Three-liquid coating composition set, three-liquid coating composition, and in-mold coating method

Abstract

The purpose of the present invention is to provide a set for a three-part coating composition, which is capable of forming a coating film that has a low VOC content, is capable of shortening the cleaning process of a coating device when multicolored, has excellent hardness and adhesion, and suppresses color unevenness. The present invention relates to a set for a three-part coating composition, the set comprising a main agent (A) containing a compound (a1) containing an isocyanate-reactive group, a curing agent (B) containing a polyisocyanate compound (b1), and a pigment slurry (C) containing a compound (c1) containing an isocyanate-reactive group and a pigment (c2), the viscosity (VA) of the main agent (A) under specific conditions is within the range of 20-1800 mPa.s, the viscosity (VB) of the curing agent (B) under specific conditions is within the range of 20-1800 mPa.s, and the viscosity (VC) of the pigment slurry (C) under specific conditions is within the range of 20-1800 mPa.s.

Description

Technical Field

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

[0002] Conventionally, in order 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 coating compositions and lowering air conditioning energy consumption during coating.

[0003] Furthermore, in recent years, in various technical fields, there has been a demand for coating film performance such as coating film hardness and high adhesion between the coating film and the substrate, while also being required to suppress color unevenness.

[0004] Furthermore, when the coating composition is multicolored, there is a problem that cleaning of the coating equipment is laborious when the coating color is changed.

[0005] Patent Document 1 discloses a two-component coating material composition comprising a coating base component A and a curing component B, wherein the coating base component A comprises: i. one or more polyols A1 selected from the group of polyols containing ester groups, having a hydroxyl value of 300 to 500 mgKOH / g and a hydroxyl functionality exceeding 2; ii. a polyol having the general formula (I): R 1 -(OH) p (Where R 1 is a p-valent branched, cyclic or linear, saturated or unsaturated aliphatic hydrocarbon radical having 5 to 18 carbon atoms, the radical R 1 Optionally containing one or more tertiary amino groups and one or more aliphatic polyols A2 where p is 2 to 6; iii. General formula (II): R 2 -(C=O) r -O-(AO) s -R 3 (Where R 2 is a saturated or unsaturated aliphatic hydrocarbon radical having 6 to 30 carbon atoms, R 3is H, a free radical PO(OH)2, or a free radical of an optionally partially phosphorylated monosaccharide or disaccharide or a free radical of an optionally partially phosphorylated sugar alcohol, AO represents one or more alkylene oxide free radicals selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide, r is 0 or 1, s is 0 to 30) of 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 mgKOH / g; and ix. any one or more additives A9 selected from the group consisting of wetting agents and / or dispersants, rheological additives and flow control agents; the aforementioned curing component B contains i. one or more species having an average of 2.4 to 5 NCO groups The two-component coating material composition comprises a solid content of at least 96% by mass based on ASTM D2369 (2015) relative to the total mass of the two-component coating material composition, and 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 coating base component A is 1:1.15 to 1:0.95. The two-component coating material composition can generally be released from the metal mold surface without damage without using an external release agent, and on the other hand, it has extremely good adhesion to the substrate and can be re-coated through further coating films such as primer layers and clearcoat layers, thereby forming an extremely high-quality surface without the need for costly and inconvenient cleaning and / or polishing steps.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application No. 2020-528103 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] The technique described in Patent Document 1 has a low VOC content in the obtained two-component coating composition, but has the problem of requiring time and effort to clean the coating equipment when multiple colors are applied.

[0011] The present invention aims to provide a three-component coating composition kit capable of forming a coating film having a low VOC content, a process that can reduce the cost of cleaning the coating equipment when multi-coloring is carried out, excellent hardness and adhesion, and suppressed color unevenness.

