hydroxyl group-containing polyether resin may be an alkylene oxide adduct of a hydroxyl group-containing monomer, a ring-opening (co)polymer of an alkylene oxide or a cyclic ether (such as tetrahydrofuran), etc. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, a (block or random) copolymer of ethylene glycol-propylene glycol, polyhexamethylene glycol, polyoctamethylene glycol, etc. The above hydroxyl group-containing polyether resins can be used alone or in combination of two or more.

[0056] The hydroxyl value of the hydroxyl-containing polyether resin is preferably within the range of 50 to 600 mgKOH / g, more preferably within the range of 70 to 500 mgKOH / g, and even more preferably within the range of 90 to 400 mgKOH / g, from the viewpoints of the hardness and adhesion of the coating film to be formed.

[0057] The number average molecular weight of the hydroxyl group-containing polyether resin is preferably within the range of 250 to 2500, more preferably within the range of 300 to 1500, and even more preferably within the range of 350 to 1000, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film formed.

[0058] When the hydroxyl-containing compound (a11) contains the above-mentioned hydroxyl-containing polyether resin, the content of the hydroxyl-containing polyether resin is preferably within the range of 20 to 100 mass %, more preferably within the range of 40 to 100 mass %, and even more preferably within the range of 50 to 100 mass %, based on the total solid content of the hydroxyl-containing compound (a11), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film to be formed.

[0059] The hydroxyl group-containing polycarbonate resin is a compound obtained by a conventional polycondensation reaction between a known polyol component and a carbonylating agent. Examples of the polyol component include a diol component and a polyhydric alcohol component such as a trihydric or higher alcohol.

[0060] Examples of the diol component include linear diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol; 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,6-hexanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2, Examples of the diol components include branched diols such as 4-trimethyl-1,3-pentanediol and 2-ethyl-1,3-hexanediol, alicyclic diols such as 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol, aromatic diols such as p-xylenediol and p-tetrachloroxylenediol, ether-based diols such as diethylene glycol and dipropylene glycol, and polylactone diols obtained by adding a lactone compound such as ε-caprolactone to these diol components. These diol components can be used alone or in combination of two or more kinds.

[0061] Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, a dimer of trimethylolpropane, pentaerythritol, and polylactone polyols obtained by adding a lactone compound such as ε-caprolactone to these trihydric or higher alcohols. These trihydric or higher alcohols can be used alone or in combination of two or more kinds.

[0062] The carbonylating agent may be a known one. Specific examples include alkylene carbonate, dialkyl carbonate, diallyl carbonate, phosgene, etc., and these may be used alone or in combination of two or more. Among these, preferred examples include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, etc.

[0063] The hydroxyl value of the hydroxyl-containing polycarbonate resin is preferably within the range of 50 to 800 mgKOH / g, more preferably within the range of 70 to 700 mgKOH / g, and even more preferably within the range of 90 to 600 mgKOH / g, from the viewpoints of the hardness and adhesion of the coating film to be formed.

[0064] The number average molecular weight of the hydroxyl group-containing polycarbonate resin is preferably within the range of 250 to 2500, more preferably within the range of 300 to 1800, and even more preferably within the range of 400 to 1500, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, and color unevenness of the coating film formed.

[0065] When the hydroxyl-containing compound (a11) contains the above-mentioned hydroxyl-containing polycarbonate resin, the content of the hydroxyl-containing polycarbonate resin is preferably within the range of 5 to 80 mass %, more preferably within the range of 10 to 50 mass %, and even more preferably within the range of 10 to 40 mass %, based on the total solid content of the hydroxyl-containing compound (a11), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film to be formed.

[0066] The hydroxyl group-containing acrylic resin can be produced, for example, by copolymerizing a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer by a method known per se, such as a solution polymerization method in an organic solvent or an emulsion polymerization method in water.

[0067] The hydroxyl-containing polymerizable unsaturated monomer is a compound having one or more hydroxyl groups and one or more polymerizable unsaturated bonds in one molecule. Examples of the hydroxyl-containing polymerizable unsaturated monomer include monoesters of (meth)acrylic acid and dihydric alcohols having 2 to 8 carbon atoms, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; ε-caprolactone-modified monoesters of (meth)acrylic acid and dihydric alcohols having 2 to 8 carbon atoms; N-hydroxymethyl (meth)acrylamide; allyl alcohol; and (meth)acrylates having polyoxyethylene chains whose molecular terminals are hydroxyl groups.

[0068] However, in the present invention, a monomer corresponding to the polymerizable unsaturated monomer having an ultraviolet absorbing functional group (xvii) described later should be defined as another polymerizable unsaturated monomer copolymerizable with the above-mentioned hydroxyl group-containing polymerizable unsaturated monomer, and is excluded from the hydroxyl group-containing polymerizable unsaturated monomer. These can be used alone or in combination of two or more kinds.

[0069] As other polymerizable unsaturated monomers copolymerizable with the above-mentioned hydroxyl group-containing polymerizable unsaturated monomers, for example, the following monomers (i) to (xx) can be used. These polymerizable unsaturated monomers can be used alone or in combination of two or more kinds.

[0070] (i) Alkyl or cycloalkyl (meth)acrylates: for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, tricyclodecanyl (meth)acrylate, and the like. (ii) Polymerizable unsaturated monomers having an isobornyl group: isobornyl (meth)acrylate, etc. (iii) Polymerizable unsaturated monomers having an adamantyl group: adamantyl (meth)acrylate, etc. (iv) Polymerizable unsaturated monomers having a tricyclodecenyl group: tricyclodecenyl (meth)acrylate, etc. (v) Aromatic ring-containing polymerizable unsaturated monomers: benzyl (meth)acrylate, styrene, α-methylstyrene, vinyltoluene, and the like.

[0071] (vi) Polymerizable unsaturated monomers having an alkoxysilyl group: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, and the like. (vii) Polymerizable unsaturated monomers having a fluorinated alkyl group: perfluoroalkyl (meth)acrylates such as perfluorobutylethyl (meth)acrylate and perfluorooctylethyl (meth)acrylate; fluoroolefins, and the like. (viii) Polymerizable unsaturated monomers having a photopolymerizable functional group such as a maleimide group. (ix) Vinyl compounds: N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate, etc. (x) Carboxyl group-containing polymerizable unsaturated monomers: (meth)acrylic acid, maleic acid, crotonic acid, β-carboxyethyl (meth)acrylate, etc.

[0072] (xi) Nitrogen-containing polymerizable unsaturated monomers: (meth)acrylonitrile, (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, methylene bis(meth)acrylamide, ethylene bis(meth)acrylamide, adducts of glycidyl (meth)acrylate and amine compounds, and the like. (xii) Polymerizable unsaturated monomers having two or more polymerizable unsaturated groups in one molecule: allyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, etc. (xiii) Epoxy group-containing polymerizable unsaturated monomers: glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, 3,4-epoxycyclohexylpropyl (meth)acrylate, allyl glycidyl ether, and the like. (xiv) (meth)acrylates having a polyoxyethylene chain whose molecular terminal is an alkoxy group. (xv) Polymerizable unsaturated monomers having a sulfonic acid group: 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth)acrylate, allylsulfonic acid, 4-styrenesulfonic acid, and the like; sodium salts and ammonium salts of these sulfonic acids.

[0073] (xvi) Polymerizable unsaturated monomers having a phosphoric acid group: acid phosphooxyethyl (meth)acrylate, acid phosphooxypropyl (meth)acrylate, acid phosphooxypoly(oxyethylene)glycol (meth)acrylate, acid phosphooxypoly(oxypropylene)glycol (meth)acrylate, and the like. (xvii) Polymerizable unsaturated monomers having an ultraviolet absorbing functional group: 2-hydroxy-4(3-methacryloyloxy-2-hydroxypropoxy)benzophenone, 2-hydroxy-4-(3-acryloyloxy-2-hydroxypropoxy)benzophenone, 2,2'-dihydroxy-4-(3-methacryloyloxy-2-hydroxypropoxy)benzophenone, 2,2'-dihydroxy-4-(3-acryloyloxy-2-hydroxypropoxy)benzophenone, 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole, and the like. (xviii) Light-stable polymerizable unsaturated monomers: 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, etc. (xix) Polymerizable unsaturated monomers having a carbonyl group: acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrol, vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), and the like. (xx) Polymerizable unsaturated monomers having an acid anhydride group: maleic anhydride, itaconic anhydride, citraconic anhydride, etc.

[0074] In this specification, the polymerizable unsaturated group refers to an unsaturated group capable of radical polymerization. Examples of such polymerizable unsaturated groups include vinyl groups, (meth)acryloyl groups, (meth)acrylamide groups, vinyl ether groups, allyl groups, propenyl groups, isopropenyl groups, and maleimide groups.

[0075] In addition, in this specification, "(meth)acrylate" means acrylate and / or methacrylate. "(meth)acrylic acid" means acrylic acid and / or methacrylic acid. "(meth)acryloyl" means acryloyl and / or methacryloyl. "(meth)acrylamide" means acrylamide and / or methacrylamide.

[0076] The hydroxyl value of the hydroxyl-containing acrylic resin is preferably within the range of 5 to 240 mgKOH / g, more preferably within the range of 20 to 220 mgKOH / g, and even more preferably within the range of 25 to 200 mgKOH / g, from the viewpoints of the hardness and adhesion of the coating film to be formed.

[0077] The number average molecular weight of the hydroxyl-containing acrylic resin is preferably within the range of 250 to 2500, more preferably within the range of 300 to 1800, and even more preferably within the range of 500 to 1500, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film to be formed.

[0078] The glass transition temperature (Tg) of the hydroxyl-containing acrylic resin is preferably within the range of -60 to 80°C, more preferably within the range of -50 to 70°C, and even more preferably within the range of -40 to 60°C, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film formed.

[0079] In this specification, the glass transition temperature (Tg) of the hydroxyl-containing acrylic resin is a value calculated by the following formula. 1 / Tg(K)=W1 / T1+W2 / T2+...Wn / Tn Tg(℃)=Tg(K)-273 In the formula, W1, W2, ...Wn are the mass fractions of each monomer, and T1, T2...Tn are the glass transition temperatures Tg (K) of the homopolymers of each monomer.

[0080] The glass transition temperatures of the homopolymers of each monomer are values ​​according to POLYMER HANDBOOK Fourth Edition, edited by J. Brandrup, Eh Immergut, and EA Grulke (1999). The glass transition temperatures of monomers not described in the literature are calculated by dividing the homopolymers of the monomers by weight-average molecular weight of 50, The static glass transition temperature is determined when the compound is synthesized so that the temperature is about 10,000.

[0081] When the hydroxyl-containing compound (a11) contains the above-mentioned hydroxyl-containing acrylic resin, the content of the hydroxyl-containing acrylic resin is preferably within the range of 5 to 100 mass %, more preferably within the range of 10 to 75 mass %, and even more preferably within the range of 15 to 50 mass %, based on the total solid content of the hydroxyl-containing compound (a11), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed.

[0082] Examples of the hydroxyl group-containing compound (a11) include hydroxyl group-containing monomers such as ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,2-butanediol, 2 -butyl-2-ethyl-1,3-propanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-4,3-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol ol, 2,5-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, hydroxypivalic acid neopentyl glycol ester, hydrogenated bisphenol A, hydrogenated bisphenol F, glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tris(2-hydroxyethyl)isocyanuric acid, sorbitol, mannitol, hydroxyacetone, 4-(2-hydroxyethyl)morpholine, benzyl alcohol, 2-phenylethanol, 2-phenoxyethanol, naphthalene-1-ol, (1,3-benzoxol-5-yl)methanol, nonylphenol, dinonylphenol, nonylphenol ethoxylate, monostyrenated phenol, distyrenated phenol, tristyrenated phenol, etc. These can be used alone or in combination of two or more.

