Coating composition and in-mold coating method

Abstract

A coating composition which contains an isocyanate reactive group-containing compound (A) and a polyisocyanate compound (B), wherein: the polyisocyanate compound (B) includes a polyisocyanate compound (B1) that contains two or more isocyanate groups and one or more alkoxysilyl groups in each molecule; and the solid content concentration is 90 mass% or more.

Description

Paint composition and in-mold coating method

[0001] This disclosure relates to a paint composition and an in-mold coating method.

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

[0003] Generally, automobile bodies consist of metal materials that form the body and resin materials that form bumpers and other parts. In recent years, due to improvements in the strength of resin materials, there has been a shift from metal materials to lighter resin materials in parts that previously used metal materials. Among these, the application of polycarbonate resin materials, which have excellent weather resistance and impact resistance, is being considered, but because they have the drawback of being easily scratched, it is common to protect the surface of the resin material with paint. There are various methods for painting resin materials, and one of them is in-mold coating. In-mold coating is a painting method in which, after molding the resin material in a mold, paint is injected between the molded product and the inner wall of the mold, and after the paint has hardened, the molded product with the painted film is removed from the mold. In this painting method, painting and hardening are carried out in a closed system. In this painting method, it is required to be virtually solvent-free in order to avoid defects in the paint film such as air bubbles.

[0004] In the above-mentioned in-mold coating, scratch resistance of the coating film, high adhesion between the coating film and the resin material, and release properties of the coating film from the mold are required.

[0005] Patent Document 1 describes a two-component coating material composition comprising a paint base component A and a curing component B, wherein the paint base component A is: i. one or more polyols A1 selected from the group of polyols containing ester groups, having a hydroxyl value of 300 to 500 mg KOH / g and a hydroxyl group functional value of more than 2; ii. a polyol of general formula (I) R that does not contain ether groups and ester groups. １-(OH) ｐ (I) (wherein, 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 contains one or more tertiary amino groups, and p is 2 to 6) one or more aliphatic polyols A2, iii. General formula (II) R ２ -(C=O) ｒ -O-(AO) ｓ -R ３ (II) (wherein, 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 optionally partially phosphorylated monosaccharide or disaccharide radical or optionally partially phosphorylated algitol radical, where 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) one or more species A3, iv. One or more crosslinking catalysts A4 selected from the group consisting 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, vi. Any one or more polyether diols A6, vii. Any one or more polyether-modified alkylpolysiloxanes A7, viii. Any one or more pigments A8 and / or one or more fillers A8, 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 above curing component B is i. A two-component coating material composition is disclosed, comprising one or more polyisocyanates B1 having an average of 2.4 to 5 NCO groups, wherein the two-component coating material composition contains at least 96% by mass of solids according to ASTM D2369 (2015) with respect to the total mass of the two-component coating material composition, and 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 1:1.15 to 1:0.95.

[0006] The above two-component coating material composition enables damage-free release from mold surfaces, usually metal, without the use of external release agents, while ensuring excellent adhesion to the substrate. It can also be recoated with further coating films, such as a base coat and a clear coat, and can form a surface of extremely high quality without costly and inconvenient cleaning and / or polishing processes.

[0007] Japanese National Specific Schedule 2020-528103

[0008] In the technology described in Patent Document 1, although the resulting paint composition has a low VOC content and excellent release properties between the formed coating and the mold, the scratch resistance of the formed coating, the adhesion between the coating and the polycarbonate resin substrate when immersed in high-temperature water (high-temperature water-resistant adhesion), and the resistance to heat-induced yellowing were sometimes insufficient.

[0009] The present disclosure aims to provide a coating composition that can form a coating film with excellent scratch resistance, adhesion to polycarbonate resin substrates (high temperature water resistance), resistance to heat yellowing, and release properties from molds, and has a low VOC content.

[0010] As a result of diligent research to achieve the above objective, the Disclosers have found that the above objective can be achieved by a coating composition comprising an isocyanate-reactive group-containing compound (A) and a polyisocyanate compound (B), wherein the coating composition comprises a compound (B1) containing an isocyanate group and an alkoxysilyl group, and has a solid content concentration of 90% by mass or more.

[0011] In other words, this disclosure relates to the following <1> to <7>.

[0012] <1> A paint composition comprising an isocyanate-reactive group-containing compound (A) and a polyisocyanate compound (B), wherein the polyisocyanate compound (B) comprises a polyisocyanate compound (B1) containing two or more isocyanate groups and one or more alkoxysilyl groups in one molecule, and the solid content concentration is 90% by mass or more.

[0013] <2> The paint composition according to <1>, wherein the Si element content is in the range of 0.5 to 5% by mass with respect to the total amount of resin solids in the paint composition.

[0014] <3> The paint composition according to <1> or <2>, wherein the polyisocyanate compound (B) further comprises a polyisocyanate compound (B2) that does not contain an alkoxysilyl group and contains three or more isocyanate groups in one molecule.

[0015] <4> The paint composition according to any one of <1> to <3>, further comprising a curing catalyst (C).

[0016] <5> A paint composition according to any one of <1> to <4>, further comprising an internal mold release agent (D).

[0017] <6> A paint composition according to any one of <1> to <5>, further comprising an antioxidant (E).

[0018] <7> An in-mold coating method comprising the steps of injecting an in-mold coating paint composition between a molded substrate and the inner wall of a mold, curing the in-mold coating paint composition, and then removing the coated molded product from the mold, wherein the in-mold coating paint composition is the paint composition described in any one of <1> to <6>.

[0019] According to this disclosure, it is possible to provide a coating composition that can form a coating film with excellent scratch resistance, high-temperature water adhesion, heat yellowing resistance, and mold release properties, and has a low VOC content.

[0020] The following details the present disclosure, but these are merely examples of desirable embodiments and the disclosure is not limited to these.

[0021] [Paint Composition] The paint composition according to the present disclosure is a paint composition comprising an isocyanate-reactive group-containing compound (A) and a polyisocyanate compound (B), wherein the polyisocyanate compound (B) comprises a polyisocyanate compound (B1) containing two or more isocyanate groups and one or more alkoxysilyl groups in one molecule, and has a solid content concentration of 90% by mass or more.

[0022] In this specification, "solid content" refers to non-volatile components such as resins, curing agents, and pigments that remain after drying at 80°C for 30 minutes. 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 it at 80°C for 30 minutes, and then weighing the mass of the components remaining after drying.

[0023] Furthermore, in this specification, "solid content concentration" means the mass percentage of the solid content in the composition. For this reason, the solid content concentration of a composition can be calculated, for example, by weighing 1.0 g of the composition into a heat-resistant container such as an aluminum foil cup, spreading the composition on the bottom surface of the container, drying it at 80°C for 30 minutes, weighing the mass of the components remaining in the composition after drying, and determining the ratio of the mass of the components remaining after drying to the total mass of the composition before drying.

[0024] The solid content concentration in the coating composition according to this disclosure is 90% by mass or more. By having a solid content concentration of 90% by mass or more in the coating composition, the VOC content in the resulting coating composition can be reduced.

[0025] The solid content concentration of the coating composition according to this disclosure is preferably in the range of 93 to 100% by mass, more preferably in the range of 95 to 100% by mass, and even more preferably in the range of 97 to 100% by mass, from the viewpoint of reducing the VOC content in the obtained coating composition, high-temperature water adhesion, scratch resistance, and mold release properties.

[0026] [Isocyanate-Reactive Group-Containing Compound (A)] Isocyanate-reactive group-containing compound (A) is a compound having at least one isocyanate-reactive group in one molecule. The isocyanate-reactive group is not particularly limited as long as it is a group that is reactive with an isocyanate group. Examples of the isocyanate-reactive group-containing compound (A) include a hydroxyl group-containing compound (A1), an amino group-containing compound (A2), a thiol group-containing compound (A3), and any combination thereof.

[0027] The isocyanate-reactive group-containing compound (A) is preferably selected from the group consisting of hydroxyl group-containing compound (A1) and amino group-containing compound (A2), and more preferably contains hydroxyl group-containing compound (A1), from the viewpoint of adhesion of the formed coating film to the polycarbonate resin substrate.

[0028] [Hydroxygroup-containing compound (A1)] The above hydroxygroup-containing compound (A1) is a compound having at least one hydroxyl group in one molecule. Examples of the hydroxygroup-containing compound (A1) as hydroxygroup-containing oligomers and hydroxygroup-containing polymers include hydroxygroup-containing polyester resin, hydroxygroup-containing polycaprolactone resin, hydroxygroup-containing polyether resin, hydroxygroup-containing polycarbonate resin, hydroxygroup-containing acrylic resin, hydroxygroup-containing acrylic-modified polyester resin, hydroxygroup-containing polyurethane resin, hydroxygroup-containing epoxy resin, hydroxygroup-containing alkyd resin, and any combination thereof. In particular, it is preferable to include a hydroxygroup-containing acrylic resin from the viewpoint of reducing the VOC content in the resulting paint composition, as well as scratch resistance, high-temperature water adhesion, heat yellowing resistance, and mold release properties.

[0029] The above-mentioned 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 for itself, such as solution polymerization or emulsion polymerization in water, and production by solution polymerization is preferred.

[0030] When producing the above-mentioned hydroxyl group-containing acrylic resin by solution polymerization, it is preferable that the solution used in the solution polymerization method contains a polyhydric alcohol.

[0031] The above-mentioned hydroxyl group-containing polymerizable unsaturated monomer is a compound having one or more hydroxyl groups and polymerizable unsaturated bonds in one molecule. Examples of the hydroxyl group-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 forms of the 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 with hydroxyl groups at the molecular ends.

[0032] However, in this disclosure, monomers corresponding to the polymerizable unsaturated monomers having an ultraviolet-absorbing functional group (xvii) described later should be defined as other polymerizable unsaturated monomers copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomers, and are excluded from the hydroxyl group-containing polymerizable unsaturated monomers. These can be used individually or in combination of two or more.

[0033] Other polymerizable unsaturated monomers copolymerizable with the above-mentioned hydroxyl group-containing polymerizable unsaturated monomers include, for example, the monomers (i) to (xx) listed below. These polymerizable unsaturated monomers can be used individually or in combination of two or more.

[0034] (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, etc.

[0035] (ii) Polymerizable unsaturated monomers having an isobornyl group: isobornyl (meth)acrylate, etc.

[0036] (iii) Polymerizable unsaturated monomers having an adamantyl group: adamantyl (meth)acrylate, etc.

[0037] (iv) Polymerizable unsaturated monomers having a tricyclodecenyl group: tricyclodecenyl (meth)acrylate, etc.

[0038] (v) Polymerizable unsaturated monomers containing an aromatic ring: benzyl (meth)acrylate, styrene, α-methylstyrene, vinyltoluene, etc.

[0039] (vi) Polymerizable unsaturated monomers having an alkoxysilyl group: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, etc.

[0040] (vii) Polymerizable unsaturated monomers having a fluorinated alkyl group: perfluoroalkyl (meth)acrylates such as perfluorobutylethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate; fluoroolefins, etc.

[0041] (viii) Polymerizable unsaturated monomers having a photopolymerizable functional group such as a maleimide group.

[0042] (ix) Vinyl compounds: N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate, etc.

[0043] (x) Polymerizable unsaturated monomers containing a carboxyl group: (meth)acrylic acid, maleic acid, crotonic acid, β-carboxyethyl (meth)acrylate, etc.

[0044] (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, methylenebis(meth)acrylamide, ethylenebis(meth)acrylamide, adducts of glycidyl (meth)acrylate and amine compounds, etc.

[0045] (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.

[0046] (xiiii) 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, etc.