[0012] Solutions for solving problems

[0013] The present inventors have conducted intensive studies to achieve the above-mentioned object and have found that the above-mentioned object can be achieved by the following kit: the kit is a kit for a three-component coating composition, the kit comprising a main agent (A) containing a compound (a1) containing an isocyanate-reactive group, a curing agent (B) containing a polyisocyanate compound (b1), and a pigment slurry (C) containing an isocyanate-reactive group-containing compound (c1) and a pigment (c2), wherein the main agent (A) is quenched at a shear rate of 100 sec -1 、Viscosity at 65℃ (V A ) is in the range of 20 to 1800 mPa·s, the curing agent (B) is at a shear rate of 100 sec -1 、Viscosity at 65℃ (V B ) is in the range of 20 to 1800 mPa·s, the pigment slurry (C) is subjected to a shear rate of 100 sec -1 、Viscosity at 65℃(V C ) is in the range of 20 to 1800 mPa·s.

[0014] That is, the present invention relates to the following <1> to <7>.

[0015] <1> A kit for a three-component coating composition, comprising: a main component (A) containing (a1) an isocyanate-reactive group-containing compound, a curing agent (B) containing (b1) a polyisocyanate compound, and a pigment slurry (C) containing (c1) an isocyanate-reactive group-containing compound and (c2) a pigment, wherein the main component (A) is soluble in water at a shear rate of 100 sec -1 、Viscosity at 65℃ (V A ) is in the range of 20 to 1800 mPa·s, the curing agent (B) is at a shear rate of 100 sec -1 、Viscosity at 65℃(V B ) is in the range of 20 to 1800 mPa·s, the pigment slurry (C) is subjected to a shear rate of 100 sec -1 、Viscosity at 65℃ (V C ) is in the range of 20 to 1800 mPa·s.

[0016] <2> The three-component coating composition according to <1>, wherein the solid content concentration is 95% by mass or more.

[0017] <3> The set according to <1> or <2>, wherein the solid content concentration of the pigment slurry (C) is within a range of 85 to 98% by mass.

[0018] <4> The kit according to any one of <1> to <3>, wherein the isocyanate-reactive group-containing compound (c1) contains an isocyanate-reactive group-containing compound having a number average molecular weight within a range of 250 to 2500.

[0019] <5> The set according to any one of <1> to <4>, wherein the content of the pigment (c2) is within a range of 1.0 to 65% by mass based on the total amount of the pigment slurry (C).

[0020] <6> The set according to any one of <1> to <5>, wherein the (V A ), said (V B ) and (V C ) satisfies the following formulas (1) and (2):

[0021] 0.4≤(V B ) / (V A )≤2.5 Formula (1)

[0022] 0.3≤(V C ) / (V A )≤3.0Formula (2).

[0023] <7> A three-component coating composition comprising: a main component (A) containing a compound (a1) containing an isocyanate-reactive group, a curing agent (B) containing a polyisocyanate compound (b1), and a pigment slurry (C) containing a compound (c1) containing an isocyanate-reactive group and a pigment (c2), wherein the main component (A) is resistant to catalytic oxidation at a shear rate of 100 sec -1 、Viscosity at 65℃(V A ) is in the range of 20 to 1800 mPa·s, the curing agent (B) is at a shear rate of 100 sec -1 、Viscosity at 65℃(V B ) is in the range of 20 to 1800 mPa·s, the pigment slurry (C) is subjected to a shear rate of 100 sec -1 、Viscosity at 65℃(V C ) is in the range of 20 to 1800 mPa·s.

[0024] <8> An in-mold coating method comprising the steps of injecting an in-mold coating composition between a molded substrate and an inner wall of a mold, curing the in-mold coating composition, and then removing the coated molded article from the mold, wherein the in-mold coating composition is a three-component coating composition formed from the set described in any one of <1> to <6> or the three-component coating composition described in <7>.

[0025] Effects of the Invention

[0026] According to the present invention, a three-component coating composition kit can be provided that has a low VOC content, reduces the cleaning cost of coating equipment when multi-coloring is achieved, and forms a coating film having excellent hardness and adhesion and suppressed color unevenness. DETAILED DESCRIPTION

[0027] The present invention will be described in detail below, but this is merely an example of a preferred embodiment, and the present invention is not limited to these contents.