[0083] When the hydroxyl-containing compound (a11) contains the hydroxyl-containing monomer, the content of the hydroxyl-containing monomer is, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film to be formed, preferably in the range of 5 to 100 mass %, more preferably in the range of 5 to 50 mass %, and even more preferably in the range of 5 to 30 mass %, based on the total solid content of the hydroxyl-containing compound (a11).

[0084] When the isocyanate-reactive group-containing compound (a1) contains the hydroxyl group-containing compound (a11), the content of the hydroxyl group-containing compound (a11) is preferably within the range of 50 to 100 mass%, more preferably within the range of 60 to 100 mass%, and even more preferably within the range of 70 to 100 mass%, based on the total solid content of the isocyanate-reactive group-containing compound (a1), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed.

[0085] [Amino group-containing compound (a12)] The amino group-containing compound (a12) is a compound having at least one primary amino group and / or secondary amino group in the molecule.

[0086] Examples of the amino group-containing compound (a12) include aliphatic polyamines such as ethylenediamine, pentamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, N,N'-bis-(3-aminopropyl)ethylenediamine, and tetraethylenepentamine; 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4-methyl-1,3-cyclohexanediamine, 2-methyl- Alicyclic polyamines such as 1,3-cyclohexanediamine, isophoronediamine, 4,4'-methylenebis(cyclohexylamine), 3,3'-dimethyl-4,4'-methylenebis(cyclohexylamine), N,N'-(isophoronediamino)bispropionitrile, N,N'-di-sec-butyl-4,4'-methylenebis(cyclohexylamine), 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, and norbornanediamine; Heterocyclic polyamines such as piperazine and N-(2-aminoethyl)piperazine; 2,4-toluenediamine, 2,6-toluenediamine, 4,4'-diaminodiphenylmethane, diethyltoluenediamine, dimethylthiotoluenediamine, 4,4'-methylenebis[N-(1-methylpropyl)aniline], 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, 4,4'-(1,3-phenylenediisopropyl)benzene, aromatic polyamines such as 4,4'-(1,4-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, aminobenzylamine, m-xylylenediamine, p-xylylenediamine, and N,N'-di-sec-butyl-p-phenylenediamine; polyether polyamine compounds such as polyoxypropylenediamine, polyoxyethylenediamine, poly(oxyethylene / oxypropylene)diamine, trimethylolpropanepoly(oxypropylene)triamine, and glycerylpoly(oxypropylene)triamine;Polyaspartic acid ester compounds such as N,N'-(2-methylpentane-1,5-diyl)bisaspartate tetraethyl, N,N'-[methylenebis(cyclohexane-4,1-diyl)]bisaspartate tetraethyl, N,N'-[methylenebis(2-methylcyclohexane-4,1-diyl)]bisaspartate tetraethyl, α-{2-[(1,4-diethoxy-1,4-dioxobutan-2-yl)amino]propyl}-ω-{2-[(1,4-diethoxy-1,4-dioxobutan-2-yl)amino]propoxy}poly[oxy(methylethylene)]; aminosilane compounds such as N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane, and γ-anilinopropyltrimethoxysilane. These can be used alone or in combination of two or more kinds.

[0087] As the amino group-containing compound (a12), commercially available products can be used. Examples of commercially available product names include "Baxxodur EC110", "DETA", "N4 Amine", "Baxxodur EC210", "Baxxodur EC201", "Baxxodur EC330", "Baxxodur EC331", "Baxxodur PC136", "Baxxodur EC130", "Baxxodur EC280", "Baxxodur EC301", "Baxxodur EC302", "Baxxodur EC303", "Baxxodur EC310", and "Baxxodur EC311" (all of which are product names manufactured by BASF), "Clearlink 1000", "Unilink 4200", and "Unilink 4100" (all of which are product names manufactured by DORF KETAL), "JEFFAMINE M-600", "JEFFAMINE M-1000", "JEFFAMINE M-2005", "JEFFAMINE M-2070", and "JEFFAMINE M-3085", "JEFFAMINE D-230", "JEFFAMINE D-400", "JEFFAMINE D-2000", "JEFFAMINE D-4000", "JEFFAMINE ED-600", "JEFFAMINE ED-900", "JEFFAMINE ED-2003", "JEFFAMINE EDR-148", "JEFFAMINE RT-1000", "JEFFAMINE T-403", "JEFFAMINE T-3000", "JEFFAMINE T-5000" (all trade names, manufactured by HUNTSMAN), "MXDA", "1,3-BAC" (all trade names, manufactured by Mitsubishi Gas Chemical Co., Ltd.), "WANAMINE MDA-100H", "Ethacure 100 Plus", "Ethacure 300", "Ethacure 420", "Bisaniline-M", "Bisaniline-P" (all trade names, manufactured by Mitsui Chemicals Fine Co., Ltd.), "VESTAMIN "VESTAMIN IPD", "VESTAMIN TMD", "VESTAMIN PACM", "ANCAMINE 2049", "AMICURE IC-321", "AMICURE IC-322" (all product names, manufactured by EVONIK Industries), "DEH20", "DEH24", "DEH26", "DEH29", "DEH39", "DEH444", "DEH445", "DEH4042", "DEH4044", "DEH487", "DEH488", "DEH530", "DEH" (all trade names, manufactured by The Dow Chemical Company), "Desmophen NH1220", "Desmophen NH1420", "Desmophen NH1422", "Desmophen NH1423", "Desmophen NH1520", "Desmophen NH1521", "Desmophen NH1523", "Desmophen NH1723LF", "Desmophen NH2885", "Desmophen NH2886" (all trade names, manufactured by Covestro), "FEISPARTIC F220", "FEISPARTIC F420", "FEISPARTIC F520", "FEISPARTIC F2850", "FEISPARTIC F2872", "FEISPARTIC F221", "FEISPARTIC F321", "FEISPARTIC F525", "FEISPARTIC F421", "FEISPARTIC F524", "FEISPARTIC F330", "FEISPARTIC D2925", "FEISPARTIC D2903" (all trade names, manufactured by Feiyang Protech), "TSE-EZASP 7980", "TSE-EZASP 7981", "TSE-EZASP 9033", "TSE-EZASP 8443" (all trade names, manufactured by TSE Industries), "Altor 200", "Altor 201", "Altor 202", "Altor 205LV" (all trade names, manufactured by Cargill), etc.

[0088] From the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film formed, the amino group-containing compound (a12) preferably contains at least one compound selected from aliphatic polyamines, alicyclic polyamines, polyether polyamine compounds, and polyaspartic acid ester compounds, more preferably contains at least one compound selected from alicyclic polyamines and polyaspartic acid esters, and even more preferably contains a polyaspartic acid ester compound.

[0089] As the polyaspartic acid ester compound, commercially available products can be used. Examples of trade names of commercially available products include Desmophen NH1220, Desmophen NH1420, Desmophen NH1422, Desmophen NH1423, Desmophen NH1520, Desmophen NH1521, Desmophen NH1523, Desmophen NH1723LF, Desmophen NH2885, and Desmophen NH2886 (all trade names, manufactured by Covestro), FEISPARTIC F220, FEISPARTIC F420, FEISPARTIC F520, FEISPARTIC F2850, FEISPARTIC F2872, FEISPARTIC F221, FEISPARTIC F321, and FEISPARTIC F525", "FEISPARTIC F421", "FEISPARTIC F524", "FEISPARTIC F330", "FEISPARTIC D2925", "FEISPARTIC D2903" (all product names manufactured by Feiyang Protech), "TSE-EZASP 7980", "TSE-EZASP 7981", "TSE-EZASP 9033", "TSE-EZASP 8443" (all product names manufactured by TSE Industries), "Altor 200", "Altor 201", "Altor 202", "Altor 205LV" (all product names manufactured by Cargill), and the like.

[0090] When the isocyanate-reactive group-containing compound (a1) contains the amino group-containing compound (a12), the content of the amino group-containing compound (a12) is preferably within the range of 10 to 100 mass%, more preferably within the range of 40 to 95 mass%, and even more preferably within the range of 50 to 90 mass%, based on the total solid content of the isocyanate-reactive group-containing compound (a1), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed.

[0091] [Thiol group-containing compound (a13)] The thiol group-containing compound (a13) is a compound having at least one thiol group in one molecule.

[0092] Examples of the thiol group-containing compound (a13) include pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), tetramethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), trimethylolpropane dipropanethiol, pentaerythritol hexakis(3-mercaptopropionate), trimethylolpropane dipropanethiol, and pentaerythritol hexakis(3-mercaptopropionate). Examples of such compounds include erythritol tripropanethiol, pentaerythritol tetrapropanethiol, 1,4-bis(mercaptomethyl)benzene, pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), tetramethylene glycol bis(3-mercaptobutyrate), tris-[(3-mercaptobutyroyloxy)-ethyl]-isocyanurate, trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), etc. These compounds can be used alone or in combination of two or more.

[0093] As the thiol group-containing compound (a13), commercially available products can be used. Examples of commercially available product names include "TMMP-LV", "TEMPIC", "PEMP-LV", "DPMP", "EGMP-4", "BDMP", "Multhiol Y-2", "Multhiol Y-3", "Multhiol Y-4", "PXDT" (all of which are product names, manufactured by SC Organic Chemical Co., Ltd.), "BDTG", "HDTG", "TMTG", "PETG", "EGTP", "BDTP", "TMTP", "PETP" (all of which are product names, manufactured by Yodo Chemical Co., Ltd.), "ADEKA HARDENER EH-317" (all of which are product names, manufactured by ADEKA Corporation), "Karenz MT PEI", "Karenz MT BDI", "Karenz MT BD1", "Karenz MT TPMB", "Karenz MT NRI" (all of which are product names, manufactured by Showa Denko Co., Ltd.), "jER Cure QX11", "jER Cure QX40" (all of which are product names, manufactured by Mitsubishi Chemical Co., Ltd.), etc.

[0094] When the isocyanate-reactive group-containing compound (a1) contains the thiol group-containing compound (a13), the content of the thiol group-containing compound (a13) is preferably within the range of 10 to 100 mass%, more preferably within the range of 30 to 95 mass%, and even more preferably within the range of 50 to 90 mass%, based on the total solid content of the isocyanate-reactive group-containing compound (a1), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed.

[0095] The content of the isocyanate-reactive group-containing compound (a1) in the main component (A) is preferably within the range of 30 to 99.5 mass %, more preferably within the range of 50 to 99 mass %, and even more preferably within the range of 70 to 98 mass %, based on the total amount of the main component (A), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film to be formed.

[0096] [Other ingredients] The main component (A) may further contain an ultraviolet absorbing agent and / or a light stabilizer, and may also contain other additives, such as an internal mold release agent, a solvent (organic solvent, water), a pigment, a catalyst, a dehydrating agent, an antioxidant, a surface conditioner, an antifoaming agent, an emulsifier, a surfactant, an antifouling agent, a wetting agent, a thickener, a dye, an anti-scratch agent, a gloss adjuster, etc., that are commonly used in the field of coatings.