[0047] (xiv) A (meth)acrylate having a polyoxyethylene chain with an alkoxy group at the molecular terminus.

[0048] (xv) Polymerizable unsaturated monomers having a sulfonic acid group: 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth)acrylate, allylsulfonic acid, 4-styrenesulfonic acid, etc.; sodium salts and ammonium salts of these sulfonic acids, etc.

[0049] (xvi) Polymerizable unsaturated monomers having a phosphate group: acid phosphooxyethyl (meth)acrylate, acid phosphooxypropyl (meth)acrylate, acid phosphooxypoly(oxyethylene) glycol (meth)acrylate, acid phosphooxypoly(oxypropylene) glycol (meth)acrylate, etc.

[0050] (xvii) Polymerizable unsaturated monomers having UV-absorbing functional groups: 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, etc.

[0051] (xviiii) Photostable 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.

[0052] (xix) Polymerizable unsaturated monomers having a carbonyl group: acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl styrene, vinyl alkyl ketones having 4 to 7 carbon atoms (e.g., vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), etc.

[0053] (xx) Polymerizable unsaturated monomers having an acid anhydride group: maleic anhydride, itaconic anhydride, citraconic anhydride, etc.

[0054] In this specification, a polymerizable unsaturated group means an unsaturated group that can undergo 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, maleimide groups, and the like.

[0055] Furthermore, 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.

[0056] The above hydroxyl group-containing compound (A1) preferably has a number average molecular weight of 800 or more, more preferably 1000 or more, even more preferably 1200 or more, and preferably 3000 or less, more preferably 2500 or less, and even more preferably 2200 or less, from the viewpoint of reducing the VOC content in the resulting paint composition and the high-temperature water adhesion, scratch resistance, and heat yellowing resistance of the formed coating film.

[0057] In this specification, the number-average molecular weight and weight-average molecular weight are values ​​obtained by converting the retention time (retention volume) measured using a gel permeation chromatograph (GPC) to 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 measurement can be performed using an "HLC-8120GPC" (product name, manufactured by Tosoh Corporation) as the gel permeation chromatograph, with a total of four columns: "TSKgel G4000HXL", "TSKgel G3000HXL", "TSKgel G2500HXL", and "TSKgel G2000HXL" (product names, all manufactured by Tosoh Corporation), a differential refractometer as the detector, and under the conditions of mobile phase: tetrahydrofuran, measurement temperature: 40°C, and flow rate: 1 mL / min.

[0058] The glass transition temperature (Tg) of the hydroxyl group-containing acrylic resin is preferably -20°C or higher, more preferably -10°C or higher, even more preferably 0°C or higher, and preferably 70°C or lower, more preferably 60°C or lower, and even more preferably 50°C or lower, from the viewpoint of reducing the VOC content in the resulting paint composition and improving the high-temperature water-resistant adhesion of the formed coating film.

[0059] In this specification, the glass transition temperature (Tg) of the hydroxyl group-containing acrylic resin is the value calculated by the following formula.

[0060] 1 / Tg(K) = W1 / T1 + W2 / T2 + ...Wn / Tn Tg(°C) = 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.

[0061] The glass transition temperatures of each monomer homopolymer are based on the values ​​in *Polymer Handbook Fourth Edition*, edited by J. Brandrup, E. h. Immergut, and E. A. Grulke (1999). For monomers not listed in this literature, the static glass transition temperature is determined when the homopolymer of that monomer is synthesized to have a weight-average molecular weight of approximately 50,000.

[0062] The hydroxyl value of the above-mentioned hydroxyl group-containing acrylic resin is preferably 50 mg KOH / g or more, more preferably 70 mg KOH / g or more, even more preferably 100 mg KOH / g or more, and preferably 200 mg KOH / g or less, more preferably 190 mg KOH / g or less, and even more preferably 180 mg KOH / g or less, from the viewpoint of the high-temperature water-resistant adhesion of the formed coating film.

[0063] The above polyhydric alcohols are compounds having two or more hydroxyl groups in one molecule. Examples of such polyhydric alcohols 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, and 1,2-pene. Tanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, tetramethylene glycol, 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, tricyclodecanedimethanol, neopentyl hydroxypivalate Examples include dihydric alcohols such as bisglycol esters, hydrogenated bisphenol A, dimethylolpropionic acid, and isosorbide; 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; fatty acid esters of glycerin, and any combination thereof.

[0064] The amount of polyhydric alcohol blended is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 40% by mass or more, and preferably 150% by mass or less, more preferably 130% by mass or less, and even more preferably 100% by mass or less, based on the total amount of hydroxyl group-containing acrylic resin, from the viewpoint of reducing the VOC content in the resulting paint composition.

[0065] The solution used in the above solution polymerization method may contain organic solvents other than polyhydric alcohols as needed.

[0066] Examples of the above-mentioned organic solvents include aromatic solvents such as toluene, xylene, and "Swazol 1000" (manufactured by Cosmo Oil Co., Ltd., trade name, high-boiling point petroleum solvent); ester solvents such as ethyl acetate, butyl acetate, propyl propionate, butyl propionate, 1-methoxy-2-propyl acetate, 2-ethoxyethyl propionate, 3-methoxybutyl acetate, ethylene glycol ethyl ether acetate, and propylene glycol methyl ether acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; alcohol solvents such as isopropanol, n-butanol, isobutanol, and 2-ethylhexanol; and any combination thereof.

[0067] When the hydroxyl group-containing compound (A1) contains the hydroxyl group-containing acrylic resin, the content of the hydroxyl group-containing acrylic resin is preferably 10% by mass or more, more preferably 25% by mass or more, even more preferably 40% by mass or more, and preferably 100% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, based on the total solid content of the hydroxyl group-containing compound (A1), from the viewpoint of the high-temperature water adhesion resistance, scratch resistance, and heat yellowing resistance of the formed coating film.

[0068] Examples of hydroxyl group-containing monomers constituting the above hydroxyl group-containing compound (A1) 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- Examples include hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, neopentyl glycol hydroxypivalate, 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-benzooxyol-5-yl)methanol, nonylphenol, dinonylphenol, nonylphenol ethoxylate, monostyrene-modified phenol, distylen-modified phenol, tristyrene-modified phenol, and any combination thereof.

[0069] From the viewpoint of the heat resistance of the formed coating film to yellowing, it is preferable that the above-mentioned hydroxyl group-containing monomer includes a hydroxyl group-containing monomer having an alicyclic skeleton.

[0070] Examples of hydroxyl group-containing monomers having the above-mentioned alicyclic skeleton include 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, and any combination thereof.

[0071] When the constituent monomers of the above-mentioned hydroxyl group-containing compound (A1) include a hydroxyl group-containing monomer, the content of the hydroxyl group-containing monomer is preferably in the range of 5 to 100% by mass, more preferably in the range of 5 to 70% by mass, and even more preferably in the range of 5 to 60% by mass, based on the total solid content of the hydroxyl group-containing compound (A1), from the viewpoint of the high-temperature water adhesion resistance, scratch resistance, and heat yellowing resistance of the formed coating film.

[0072] The above-mentioned hydroxyl group-containing polyester resin can usually be produced by an esterification reaction or transesterification reaction between an acid component and an alcohol component.

[0073] As the acid component, compounds commonly used as polycarboxylic acids in the production of the hydroxyl group-containing polyester resin can be used. Examples of such polycarboxylic acids include aliphatic polybasic acids, alicyclic polybasic acids, and aromatic polybasic acids.

[0074] The above-mentioned alicyclic polybasic acids are generally compounds having one or more alicyclic structures and two or more carboxyl groups in one molecule, acid anhydrides of the compound, and esters of the compound. The alicyclic structure can mainly be a 4- to 6-membered ring structure. Examples of alicyclic polybasic acids 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 polycarboxylic acids; lower alkyl esters of the alicyclic polycarboxylic acids having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms; and any combination thereof.

[0075] The above-mentioned aliphatic polybasic acids are generally aliphatic compounds having two or more carboxyl groups in one molecule, acid anhydrides of the aliphatic compounds, and esters of the aliphatic compounds. Examples of aliphatic polybasic acids include aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, brassic acid, octadecanediic acid, citric acid, and butanetetracarboxylic acid; anhydrides of the aliphatic polycarboxylic acids; lower alkyl esters of the aliphatic polycarboxylic acids having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms; and any combination thereof.

[0076] The above-mentioned aromatic polybasic acids are generally aromatic compounds having two or more carboxyl groups in one molecule, acid anhydrides of the aromatic compounds, and esters of the aromatic compounds. Examples of aromatic polybasic acids 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 polycarboxylic acids; lower alkyl esters of the aromatic polycarboxylic acids having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms; and any combination thereof.

[0077] 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 include, for example, fatty acids such as coconut oil fatty acid, cottonseed oil fatty acid, hemp seed 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; hydroxycarboxylic acids such as lactic acid, 3-hydroxybutanoic acid, and 3-hydroxy-4-ethoxybenzoic acid, and any combination thereof.

[0078] As the alcohol component mentioned above, polyhydric alcohols having two or more hydroxyl groups in one molecule can be suitably used. Examples of such polyhydric alcohols 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, tricyclodecanedimethyl Examples include dihydric alcohols such as hydroxypivalate 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; alkylene oxide adducts of bisphenol A, polyether diol compounds such as 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; fatty acid esters of glycerin, and any combination thereof.

[0079] If the above alcohol component includes a polyhydric alcohol, it is preferable that the polyhydric alcohol includes a polyhydric alcohol having an alicyclic skeleton from the viewpoint of preventing heat yellowing of the formed coating film. Examples of polyhydric alcohols having an alicyclic skeleton include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 4,4-bicyclohexanol, 4-(2-hydroxyethyl)cyclohexanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,3-cyclopentanediol, tricyclodecanedimethanol, 1,3-adamantanediol, pentacyclopentadecanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, and any combination thereof.

[0080] Other alcohol components besides the polyhydric alcohols mentioned above can also be used. Such alcohol components are not particularly limited and include, for example, 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, a glycidyl ester of a synthetic highly branched saturated fatty acid) with an acid.

[0081] The method for producing the above-mentioned hydroxyl group-containing polyester resin is not particularly limited and can be carried out according to conventional methods. For example, a hydroxyl group-containing polyester polyol resin can be produced by heating the above-mentioned acid component and the above-mentioned alcohol component in a nitrogen stream at a temperature of about 150 to 250°C for about 5 to 10 hours to carry out an esterification reaction or transesterification reaction between the acid component and the alcohol component.

[0082] When carrying out esterification or transesterification reactions of the above acid component and the above alcohol component, these components may be added to the reaction vessel all at once, or one or both may be added in several stages. First, the above hydroxyl group-containing polyester resin may be synthesized, and then the resulting hydroxyl group-containing polyester resin may be reacted with an acid anhydride to perform half-esterification to obtain a carboxyl group and hydroxyl group-containing polyester resin. First, the carboxyl group-containing polyester resin may be synthesized, and then the above alcohol component may be added to produce the hydroxyl group-containing polyester resin.

[0083] In the above esterification or transesterification reactions, known catalysts such as dibutyltin oxide, antimony trioxide, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, and tetraisopropyl titanate can be used as catalysts to accelerate the reaction.

[0084] The above-mentioned hydroxyl group-containing polyester resin can be modified with fatty acids, monoepoxy compounds, polyisocyanate compounds, etc., during or after the manufacture of the resin.

[0085] Examples of the above fatty acids include coconut oil fatty acids, cottonseed oil fatty acids, hemp seed 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, and safflower oil fatty acids. As for the above monoepoxy compound, for example, "Cardura E10P" (trade name, manufactured by Hexion, a glycidyl ester of synthetic highly branched saturated fatty acids) can be suitably used.