[0028] [Kit for three-component coating composition and three-component coating composition]

[0029] The kit for a three-component coating composition of the present invention (hereinafter sometimes referred to as a "kit") is a kit comprising a main component (A) containing an isocyanate-reactive group-containing compound (a1), a curing agent (B) containing a polyisocyanate compound (b1), and a pigment slurry (C) containing an isocyanate-reactive group-containing compound (c1) and a pigment (c2), wherein the main component (A) is subjected to a shear rate of 100 sec -1 、Viscosity at 65℃ (V A ) is in the range of 20 to 1800 mPa·s, the curing agent (B) is at a shear rate of 100 sec -1 、Viscosity at 65℃ (V B ) is in the range of 20 to 1800 mPa·s, the pigment slurry (C) is subjected to a shear rate of 100 sec -1 、Viscosity at 65℃ (V C ) is in the range of 20 to 1800 mPa·s.

[0030] The three-component coating composition of the present invention can be formed by mixing a main component (A), a curing agent (B), and a pigment slurry (C).

[0031] It should be noted that the viscosity (V A ), viscosity (V B ) and viscosity (V C ) is described in the examples.

[0032] The kit of the present invention can form a three-component coating composition. The reason why this three-component coating composition can form a coating film with a low VOC content, a reduced cleaning process for coating equipment when multi-coloring is achieved, excellent hardness and adhesion, and suppressed color unevenness is speculated as follows.

[0033] When creating multiple colors with a two-component coating composition consisting of a base containing a pigment and a curing agent, changing colors requires cleaning the base tank and piping, or preparing a number of base tanks corresponding to the number of colors and cleaning only the piping. Since the capacity of a large base tank is often larger, cleaning the large tank and piping requires more effort. Furthermore, when preparing multiple base tanks, the large size of the tanks creates a significant burden on the painting site.

[0034] When a three-component coating composition comprising a base (A), a curing agent (B), and a pigment slurry (C) is multicolored, it is necessary to clean the tank and piping for the pigment slurry (C) when changing colors, or to prepare tanks for the pigment slurry (C) corresponding to the number of colors and only clean the piping. Since the capacity of the tank for the pigment slurry (C) used in small quantities often becomes smaller, cleaning the tank and piping for the pigment slurry (C) requires less effort when cleaning the tank for the pigment slurry (C) with a smaller capacity. Furthermore, when preparing multiple tanks for the pigment slurry (C), the smaller the tank, the less burden on the coating site.

[0035] However, while three-component coating compositions can reduce the number of steps required to clean coating equipment when changing colors when multiple colors are used, it is known that when a coating composition with a low VOC content is used as a three-component coating composition, color unevenness is likely to occur, and hardness and adhesion are likely to decrease.

[0036] It is speculated that if the above-mentioned low-VOC coating composition is a three-component coating composition, color unevenness is likely to occur and hardness and adhesion are likely to decrease because it is difficult to adjust the viscosity of the low-VOC coating composition using a solvent, and therefore the three liquids of the main agent (A), curing agent (B) and pigment slurry (C) are difficult to mix.

[0037] Therefore, the present inventors have conducted intensive research and found that by making the main agent (A) -1 、Viscosity at 65℃ (V A ) is in the range of 20 to 1800 mPa·s, the curing agent (B) is at a shear rate of 100 sec -1 、Viscosity at 65℃ (V B ) is in the range of 20 to 1800 mPa·s, the pigment slurry (C) is subjected to a shear rate of 100 sec -1 、Viscosity at 65℃ (V C ) is within the range of 20 to 1800 mPa·s, even the three-component coating composition having a low VOC content can form a coating film having excellent hardness and adhesion and suppressed color unevenness.

[0038] Regarding the kit of the present invention, it is speculated that the reason why even the three-component coating composition with a low VOC content can suppress color unevenness and has excellent hardness and adhesion is that the three components of the base agent (A), the curing agent (B), and the pigment slurry (C) are easily mixed, and the entire coating film is uniformly cured.

[0039] From the perspectives of reducing the VOC content in the resulting coating composition and improving the hardness and color unevenness of the resulting coating film, the solids concentration of the three-component coating composition formed from the kit of the present invention or the three-component coating composition of the present invention is preferably 95% by mass or greater, more preferably 96% by mass or greater, and even more preferably 97% by mass or greater. The upper limit of the solids concentration is 100% by mass.