[0097] <Ultraviolet absorbing agent> As the ultraviolet absorbing agent, a conventionally known agent can be used, for example, a benzotriazole-based absorbent, a triazine-based absorbent, a salicylic acid derivative-based absorbent, a benzophenone-based absorbent, etc. The ultraviolet absorbing agent may have a polymerizable unsaturated group.

[0098] Specific examples of the benzotriazole-based absorbent include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, Examples of the benzotriazole include 2-(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-{2'-hydroxy-3'-(3'',4'',5'',6''-tetrahydrophthalimidomethyl)-5'-methylphenyl}benzotriazole, and 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole.

[0099] Specific examples of the triazine-based absorbents include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-1,3,5-triazine, 2-[4((2-hydroxy-3-dodecyloxypropyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-((2-hydroxy-3-tridecyloxypropyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

[0100] Specific examples of the salicylic acid derivative-based absorbents include phenyl salicylate, p-octylphenyl salicylate, and 4-tert-butylphenyl salicylate.

[0101] Specific examples of the benzophenone-based absorbent include 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, and naphthyloxybenzophenone. Examples of such compounds include thorium 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, resorcinol monobenzoate, 2,4-dibenzoylresorcinol, 4,6-dibenzoylresorcinol, hydroxydodecylbenzophenone, and 2,2'-dihydroxy-4(3-methacryloxy-2-hydroxypropoxy)benzophenone.

[0102] In addition, examples of commercially available ultraviolet absorbents include "TINUVIN 1130", "TINUVIN 900", "TINUVIN 928", "TINUVIN 384-2", "TINUVIN 479", "TINUVIN 477", "TINUVIN 405", "TINUVIN 400" (product names manufactured by BASF, TINUVIN is a registered trademark), and "RUVA 93" (product name manufactured by Otsuka Chemical Co., Ltd.).

[0103] When the main component (A) contains the above-mentioned ultraviolet absorber, the content of the ultraviolet absorber is preferably within the range of 0.5 to 10 mass %, more preferably within the range of 0.8 to 5.0 mass %, and even more preferably within the range of 1.0 to 4.0 mass %, based on the total amount of the main component (A), from the viewpoints of the weather resistance and adhesion of the coating film to be formed.

[0104] <Light stabilizer> The light stabilizer is used as a radical chain inhibitor that captures active radical species generated during the deterioration process of the coating film, and examples thereof include light stabilizers of hindered amine compounds.

[0105] Examples of the hindered amine compound include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, 4-benzoyloxy-2,2',6,6'-tetramethylpiperidine, bis(1,2,2,6,6-pentamethyl-4-piperidyl){[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl}butylmalonate, and the like. Examples of the light stabilizer include, but are not limited to, monomeric types such as poly([6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)iminol]}, oligomeric types such as poly([6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)iminol]}, and polyester bond types such as a polyesterification product of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and succinic acid. As the light stabilizer, known polymerizable light stabilizers can also be used.

[0106] Examples of commercially available light stabilizers include "TINUVIN 123", "TINUVIN 152", "TINUVIN 249", "TINUVIN 292" (manufactured by BASF, product names, TINUVIN is a registered trademark), "HOSTAVIN 3058" (manufactured by Clariant, product name, Hostavin is a registered trademark), and "ADK STAB LA-82" (manufactured by ADEKA Corporation, product name, ADK STAB is a registered trademark).

[0107] When the main component (A) contains the above-mentioned light stabilizer, the content of the light stabilizer is preferably within the range of 0.5 to 10 mass %, more preferably within the range of 0.8 to 9.0 mass %, and even more preferably within the range of 1.0 to 8.0 mass %, based on the total amount of the main component (A), from the viewpoints of the weather resistance and adhesion of the coating film to be formed.

[0108] <Internal release agent> When the coating composition of the present invention is used as an in-mold coating composition, it is preferable that the main component (A) contains an internal mold release agent from the viewpoint of the releasability between the formed coating film and the mold.

[0109] Examples of the internal mold releasing agent include saturated fatty acids such as stearic acid and palmitic acid; saturated fatty acid salts such as zinc stearate, aluminum stearate, magnesium stearate, calcium stearate, sodium stearate, potassium stearate, barium stearate, zinc palmitate, aluminum palmitate, magnesium palmitate, calcium palmitate, and sodium palmitate; saturated fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, N,N-dimethyllauric acid amide, N,N-dimethylmyristic acid amide, N,N-dimethylpalmitic acid amide, N,N-dimethylstearic acid amide, N,N-diethyllauric acid amide, N,N-diethylmyristic acid amide, N,N-diethylpalmitic acid amide, and N,N-diethylstearic acid amide; unsaturated fatty acids such as palmitoleic acid and oleic acid; zinc palmitoleate, aluminum palmitoleate, palmitic acid amide, unsaturated fatty acid salts such as magnesium oleate, calcium palmitoleate, sodium palmitoleate, potassium palmitoleate, barium palmitoleate, zinc oleate, aluminum oleate, magnesium oleate, calcium oleate, sodium oleate, potassium oleate, and barium oleate; unsaturated fatty acid amides such as palmitoleic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, N-oleyl palmitic acid amide, N-stearyl erucic acid amide, N,N-dimethyl oleic acid amide, and N,N-diethyl oleic acid amide; nonionic surfactants such as polyoxyethylene alkyl ethers and sorbitan alkyl esters; fluorine-based compounds such as polytetrafluoroethylene, fluoropolyethers, perfluoroalkyl esters, and perfluoroalkyl ester salts; phosphate ester compounds such as phosphoric acid monoesters and / or phosphoric acid diesters having alkyl chains or oxyethylene chains, etc.;Stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearate monosorbitate, stearate stearyl, palmitic acid monoglyceride, palmitic acid diglyceride, palmitic acid triglyceride, behenic acid monoglyceride, behenic acid diglyceride, behenic acid triglyceride, behenyl behenate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propionate Examples of fatty acid esters include ethylene glycol monostearate, stearyl stearate, palmityl palmitate, methyl stearate, butyl stearate, methyl laurate, methyl palmitate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, and 2-ethylhexyl stearate; soybean oil lecithin, silicone oil, and fatty acid alcohol dibasic acid esters, which may be used alone or in combination of two or more kinds;

[0110] When the main agent (A) contains the above-mentioned internal release agent, the content of the internal release agent is preferably within the range of 0.4 to 5.0 mass %, more preferably within the range of 0.5 to 4.0 mass %, and even more preferably within the range of 0.5 to 3.0 mass %, based on the total amount of the main agent (A), from the viewpoints of the adhesion of the coating film to be formed and the releasability between the coating film to be formed and the mold.

[0111] <Solvent> Examples of the solvent include organic solvents, water, etc. Examples of the organic solvent include ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester-based solvents such as ethyl acetate, butyl acetate, methyl benzoate, ethyl ethoxypropionate, ethyl propionate, and methyl propionate; ether-based solvents such as tetrahydrofuran, dioxane, and dimethoxyethane; glycol ether-based solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; aromatic solvents such as toluene, xylene, and "Swasol 1000" (trade name, high-boiling petroleum solvent, manufactured by Cosmo Oil Co., Ltd.); and aliphatic hydrocarbon-based solvents such as hexane and heptane.

[0112] When the main agent (A) contains the above-mentioned solvent, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film formed, the content of the solvent is preferably within the range of 0.1 to 5 mass %, more preferably within the range of 0.3 to 4 mass %, and even more preferably within the range of 0.5 to 3 mass %, based on the total amount of the main agent (A).

[0113] <Catalyst> As the above catalyst, any of the conventionally known catalysts can be used. Examples of the catalyst include tin octylate, dibutyltin diacetate, dibutyltin di(2-ethylhexanoate), dibutyltin dilaurate, dioctyltin diacetate, dioctyltin di(2-ethylhexanoate), dioctyltin dineodecanoate, dioctyltin diversatate, dibutyltin oxide, dibutyltin sulfide, dioctyltin oxide, dibutyltin fatty acid salts, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, zinc fatty acids, bismuth octanoate, bismuth 2-ethylhexanoate, bismuth oleate, bismuth neodecanoate, bismuth versatate, bismuth naphthenate, cobalt naphthenate, calcium octylate, naphthenic acid Copper, tetra(2-ethylhexyl)titanate, tetra(n-butyl)titanate, titanium diisopropoxybis(acetylacetonate), titanium tetraacetylacetonate, titanium diisopropoxybis(ethylacetoacetate), titanium butoxide dimer, zirconium tetra-normal propoxide, zirconium tetra-normal butoxide, zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate and other organometallic compounds; triethylamine, N,N'-dimethylcyclohexylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N' ',N''-Pentamethyldiethylenetriamine, N,N,N',N' ',N' '-Pentamethyldipropylenetriamine, 1,4-diazabicyclo[2.2.2.]octane (DABCO), 1,8-diazabicyclo[5.4.0.]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0.]-5-nonene (DBN), N-methyl-N'-(2-dimethylaminoethyl)piperazine, N-ethylmorpholine, 1,2-dimethylimidazole, dimethylethanolamine, dimethylaminoethoxyethanol, N-methyl-N'-(2-hydroxyethyl)piperazine, 2-hydroxyethyl-1,4-diazabicyclo[2.2.2.]octane, 1,1'-{[3-(dimethylamino)propyl]imino}bis(2-propanol), bis(2-dimethylaminoethyl)ether, bis(2-morpholinoethyl)ether, and other tertiary amine compounds, neutralized salts of the tertiary amine compounds, and quaternary ammonium salts such as carboxylates of tetraalkylammonium, tetraarylammonium, and alkylarylammonium, and halides of tetraalkylammonium, tetraarylammonium, and alkylarylammonium, and these can be used alone or in combination of two or more kinds.

[0114] When the main component (A) contains the above catalyst, from the viewpoints of the hardness and adhesion of the coating film to be formed, the amount of the catalyst is preferably within the range of 0.005 to 5.0 mass %, and more preferably within the range of 0.01 to 3.0 mass %, based on the total amount of the main component (A).

[0115] In addition, when the coating composition of the present invention contains the above catalyst, it may also contain organic acids such as acetic acid, propionic acid, butyric acid, isopentanoic acid, hexanoic acid, 2-ethylbutyric acid, naphthenic acid, octylic acid, nonanoic acid, decanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, versatic acid, isobutyric anhydride, itaconic anhydride, acetic anhydride, citraconic anhydride, propionic anhydride, maleic anhydride, butyric anhydride, citric anhydride, trimellitic anhydride, pyromellitic anhydride, and phthalic anhydride; inorganic acids such as hydrochloric acid and phosphoric acid; and metal coordination compounds such as acetylacetone and imidazole-based compounds.

[0116] <Dehydrating agent> As the dehydrating agent, conventionally known inorganic dehydrating agents and organic dehydrating agents can be used. Examples of the inorganic dehydrating agent include calcium compounds such as calcium hydride, calcium oxide (quicklime), calcium chloride, calcium sulfate (gypsum), etc.; barium compounds such as barium oxide, etc.; magnesium compounds such as magnesium sulfate, etc.; sodium compounds such as sodium sulfate, sodium carbonate, etc.; copper compounds such as copper sulfate, etc.; inorganic silicon compounds such as silica gel, etc.; aluminum compounds such as aluminum oxide (hydraulic alumina, lithium aluminum hydride, non-crystalline silica alumina, crystalline aluminosilicates (molecular sieves), etc., and these can be used alone or in combination of two or more kinds.