[0086] Examples of the above polyisocyanate compounds 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(cyclohexyl isocyanate), 1,3-(isocyanatomethyl)cyclohexane, and 1,4-(isocyanatomethyl)cyclohexane; and trimethylene diisocyanate. Examples include aromatic diisocyanate compounds such as cyanates, xylylene diisocyanate, tetramethylxylylene diisocyanate, and diphenylmethane diisocyanate; organic polyisocyanates themselves, such as trivalent or higher polyisocyanates like lysine triisocyanate and 4-(isocyanatomethyl)octamethylene diisocyanate; adducts of these organic polyisocyanates with polyhydric alcohols, low molecular weight polyester resins, water, etc.; cyclization polymers of these organic polyisocyanates (e.g., isocyanurates), biuret-type adducts, and any combination thereof.

[0087] When the hydroxyl group-containing compound (A1) contains the hydroxyl group-containing polyester resin, from the viewpoint of reducing the VOC content in the resulting paint composition and improving the high-temperature water adhesion, scratch resistance, and heat yellowing resistance of the formed coating film, it preferably has a number average molecular weight of 300 or more, more preferably 400 or more, even more preferably 450 or more, and preferably 1000 or less, more preferably 850 or less, and even more preferably 600 or less.

[0088] The hydroxyl value of the above-mentioned hydroxyl group-containing polyester resin is preferably 20 mg KOH / g or more, more preferably 100 mg KOH / g or more, even more preferably 300 mg KOH / g or more, and preferably 600 mg KOH / g or less, more preferably 580 mg KOH / g or less, and even more preferably 560 mg KOH / g or less, from the viewpoint of the high-temperature water adhesion resistance, scratch resistance, and heat yellowing resistance of the formed coating film.

[0089] The glass transition temperature (Tg) of the above-mentioned hydroxyl group-containing polyester resin is preferably -80°C or higher, more preferably -70°C or higher, even more preferably -60°C or higher, and preferably 10°C or lower, more preferably 5°C or lower, and even more preferably 0°C or lower, from the viewpoint of the high-temperature water-resistant adhesion of the formed coating film.

[0090] The glass transition temperature can be measured, for example, using a differential scanning calorimeter "DSC-50Q" (manufactured by Shimadzu Corporation, product name). The sample is placed in a measuring cup, the solvent is completely removed by vacuum suction, and then the change in heat quantity is measured in the range of -100°C to 150°C at a heating rate of 3°C / min. The point of change at the first baseline on the low-temperature side is defined as the static glass transition temperature.

[0091] When the hydroxyl group-containing compound (A1) contains a hydroxyl group-containing polyester resin, the content of the hydroxyl group-containing polyester resin is preferably in the range of 10 to 100% by mass, more preferably in the range of 20 to 100% by mass, and even more preferably in the range of 40 to 100% by mass, based on the total solid content of the hydroxyl group-containing compound (A1), from the viewpoint of reducing the VOC content in the resulting paint composition and improving the high-temperature water adhesion, scratch resistance, and heat yellowing resistance of the formed coating film.

[0092] The above-mentioned hydroxyl group-containing polycaprolactone resin can be obtained, for example, by ring-opening polymerization of ε-caprolactone using a divalent to tetravalent polyhydric alcohol as an initiator. Examples of such divalent or higher polyhydric alcohols include ethylene glycol, glycerin, trimethylolethane, trimethylolpropane, diglycerin, ditrimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, tris(2-hydroxyethyl)isocyanuric acid, polyhydric alcohol compounds obtained by reacting dimethylolalkanoic acid with monoepoxy compounds (for example, "Cardura E10P; glycidyl ester of synthetic highly branched saturated fatty acid" manufactured by HEXION Specialty Chemicals), and any combination thereof.

[0093] The hydroxyl group-containing polycaprolactone resin mentioned above can be a commercially available product. Examples of commercially available products include "Praxel 205", "Praxel 205H", "Praxel L205AL", "Praxel 205U", "Praxel 208", "Praxel 210", "Praxel 210N", "Praxel 210CP", "Praxel 212", "Praxel L212AL", "Praxel 220", "Praxel 220N", "Praxel 220CPB", "Praxel 220CPT", "Praxel 220UA", and "Praxel 22 "0NP1", "Praxel L220AL", "Praxel 220EB", "Praxel 230", "Praxel 230N", "Praxel 240", "Praxel 303", "Praxel 305", "Praxel 308", "Praxel 309", "Praxel 312", "Praxel 320", "Praxel L320AL", "Praxel 410", "Praxel E2404", "Praxel E2405" (all product names, manufactured by Daicel Corporation), "TONE Examples include "0201", "TONE 0230", "TONE 0249", "TONE 0301", "TONE 0305", "TONE 0310", "TONE 1241", "TONE 1278", "TONE 2221" (all product names, manufactured by The Dow Chemical), "Capa 2043", "Capa 2101", "Capa 2201", "Capa 2205", "Capa 2209", "Capa 2201A", "Capa 2203A", "Capa 3031", "Capa 3050J", "Capa 3091", "Capa 4101" (all product names, manufactured by Ingevity), and any combination thereof.

[0094] The hydroxyl group-containing polycaprolactone resin described above preferably has a number average molecular weight of 300 or more, more preferably 350 or more, even more preferably 400 or more, and preferably 2000 or less, more preferably 1250 or less, and even more preferably 1000 or less, from the viewpoint of reducing the VOC content in the resulting paint composition and improving the high-temperature water adhesion, scratch resistance, and heat yellowing resistance of the formed coating film.

[0095] The hydroxyl value of the hydroxyl group-containing polycaprolactone resin is preferably in the range of 50 to 900 mg KOH / g, more preferably 50 mg KOH / g or more, more preferably 100 mg KOH / g or more, even more preferably 130 mg KOH / g or more, and more preferably 900 mg KOH / g or less, more preferably 750 mg KOH / g or less, and even more preferably 600 mg KOH / g or less.

[0096] When the hydroxyl group-containing compound (A1) contains a hydroxyl group-containing polycaprolactone resin, the content of the hydroxyl group-containing polycaprolactone resin is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less, based on the total solid content of the hydroxyl group-containing compound (A1), from the viewpoint of the high-temperature water adhesion resistance, scratch resistance, and heat yellowing resistance of the formed coating film.

[0097] As the hydroxyl group-containing polyether resin described above, alkylene oxide adducts of hydroxyl group-containing monomers, ring-opening (co)polymers of alkylene oxides or cyclic ethers (such as tetrahydrofuran) can be used. Specifically, examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, (block or random) copolymers of ethylene glycol-propylene glycol, polyhexamethylene glycol, polyoctamethylene glycol, and any combination thereof.

[0098] The hydroxyl group-containing polyether resin described above preferably has a number average molecular weight of 300 or more, more preferably 350 or more, and even more preferably 400 or more, and preferably 1000 or less, more preferably 850 or less, and even more preferably 600 or less, from the viewpoint of reducing the VOC content in the resulting paint composition and improving the high-temperature water adhesion, scratch resistance, and heat yellowing resistance of the formed coating film.

[0099] The hydroxyl value of the above-mentioned hydroxyl group-containing polyether resin is preferably 50 mg KOH / g or more, more preferably 70 mg KOH / g or more, even more preferably 90 mg KOH / g or more, and preferably 600 mg KOH / g or less, more preferably 500 mg KOH / g or less, and even more preferably 400 mg KOH / g or less, from the viewpoint of the high-temperature water-resistant adhesion of the formed coating film.

[0100] When the hydroxyl group-containing compound (A1) contains a hydroxyl group-containing polyether resin, the content of the hydroxyl group-containing polyether resin is preferably 5% by mass or more, more preferably 7% by mass or more, even more preferably 10% by mass or more, and preferably 100% by mass or less, more preferably 50% by mass or less, and even more preferably 25% by mass or less, based on the total solid content of the hydroxyl group-containing compound (A1), from the viewpoint of reducing the VOC content in the resulting paint composition and the high-temperature water adhesion, scratch resistance, and heat yellowing resistance of the formed coating film.

[0101] The above-mentioned hydroxyl group-containing polycarbonate resin is a compound obtained by polycondensation reaction of a known polyol component and a carbonylating agent using a conventional method. Examples of polyol components include diol components and polyhydric alcohol components such as trihydric or higher alcohols.

[0102] The above diol components 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, and 2,2,4-trimethic acid. Examples include branched diols such as 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; polylactone diols obtained by adding lactone compounds such as ε-caprolactone to these diol components, and any combination thereof.

[0103] Examples of trivalent or higher alcohols include glycerin, trimethylolethane, trimethylolpropane, trimethylolpropane dimers, pentaerythritol; polylactone polyols obtained by adding lactone compounds such as ε-caprolactone to these trivalent or higher alcohols, and any combination thereof.

[0104] Known carbonylating agents can be used as described above. Specifically, examples include alkylene carbonates, dialkyl carbonates, diallyl carbonates, phosgene, etc., and one or more of these can be used in combination. Among these, preferred examples include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, etc.

[0105] The hydroxyl group-containing polycarbonate resin described above preferably has a number average molecular weight of 300 or more, more preferably 400 or more, and even more preferably 450 or more, and preferably 1500 or less, more preferably 1250 or less, and even more preferably 1000 or less, from the viewpoint of reducing the VOC content in the resulting paint composition and the high-temperature water adhesion, scratch resistance, and heat yellowing resistance of the formed coating film.

[0106] The hydroxyl value of the above-mentioned hydroxyl group-containing polycarbonate resin is preferably 50 mg KOH / g or more, more preferably 70 mg KOH / g or more, even more preferably 90 mg KOH / g or more, and preferably 600 mg KOH / g or less, more preferably 500 mg KOH / g or less, and even more preferably 400 mg KOH / g or less, from the viewpoint of the high-temperature water-resistant adhesion of the formed coating film.

[0107] When the above-mentioned hydroxyl group-containing compound (A1) contains a hydroxyl group-containing polycarbonate resin, the content of the hydroxyl group-containing polycarbonate resin is preferably in the range of 10 to 100% by mass, more preferably in the range of 25 to 100% by mass, and even more preferably in the range of 40 to 100% by mass, based on the total solid content of the hydroxyl group-containing compound (A1), from the viewpoint of high-temperature water adhesion resistance, scratch resistance, and heat yellowing resistance of the formed coating film.

[0108] When the isocyanate-reactive group-containing compound (A) contains the hydroxyl group-containing compound (A1), the content of the hydroxyl group-containing compound (A1) is preferably in the range of 50 to 100% by mass, more preferably in the range of 60 to 100% by mass, and even more preferably in the range of 70 to 100% by mass, based on the total solid content of the isocyanate-reactive group-containing compound (A), from the viewpoint of the high-temperature water adhesion resistance, scratch resistance, and heat yellowing resistance of the formed coating film.

[0109] [Amino group-containing compound (A2)] An amino group-containing compound (A2) is a compound having at least one primary amino group and / or a secondary amino group in its molecule.

[0110] Examples of the above amino group-containing compound (A2) 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, and 2-methyl-1 Alicyclic polyamines such as 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, norbornanediamine; Heterocyclic polyamines such as perazine 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 Aromatic polyamines such as bisaniline (lydene), 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;Examples include polyaspartate 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)], etc.; aminosilane compounds such as N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-anilinopropyltrimethoxysilane, etc., and any combination thereof.

[0111] The above amino group-containing compound (A2) preferably contains at least one compound selected from the group consisting of aliphatic polyamines, alicyclic polyamines, polyether polyamine compounds, and polyaspartic acid ester compounds, from the viewpoint of preventing heat yellowing of the formed coating film, and more preferably contains at least one compound selected from the group consisting of alicyclic polyamines and polyaspartic acid esters.