[0040] In this specification, "solid content" refers to the non-volatile components such as resin, curing agent, and pigment remaining after drying at 80°C for 30 minutes. This solid content can be determined by, for example, measuring a sample in a heat-resistant container such as an aluminum foil cup, spreading and spreading the sample on the bottom of the container, drying at 80°C for 30 minutes, and weighing the remaining components after drying.

[0041] In this specification, "solids concentration" refers to the mass ratio of the solid components contained in a composition. Therefore, the solids concentration of a composition can be calculated, for example, by measuring 1.0 g of the composition into a heat-resistant container such as an aluminum foil cup, spreading the composition on the bottom of the container, and drying it at 80°C for 30 minutes. The mass of the components remaining in the composition after drying is then measured, and the ratio of the mass of the components remaining after drying to the total mass of the composition before drying is calculated.

[0042] From the viewpoints of hardness, adhesion and color unevenness of the formed coating film, the main agent (A) is preferably used at a shear rate of 100 sec -1 、Viscosity at 65℃(V A ), the aforementioned curing agent (B) at a shear rate of 100 sec -1 、Viscosity at 65℃(V B ) and the aforementioned pigment slurry (C) at a shear rate of 100 sec -1 、Viscosity at 65℃(V C ) preferably satisfies the following formula (1) and formula (2):

[0043] 0.1≤(V B ) / (V A )≤7.1

[0044] 0.2≤(V C ) / (V A )≤5.6.

[0045] From the viewpoints of hardness, adhesion and color unevenness of the formed coating film, the main agent (A) is preferably used at a shear rate of 100 sec -1 、Viscosity at 65℃(V A ), the aforementioned curing agent (B) at a shear rate of 100 sec -1 、Viscosity at 65℃(V B ) and the aforementioned pigment slurry (C) at a shear rate of 100 sec -1 、Viscosity at 65℃(V C ) more preferably satisfies the following formula (1) and formula (2):

[0046] 0.4≤(V B ) / (V A )≤2.5 Formula (1)

[0047] 0.3≤(V C ) / (V A )≤3.0Formula (2).

[0048] From the viewpoint of hardness and adhesion of the formed coating film, the main agent (A) is -1 、Viscosity at 65℃(V A ) and the aforementioned curing agent (B) at a shear rate of 100 sec -1 、Viscosity at 65℃(V B ) more preferably satisfies 0.4≤(V B ) / (V A )≤2.0, and more preferably 0.4≤(V B ) / (V A )≤1.5.

[0049] From the viewpoint of uneven color of the formed coating film, the main agent (A) is -1 、Viscosity at 65℃(V A ) and pigment slurry (C) at a shear rate of 100 sec -1 、Viscosity at 65℃(V C ) more preferably satisfies 0.3≤(V C ) / (V A )≤2.5, and more preferably 0.4≤(V C ) / (V A )≤2.0.

[0050] [Main agent (A)]

[0051] The main agent (A) contains an isocyanate-reactive group-containing compound (a1).

[0052] [Isocyanate-Reactive Group-Containing Compound (a1)]

[0053] The isocyanate-reactive group-containing compound (a1) is a compound having at least one isocyanate-reactive group in one molecule.

[0054] The isocyanate-reactive group is not particularly limited as long as it is a group reactive toward an isocyanate group. Examples of the isocyanate-reactive group include a hydroxyl group, an amino group, and a thiol group. From the perspectives of the hardness, adhesion, and color unevenness of the resulting coating film, the isocyanate-reactive group preferably contains at least one selected from a hydroxyl group and an amino group, and more preferably contains a hydroxyl group.

[0055] Therefore, as the above-mentioned isocyanate-reactive group-containing compound (a1), a hydroxyl-containing compound (a11), an amino-containing compound (a12), a mercapto-containing compound (a13), etc. can be listed. From the viewpoint of the hardness, adhesion and color unevenness of the coating film formed, it is preferred to contain at least one compound selected from the hydroxyl-containing compound (a11) and the amino-containing compound (a12), and it is more preferred to contain the hydroxyl-containing compound (a11).