[0117] Examples of the organic dehydrating agent include alkyl orthoformates, alkyl orthoacetates, alkyl orthoborates, vinylsilanes, alkoxysilane compounds, monoisocyanate compounds, aliphatic acid anhydrides such as acetic anhydride, and aromatic acid anhydrides such as benzoic anhydride, and these can be used alone or in combination of two or more kinds. When the main component (A) contains the above-mentioned dehydrating agent, from the viewpoints of reducing the VOC content in the resulting coating composition and improving the adhesion of the coating film formed, the amount of the dehydrating agent is preferably within the range of 0.1 to 5.0 mass %, and more preferably within the range of 0.3 to 3.0 mass %, based on the total amount of the main component (A).

[0118] The above base material (A) is subjected to a shear rate of 100 sec -1 , viscosity at 65℃ (V A ) is in the range of 20 to 1800 mPa s.

[0119] The above base material (A) is subjected to a shear rate of 100 sec -1 , viscosity at 65℃ (V A From the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film formed, the viscosity is preferably in the range of 50 to 1500 mPa s, more preferably in the range of 100 to 1000 mPa s, and even more preferably in the range of 150 to 800 mPa s.

[0120] The solids concentration of the main agent (A) is preferably within the range of 95 to 100 mass %, more preferably within the range of 96 to 99.5 mass %, and even more preferably within the range of 97 to 99 mass %, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, and color unevenness of the coating film formed. In the kit according to the present invention and the three-component coating composition according to the present disclosure, the content of the main component (A) is preferably within the range of 10 to 70 mass %, more preferably within the range of 15 to 60 mass %, and even more preferably within the range of 25 to 50 mass %, based on the total amount of the three-component coating composition, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film formed.

[0121] [Hardening agent (B)] The curing agent (B) includes a polyisocyanate compound (b1).

[0122] [Polyisocyanate compound (b1)] The polyisocyanate compound (b1) is a compound having at least two isocyanate groups in one molecule, and includes, for example, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of the polyisocyanates.

[0123] The polyisocyanate compound (b1) preferably contains the aliphatic polyisocyanate from the viewpoints of reducing the VOC content in the resulting coating composition and improving the hardness, adhesion, and color unevenness of the coating film formed.

[0124] Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, methyl 2,6-diisocyanatohexanoate (common name: lysine diisocyanate), aliphatic diisocyanates such as 2-isocyanatoethyl 2,6-diisocyanatohexanoate, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane.

[0125] Examples of the alicyclic polyisocyanate include alicyclic diisocyanates such as 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name: isophorone diisocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, and norbornane diisocyanate; 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2-(3-isocyanatopropyl)-2,5-di(isocyanatomethyl)-bicyclo(2.2.1)hepta, 2-(3-isocyanatopropyl)-2,6-di(isocyanatomethyl)-bicyclo(2.2.1)heptane, 3-(3-isocyanatopropyl)-2,5-di(isocyanatomethyl)-bicyclo(2.2.1)heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane, 6-(2-isocyanatoethyl)-2-isocyanatoethyl alicyclic triisocyanates such as 2-isocyanatoethyl-3-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane, and 6-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane.

[0126] Examples of the aromatic aliphatic polyisocyanate include aromatic aliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω,ω'-diisocyanato-1,4-diethylbenzene, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (common name: tetramethylxylylene diisocyanate) or a mixture thereof; and aromatic aliphatic triisocyanates such as 1,3,5-triisocyanatomethylbenzene.

[0127] Examples of the aromatic polyisocyanate include aromatic diisocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, 4,4'-toluidine diisocyanate, and 4,4'-diphenylether diisocyanate; aromatic triisocyanates such as triphenylmethane-4,4',4''-triisocyanate, 1,3,5-triisocyanatobenzene, and 2,4,6-triisocyanatotoluene; and aromatic tetraisocyanates such as 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate.

[0128] Examples of the polyisocyanate derivatives include dimers, trimers, biurets, allophanates, uretdione, uretonimine, isocyanurates, iminooxadiazinedione, polymethylene polyphenyl polyisocyanates (crude MDI, polymeric MDI), crude TDI, and the like of the polyisocyanate compounds described above. Among these, from the viewpoint of the hardness and adhesion of the coating film to be formed, it is preferable to contain at least one selected from allophanates, uretdione, and isocyanurates, it is more preferable to contain at least one selected from uretdione and isocyanurates, and it is even more preferable to contain isocyanurates.

[0129] The above polyisocyanates and derivatives thereof may be used alone or in combination of two or more. Among these polyisocyanates, it is preferable to use aliphatic diisocyanates, aliphatic triisocyanates, alicyclic diisocyanates, araliphatic diisocyanates, and derivatives thereof alone or in combination of two or more.

[0130] The polyisocyanate compound (b1) may be a prepolymer obtained by reacting the polyisocyanate or its derivative with a compound capable of reacting with the polyisocyanate under conditions of excess isocyanate group. Examples of the compound capable of reacting with the polyisocyanate include compounds having active hydrogen groups such as hydroxyl groups and amino groups, and specific examples of the compound that can be used include polyhydric alcohols, low molecular weight polyester resins, amines, water, etc.

[0131] As the polyhydric alcohol, the polyhydric alcohols exemplified in the above-mentioned hydroxyl group-containing polyester resin can be used.

[0132] From the viewpoints of the hardness and adhesion of the coating film to be formed, the polyisocyanate compound (b1) is preferably used in such a ratio that the ratio of isocyanate groups in the polyisocyanate compound (b1) to isocyanate reactive groups in the isocyanate reactive group-containing compound (a1) and the isocyanate reactive group-containing compound (c1) described below falls within a range of 0.7 to 2.0, and more preferably falls within a range of 0.9 to 1.5.

[0133] The content of the polyisocyanate compound (b1) in the curing agent (B) is preferably within a range of 30 to 100 mass %, more preferably within a range of 40 to 99.5 mass %, and even more preferably within a range of 50 to 99 mass %, based on the total amount of the curing agent (B), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed.

[0134] [Other ingredients] In addition to the above, the curing agent (B) may further contain a curing agent other than the polyisocyanate compound (b1). In addition, the curing agent (B) may appropriately contain other additive components that are commonly used in the field of coating, such as ultraviolet absorbers, light stabilizers, internal mold release agents, solvents (organic solvents, water), pigments, catalysts, dehydrating agents, antioxidants, surface conditioners, defoamers, emulsifiers, surfactants, antifouling agents, wetting agents, thickeners, dyes, scratch resistance improvers, gloss adjusters, etc., as necessary.

[0135] <Curing agents other than polyisocyanate compounds (b1)> As the curing agent other than the polyisocyanate compound (b1), for example, a carbodiimide group-containing compound can be mentioned.

[0136] <Carbodiimide group-containing compound> The carbodiimide group-containing compound is a compound having at least one carbodiimide group in one molecule, and for example, a compound obtained by subjecting isocyanate groups of an isocyanate group-containing compound to a carbon dioxide-removal reaction can be used. However, in the present invention, a compound having a carbodiimide group and two or more isocyanate groups is not included in the carbodiimide group-containing compound, but is included in the polyisocyanate compound (b1).

[0137] The carbodiimide group-containing compound may be a commercially available product. Examples of the commercially available product include "Carbodilite V-02B", "Elastostab H01", "Carbodilite V-03", "Carbodilite V-09", "Carbodilite V-09GB", "Carbodilite V-09M", and "Carbodilite V-04PF" (all of which are product names manufactured by Nisshinbo Chemical Co., Ltd.), "Stabaxol I", "Stabaxol I LF", "Stabaxol P", "Stabaxol P100", and "Stabaxol P200" (all of which are product names manufactured by LANXESS).

[0138] The carbodiimide group-containing compound preferably contains a solventless carbodiimide group-containing compound from the viewpoints of reducing the VOC content in the resulting coating composition and preventing adhesion and color unevenness of the coating film formed.

[0139] The above-mentioned solvent-free carbodiimide group-containing compound may be a commercially available product, whose trade name includes "Carbodilite V-02B," "Elastostab H01," and "Carbodilite V-04PF" (all trade names manufactured by Nisshinbo Chemical Inc.).

[0140] The number average molecular weight of the carbodiimide group-containing compound is preferably within the range of 500 to 5,000, more preferably within the range of 600 to 3,000, and even more preferably within the range of 700 to 1,500, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, and color unevenness of the coating film formed.

[0141] Furthermore, when the curing agent (B) contains the above-mentioned carbodiimide group-containing compound, the content of the carbodiimide group-containing compound is preferably within the range of 0.5 to 5.0 mass %, more preferably within the range of 0.8 to 4.0 mass %, and even more preferably within the range of 1.0 to 3.0 mass %, based on the total amount of the curing agent (B), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed.

[0142] <Solvent> As the solvent, for example, the solvents exemplified for the main component (A) can be used.

[0143] When the curing agent (B) contains the above-mentioned solvent, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film formed, the content of the solvent is preferably within the range of 0.1 to 5 mass %, more preferably within the range of 0.2 to 4 mass %, and even more preferably within the range of 0.3 to 3 mass %, based on the total amount of the curing agent (B).

[0144] <Dehydrating agent> As the dehydrating agent, for example, the dehydrating agents exemplified in the main component (A) can be used.

[0145] When the curing agent (B) contains the above-mentioned dehydrating agent, from the viewpoints of the hardness and adhesion of the coating film to be formed, the blending amount of the dehydrating agent is preferably within the range of 0.1 to 5 mass %, and more preferably within the range of 0.3 to 3 mass %, based on the total amount of the curing agent (B).

[0146] The above hardener (B) is subjected to a shear rate of 100 sec -1 , viscosity at 65℃ (V B ) is in the range of 20 to 1800 mPa s.

[0147] The above hardener (B) is subjected to a shear rate of 100 sec -1 , viscosity at 65℃ (V B From the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film formed, the viscosity is preferably in the range of 50 to 1500 mPa s, more preferably in the range of 100 to 1000 mPa s, and even more preferably in the range of 150 to 600 mPa s.

[0148] The solids concentration of the curing agent (B) is preferably within the range of 95 to 100 mass %, more preferably within the range of 96 to 100 mass %, and even more preferably within the range of 97 to 100 mass %, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, and color unevenness of the coating film formed.

[0149] The content of the curing agent (B) in the kit according to the present invention and the three-component coating composition according to the present disclosure is preferably within the range of 20 to 80 mass %, more preferably within the range of 30 to 75 mass %, and even more preferably within the range of 40 to 70 mass %, based on the total amount of the three-component coating composition, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film formed.

[0150] [Pigment Paste (C)] The pigment paste (C) contains an isocyanate-reactive group-containing compound (c1) and a pigment (C2).

[0151] [Isocyanate-reactive group-containing compound (c1)] The isocyanate-reactive group-containing compound (c1) is a compound having at least one isocyanate-reactive group in one molecule.

[0152] From the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed, the isocyanate-reactive group-containing compound (c1) preferably contains an isocyanate-reactive group-containing compound having a number average molecular weight in the range of 250 to 2500, more preferably contains an isocyanate-reactive group-containing compound having a number average molecular weight in the range of 300 to 1800, and even more preferably contains an isocyanate-reactive group-containing compound having a number average molecular weight in the range of 300 to 1500.