[0112] The above amino group-containing compound (A2) preferably has a number average molecular weight of 300 or more, more preferably 400 or more, and even more preferably 450 or more, and preferably 1000 or less, more preferably 850 or less, and even more preferably 600 or less, from the viewpoint of reducing the VOC content in the resulting paint composition and the high-temperature water adhesion, scratch resistance, and heat yellowing resistance of the formed coating film.

[0113] The above amino group-containing compound (A2) can be a commercially available product. 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", "Baxxodur EC311" (all product names, manufactured by BASF Corporation), "Clearlink 1000", "Unilink 4200", "Unilink 4100'' (all product names, manufactured by DORF KETAL), ``JEFFAMINE M-600'', ``JEFFAMINE M-1000'', ``JEFFAMINE M-2005'', ``JEFFAMINE M-2070'', ``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 product names, manufactured by HUNTSMAN), "MXDA", "1,3-BAC (all product names, manufactured by Mitsubishi Gas Chemical Company, Inc.), "WANAMINE MDA-100H", "Etacure 100 Plus", "Etacure 300", "Etacure 420", "Bisaniline-M", "Bisaniline-P" (all product names, manufactured by Mitsui Chemicals Fine, Inc.), "VESTAMIN IPD", "VESTAMIN TMD", "VESTAMIN PACM", "ANCAMINE 2049" (all product names, manufactured by EVONIK Industries), “D.E.H.20”, “D.E.H.24”, “D.E.H.26”, “D.E.H.29”, “D.E.H.39”, “D.E.H.444”, “D.E.H. 445", "D.E.H.4042", "D.E.H.4044", "D.E.H.487", "D.E.H.488", "D.E.H.530", "D.E.H." Dow Chemical Corporation, "Desmofen NH1220", "Desmofen NH1420", "Desmofen NH1422", "Desmofen NH1423", "Desmofen NH1520", "Desmofen NH1521", "Desmofen NH1523" (all product names, manufactured by Sumika Covestro Urethane Co., Ltd.), "FEISPARTIC F220", "FEISPARTIC F420", "FEISPARTIC F520", "FEISPARTIC F2850" (all product names, manufactured by Feiyang Protech), "TSE-EZASP Examples include "9033" (product name, manufactured by TSE Industries), and any combination thereof.

[0114] The above-mentioned alicyclic polyamines can be commercially available. Examples of commercially available product names include "Baxxodur EC210", "Baxxodur EC201", "Baxxodur EC330", "Baxxodur EC331", "Baxxodur PC136" (all product names, manufactured by BASF Corporation), "Clearlink 1000" (all product names, manufactured by DORF KETAL), "1,3-BAC" (all product names, manufactured by Mitsubishi Gas Chemical Company, Inc.), "WANAMINE MDA-100H" (all product names, manufactured by Mitsui Chemicals Fine, Inc.), "VESTAMIN IPD", "VESTAMIN PACM", "ANCAMINE 2049" (all product names, manufactured by EVONIK (Manufactured by Industries, Inc.) "D.E.H. 487", "D.E.H. 488", "D.E.H. 530", "D.E.H." (all product names, manufactured by The Dow Chemical), "Desmofen NH1420", "Desmofen NH1422", "Desmofen NH1423", "Desmofen NH1520", "Desmofen NH1521", "Desmofen NH1523" (all product names, manufactured by Sumika Covestro Urethane Co., Ltd.), "FEISPARTIC F420", "FEISPARTIC F520" (all product names, manufactured by Feiyang Examples include Protech's "TSE-EZASP 9033" (product names, manufactured by TSE Industries), and any combination thereof.

[0115] When the isocyanate-reactive group-containing compound (A) contains the amino group-containing compound (A2), the content of the amino group-containing compound (A2) is preferably in the range of 10 to 100% by mass, more preferably in the range of 25 to 100% by mass, and even more preferably in the range of 40 to 100% by mass, based on the total solid content of the isocyanate-reactive group-containing compound (A), from the viewpoint of the high-temperature water adhesion resistance, scratch resistance, and heat yellowing resistance of the formed coating film.

[0116] [Thiol group-containing compound (A3)] The above thiol group-containing compound (A3) is a compound having at least one thiol group in one molecule.

[0117] Examples of the thiol group-containing compound (A3) 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 dipropanthol, and pentaerythritol. Examples include repropanthol, pentaerythritol tetrapropanthol, 1,4-bis(mercaptomethyl)benzene, pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropanetris(3-mercaptobutyrate), tetramethylene glycol bis(3-mercaptobutyrate), tris-[(3-mercaptobutyroyloxy)-ethyl]-isocyanurate, trimethylolpropanetris(thioglycolate), pentaerythritol tetrakis(thioglycolate), and any combination thereof.

[0118] The thiol group-containing compound (A3) described above can be a commercially available product. Examples of commercially available product names include "TMMP-LV", "TEMPIC", "PEMP-LV", "DPMP", "EGMP-4", "BDMP", "Multihol Y-3", "Multihol Y-4", "PXDT" (all product names, manufactured by SC Organic Chemicals Co., Ltd.), "BDTG", "HDTG", "TMTG", "PETG", "EGTP", "BDTP", "TMTP", "PETP" (all product names, manufactured by Yodo Chemical Co., Ltd.), "Adeka Hardener EH-317" (all product names, manufactured by Adeka Corporation), "Karens MT PEI", "Karens MT BDI", "Karens MT BD1", "Karens MT TPMB", "Karens MT NRI" (all product names, manufactured by Showa Denko K.K.), "jER Cure QX11", "jER Cure QX40" (all product names, manufactured by Mitsubishi Chemical Corporation), and any combination thereof.

[0119] The thiol group-containing compound (A3) described above preferably has a number average molecular weight of 380 or more, more preferably 400 or more, even more preferably 450 or more, and preferably 1000 or less, more preferably 850 or less, even more preferably 600 or less, from the viewpoint of reducing the VOC content in the resulting paint composition and improving the high-temperature water adhesion, scratch resistance, and heat yellowing resistance of the formed coating film.

[0120] When the isocyanate-reactive group-containing compound (A) contains the thiol group-containing compound (A3), the content of the thiol group-containing compound (A3) is preferably in the range of 5 to 100% by mass, more preferably in the range of 7 to 100% by mass, and even more preferably in the range of 10 to 100% by mass, based on the total solid content of the isocyanate-reactive group-containing compound (A), from the viewpoint of the high-temperature water adhesion resistance, scratch resistance, and heat yellowing resistance of the formed coating film.

[0121] In the paint composition according to this disclosure, the content of the isocyanate-reactive group-containing compound (A) is preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the paint composition, from the viewpoint of reducing the VOC content in the obtained paint composition and the high-temperature water adhesion, scratch resistance, and heat yellowing resistance of the formed coating film.

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

[0123] Examples of the above aliphatic polyisocyanates 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, and 2,6-methyl diisocyanatohexanoate (common name: lysine diisocyanate). Examples of aliphatic triisocyanates include aliphatic diisocyanates such as 2,6-diisocyanatohexanoate 2-isocyanatoethyl, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, and any combination thereof.

[0124] Examples of the above alicyclic polyisocyanates 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 mixtures thereof, norbornane diisocyanate, etc.; 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2-(3-isocyanatopropyl)-2,5-di(isocyanatomethyl)-bicyclo(2.2.1)heptane, 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-isocyanatomethyl-3-(3 Examples include alicyclic triisocyanates such as (-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, and any combination thereof.

[0125] Examples of the above-mentioned aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω,ω'-diisocyanato-1,4-diethylbenzene, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (common name: tetramethylxylylene diisocyanate) or mixtures thereof; aromatic aliphatic triisocyanates such as 1,3,5-triisocyanatomethylbenzene, and any combination thereof.

[0126] Examples of the above-mentioned aromatic polyisocyanates include aromatic diisocyanates such as m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate, 2,4'- or 4,4'-diphenylmethanediisocyanate or mixtures thereof, 2,4- or 2,6-tolylenediisocyanate or mixtures thereof, 4,4'-toluidinediisocyanate, and 4,4'-diphenyletherdiisocyanate; aromatic triisocyanates such as triphenylmethane-4,4',4''-triisocyanate, 1,3,5-triisocyanatobenzene, and 2,4,6-triisocyanatotoluene; aromatic tetraisocyanates such as 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, and any combination thereof.

[0127] Examples of derivatives of the above-mentioned polyisocyanates include dimers, trimers, biuretes, allophanates, uretdiones, uretonimines, isocyanurates, iminooxadiazinediones, polymethylene polyphenyl polyisocyanates (crude MDI, polymeric MDI), crude TDIs, and any combination thereof.

[0128] Of these polyisocyanates, aliphatic diisocyanates, aliphatic triisocyanates, alicyclic diisocyanates, aromatic aliphatic diisocyanates, and their derivatives are preferably used individually or in combination of two or more.

[0129] As the polyisocyanate compound (B) above, a prepolymer obtained by reacting the polyisocyanate or a derivative thereof with a compound that can react with the polyisocyanate under conditions of excess isocyanate groups may be used. Examples of compounds that can react with the polyisocyanate include compounds having active hydrogen groups such as hydroxyl groups and amino groups, and specifically, for example, polyhydric alcohols, low molecular weight polyester resins, amines, water, etc. As the polyhydric alcohol above, the polyhydric alcohol used in the description of the hydroxyl group-containing polyester resin above can be used.

[0130] [Polyisocyanate compound (B1) containing two or more isocyanate groups and one or more alkoxysilyl groups in one molecule] In the paint composition of the present disclosure, the polyisocyanate compound (B) includes a polyisocyanate compound (B1) (hereinafter sometimes abbreviated as "polyisocyanate compound (B1)") containing two or more isocyanate groups and one or more alkoxysilyl groups in one molecule, from the viewpoint of scratch resistance of the formed coating film, adhesion between the coating film and the polycarbonate resin substrate when immersed in high-temperature water (high-temperature water-resistant adhesion), and heat-resistant yellowing. By including polyisocyanate compound (B) (B1) in the polyisocyanate compound (B) of the present disclosure, siloxane bonds are formed in addition to urethane bonds, improving the crosslinking density of the coating film. As a result, the high-temperature water-resistant adhesion, scratch resistance, and heat-resistant yellowing of the formed coating film can be improved. When the coating composition of this disclosure contains a polyisocyanate compound (B1), the Si element concentration can be defined as a mass % of the total amount of resin solids in the coating composition. Preferably, the Si element is 0.5% by mass or more, more preferably 0.7% by mass or more, even more preferably 1.0% by mass or more, and preferably 5.0% by mass or less, more preferably 4.5% by mass or less, and even more preferably 4.0% by mass or less, based on the total amount of resin solids in the coating composition.

[0131] In the paint composition described above, the Si element concentration is a calculated value derived from the mass % of Si elements in the polyisocyanate compound (B1) and the percentage (mass %) of the raw materials relative to the total amount of resin solids in the paint composition.

[0132] In the coating composition according to this disclosure, the content of the polyisocyanate compound (B1) is preferably in the range of 10 to 100% by mass, more preferably in the range of 15 to 100% by mass, and even more preferably in the range of 30 to 100% by mass, based on the total amount of the polyisocyanate compound (B).

[0133] The polyisocyanate compound (B1) containing two or more isocyanate groups and one or more alkoxysilyl groups in one molecule is not particularly limited, but examples include the silane group-containing thioallophanate described in Japanese Patent Publication No. 2017-524759.