[0153] The isocyanate-reactive group is not particularly limited as long as it is a group that is reactive to an isocyanate group. Examples of the isocyanate-reactive group include a hydroxyl group, an amino group, and a thiol group, and from the viewpoint of the hardness, adhesion, and color unevenness of the coating film formed, it is preferable to include at least one selected from a hydroxyl group and an amino group, and more preferably to include a hydroxyl group.

[0154] Therefore, examples of the isocyanate-reactive group-containing compound (c1) include a hydroxyl group-containing compound (c11), an amino group-containing compound (c12), a thiol group-containing compound (c13), etc., and from the viewpoints of the hardness, adhesion, color unevenness, etc. of the coating film to be formed, it is preferable to contain at least one compound selected from the hydroxyl group-containing compound (c11) and the amino group-containing compound (c12), and it is more preferable to contain the hydroxyl group-containing compound (c11).

[0155] [Hydroxyl-containing compounds (c11)] The hydroxyl-containing compound (c11) is a compound having at least one hydroxyl group in one molecule. Examples of the hydroxyl-containing compound (c11) include hydroxyl-containing oligomers and hydroxyl-containing polymers, such as hydroxyl-containing polyester resins, hydroxyl-containing polycaprolactone resins, hydroxyl-containing polyether resins, hydroxyl-containing polycarbonate resins, hydroxyl-containing acrylic resins, hydroxyl-containing polyurethane resins, hydroxyl-containing epoxy resins, and hydroxyl-containing alkyd resins. Among them, from the viewpoints of reducing the VOC content in the resulting coating composition, and the hardness, adhesion, and color unevenness of the coating film formed, it is preferable to include at least one resin selected from hydroxyl-containing polyester resins, hydroxyl-containing polycaprolactone resins, and hydroxyl-containing polyether resins, and more preferably to include at least one resin selected from hydroxyl-containing polyester resins and hydroxyl-containing polycaprolactone resins. Each of these can be used alone or in combination of two or more.

[0156] As the hydroxyl-containing polyester resin, for example, the hydroxyl-containing polyester resins exemplified in the main component (A) can be used.

[0157] The hydroxyl value of the hydroxyl-containing polyester resin is preferably within the range of 50 to 800 mgKOH / g, more preferably within the range of 100 to 700 mgKOH / g, and even more preferably within the range of 300 to 600 mgKOH / g, from the viewpoints of the hardness and adhesion of the coating film to be formed.

[0158] The number average molecular weight of the hydroxyl group-containing polyester resin is preferably within the range of 250 to 2500, more preferably within the range of 300 to 1800, and even more preferably within the range of 350 to 1500, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film formed.

[0159] The glass transition temperature (Tg) of the hydroxyl-containing polyester resin is preferably within the range of -80 to 10°C, more preferably within the range of -70 to 5°C, and even more preferably within the range of -60 to 0°C, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film formed.

[0160] When the hydroxyl-containing compound (c11) contains the above-mentioned hydroxyl-containing polyester resin, the content of the hydroxyl-containing polyester resin is, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film to be formed, preferably in the range of 50 to 100 mass%, more preferably in the range of 60 to 95 mass%, and even more preferably in the range of 75 to 90 mass%, based on the total solid content of the hydroxyl-containing compound (c11).

[0161] As the hydroxyl group-containing polycaprolactone resin, for example, the hydroxyl group-containing polycaprolactone resins exemplified in the main component (A) can be used. The hydroxyl value of the hydroxyl-containing polycaprolactone resin is preferably within the range of 50 to 900 mgKOH / g, more preferably within the range of 100 to 750 mgKOH / g, and even more preferably within the range of 130 to 600 mgKOH / g, from the viewpoints of the hardness and adhesion of the coating film to be formed.

[0162] The number average molecular weight of the hydroxyl group-containing polycaprolactone resin is preferably within the range of 250 to 2500, more preferably within the range of 280 to 1500, and even more preferably within the range of 300 to 1000, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film formed.

[0163] When the hydroxyl-containing compound (c11) contains the above-mentioned hydroxyl-containing polycaprolactone resin, the content of the hydroxyl-containing polycaprolactone resin is preferably within the range of 5 to 100 mass%, more preferably within the range of 10 to 75 mass%, and even more preferably within the range of 10 to 50 mass%, based on the total solid content of the hydroxyl-containing compound (c11), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed.

[0164] As the hydroxyl group-containing polyether resin, for example, the polyether resins exemplified in the main component (A) can be used.

[0165] The hydroxyl value of the hydroxyl-containing polyether resin is preferably within the range of 50 to 600 mgKOH / g, more preferably within the range of 70 to 500 mgKOH / g, and even more preferably within the range of 90 to 400 mgKOH / g, from the viewpoints of the hardness and adhesion of the coating film to be formed.

[0166] The number average molecular weight of the hydroxyl group-containing polyether resin is preferably within the range of 250 to 2500, more preferably within the range of 300 to 1500, and even more preferably within the range of 350 to 1000, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film formed.

[0167] When the hydroxyl-containing compound (c11) contains the above-mentioned hydroxyl-containing polyether resin, the content of the hydroxyl-containing polyether resin is preferably within the range of 20 to 100 mass%, more preferably within the range of 40 to 100 mass%, and even more preferably within the range of 50 to 100 mass%, based on the total solid content of the hydroxyl-containing compound (c11), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed.

[0168] As the hydroxyl group-containing polycarbonate resin, for example, the polycarbonate resins exemplified in the main component (A) can be used. The hydroxyl value of the hydroxyl-containing polycarbonate resin is preferably within the range of 50 to 800 mgKOH / g, more preferably within the range of 70 to 700 mgKOH / g, and even more preferably within the range of 90 to 600 mgKOH / g, from the viewpoints of the hardness and adhesion of the coating film to be formed.

[0169] The number average molecular weight of the hydroxyl group-containing polycarbonate resin is preferably within the range of 250 to 2500, more preferably within the range of 300 to 1800, and even more preferably within the range of 400 to 1500, from the viewpoints of reducing the VOC content in the resulting coating composition and preventing adhesion and color unevenness of the coating film formed.

[0170] When the hydroxyl-containing compound (c11) contains the above-mentioned hydroxyl-containing polycarbonate resin, the content of the hydroxyl-containing polycarbonate resin is, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film to be formed, preferably in the range of 5 to 80 mass %, more preferably in the range of 10 to 50 mass %, and even more preferably in the range of 10 to 40 mass %, based on the total solid content of the hydroxyl-containing compound (c11).

[0171] As the hydroxyl group-containing acrylic resin, for example, the acrylic resins exemplified in the main component (A) can be used.

[0172] The hydroxyl value of the hydroxyl-containing acrylic resin is preferably within the range of 5 to 240 mgKOH / g, more preferably within the range of 20 to 220 mgKOH / g, and even more preferably within the range of 25 to 200 mgKOH / g, from the viewpoints of the hardness and adhesion of the coating film to be formed.

[0173] The number average molecular weight of the hydroxyl-containing acrylic resin is preferably within the range of 250 to 2500, more preferably within the range of 300 to 1800, and even more preferably within the range of 500 to 1500, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film to be formed.

[0174] The glass transition temperature (Tg) of the hydroxyl-containing acrylic resin is preferably within the range of -60 to 80°C, more preferably within the range of -50 to 70°C, and even more preferably within the range of -40 to 60°C, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film formed.

[0175] When the hydroxyl-containing compound (c11) contains the above-mentioned hydroxyl-containing acrylic resin, the content of the hydroxyl-containing acrylic resin is preferably within the range of 5 to 100 mass%, more preferably within the range of 10 to 75 mass%, and even more preferably within the range of 15 to 50 mass%, based on the total solid content of the hydroxyl-containing compound (c11), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed.

[0176] As the hydroxyl group-containing compound (c11), for example, the hydroxyl group-containing monomers exemplified in the main component (A) can be used. When the hydroxyl-containing compound (c11) contains the hydroxyl-containing monomer, the content of the hydroxyl-containing monomer is, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed, preferably in the range of 5 to 100 mass %, more preferably in the range of 5 to 50 mass %, and even more preferably in the range of 5 to 30 mass %, based on the total solid content of the hydroxyl-containing compound (c11).

[0177] When the isocyanate-reactive group-containing compound (c1) contains the hydroxyl group-containing compound (c11), the content of the hydroxyl group-containing compound (c11) is preferably within the range of 50 to 100 mass%, more preferably within the range of 60 to 100 mass%, and even more preferably within the range of 70 to 100 mass%, based on the total solid content of the isocyanate-reactive group-containing compound (c1), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed.

[0178] [Amino group-containing compound (c12)] As the amino group-containing compound (c12), for example, the amino group-containing compounds (c12) exemplified in the main component (A) can be used. When the isocyanate-reactive group-containing compound (c1) contains the amino group-containing compound (c12), the content of the amino group-containing compound (c12) is preferably within the range of 10 to 100 mass%, more preferably within the range of 40 to 95 mass%, and even more preferably within the range of 50 to 90 mass%, based on the total solid content of the isocyanate-reactive group-containing compound (c1), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed.

[0179] [Thiol group-containing compound (c13)] As the thiol group-containing compound (c13), for example, the thiol group-containing compound (c13) exemplified in the main component (A) can be used. When the isocyanate-reactive group-containing compound (c1) contains the thiol group-containing compound (c13), the content of the thiol group-containing compound (c13) is preferably within the range of 10 to 100 mass%, more preferably within the range of 30 to 95 mass%, and even more preferably within the range of 50 to 90 mass%, based on the total solid content of the isocyanate-reactive group-containing compound (c1), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed.

[0180] The content of the isocyanate-reactive group-containing compound (c1) in the pigment paste (C) is preferably within a range of 10 to 99 mass %, more preferably within a range of 15 to 90 mass %, and even more preferably within a range of 20 to 80 mass %, based on the total amount of the pigment paste (C), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed.

[0181] [Pigment (c2)] Examples of the pigment (c2) include luster pigments, color pigments, extender pigments, etc. The pigments can be used alone or in combination of two or more kinds. Examples of the above-mentioned luster pigments include aluminum (including vapor-deposited aluminum), copper, zinc, brass, nickel, glass flakes, aluminum oxide, mica, aluminum oxide coated with titanium oxide and / or iron oxide, and mica coated with titanium oxide and / or iron oxide.

[0182] Examples of the color pigment include titanium oxide, zinc oxide, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, threne pigments, perylene pigments, dioxazine pigments, diketopyrrolopyrrole pigments, and heat-shielding pigments. Examples of the extender pigment include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white.

[0183] The content of the pigment (c2) in the pigment paste (C) is preferably within the range of 1.0 to 70 mass %, more preferably within the range of 1.0 to 65 mass %, even more preferably within the range of 2.0 to 64 mass %, and even more preferably within the range of 3.0 to 62 mass %, based on the total amount of the pigment paste (C), from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness and color unevenness of the coating film to be formed.

[0184] [Other ingredients] In addition to the above, the pigment paste (C) may further contain an ultraviolet absorbing agent and / or a light stabilizer. If necessary, it may also contain other additives that are commonly used in the field of coating, such as an internal mold release agent, a solvent (organic solvent, water), a pigment, a catalyst, a dehydrating agent, an antioxidant, a surface conditioner, an antifoaming agent, an emulsifier, a surfactant, an antifouling agent, a wetting agent, a thickener, a dye, an agent for improving scratch resistance, and a gloss adjuster.