[0134] A commercially available polyisocyanate compound (B1) can be used. Examples of commercially available products include DESMODUR 2873 (trade name, manufactured by Sumika Covestro Urethane Co., Ltd.), X-12-1159L, X-48-1801 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), etc. All of the above example commercial products are compounds that have three alkoxylyl groups in one molecule.

[0135] In the polyisocyanate compound (B1), it is preferable that there be two or more alkoxysilyl groups per molecule, and more preferably three or more, from the viewpoint of high-temperature water adhesion resistance, scratch resistance, and heat yellowing resistance of the formed coating film.

[0136] [Polyisocyanate compound (B2) that does not contain alkoxysilyl groups and contains three or more isocyanate groups in one molecule] In the paint composition of the present disclosure, the polyisocyanate compound (B) preferably contains a polyisocyanate compound (B2) that does not contain alkoxysilyl groups and contains three or more isocyanate groups in one molecule (hereinafter sometimes abbreviated as "polyisocyanate compound (B2)") from the viewpoint of the release properties of the formed coating film from the mold. By including a polyisocyanate compound (B) containing three or more isocyanate groups in the polyisocyanate compound (B2) of the present disclosure, the release properties of the formed coating film from the mold can be improved. Examples of polyisocyanate compounds (B2) include the polyisocyanate derivatives mentioned above, such as modified products containing isocyanurate groups, biuret groups, or allophanate groups, and trifunctional or higher isocyanate-terminated urethane prepolymers (adduct modified products) obtained by reacting a diisocyanate compound with a polyol having three or more hydroxyl groups in one molecule.

[0137] A commercially available polyisocyanate compound (B2) can be used. Commercial product names include DESMODUR ultra N3900, DESMODUR ultra N3600, DESMODUR ultra N3700, DESMODUR N3500, DESMODUR N3800, DESMODUR N3200, DESMODUR N100, DESMODUR N75BA, DESMODUR ultra N3390BA, DESMODUR ultra N3790BA, DESMODUR N3580BA (all product names, manufactured by Sumika Covestro Urethane Co., Ltd.), Duranate TLA-100, Duranate Examples include TPA-100, Duranate 24A-100, Duranate MFA-75B, Duranate MFA-100, Duranate MHG-80B (all product names, Asahi Kasei Corporation), Coronate 2715, Coronate 2785, Coronate 2793 (all product names, manufactured by Tosoh Corporation), Takenate D-165N, Takenate D-140N, Takenate D-160N, Takenate D-110N (all product names, manufactured by Mitsui Chemicals, Inc.), and any combination thereof.

[0138] In the coating composition according to this disclosure, the content of the polyisocyanate compound (B2) is preferably in the range of 0 to 90% by mass, more preferably in the range of 0 to 85% by mass, and even more preferably in the range of 0 to 70% by mass, based on the total amount of the polyisocyanate compound (B).

[0139] From the viewpoint of adhesion of the formed coating film to the polycarbonate resin substrate and release properties from the mold, the molar ratio of isocyanate groups in the polyisocyanate compound (B) to isocyanate reactive groups in the isocyanate reactive group-containing compound (A) is preferably 0.7 or more, more preferably 0.9 or more, and preferably 2.0 or less, and more preferably 1.5.

[0140] In the coating composition according to this disclosure, the content of the polyisocyanate compound (B) is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less, based on the total solid content of the coating composition, from the viewpoint of high-temperature water adhesion resistance, scratch resistance, and heat yellowing resistance of the formed coating film.

[0141] [Curing Catalyst (C)] The coating composition of this disclosure preferably contains a curing catalyst (C). By containing a curing catalyst (C), the release properties of the formed coating film from the mold can be improved.

[0142] Examples of the above curing catalyst (C) include tin octoate, dibutyltin diacetate, dibutyltin di(2-ethylhexanoate), dibutyltin dilaurate, dioctyltin diacetate, dioctyltin di(2-ethylhexanoate), dioctyltin dineodecanoate, dioctyltin diversate, dibutyltin oxide, dibutyltin sulfide, dioctyltin oxide, dibutyltin fatty acid salt, lead 2-ethylhexanoate, zinc octoate, zinc naphthenate, zinc fatty acid derivatives, bismuth octanoate, bismuth 2-ethylhexanoate, bismuth oleate, bismuth neodecanoate, Organometallic compounds such as bismuth versatate, bismuth naphthenate, cobalt naphthenate, calcium octylate, copper naphthenate, tetra(2-ethylhexyl) titanate, tetra(n-butyl) titanate, titanium diisopropoxybis(acetylacetonate), titanium tetraacetylacetonate, titanium diisopropoxybis(ethylacetoacetate), titanium butoxide dimer, zirconium tetran-n-propoxide, zirconium tetran-n-butoxide, zirconium tetraacetylacetonate, and zirconium triputoxymonoacetylacetonate;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. Examples include tertiary amine compounds such as ]-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, and bis(2-morpholinoethyl) ether; neutralized salts of said tertiary amine compounds; tetraalkylammonium, tetraarylammonium and alkylarylammonium carboxylates; quaternary ammonium salts such as tetraalkylammonium, tetraarylammonium and alkylarylammonium halides; and any combination thereof.

[0143] In particular, the coating composition relating to this disclosure, from the viewpoint of the release properties of the formed coating film from the mold, uses the following curing catalysts (C): dioctyltin diversatate, dibutyltin dilaurate, dioctyltin diacetate, dioctyltin dineodecanoate, zinc octoate, zinc naphthenate, zinc fatty acids, bismuth octanoate, bismuth 2-ethylhexanoate, bismuth oleate, bismuth neodecanoate, bismuth versatate, bismuth naphthenate, tetra(2-ethylhexyl Titanate, tetra(n-butyl) titanate, titanium diisopropoxybis(acetylacetonate), titanium tetraacetylacetonate, titanium diisopropoxybis(ethylacetoacetate), titanium butoxide dimer, zirconium tetran-n-propoxide, zirconium tetran-n-butoxide, zirconium tetraacetylacetonate, zirconium triputoxymonoacetylacetonate, 1,4-diazabicyclo[2.2.2.]octane (DABCO), 1,8-diazabicyclo[5.4.0.]-7-undecene (DBU) and 1,5-diazabicyclo[4.3.0.] Preferably, the catalyst contains at least one curing catalyst selected from the group consisting of ]-5-nonene (DBN), including dioctyl tin diversate, dibutyl tin dilaurate, dioctyl tin diacetate, dioctyl tin dineodecanoate, zinc octoate, zinc naphthenate, zinc fatty acids, zirconium tetran-n-propoxide, zirconium tetran-n-butoxide, zirconium tetraacetylacetonate, 1,4-diazabicyclo[2.2.2.]octane (DABCO), 1,8-diazabicyclo[5.4.0.]-7-undecene (DBU), and 1,5-diazabicyclo[4.3.0. It is more preferable to include at least one curing catalyst selected from the group consisting of ]-5-nonene (DBN), and even more preferable to include at least one curing catalyst selected from the group consisting of dioctyl tin diversate, dibutyl tin dilaurate, dioctyl tin diacetate, and dioctyl tin dineodecanoate.

[0144] The content of the curing catalyst (C) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 2.0% by mass or less, and more preferably 1.5% by mass or less, based on the total solid content of the paint composition, from the viewpoint of heat resistance to yellowing of the formed coating film and release properties from the mold.

[0145] [Internal release agent (D)] When the coating composition according to this disclosure is used as an in-mold coating coating composition, it is preferable to include an internal release agent (D) from the viewpoint of release properties between the formed coating film and the mold. Examples of the above internal release agent (D) 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, 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, N,N-diethylstearic acid amide; unsaturated fatty acids such as palmitoleic acid and oleic acid; zinc palmitoleate, aluminum palmitoleate, Unsaturated fatty acid salts such as magnesium lumitoleate, 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 palmitoleamide, oleamide, erucamide, behenamide, N-oleyl palmitamide, N-stearyl erucamide, N,N-dimethyloleamide, and N,N-diethyloleamide; nonionic surfactants such as polyoxyethylene alkyl ethers and sorbitan alkyl esters; fluorinated compounds such as polytetrafluoroethylene, fluoropolyethers, perfluoroalkyl esters, and perfluoroalkyl ester salts; phosphate ester compounds such as phosphate monoesters and / or phosphate diesters having alkyl chains or oxyethylene chains;Fatty acid esters such as monoglyceride stearate, diglyceride stearate, triglyceride stearate, monosorbitate stearate, stearyl stearate, monoglyceride palmitate, diglyceride palmitate, triglyceride palmitate, monoglyceride behenate, diglyceride behenate, triglyceride behenate, behenyl behenate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetraperargonate, propylene 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; and any combination thereof.

[0146] The above-mentioned internal release agent (D) preferably contains a fatty acid amide, more preferably a tertiary fatty acid amide, and even more preferably a tertiary dimethyl fatty acid amide, from the viewpoint of the high-temperature water resistance of the formed coating film and release properties from the mold.

[0147] Examples of the above-mentioned fatty acid amides include 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; and unsaturated fatty acid amides such as palmitoleic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, N-oleylpalmitic acid amide, N-stearylerucic acid amide, N,N-dimethyloleic acid amide, and N,N-diethyloleic acid amide.

[0148] A commercially available internal release agent containing the above-mentioned fatty acid amide can be used. Examples of commercially available product names include "INT-120IMC" (product name, manufactured by AXEL PLASTICS), "Amid AP-1", "Diamid Y", "Diamid O-200", "Diamid I-200" (product names, manufactured by Mitsubishi Chemical Corporation), "Neutron", "Neutron-2", "Neutron-S", "Neutron BNT-22H", "Neutron PNT-34", "Neutron SNT-F" (product names, manufactured by Nippon Seika Co., Ltd.), "Alflow S-10", "Alflow E-10", "Alflow P-10", "Oleoyl Sarcosine 221P" (product names, manufactured by NOF Corporation), "ArmoSlip CP Powder", "ArmoSlip HT Powder", "ArmoSlip E" (product names, manufactured by Lion Specialty Chemicals), "Fatty Acid Amid S", "Fatty Acid Amid O-N", "Fatty Acid Amid E" (product names, manufactured by Kao Corporation), and others.

[0149] If the internal release agent (D) contains the fatty acid amide, the amount of the fatty acid amide is preferably in the range of 30 to 100% by mass, more preferably in the range of 50 to 100% by mass, and even more preferably in the range of 70 to 100% by mass, based on the total solid content of the internal release agent (D), from the viewpoint of the high-temperature water resistance of the formed coating film and release properties from the mold.

[0150] Examples of the above-mentioned tertiary fatty acid amides include 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, N,N-diethylstearic acid amide, N,N-dimethyloleic acid amide, and N-oleoylsarcosine.

[0151] Commercially available internal release agents containing the above-mentioned tertiary fatty acid amide can be used. Examples of commercially available products include "INT-120IMC" (product name, manufactured by AXEL PLASTICS).

[0152] If the internal release agent (D) contains a tertiary fatty acid amide, the content of the tertiary fatty acid amide is preferably in the range of 20 to 100% by mass, more preferably in the range of 35 to 100% by mass, and even more preferably in the range of 50 to 100% by mass, based on the total solid content of the internal release agent (D), from the viewpoint of the high-temperature water resistance of the formed coating film and release properties from the mold.

[0153] Examples of the above-mentioned tertiary dimethylamide fatty acids include N,N-dimethyllaurate amide, N,N-dimethylmyristic acid amide, N,N-dimethylpalmitic acid amide, N,N-dimethylstearic acid amide, and N,N-dimethyloleic acid amide.

[0154] Commercially available internal release agents containing the above-mentioned tertiary dimethylamide fatty acid can be used. Examples of commercially available products include "INT-120IMC" (product name, manufactured by AXEL PLASTICS).

[0155] If the internal release agent (D) contains the tertiary fatty acid dimethylamide, the content of the tertiary fatty acid dimethylamide is preferably in the range of 20 to 100% by mass, more preferably in the range of 35 to 100% by mass, and even more preferably in the range of 50 to 100% by mass, based on the total solid content of the internal release agent (D), from the viewpoint of the high-temperature water resistance of the formed coating film and release properties from the mold.

[0156] If the mold coating paint composition according to this disclosure contains the internal mold release agent (D), the content of the internal mold release agent (D) is preferably 0.12% by mass or more, more preferably 0.15% by mass or more, even more preferably 0.18% by mass or more, and preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.0% by mass or less, based on the total solid content of the mold coating paint composition, from the viewpoint of the high temperature water resistance of the formed coating film and release properties from the mold.

[0157] [Antioxidant (E)] The paint composition of this disclosure preferably contains an antioxidant (E). The inclusion of an antioxidant (E) in the paint composition of this disclosure can improve the heat resistance of the formed coating film to prevent yellowing.

[0158] Examples of the above antioxidant (E) include 4,6-bis(octylthiomethyl)-o-cresol, pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate, octadecyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate], N,N'-hexane-1,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)), 3,3',3',5,5',5'-hexa-tert-butyl-a,a',a'-( Mesitylene-2,4,6-triyl)tri-p-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate), benzenepropanoic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl ester, 3,5-di-tert-butyl-4-hydroxycinnamic acid, hexamethylene Bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(dodecylthio)methyl]-6-methylphenol, bis[3-[3-(tert-butyl)-4-hydroxy-5-methylphenyl]propanoic acid], 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl), 1,1,3-tris(2-methyl-4-hydroxyphenyl) Roxy-5-tert-butylphenyl)butane, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 3-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate-n-octadecyl, 3,3'-thiodipropionate didodecyl, 3,3'-thiodipropionate dioctadecyl, bis[3-(dodecylthio)propionate]2,2-bis[[3-(dodecylthio)-1-oxopropyloxy]methyl]-1,3-propanediyl, 3,3'-thiobispropionate ditridecyl, tris(2,Examples include, but are not limited to, 4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,2-methylenebis(4,6-di-t-butylphenyl)-2-ethylhexyl phosphite, tris(nonylphenyl) phosphite, tetraalkyl(C12-15)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl isodecyl phosphite, tridecyl phosphite, triphenyl phosphite, and any combination thereof.

[0159] Examples of commercially available antioxidants include Irganox 1520L, Irganox 1010, Irganox 1076, Irganox 1098, Irganox 1330, Irganox 3114, Irganox 245, Irganox 1135, Irganox 3125, Irganox 259, Irganox 1035, Irganox 1726, Irganox PS 800FL, and Irganox PS 802FL, Irgafos168, Irgafos168FF (manufactured by BASF Corporation, product names; Irganox and Irgafos are registered trademarks), SumiLizer GA-80, SumiLizer MDP-S, SumiLizer WX-R, SumiLizer WX-RC, SumiLizer TP-D, SumiLizer GP, SumiLizer GS(F), SumiLizer GM(F) (all manufactured by Sumitomo Chemical) Manufactured by Gaku Co., Ltd., product name, SumiRizer is a registered trademark), Adeka Stub AO-20, Adeka Stub AO-30, Adeka Stub AO-40, Adeka Stub AO-50, Adeka Stub AO-50F, Adeka Stub AO-50T, Adeka Stub AO-60, Adeka Stub AO-60G, Adeka Stub AO-80, Adeka Stub AO-330, Adeka Stub AO-26, Adeka Stub Examples include AO-412S, Adeka Stab AO-503, Adeka Stab PEP-8, Adeka Stab PEP-36, Adeka Stab HP-10, Adeka Stab 2112, Adeka Stab 2112RG, Adeka Stab 1178, Adeka Stab 1500, Adeka Stab C, Adeka Stab 135A, Adeka Stab 3010, Adeka Stab TPP (all manufactured by ADEKA Corporation, product names; Adeka Stab is a registered trademark).

[0160] If the coating composition according to this disclosure contains the above-mentioned antioxidant, the content of the antioxidant is preferably 0.05% by mass or more, more preferably 0.08% by mass or more, even more preferably 0.1% by mass or more, and preferably 3.0% by mass or less, more preferably 2.5% by mass or less, and even more preferably 2.0% by mass or less, based on the total solid content of the coating composition, from the viewpoint of preventing heat yellowing of the formed coating film.

[0161] [Other Components] In addition to the above, the coating composition according to this disclosure may further contain ultraviolet absorbers and / or light stabilizers. If necessary, other additive components commonly used in the field of coatings, such as crosslinking agents, solvents (organic solvents, water), pigments, surface modifiers, defoamers, emulsifiers, surfactants, antifouling agents, wetting agents, thickeners, dyes, scratch-resistant agents, gloss modifiers, etc., may be appropriately included.

[0162] As the ultraviolet absorber, conventionally known absorbers can be used, such as benzotriazole-based absorbers, triazine-based absorbers, salicylic acid derivative-based absorbers, and benzophenone-based absorbers. The above ultraviolet absorbers may also have polymerizable unsaturated groups.

[0163] Specific examples of the above benzotriazole-based absorbents 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, and 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole. Examples include rolobenzotriazole, 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.

[0164] Specific examples of the above-mentioned 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.

[0165] Specific examples of the salicylic acid derivative-based absorbents mentioned above include phenyl salicylate, p-octylphenyl salicylate, and 4-tert-butylphenyl salicylate.

[0166] Specific examples of the above benzophenone-based absorbents 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 Examples 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-methacrylateoxy-2-hydroxypropoxy)benzophenone.

[0167] Examples of commercially available UV absorbers include "TINUVIN 1130", "TINUVIN 900", "TINUVIN 928", "TINUVIN 384-2", "TINUVIN 479", "TINUVIN 477", "TINUVIN 405", "TINUVIN 400" (manufactured by BASF Corporation, product names; TINUVIN is a registered trademark), and "RUVA 93" (manufactured by Otsuka Chemical Co., Ltd., product name).

[0168] If the coating composition according to this disclosure contains the above-mentioned ultraviolet absorber, the amount of the ultraviolet absorber is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, and preferably 10.0% by mass or less, more preferably 5.0% by mass or less, and even more preferably 3.0% by mass or less, based on the total amount of solids in the coating composition, from the viewpoint of weather resistance of the formed coating film.

[0169] Light stabilizers The above-mentioned light stabilizers are used as radical chain inhibitors that capture active radical species generated during the deterioration process of the coating film. Examples include light stabilizers made of hindered amine compounds.

[0170] Examples of the above hindered amine compounds 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, and bis(1,2,2,6,6-pentamethyl-4-piperidyl){[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl}butylmaloney. Examples of light stabilizers include monomer-type light stabilizers 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-bonded light stabilizers such as polyesters of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and succinic acid, but are not limited to these. Known polymerizable light stabilizers can also be used as light stabilizers.

[0171] Examples of commercially available light stabilizers include "TINUVIN 123", "TINUVIN 152", "TINUVIN 249", "TINUVIN 292" (manufactured by BASF Corporation, product names; TINUVIN is a registered trademark), "HOSTAVIN 3058" (manufactured by Clariant, product name; Hostavin is a registered trademark), and "ADEKA STABB LA-82" (manufactured by ADEKA Corporation, product name; ADEKA STABB is a registered trademark).

[0172] If the coating composition according to this disclosure contains the above-mentioned light stabilizer, the content of the light stabilizer is preferably 0.05% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, and preferably 10.0% by mass or less, more preferably 7.5% by mass or less, and even more preferably 5.0% by mass or less, based on the total solid content of the coating composition, from the viewpoint of weather resistance of the formed coating film.

[0173] Solvent As the solvent, for example, an organic solvent or water can be used. Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate, butyl acetate, methyl benzoate, ethyl ethoxypropionate, ethyl propionate, and methyl propionate; ether solvents such as tetrahydrofuran, dioxane, and dimethoxyethane; glycol ether 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 "Swazol 1000" (manufactured by Cosmo Oil Co., Ltd., trade name, high boiling point petroleum solvent); and aliphatic hydrocarbon solvents such as hexane and heptane.

[0174] The solvent content in the paint composition according to this disclosure is in the range of 0 to 10% by mass, based on the total amount of the paint composition.

[0175] In the paint composition according to this disclosure, the content of the solvent is preferably in the range of 0 to 5% by mass, and more preferably in the range of 0 to 3% by mass, from the viewpoint of reducing the VOC content in the resulting paint composition.

[0176] Pigments: Examples of the above-mentioned pigments include luminous pigments, coloring pigments, extender pigments, and any combination thereof.

[0177] Examples of the above-mentioned luminous 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.

[0178] Examples of the above-mentioned coloring pigments include titanium dioxide, zinc oxide, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, surene pigments, perylene pigments, dioxazine pigments, diketopyrrolopyrrole pigments, and heat-shielding pigments.

[0179] Examples of the above-mentioned extender pigments include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica (including colloidal silica), and alumina white.

[0180] If the coating composition according to this disclosure contains the above-mentioned pigment, the amount of the pigment is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, and preferably 40.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 20.0% by mass or less, based on the total amount of solids in the coating composition, from the viewpoint of reducing the VOC content in the resulting coating composition and the adhesion of the formed coating film to the polycarbonate resin substrate.

[0181] Method for forming a coating film using a coating composition: By applying the coating composition according to this disclosure onto a substrate, a wet coating film (uncured coating film) is formed, and then the wet coating film is cured to form the desired coating film.

[0182] The above-mentioned substrate is preferably a resin material from the viewpoint of adhesion of the formed coating film and release properties between the formed coating film and the mold.

[0183] Examples of the above resin materials include polycarbonate resin, 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 like Epicote (trade name: manufactured by Yuka Shell Epoxy Co., Ltd.), polyimide resin, novolac resin, phenolic resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-ethylene-styrene (AES) resin, and acrylic resins. Examples include lilonitrile-styrene-acrylate (ASA) resin, vinyl chloride resin, vinylidene chloride resin, polyurethane resin, cellulose ester resin (e.g., triacetylcellulose, diacetylcellulose, propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose), polyamide resin, polystyrene resin (e.g., syndiotactic polystyrene), polyolefin resin (e.g., polypropylene, polyethylene, polymethylpentene), polysulfone resin, polyethersulfone resin, polyarylate resin, polyetherimide resin, polyetherketone resin, various fiber-reinforced plastic materials (hereinafter sometimes abbreviated as FRP materials or simply FRP), as well as polymer alloys thereof, recycled materials thereof, etc. Furthermore, a base material may be a mixture of the resin material with a compound containing reactive functional groups such as hydroxyl groups, amino groups, mercapto groups, silanol groups, vinyl groups, epoxy groups, or wood fibers, cellulose nanofibers, kenaf, etc.

[0184] When the substrate relating to this disclosure is a resin material, it is preferable that the resin material is at least one resin material selected from the group consisting of polycarbonate resin and polymer alloys of polycarbonate resin and other resins.

[0185] The above-mentioned substrate may, for example, be a resin material on which a primer paint, intermediate paint, or topcoat paint has been applied, thereby forming a primer layer, intermediate layer, or topcoat layer in advance.

[0186] The above-mentioned substrate may have been subjected to at least one physical treatment (physical treatment) selected from the group consisting of plasma treatment, corona discharge treatment, active energy ray treatment, flame treatment, blast treatment, polishing treatment, and the like.

[0187] Furthermore, it is preferable to apply the coating composition according to this disclosure directly onto a substrate.