[0185] <Ultraviolet absorbing agent> As the ultraviolet absorbing agent, for example, the ultraviolet absorbing agents exemplified in the main component (A) can be used. When the pigment paste (C) contains the ultraviolet absorber, the content of the ultraviolet absorber is preferably within the range of 0.5 to 10 mass %, more preferably within the range of 0.8 to 5.0 mass %, and even more preferably within the range of 1.0 to 4.0 mass %, based on the total amount of the pigment paste (C) coating composition, from the viewpoints of weather resistance, adhesion, and the like of the coating film to be formed.

[0186] <Light stabilizer> As the light stabilizer, for example, the light stabilizers exemplified in the main component (A) can be used. When the pigment paste (C) contains the above-mentioned light stabilizer, the content of the light stabilizer is preferably within a range of 0.5 to 10 mass %, more preferably within a range of 0.8 to 9.0 mass %, and even more preferably within a range of 1.0 to 8.0 mass %, based on the total amount of the pigment paste (C), from the viewpoints of the weather resistance and adhesion of the coating film to be formed.

[0187] <Internal release agent> When the coating composition of the present invention is used as an in-mold coating composition, the pigment paste (C) may contain an internal mold release agent from the viewpoint of the releasability between the coating film to be formed and the mold. As the internal mold release agent, for example, the internal mold release agents exemplified in the main component (A) can be used. When the pigment paste (C) contains the above-mentioned internal release agent, the content of the internal release agent is preferably within the range of 0.4 to 8.0 mass %, more preferably within the range of 0.5 to 7.0 mass %, and even more preferably within the range of 0.5 to 6.0 mass %, based on the total amount of the pigment paste (C), from the viewpoints of the adhesion of the coating film to be formed and the releasability between the coating film to be formed and the mold.

[0188] <Solvent> As the solvent, for example, the solvents exemplified for the main component (A) can be used. When the pigment paste (C) contains the above-mentioned solvent, from the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, and the like of the coating film to be formed, the content of the solvent is preferably within the range of 2 to 15 mass %, more preferably within the range of 2 to 13 mass %, and even more preferably within the range of 2 to 10 mass %, based on the total amount of the pigment paste (C).

[0189] <Catalyst> As the catalyst, for example, the catalysts exemplified for the main component (A) can be used. When the pigment paste (C) contains the above catalyst, the amount of the catalyst is preferably within a range of 0.01 to 5.0 mass % and more preferably within a range of 0.1 to 3.0 mass % based on the total amount of the pigment paste (C), from the viewpoints of the hardness and adhesion of the coating film to be formed.

[0190] <Dehydrating agent> As the dehydrating agent, for example, the dehydrating agents exemplified in the main component (A) can be used. When the pigment paste (C) contains the dehydrating agent, the amount of the dehydrating agent is preferably within a range from 0.1 to 5.0 mass % and more preferably within a range from 0.3 to 3.0 mass % based on the total amount of the pigment paste (C), from the viewpoints of the hardness and adhesion of the coating film to be formed.

[0191] The above pigment paste (C) is subjected to a shear rate of 100 sec -1 , viscosity at 65℃ (V C ) is in the range of 20 to 1800 mPa s.

[0192] The above pigment paste (C) is subjected to a shear rate of 100 sec -1 , viscosity at 65℃ (V C From the viewpoints of reducing the VOC content in the resulting coating composition and of the hardness, adhesion, color unevenness, etc. of the coating film formed, the viscosity is preferably in the range of 50 to 1500 mPa s, more preferably in the range of 100 to 1000 mPa s, and even more preferably in the range of 150 to 800 mPa s.

[0193] The solids concentration of the pigment paste (C) is preferably within the range of 84 to 99 mass %, more preferably within the range of 85 to 98 mass %, even more preferably within the range of 87 to 98 mass %, and even more preferably within the range of 90 to 98 mass %, from the viewpoints of reducing the VOC content in the resulting coating composition and of preventing adhesion and color unevenness of the coating film formed.

[0194] The content of the pigment paste (C) in the kit according to the present invention and the three-component paint composition according to the present disclosure is, from the viewpoints of reducing the VOC content in the resulting paint composition and of the hardness, adhesion, color unevenness, and the like of the coating film formed, preferably within the range of 3 to 50 mass %, more preferably within the range of 4 to 40 mass %, and even more preferably within the range of 5 to 30 mass %, based on the total amount of the three-component paint composition.

[0195] <Method of forming a coating film using a three-liquid type coating composition> The kit according to the present invention and the three-component coating composition according to the present disclosure can be applied onto a substrate to form a wet coating film (uncured coating film), and then the wet coating film can be cured to form the desired coating film.

[0196] The substrate is preferably a resin material from the viewpoint of adhesion of the coating film to be formed. Examples of the resin material include acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate, polyethylene naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, and polybutylene terephthalate, epoxy resins such as commercially available products such as Epicoat (product name: manufactured by Yuka Shell Epoxy Co., Ltd.), polycarbonate resins, polyimide resins, novolac resins, phenolic resins, acrylonitrile-butadiene-styrene (ABS) resins, acrylonitrile-ethylene-styrene (AES) resins, and acrylic resins such as acrylic terephthalate. Examples of such resins include lylonitrile-styrene-acrylate (ASA) resins, vinyl chloride resins, vinylidene chloride resins, polyurethane resins, cellulose ester resins (e.g., triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetylpropionyl cellulose, nitrocellulose), polyamide resins, polystyrene resins (e.g., syndiotactic polystyrene), polyolefin resins (e.g., polypropylene, polyethylene, polymethylpentene), polysulfone resins, polyethersulfone resins, polyarylate resins, polyetherimide resins, polyetherketone resins, various fiber reinforced plastic materials (hereinafter sometimes abbreviated as FRP materials or simply FRP), and polymer alloys thereof.

[0197] The substrate may be, for example, a resin material coated with a primer paint, an intermediate coat paint, a top coat paint, or the like, so that a primer layer, an intermediate coat layer, a top coat layer, or the like is formed in advance.

[0198] The substrate may be one that has been subjected to at least one physical treatment (physical treatment) selected from plasma treatment, corona discharge treatment, active energy ray treatment, flame treatment, blast treatment, polishing treatment, and the like.

[0199] It is preferable that the three-component coating composition formed from the kit according to the present invention and the three-component coating composition according to the present disclosure are applied directly onto a substrate. Furthermore, the uses of the three-component paint composition formed from the kit of the present invention and the substrate to which the three-component paint composition of the present disclosure is applied are not particularly limited, and examples thereof include exterior panels of automobile bodies such as passenger cars, trucks, motorcycles, buses, etc.; interior and exterior automobile parts such as bumpers, center pillars, mirrors, door handles, instrument panels, door trims, center consoles, etc.; furniture and building material-related parts such as chairs, vanity mirrors, window frames, gates, etc.; exterior panels of household electrical appliances such as mobile phones and audio equipment, etc. The method for applying the three-component coating composition formed from the kit according to the present invention and the three-component coating composition according to the present disclosure to a substrate is not particularly limited. For example, the composition can be applied by air spray, airless spray, rotary atomizing coater, dip coating, applicator, brush, roller, in-mold coating, etc. Electrostatic application may be performed during application.

[0200] The coating thickness, in terms of cured film thickness, is preferably within the range of 5 to 2000 μm, more preferably within the range of 10 to 1500 μm, and even more preferably within the range of 15 to 1000 μm.

[0201] The three-component coating composition formed from the kit of the present invention and the three-component coating composition of the present disclosure can be cured by heating the three-component coating composition.

[0202] <Heating> Heating can be performed by any method known in the art. Specifically, for example, hot air, hot gas, infrared heater, IR radiator, oven, heat roller, hot press, microwave, etc. In the present invention, from the viewpoint of ease of operation, etc., it is preferable to perform heating by hot air, infrared heater, hot press, etc.

[0203] From the viewpoints of productivity, workability, and thermal stability of the base material, the heating temperature is preferably within the range of 30 to 200°C, more preferably within the range of 50 to 180°C, and even more preferably within the range of 70 to 160°C.

[0204] The heating time is preferably within a range of 20 seconds to 60 minutes, and more preferably within a range of 40 seconds to 10 minutes.

[0205] The three-component coating composition of the present invention can be suitably used in coating by the in-mold coating method, which has the advantage that a coating composition with a low VOC content can be used and that the air conditioning energy required during coating can be reduced, thereby reducing the environmental load.

[0206] <In-mold coating method> The in-mold coating method of the present invention comprises the steps of injecting the coating composition of the present invention (hereinafter, when the coating composition of the present invention is used in the in-mold coating method, it will be referred to as the in-mold coating coating composition) between a molded substrate and the inner wall of a mold, curing the in-mold coating coating composition, and then removing the coated molded article from the mold.

[0207] The in-mold coating method can be any conventional method for molding and coating in a mold without any particular limitation. Specifically, for example, the methods described in JP-A-2000-141407 and JP-A-2008-525212 can be used.

[0208] The resin molding mold used when molding the resin material and the in-mold coating mold used when coating the in-mold with the in-mold coating paint composition may be the same or different. When the resin molding die and the in-mold coating die are the same, for example, a resin material heated and melted in an injection cylinder is injected between the resin molding dies having the shape of the desired molded product, cooled and pressurized in the resin molding die to form the resin material into a molded product, and the resin molding die is then separated from the surface of the molded product made of the resin material. Next, the main agent (A), the curing agent (B) and the pigment paste (C) are mixed to prepare an in-mold coating paint composition, a gap sufficient for injecting the in-mold coating paint composition is provided between the surface of the molded product made of the resin material and the in-mold coating die, the in-mold coating paint composition is injected between the surface of the molded product made of the resin material and the inner wall of the in-mold coating die, the in-mold coating die is closed, and an uncured in-mold coating film is formed on the molded product made of the resin material. Next, the uncured in-mold coating film formed on the molded product made of the resin material is heated and molded into the desired shape, and an in-mold coated molded product having a cured in-mold coating film formed on the molded product made of the resin material can be obtained.

[0209] When the resin molding die and the in-mold coating die are different, for example, a resin material that has been heated and melted in an injection cylinder is injected between the resin molding dies having the shape of the desired molded product, cooled and pressurized in the resin molding die to form the resin material into a molded product, and the resin molding die is then separated and removed from the surface of the molded product made of the resin material. Next, the main agent (A), the curing agent (B) and the pigment paste (C) are mixed to prepare an in-mold coating paint composition, the in-mold coating die is brought close to the surface of the resin molding, a gap sufficient for injecting the in-mold coating paint composition is provided between the surface of the molded product made of the resin material and the in-mold coating die, the in-mold coating paint composition is injected between the surface of the molded product made of the resin material and the inner wall of the in-mold coating die, the in-mold coating die is closed, and an uncured in-mold coating film is formed on the molded product made of the resin material. Next, the uncured in-mold coating film formed on the molded product made of the resin material is heated and molded into the desired shape, thereby obtaining an in-mold coated molded product in which a cured in-mold coating film is formed on the molded product made of the resin material. From the viewpoint of releasability between the in-mold coated molding and the in-mold coated mold, an external mold release agent may be applied to the mold. As the external mold release agent, for example, a fluorine-based, silicone-based, surfactant-based, wax-based, or other external mold release agent can be used.

[0210] The heating temperature when melting the resin in the injection cylinder is arbitrarily determined depending on the type of resin material, etc., but is preferably 80 to 300° C. The temperature of the mold when injecting the resin material is arbitrarily determined depending on the molding time, the type of resin material, etc., but is preferably 30 to 120° C.