[0188] The applications of the substrates to which the coating composition relating to this disclosure is applied are not particularly limited, and examples include the exterior panels of automobile bodies such as passenger cars, trucks, motorcycles, and buses; interior and exterior automotive parts such as bumpers, center pillars, mirrors, door handles, instrument panels, door trims, and center consoles; furniture and building material-related parts such as chairs, cosmetic mirrors, window frames, and gates; and exterior panels of household electrical appliances such as mobile phones and audio equipment.

[0189] The method for applying the coating composition according to this disclosure onto a substrate is not particularly limited. For example, it can be applied by air spray, airless spray, rotary atomizing coating machine, dipping coating, applicator, brush, roller, in-mold coating, etc. Electrostatic application may also be performed during application.

[0190] From the viewpoint of the release properties of the formed coating film from the mold, the cured coating film is preferably 70 μm or more, more preferably 80 μm or more, even more preferably 90 μm or more, and preferably 1000 μm or less, more preferably 900 μm or less, and even more preferably 800 μm or less.

[0191] The coating composition according to this disclosure can be cured on a substrate to which it has been applied by heating the coating composition.

[0192] Heating can be carried out using methods known in this field as appropriate. Specifically, for example, it can be done using hot air, hot gas, infrared heaters, IR radiators, ovens, hot rollers, hot presses, and microwaves. In this embodiment, from the viewpoint of ease of work, it is preferable to heat using hot air, infrared heaters, hot presses, etc.

[0193] The heating temperature is preferably 30°C or higher, more preferably 50°C or higher, even more preferably 60°C or higher, and preferably 130°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower, from the viewpoint of productivity, workability, adhesion of the formed coating film to the polycarbonate resin substrate, and release from the mold.

[0194] The heating time described above is preferably 20 seconds or more, more preferably 40 seconds or more, and preferably 60 minutes or less, and more preferably 10 minutes or less, from the viewpoint of productivity, workability, adhesion of the formed coating film to the polycarbonate resin substrate, and release from the mold.

[0195] In-mold coating method The in-mold coating method according to this embodiment includes the steps of injecting a coating composition according to this disclosure (hereinafter referred to as the in-mold coating coating composition when the coating composition according to this disclosure is used in the in-mold coating method) between a molded substrate and the inner wall of a mold, curing the in-mold coating coating composition, and then removing the coated molded product from the mold.

[0196] As for the in-mold coating method, conventional methods of molding and coating within a mold can be used without particular limitation. Specifically, for example, the methods described in Japanese Patent Publication No. 2000-141407 and Japanese Patent Publication No. 2008-525212 can be used.

[0197] Furthermore, the resin molding die used when molding the resin material and the mold used when coating the mold with the in-mold coating paint composition may be the same or different.

[0198] 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 resin molding dies having the shape of the target molded product, cooled and pressurized within the resin molding dies to form a molded product from the resin material, and then the resin molding dies are separated from the surface of the molded product made of resin material. Next, a gap sufficient for injecting the in-mold coating paint composition is made between the surface of the molded product made of 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 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 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 to obtain 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. If the resin molding die and the first coating film mold are different, for example, the 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 dies to form a molded product from the resin material, and then the resin molding dies are separated from the surface of the molded product made of the resin material and removed. Next, the in-mold coating die is brought close to the surface of the molded product made of the resin material, 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 to obtain 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.

[0199] From the viewpoint of release properties between the mold-coated molded product and the mold-coated mold, an external release agent may be applied to the mold. For example, external release agents such as fluorine-based, silicone-based, surfactant-based, and wax-based agents can be used.

[0200] The heating temperature when melting the resin in the injection cylinder can be arbitrarily determined depending on the type of resin material, but it is preferably between 70 and 300°C. The temperature of the mold when injecting the resin material can be arbitrarily determined depending on the molding time, the type of resin material, etc., but it is preferably between 30 and 120°C.

[0201] The molding time for the resin material may be until the resin material is completely solidified, but it is sufficient that it has solidified to a strength that does not impair the molded shape when the above-mentioned mold coating composition is injected, and is usually preferably about 20 seconds to 60 minutes.

[0202] The amount of the above-mentioned mold coating composition injected is sufficient to obtain the desired film thickness. From the viewpoint of the release properties of the formed coating film from the mold, the amount is preferably such that the film thickness is 70 μm or more, more preferably 80 μm or more, even more preferably 90 μm or more, and preferably 1000 μm or less, more preferably 900 μm or less, and even more preferably 800 μm or less.

[0203] The heating temperature when heating the uncured in-mold coating film is preferably 20°C or higher, more preferably 40°C or higher, even more preferably 60°C or higher, and preferably 130°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower.

[0204] The heating time when heating the uncured in-mold coating film is preferably 20 seconds or more, more preferably 30 seconds or more, even more preferably 40 seconds or more, and preferably 10 minutes or less, more preferably 5 minutes or less, and even more preferably 4 minutes or less.

[0205] When heating and curing the uncured in-mold coating film described above, it is preferable to apply pressure.

[0206] When applying the above-mentioned pressure, it is preferable that the pressure be within the range of 2 to 14 MPa from the viewpoint of adhesion of the formed coating film to the polycarbonate resin substrate.

[0207] The embodiment will be described in more detail below with reference to manufacturing examples, embodiments, and comparative examples. These manufacturing examples, embodiments, and comparative examples are merely illustrative and are not intended to limit the scope of this disclosure. In the manufacturing examples, embodiments, and comparative examples, "parts" and "%" are based on mass unless otherwise specified. The film thickness of the coating is based on the cured coating.

[0208] The components used in the example below are as follows:

[0209] Production Example 1 of Hydroxyl-Containing Acrylic Resin Composition 40 parts of 1,4-cyclohexanedimethanol were charged into a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, nitrogen inlet tube, and dropping device. The charge was stirred at 150°C while blowing nitrogen gas into the reaction vessel, and a monomer mixture consisting of 25 parts styrene, 15 parts methyl methacrylate, 20 parts n-butyl acrylate, 40 parts 2-hydroxyethyl methacrylate, and 8 parts ditertariamyl peroxide (polymerization initiator) was added dropwise at a uniform rate over 4 hours. After that, the mixture was aged at 150°C for 1 hour and then cooled to obtain a hydroxyl-containing acrylic resin (A1-1) composition with a solid content of 100% by mass. The hydroxyl value of the hydroxyl-containing acrylic resin in the obtained hydroxyl-containing acrylic resin (A1-1) composition was 172 mgKOH / g, the number average molecular weight was 1900, and the glass transition temperature was 39.0°C.

[0210] Production Example 2 40 parts of 1,4-cyclohexanedimethanol were charged into a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, nitrogen inlet tube, and dropping device. The charge was stirred at 150°C while blowing nitrogen gas into the reaction vessel, and a monomer mixture consisting of 30 parts n-butyl acrylate, 30 parts 2-ethylhexyl acrylate, 40 parts 2-hydroxyethyl methacrylate, and 8 parts ditertariamyl peroxide (polymerization initiator) was added dropwise at a uniform rate over 4 hours. After that, the mixture was aged at 150°C for 1 hour and then cooled to obtain a hydroxyl group-containing acrylic resin (A1-2) composition with a solid content of 100% by mass. The hydroxyl value of the hydroxyl group-containing acrylic resin in the obtained hydroxyl group-containing acrylic resin (A1-2) composition was 172 mgKOH / g, the number average molecular weight was 1900, and the glass transition temperature was -27.1°C.

[0211] Production Example 3: 40 parts of 1,4-cyclohexanedimethanol were charged into a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, nitrogen inlet tube, and dropper. The charge was stirred at 150°C while blowing nitrogen gas into the reaction vessel, and a monomer mixture consisting of 30 parts styrene, 30 parts methyl methacrylate, 30 parts 2-ethylhexyl acrylate, 10 parts 2-hydroxyethyl methacrylate, and 8 parts ditertariamyl peroxide (polymerization initiator) was added dropwise at a uniform rate over 4 hours. After that, the mixture was aged at 150°C for 1 hour and then cooled to obtain a hydroxyl group-containing acrylic resin (A1-3) composition with a solid content of 100% by mass. The hydroxyl value of the hydroxyl group-containing acrylic resin in the obtained hydroxyl group-containing acrylic resin (A1-3) composition was 43 mgKOH / g, the number average molecular weight was 1900, and the glass transition temperature was 21.9°C.

[0212] Manufacturing of Pigment Dispersion (P) Manufacturing Example 4 In a container equipped with a stirring device, 4.7 parts of butyl acetate, 1 part of "Raven 5000 ULTRA III POWDER" (trade name, manufactured by BIRLA CARBON, carbon black pigment, solid content concentration 100%), 0.1 parts of "SOLSPERSE 5000S" (trade name, manufactured by LUBRISOL, phthalocyanine pigment derivative, solid content concentration 100%), and 1 part of "DISPERBY K-2013" (trade name, manufactured by Bic Chemie, dispersant, solid content concentration 100%) were added and mixed uniformly. Next, the resulting mixed solution was placed in a wide-mouthed glass bottle, glass beads with a diameter of approximately 1.3 mmφ were added as a dispersion medium, the bottle was sealed, and the mixture was dispersed in a paint shaker for 4 hours to obtain pigment dispersion (P-1).

[0213] Manufacturing Example 1 of Paint Composition In a container equipped with a stirring device, 100.0 parts of the hydroxyl group-containing acrylic resin (A1-1) composition (solids content concentration 100%) obtained in Manufacturing Example 1, 220.0 parts of "DESMODUR 2873" (trade name, manufactured by Sumika Covestro Urethane Co., Ltd., a compound containing two isocyanate groups and three alkoxysilyl groups in one molecule, NCO content: 12.3%, Si content: 5.3%, solids content concentration 100%), 0.6 parts of "Neostan U-830" (trade name, manufactured by Nitto Kasei Co., Ltd., dioctyl tin diversate, solids content concentration 100%), 0.6 parts of "Amide AP-1" (Note 15), and Irganox 0.6 parts of 1135 (product name, manufactured by BASF Corporation, phenolic antioxidant, solids content 100%), 0.1 parts of BYK-333 (product name, manufactured by Bic Chemie, surface modifier (polyether-modified polydimethylsiloxane), solids content 100%), 1.2 parts of TINUVIN 400 (product name, manufactured by BASF Corporation, triazine-based UV absorber, solids content 85%), and 2.0 parts of TINUVIN 292 (product name, manufactured by BASF Corporation, hindered amine compound light stabilizer, solids content 100%) were blended and uniformly mixed to obtain mold coating composition No. 1 with a solids content of 99.9%.

[0214] Examples 2 to 51, Comparative Examples 1 to 6 In Example 1, mold coating compositions No. 2 to No. 57 were obtained in the same manner as in Example 1, except that the formulation composition was as shown in Table 1 below.

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221] The components listed in the table are as follows:

[0222] The values ​​in the table represent the solid content (excluding butyl acetate).

[0223] (Note 1) "DESMOPHEN XP2488": Product name, manufactured by Sumika Covestro Urethane Co., Ltd., number average molecular weight 500, solid content concentration 100%, contains cyclohexanedimethanol as a diluent monomer. The above number average molecular weight represents the value for the composition containing cyclohexanedimethanol. (Note 2) "Sannix GP-400": Product name, manufactured by Sanyo Chemical Industries, Ltd., polyether resin, number average molecular weight 400, solid content concentration 100%.

[0224] (Note 3) "ETERNACOLL PH-50": Product name, manufactured by UBE Corporation, polycarbonate resin, number average molecular weight 500, solids content 100%.

[0225] (Note 4) "Plaxel 305" (product name, manufactured by Daicel Corporation, polycaprolactone resin, number average molecular weight 510, solids content 100%).