[0211] When preparing the in-mold coating paint composition by mixing the main agent (A), the curing agent (B) and the pigment paste (C), it is preferable to heat the main agent (A), the curing agent (B) and the pigment paste (C) respectively before mixing them, from the viewpoints of hardness, adhesion, color unevenness, etc. of the coating film to be formed.

[0212] When the base agent (A), the curing agent (B) and the pigment paste (C) are each heated and then mixed, the temperature is preferably within the range of 30 to 100°C, more preferably within the range of 40 to 90°C, and even more preferably within the range of 50 to 80°C, from the viewpoints of hardness, adhesion, color unevenness, etc. of the coating film to be formed.

[0213] In addition, since the main agent (A), the curing agent (B) and the pigment paste (C) may be heated when mixed, the flash point of the main agent (A) is preferably 70°C or higher, and more preferably 100°C or higher, the flash point of the curing agent (B) is preferably 70°C or higher, and more preferably 100°C or higher, and the flash point of the pigment paste (C) is preferably 70°C or higher, and more preferably 100°C or higher. The molding time of the resin material may be until the resin material is completely solidified, but it is sufficient that the resin material is solidified to a strength that does not damage the molded shape when the in-mold coating paint composition is injected, and usually, a period of about 20 seconds to 60 minutes is preferable.

[0214] The amount of the in-mold coating composition injected is an amount sufficient to obtain a desired film thickness, and is preferably an amount sufficient to obtain a cured film thickness of 15 to 2000 μm. The heating temperature when the uncured in-mold coating film is heated is preferably within the range of 20 to 160°C, more preferably within the range of 40 to 150°C, and even more preferably within the range of 60 to 140°C.

[0215] Furthermore, the heating time for heating the uncured in-mold coating film is preferably within a range of 20 seconds to 10 minutes, more preferably within a range of 30 seconds to 5 minutes, and even more preferably within a range of 40 seconds to 4 minutes.

[0216] When the uncured in-mold coating film is heated and cured, it is preferable to apply pressure. When the above pressure is applied, the pressure is preferably within the range of 2 to 14 MPa from the viewpoints of the hardness and adhesion of the coating film to be formed. EXAMPLES

[0217] The present invention will be described in more detail below with reference to Production Examples, Examples, and Comparative Examples. Note that these Production Examples, Examples, and Comparative Examples are merely illustrative and are not intended to limit the scope of the present invention. In the Production Examples, Examples, and Comparative Examples, "parts" and "%" are based on mass unless otherwise specified. Furthermore, the film thickness of the coating film is based on the cured coating film.

[0218] The components used in the following examples are as follows:

[0219] <Preparation of main agent (A)> Manufacturing Example 1 Into a vessel equipped with a stirrer, 80.0 parts of "Desmophen XP2488" (trade name, manufactured by Covestro, hydroxyl-containing polyester resin containing 26% hydroxyl-containing monomer, number average molecular weight 500, solids concentration 100%), 20.0 parts of "Placcel 303" (trade name, manufactured by Daicel Corporation, hydroxyl-containing polycaprolactone resin, number average molecular weight 310, solids concentration 100%), 1.7 parts of "Moldwiz INT-120IMC" (trade name, manufactured by AXEL PLASTICS, fatty acid tertiary dimethylamide-containing mixture, solids concentration 100%), 0.2 parts of "BYK-333" (trade name, manufactured by BYK-Chemie, surface conditioner (polyether-modified polydimethylsiloxane), solids concentration 100%), 2.9 parts of "TINUVIN 400" (trade name, manufactured by BASF, triazine-based ultraviolet absorber, solids concentration 85%), and 1.0 parts of "TINUVIN 5.7 parts of "Neon No. 292" (product name, manufactured by BASF, hindered amine compound light stabilizer, solids concentration 100%) and 1.7 parts of "Neostan U-830" (product name, manufactured by Nitto Chemical Industry Co., Ltd., dioctyltin diversatate, solids concentration 100%) were blended and mixed uniformly to obtain a base agent (A-1) with a solids concentration of 98.5%.

[0220] Manufacturing Examples 2 to 11 Main components (A-1) to (A-11) were obtained in the same manner as in Production Example 1, except that the blending compositions in Production Example 1 were as shown in Table 1 below. <Shear rate of main component (A) 100sec -1 , viscosity at 65℃ (V A ) Measurement> The main components (A-1) to (A-11) obtained in Production Examples 1 to 11 were subjected to shear rate of 100 sec -1 , viscosity at 65℃ (V A ) was measured according to the following method. The results are also shown in Table 1.

[0221] Shearing rate 100sec -1 The temperature was increased from 20°C to 80°C at a rate of 5°C / min, and the shear rate was 100 sec -1 , viscosity at 65℃ (V A) was measured using a cone and plate viscometer "MCR-302e" (trade name, manufactured by Anton Paar, diameter 25 mm, cone and plate inclined at 2°).

[0222] [Table 1] The components listed in the table are as follows:

[0223] (Note 1) "Desmophen VPLS 2249 / 1": Product name, manufactured by Covestro, hydroxyl-containing polyester resin containing 44% hydroxyl-containing monomer, number average molecular weight 1008, solid content concentration 100%, (Note 2) "ETERNACOL PH-300": Manufactured by UBE, hydroxyl group-containing polycarbonate resin, number average molecular weight 3000, solid content concentration 100%, (Note 3) "Desmophen NH1220": Trade name, manufactured by Covestro, N,N'-(2-methylpentane-1,5-diyl)bisaspartic acid tetraethyl, number average molecular weight 461, solid content concentration 100%, (Note 4) "Desmophen NH1423": Trade name, manufactured by Covestro, N,N'-[methylenebis(cyclohexane-4,1-diyl)]bisaspartic acid tetraethyl, number average molecular weight 551, solid content concentration 100%, (Note 5) "TMMP-LV": Trade name, manufactured by SC Organic Chemicals, trimethylolpropane tris(3-mercaptopropionate), number average molecular weight 399, solid content concentration 100%, (Note 6) "TEMPIC": Trade name, manufactured by SC Organic Chemicals, tris-[(3-mercaptopropionyloxy)-ethyl]isocyanurate, number average molecular weight 526, solid content concentration 100%, (Note 7) "PEMP-LV": Product name, manufactured by SC Organic Chemicals, pentaerythritol tetrakis(3-mercaptopropionate), number average molecular weight 489, solids concentration 100%.

[0224] <Preparation of Curing Agent (B)> Manufacturing Example 12 Into a container equipped with a stirrer, 40.0 parts of "Desmodur N3900" (product name, manufactured by Sumika Covestro Urethane Co., Ltd., iminooxadiazinedione of hexamethylene diisocyanate, solids concentration 100%), 20.0 parts of "Desmodur N3400" (product name, manufactured by Sumika Covestro Urethane Co., Ltd., mixture of uretdione and isocyanurate of hexamethylene diisocyanate, solids concentration 100%), 40.0 parts of "Desmodur NZ200" (product name, manufactured by Sumika Covestro Urethane Co., Ltd., mixture of isocyanurate of hexamethylene diisocyanate and isocyanurate of isophorone diisocyanate, solids concentration 100%), and "Carbodilite V-05" (product name, manufactured by Nisshinbo Chemical Inc., a carbodiimide group-containing compound having an aromatic ring structure and two isocyanate groups, carbodiimide equivalent per solid content of 262, number average molecular weight of 800, solid content concentration of 100%) was blended and mixed uniformly to obtain a curing agent (B-1) with a solid content concentration of 100.0%.

[0225] Manufacturing Examples 13-19 Curing agents (B-2) to (B-8) were obtained in the same manner as in Production Example 12, except that the blending compositions in Production Example 12 were as shown in Table 2 below.

[0226] <Shear rate of hardener (B) 100sec -1 , viscosity at 65℃ (V B ) Measurement> The curing agents (B-1) to (B-8) obtained in Production Examples 12 to 19 were subjected to a shear rate of 100 sec -1 , viscosity at 65℃ (V B ) was measured according to the following method. The results are also shown in Table 2. Shearing rate 100sec -1 The temperature was increased from 20°C to 80°C at a rate of 5°C / min, and the shear rate was 100 sec -1 , viscosity at 65℃ (V B ) was measured using a cone and plate viscometer "MCR-302e" (trade name, manufactured by Anton Paar, diameter 25 mm, cone and plate inclined at 2°).

[0227] [Table 2] The components listed in the table are as follows:

[0228] (Note 8) "Desmodur N3600": Product name, manufactured by Sumika Covestro Urethane Co., Ltd., isocyanurate of hexamethylene diisocyanate, solids concentration 100%, (Note 9) "Desmodur N3500": Product name, manufactured by Sumika Covestro Urethane Co., Ltd., allophanate of hexamethylene diisocyanate, solids concentration 100%.

[0229] <Preparation of pigment paste (C)> Manufacturing Example 20 Into a vessel equipped with a stirrer, 80.0 parts of "Desmophen XP2488" (trade name, manufactured by Covestro, hydroxyl-containing polyester resin containing 26% hydroxyl-containing monomer, number average molecular weight 500, solid content concentration 100%), 20.0 parts of "Placcel 303" (trade name, manufactured by Daicel Corporation, hydroxyl-containing polycaprolactone resin, number average molecular weight 310, solid content concentration 100%), 4.8 parts of "Raven 5000 ULTRA III POWDER" (trade name, manufactured by BIRLA CARBON, carbon black pigment, solid content concentration 100%), 0.5 parts of "SOLSPERSE 5000S" (trade name, manufactured by LUBRISOL, phthalocyanine pigment derivative, solid content concentration 100%), 2.4 parts of "DISPERBYK-2013" (trade name, manufactured by BYK-Chemie, dispersant, solid content concentration 100%), and "Moldwiz INT-120IMC" (trade name, manufactured by AXEL 1.7 parts of a mixture containing tertiary dimethylamide fatty acid manufactured by PLASTICS, solid content concentration 100%), 0.2 parts of "BYK-333" (trade name, manufactured by BYK-Chemie, surface conditioner (polyether-modified polydimethylsiloxane), solid content concentration 100%), 2.9 parts of "TINUVIN 400" (trade name, manufactured by BASF, triazine-based ultraviolet absorber, solid content concentration 85%), 5.7 parts of "TINUVIN 292" (trade name, manufactured by BASF, hindered amine compound light stabilizer, solid content concentration 100%), 1.7 parts of "Neostan U-830" (trade name, manufactured by Nitto Kasei, dioctyltin diversatate, solid content concentration 100%), and 8.7 parts of butyl acetate were added and mixed uniformly. The resulting mixed solution was then placed in a wide-mouthed glass bottle, glass beads with a diameter of about 1.3 mm were added as a dispersion medium, the bottle was sealed, and the mixture was dispersed for 3 hours using a paint shaker to obtain a pigment paste (C-1) with a solids concentration of 92.0%.

[0230] Manufacturing Examples 21-81 Pigment pastes (C-2) to (C-62) were obtained in the same manner as in Production Example 20, except that the blending compositions in Production Example 20 were as shown in Table 3 below.

[0231] <Pigment paste (C) shear rate 100sec -1 , viscosity at 65℃ (V C) Measurement> The pigment pastes (C-1) to (C-62) obtained in Production Examples 20 to 81 were subjected to shear rate of 100 sec -1 , viscosity at 65℃ (V C ) was measured according to the following method. The results are also shown in Table 3. Shearing rate 100sec -1 The temperature was increased from 20°C to 80°C at a rate of 5°C / min, and the shear rate was 100 sec -1 , viscosity at 65℃ (V B ) was measured using a cone and plate viscometer "MCR-302e" (trade name, manufactured by Anton Paar, diameter 25 mm, cone and plate inclined at 2°).