[0226] (Note 5) "DESMOPHEN NH1423": Product name, manufactured by Sumika Covestro Urethane Co., Ltd., N,N'-[methylenebis(cyclohexane-4,1-diyl)]bisaspartate tetraethyl, number average molecular weight 555, solids content 100%.

[0227] (Note 6) "DESMOPHEN NH1220": Trade name, manufactured by Sumika Covestro Urethane Co., Ltd., N,N'-(2-methylpentane-1,5-diyl)bisaspartate tetraethyl, number average molecular weight 461, solids content concentration 100%.

[0228] (Note 7) "TEMPIC": Trade name, manufactured by SC Organic Chemicals, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate(2,4,6-trioxo-1,3,5-triazinan-1,3,5-triyl)tris(ethane-2,1-diyl)=tris(3-sulfanylpropanoate), number average molecular weight 525, solids content 100%.

[0229] (Note 8) "TMMP-LV": Trade name, manufactured by SC Organic Chemicals, trimethylolpropanetris (3-mercaptopropionate), number average molecular weight 399, solid content concentration 100%.

[0230] (Note 9) "X-12-1159L": Trade name, manufactured by Shin-Etsu Chemical Co., Ltd., a polyisocyanate compound containing two isocyanate groups and three alkoxysilyl groups in one molecule, NCO content: 11.0%, Si content: 5.5%, solids content: 100%.

[0231] (Note 10) "DESMODUR N3500": Product name, manufactured by Sumika Covestro Urethane Co., Ltd., a polyisocyanate compound containing three or more isocyanate groups per molecule, solid content concentration 100%.

[0232] (Note 11) "DESMODUR Ultra N3700": Trade name, manufactured by Sumika Covestro Urethane Co., Ltd., a polyisocyanate compound containing three or more isocyanate groups per molecule, solid content concentration 100%.

[0233] (Note 12) "DESMODUR N100": Trade name, manufactured by Sumika Covestro Urethane Co., Ltd., a polyisocyanate compound containing three or more isocyanate groups per molecule, solid content concentration 100%.

[0234] (Note 13) "DESMODUR N3400": Trade name, manufactured by Sumika Covestro Urethane Co., Ltd., a polyisocyanate compound containing fewer than 3 isocyanate groups per molecule, solid content concentration 100%.

[0235] (Note 14) "K-KAT XK640": Product name, manufactured by KING INDUSTRIES, bismuth carboxylate, solids content 100%.

[0236] (Note 15) "Amid AP-1": Product name, manufactured by Mitsubishi Chemical Corporation, stearic acid amide, solid content concentration 100%.

[0237] (Note 16) "Moldwiz INT-120IMC": Product name, manufactured by AXEL PLASTICS, a mixture containing tertiary dimethylamide fatty acids, solid content concentration 100%.

[0238] (Note 17) "Daifree FB-962": Product name, manufactured by Daikin Industries, Ltd., fluorine-based polymer, solid content concentration 100%.

[0239] (Note 18) "ADEKA Stab AO-503": Product name, manufactured by ADEKA Corporation, sulfur-based antioxidant, solid content concentration 100%.

[0240] (Note 19) "KBE-9007N": Product name, manufactured by Shin-Etsu Chemical Co., Ltd., a silane coupling agent containing an isocyanate group (a monoisocyanate compound containing an alkoxysilyl group), Si content: 11.3%, solid content concentration 100%.

[0241] Example 52 of the production of in-mold coated molded product (production of in-mold coated molded product (M1-1)) First, "Makrolon AL2447" (product name, manufactured by Sumika Covestro Urethane Co., Ltd., polycarbonate resin) was filled into the injection molding cylinder and heated and melted at 270°C. Then, the molten material was injected between resin molding dies at 80°C, and the pressure was maintained for 30 seconds to cool, thereby obtaining a flat plate-shaped "Makrolon AL2447" molded product measuring 100 mm × 100 mm × 2 mm. Next, the resin molding dies were opened, and the in-mold coating paint composition No. obtained in Example 1 was poured between the obtained flat plate-shaped "Makrolon AL2447" molded product and the coating dies. After injecting 1, the inside of the coating mold was heated to 80°C and maintained at that temperature, then pressurized with a molding pressure of 5 MPa and maintained for 1 minute, after which the pressure was reduced and the coating mold was opened, thereby producing an in-mold coated product (M1-1) on a flat plate-shaped "Makrolon AL2447" molded product with a hardened coating film thickness of 200 μm.

[0242] (Preparation of molded product with in-mold coating (M2-1)) First, "Makroblend UT235M" (product name, manufactured by Sumika Covestro Urethane Co., Ltd., a polymer alloy of polyethylene terephthalate resin and polycarbonate resin) was filled into the injection molding cylinder and heated and melted at 270°C. Then, the molten material was injected between resin molding dies at 70°C, and the pressure was maintained for 30 seconds to cool, thereby obtaining a flat "Makroblend UT235M" molded product measuring 100 mm × 100 mm × 2 mm. Next, the resin molding dies were opened, and the paint composition No. obtained in Example 1 was applied between the obtained flat "Makroblend UT235M" molded product and the coating dies. After injecting 1, the inside of the coating mold was heated to 80°C and maintained at that temperature, then pressurized with a molding pressure of 5 MPa and maintained for 1 minute, after which the pressure was reduced and the coating mold was opened, thereby producing an in-mold coated product (M2-1) on a flat plate-shaped "Makroblend UT235M" molded product with a coating film of 200 μm cured thickness.

[0243] Examples 53-102, Comparative Examples 7-12 In Example 52, the molded products (M1-2) to (M1-57) and (M2-2) to (M2-57) were prepared in the same manner as in Example 52, except that the type of coating composition was as shown in Table 2 below.

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250] Evaluation of molded products with in-mold coatings: The cured coatings on each molded product with in-mold coatings were evaluated for high-temperature water resistance, scratch resistance, heat yellowing resistance, and release properties. The evaluation results are shown in Table 2.

[0251] (High-temperature water-resistant adhesion) The molded inner coatings obtained in Examples 52 to 102 and Comparative Examples 7 to 12 were immersed in 80°C hot water for 1 hour, then removed and left to stand in an environment with a temperature of 23±2°C and a relative humidity of 50±5%RH. After 24 hours, a grid pattern of cuts was made with a cutter so as to reach the substrate, creating 100 2mm x 2mm lattice holes. Subsequently, adhesive cellophane tape was applied to the surface of each molded inner coating with cuts, and the adhesive cellophane tape was rapidly peeled off at a temperature of 23±2°C and a relative humidity of 50±5%RH. The remaining state of the lattice coating film after peeling was examined, and the adhesion after the water-resistant test was evaluated based on the following criteria. A, B, and C are acceptable.

[0252] A: 100 granular coatings remain, and no small chips or lifting of the coating at the edges of the cutter's notches have occurred.

[0253] B: 100 small areas of the paint film remain, and small chips and lifting of the paint film have occurred at the edges of the cutter's notches.

[0254] C: 90 to 99 granular coating particles remain.

[0255] D: 80 to 89 Goban-type coatings remain.

[0256] E: The number of remaining Goban-type coatings is 79 or less.

[0257] (Scratch Resistance) The 20° gloss of the coating film of each mold-coated molded product obtained in Examples 52-102 and Comparative Examples 7-12 was measured using a gloss meter (Byk-Gardner, Micro Tri Gross), and this was used as the gloss before testing. Each mold-coated molded product was fixed to the test stand of a car-wash test machine (Amtec Corporation, Car-wash Lab Apparatus) in a 20°C atmosphere, and a test solution of 1.5 g of Sikron SH200 (trade name, silica fine particles with a particle size of 24 μm, manufactured by Quarzwerke) mixed with 1 liter of water was sprayed onto the test plate while the car wash brush was rotated at 127 rpm and the test stand was moved back and forth 10 times. After that, it was washed with water and dried, and wiped with isopropyl alcohol. Next, the 20° gloss was measured using a gloss meter (Byk-Gardner, device name: Micro TriGross), and this was defined as the gloss after the test. The gloss retention rate was calculated using the following formula. A, B, and C are considered acceptable.

[0258] Gloss retention rate (%) = Gloss after test / Gloss before test × 100 A: Gloss retention rate of 90% or more, B: Gloss retention rate of 80% or more but less than 90%, C: Gloss retention rate of 70% or more but less than 80%, D: Gloss retention rate of 60% or more but less than 70%, E: Gloss retention rate less than 60%.

[0259] (Heat Resistance to Yellowing) The molded products with internal coatings obtained in Examples 52 to 102 and Comparative Examples 7 to 12 were exposed to a 110°C environment for 120 hours. The degree of yellowing before and after the test was measured in accordance with JIS K7373:2006, and the degree of yellowing was calculated using the following formula. A, B, and C are acceptable.

[0260] Yellowing degree = Yellowing degree after test - Yellowing degree before test A: Yellowing degree is less than 1 B: Yellowing degree is less than 1.5 C: Yellowing degree is 1.5 or more and less than 2 D: Yellowing degree is 2 or more and less than 5 E: Yellowing degree is 5 or more (Release property) In the production of the above mold-coated molded product, when releasing the coating mold, a release test was performed in which a spatula was inserted into the gap between one of the four corners of the mold-coated molded product and the coating mold to lift the mold-coated molded product and release it from the coating mold. If the mold-coated composition could not be released, the spatula was removed, and the spatula was inserted again into the gap between one of the four corners to the right and the coating mold, and the release test was performed in the same way. The release test was performed at all four corners until the mold-coated composition was released, and was performed a maximum of four times in total. For molded products with peeling coatings, the surface of the molded product was observed visually, the number of peeled areas was counted, and the release properties were evaluated according to the following criteria. A, B, and C are considered acceptable.

[0261] A: In the first or second release test, the molded product with the in-mold coating detaches from the mold, and the number of areas where the coating has peeled off is zero.

[0262] B: In the third to fourth release test, the molded product with the in-mold coating detaches from the mold, and the number of areas where the coating has peeled off is zero.

[0263] C: In the first to fourth release tests, the molded product with the in-mold coating releases from the mold, and the number of areas where the coating has peeled off is one.

[0264] D: In the first to fourth release tests, the molded product with the in-mold coating releases from the mold, and the number of areas where the coating has peeled off is two or more.

[0265] E: Even after four release tests, the molded product with the in-mold coating does not release from the mold, or the coating completely peels off from the substrate over its entire surface.

Claims

1. A paint composition comprising an isocyanate-reactive group-containing compound (A) and a polyisocyanate compound (B), wherein the polyisocyanate compound (B) comprises a polyisocyanate compound (B1) containing two or more isocyanate groups and one or more alkoxysilyl groups in one molecule, and the solid content concentration is 90% by mass or more.

2. The paint composition according to claim 1, wherein the content of Si element is in the range of 0.5 to 5% by mass with respect to the total amount of resin solids in the paint composition.

3. The paint composition according to claim 1 or 2, wherein the polyisocyanate compound (B) further comprises a polyisocyanate compound (B2) that does not contain an alkoxysilyl group and contains three or more isocyanate groups in one molecule.

4. The paint composition according to any one of claims 1 to 3, further comprising a curing catalyst (C).

5. The paint composition according to any one of claims 1 to 4, further comprising an internal mold release agent (D).

6. The paint composition according to any one of claims 1 to 5, further comprising an antioxidant (E).

7. An in-mold coating method comprising the steps of injecting an in-mold coating paint composition between a molded substrate and the inner wall of a mold, curing the in-mold coating paint composition, and then removing the coated molded product from the mold, wherein the in-mold coating paint composition is the paint composition described in any one of claims 1 to 6.

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