[0232] [Table 3]

[0233] [Table 4]

[0234] [Table 5]

[0235] [Table 6]

[0236] [Table 7]

[0237] [Table 8] The components listed in the table are as follows:

[0238] (Note 10) "PTMG-2000": Product name, manufactured by Mitsubishi Chemical Corporation, polytetramethylene glycol, number average molecular weight 2000, solid content concentration 100%, (Note 11) "PTMG-3000": Product name, manufactured by Mitsubishi Chemical Corporation, polytetramethylene glycol, number average molecular weight 3000, solid content concentration 100%, (Note 12) "Tipake CR-95": Product name, manufactured by Ishihara Sangyo Kaisha, titanium oxide, solid content 100%, (Note 13) "Chlorinated Cyanine Blue G-314": Product name, Sanyo Pigment Co., Ltd., phthalocyanine blue pigment, solid content 100%, (Note 14) "YELLOW 2GLMA": Product name, manufactured by Dominion Color Corporation, bismuth vanadate yellow pigment, solids concentration 100%, (Note 15) "Irgazin Rubine L4025": Product name, BASF, diketopyrrolopyrrole red pigment, solids concentration 100%, (Note 16) "LG neo BLUE #325": Product name, manufactured by Oike Metallic Design Co., Ltd., vapor deposition colored aluminum pigment, solid content concentration 100%, (Note 17) "LG neo RED #325": Product name, manufactured by Oike Metallic Design Co., Ltd., vapor deposition colored aluminum pigment, solid content concentration 100%, (Note 18) "Xirallic T60-23 WNT Galaxy Blue": Product name, Merck, titanium oxide-coated alumina flake pigment, solids concentration 100%, (Note 19) "Xirallic F60-51 SW RADIENT RED": Product name, Merck, iron oxide-coated alumina flake pigment, solids concentration 100%, (Note 20) "DISPERBYK-111": Product name, manufactured by BYK-Chemie, dispersant, solids concentration 100%, (Note 21) "Borchi Gen 1757": Trade name, manufactured by Borchers Americas, dispersant, solid content concentration 100%.

[0239] <Production of in-mold coated molded products> Example 1 (Preparation of in-mold coated molded product (M1)) First, "Dialac TW20" (product name, Techno UMG, acrylonitrile-styrene-acrylate resin (ASA resin)) was filled into an injection molding cylinder and heated to melt at 230°C. After that, it was injected between a resin molding die at 60°C, and the pressure was maintained for 30 seconds before cooling to obtain a 100mm x 100mm x 2mm flat "Dialac TW20" molded product. Next, a kit was prepared consisting of the base agent (A-1) obtained in Production Example 1, the curing agent (B-1) obtained in Production Example 12, and the pigment paste (C-1) obtained in Production Example 20, and each kit was heated to 65° C. Next, the base agent (A-1), the curing agent (B-1), and the pigment paste (C-1) were mixed in a container equipped with a stirrer so that the mass ratio of the base agent (A-1), the curing agent (B-1), and the pigment paste (C-1) was 30.3 / 62.1 / 7.6 in terms of the ratio of (A-1) / (B-1) / (C-1), and mixed uniformly to obtain an in-mold coating paint composition No. 1 with a solid content concentration of 98.9%. Next, the resin molding die was opened, and the above-mentioned in-mold coating composition No. 1 was injected between the obtained flat-plate-shaped "Dialac TW20" molding and the coating film-coated die. The inside of the coating film-coated die was heated to 80°C and the temperature was maintained. The molding pressure was then applied at 5 MPa and maintained for 1 minute. The pressure was then reduced, and the coating film-coated die was opened to produce an in-mold coated molding (M1-1) in which the flat-plate-shaped "Dialac TW20" molding was coated with a coating film having a cured film thickness of 200 μm.

[0240] (Preparation of in-mold coated molded product (M2)) First, "Makroblend UT235M" (product name, manufactured by Covestro, a polymer alloy of polyethylene terephthalate resin and polycarbonate resin) was filled into an injection molding cylinder and heated to melt at 270°C. After that, it was injected into a resin molding die at 70°C, and the pressure was maintained for 30 seconds before cooling to obtain a 100mm x 100mm x 2mm plate-shaped "Makroblend UT235M" molded product. Next, the base agent (A-1) obtained in Production Example 1, the curing agent (B-1) obtained in Production Example 12, and the pigment paste (C-1) obtained in Production Example 20 were each heated to 65° C. Next, the base agent (A-1), the curing agent (B-1), and the pigment paste (C-1) were mixed in a container equipped with a stirrer so that the mass ratio of the base agent (A-1), the curing agent (B-1), and the pigment paste (C-1) was 30.3 / 62.1 / 7.6 in terms of the ratio of (A-1) / (B-1) / (C-1), and mixed uniformly to obtain an in-mold coating paint composition No. 1 with a solid content concentration of 98.9%.

[0241] Next, the resin molding mold was opened, and the above-mentioned in-mold coating composition No. 1 was injected between the obtained flat plate-like "Makroblend UT235M" molding and the coating film-coated mold. The inside of the coating film-coated mold was heated to 80°C and, while maintaining the temperature, pressurized at a molding pressure of 5 MPa and maintained for 1 minute. Thereafter, the pressure was reduced and the coating film-coated mold was opened, thereby producing an in-mold coated molding (M2-1) in which the flat plate-like "Makroblend UT235M" molding was coated with a coating film with a cured film thickness of 200 μm.

[0242] Examples 2 to 59, Comparative Examples 1 to 26 In-mold coated moldings (M1-2) to (M1-85) and (M2-2) to (M2-85) were produced in the same manner as in Example 1, except that the blending compositions in Example 1 were as shown in Table 4 below.

[0243] <Evaluation of in-mold coated moldings> The cured coating film of each of the obtained in-mold coated moldings was evaluated for color unevenness, hardness, and adhesion. The evaluation results are shown in Table 4.

[0244] (Color unevenness) The surface of each of the in-mold coated moldings obtained in Examples 1 to 59 and Comparative Examples 1 to 26 was observed with the naked eye, and the degree of color unevenness was evaluated according to the following criteria: Excellent and Good are acceptable. ◎: Almost no color unevenness is observed. ○: Slight color unevenness is observed. △: Color unevenness is observed. ×: Color unevenness is noticeable.

[0245] (hardness) The Martens hardness (N / mm) of the cured coating film of each of the in-mold coated moldings obtained in Examples 1 to 59 and Comparative Examples 1 to 26 was 2 ) was measured using a "Fisherscope (registered trademark) HM2000S" (product name, manufactured by Fisher Instruments Inc.) and evaluated based on the following criteria. The measurement conditions were as follows: indenter: square pyramidal Vickers indenter (material: diamond, facing angle: 136°), maximum test load: 20 mN, pressing speed: 20 mN / 25 seconds, temperature: 21±2°C, humidity: 50±5% relative humidity. ◎ and ◯ are acceptable. ◎: Martens hardness is 110N / mm 2 That's all. ○: Martens hardness is 100N / mm 2 More than 110N / mm 2 is less than △: Martens hardness is 75N / mm 2 Over 100N / mm 2 is less than ×: Martens hardness is 75N / mm 2 is less than.

[0246] (Adhesion) The coating film of each of the in-mold coated moldings obtained in Examples 1 to 59 and Comparative Examples 1 to 26 was cut into a grid pattern with a cutter so as to reach the base material, creating 100 cross-hatched patterns measuring 2 mm x 2 mm. Next, adhesive cellophane tape was attached to the surface of each in-mold coated molding with the cuts, and the adhesive cellophane tape was rapidly peeled off at a temperature of 23 ± 2°C and a humidity of 50 ± 5% relative humidity. The remaining state of the cross-hatched coating film after peeling was examined, and the adhesion was evaluated based on the following criteria. ◎ and ○ are acceptable. ◎: 100 square grids of coating film remain, and there are no small chips or lifting of the coating film at the edge of the cutter cut. ○: 100 cross-hatched coating films remain, and small chips or lifting of the coating film occurs at the edge of the cutter cut. △: 90 to 99 grid-like coating films remain. ×: The number of remaining grid-like coating films is 89 or less.

[0247]

Table 9

[0248]

Table 10

[0249]

Table 11

[0250]

Table 12

[0251]

Table 13

[0252]

Table 14

[0253]

Table 15

[0254]

Table 16

Claims

1. A base agent (A) containing an isocyanate-reactive group-containing compound (a1); A curing agent (B) containing a polyisocyanate compound (b1), and A pigment paste (C) containing an isocyanate-reactive group-containing compound (c1) and a pigment (c2); A kit for a three-component paint composition comprising: The base material (A) is subjected to a shear rate of 100 sec. －１ , viscosity at 65°C (V Ａ ) is in the range of 20 to 1800 mPa s, The shear rate of the curing agent (B) is 100 sec. －１ , viscosity at 65°C (V Ｂ ) is in the range of 20 to 1800 mPa s, The pigment paste (C) is subjected to a shear rate of 100 sec. －１ , viscosity at 65°C (V Ｃ ) is in the range of 20 to 1800 mPa s; kit.

2. 2. The kit according to claim 1, wherein the three-component paint composition formed from the kit has a solids concentration of 95 mass % or more.

3. The kit according to claim 1 or 2, wherein the solid content concentration of the pigment paste (C) is within the range of 85 to 98 mass%.

4. The kit according to claim 1 or 2, wherein the isocyanate-reactive group-containing compound (c1) comprises an isocyanate-reactive group-containing compound having a number average molecular weight in the range of 250 to 2500.

5. The kit according to claim 1 or 2, wherein the content of the pigment (c2) is within the range of 1.0 to 65 mass% based on the total amount of the pigment paste (C).

6. The above (V Ａ ), the above (V Ｂ ) and the above (V Ｃ ) is represented by the following formula (1) and formula (2): 0.4≦(V Ｂ ) / (V Ａ )≦2.5 Formula (1) 0.3≦(V Ｃ ) / (V Ａ )≦3.0 Formula (2) The kit according to claim 1 or 2, which satisfies the above.

7. A base agent (A) containing an isocyanate-reactive group-containing compound (a1); A curing agent (B) containing a polyisocyanate compound (b1), and A pigment paste (C) containing an isocyanate-reactive group-containing compound (c1) and a pigment (c2); A three-component coating composition comprising: The base material (A) is subjected to a shear rate of 100 sec. －１ , viscosity at 65°C (V Ａ ) is in the range of 20 to 1800 mPa s, The shear rate of the curing agent (B) is 100 sec. －１ , viscosity at 65°C (V Ｂ ) is in the range of 20 to 1800 mPa s, The pigment paste (C) is subjected to a shear rate of 100 sec. －１ , viscosity at 65°C (V Ｃ ) is in the range of 20 to 1800 mPa s; Three-component paint composition.

8. 1. An in-mold coating method comprising the steps of injecting an in-mold coating paint composition between a molded substrate and an inner wall of a mold, curing the in-mold coating paint composition, and then removing the coated molded article from the mold, The in-mold coating coating composition is a three-component coating composition formed from the kit according to claim 1 or 2, or the three-component coating composition according to claim 7. In-mold coating method.