[0056] From the viewpoints of reducing the VOC content in the obtained coating composition and the hardness, adhesion and color unevenness of the formed coating film, the above-mentioned isocyanate-reactive group-containing compound (a1) preferably contains an isocyanate-reactive group-containing compound having a number average molecular weight in the range of 250 to 2500, more preferably contains an isocyanate-reactive group-containing compound having a number average molecular weight in the range of 300 to 1800, and further preferably contains an isocyanate-reactive group-containing compound having a number average molecular weight in the range of 300 to 1500.

[0057] [Hydroxy-containing compound (a11)]

[0058] The hydroxyl-containing compound (a11) is a compound having at least one hydroxyl group in one molecule. As the hydroxyl-containing compound (a11), regarding hydroxyl-containing oligomers and hydroxyl-containing polymers, for example, hydroxyl-containing polyester resins, hydroxyl-containing polycaprolactone resins, hydroxyl-containing polyether resins, hydroxyl-containing polycarbonate resins, hydroxyl-containing acrylic resins, hydroxyl-containing polyurethane resins, hydroxyl-containing epoxy resins, hydroxyl-containing alkyd resins, etc. can be cited. Among them, from the perspectives of reducing the VOC content in the obtained coating composition and the hardness, adhesion and color unevenness of the formed coating film, it is preferred to contain at least one resin selected from hydroxyl-containing polyester resins, hydroxyl-containing polycaprolactone resins and hydroxyl-containing polyether resins, and more preferably contain at least one resin selected from hydroxyl-containing polyester resins and hydroxyl-containing polycaprolactone resins. They can be used alone or in combination of two or more.

[0059] The hydroxyl-containing polyester resin can generally be produced by an esterification reaction or an ester exchange reaction between an acid component and an alcohol component.

[0060] As the acid component, a compound commonly used as a polycarboxylic acid in the production of the hydroxyl-containing polyester resin can be used. Examples of the polycarboxylic acid include aliphatic polybasic acids, alicyclic polybasic acids, and aromatic polybasic acids.

[0061] The aforementioned aliphatic polybasic acid is generally an aliphatic compound having two or more carboxyl groups per molecule, an anhydride of such an aliphatic compound, or an ester of such an aliphatic compound. Examples of such aliphatic polybasic acids include aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, octadecanedioic acid, citric acid, and butanetetracarboxylic acid; anhydrides of such aliphatic polycarboxylic acids; and esters of such aliphatic polycarboxylic acids with lower alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Each of the aforementioned aliphatic polybasic acids can be used alone or in combination of two or more.

[0062] The aforementioned alicyclic polybasic acid is generally a compound having one or more alicyclic structures and two or more carboxyl groups in one molecule, anhydrides of such compounds, and esters of such compounds. The alicyclic structure can mainly be a 4- to 6-membered ring structure. Examples of alicyclic polybasic acids include alicyclic polybasic carboxylic 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 such alicyclic polybasic carboxylic acids; and esters of such alicyclic polybasic carboxylic acids with lower alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. The aforementioned alicyclic polybasic acids can be used alone or in combination of two or more.

[0063] The aforementioned aromatic polybasic acid is generally an aromatic compound having two or more carboxyl groups per molecule, an anhydride of such an aromatic compound, or an ester of such an aromatic compound. Examples of aromatic polybasic acids include aromatic polybasic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, trimellitic acid, and pyromellitic acid; anhydrides of such aromatic polybasic carboxylic acids; and esters of such aromatic polybasic carboxylic acids with lower alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Each of the above aromatic polybasic acids can be used alone or in combination of two or more.

[0064] In addition, acid components other than the above-mentioned aliphatic polybasic acids, alicyclic polybasic acids, and aromatic polybasic acids may also be used. The acid component is not particularly limited, and examples thereof include: fatty acids such as coconut oil fatty acid, cottonseed oil fatty acid, hempseed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, and safflower oil fatty acid; monocarboxylic acids such as isononanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexanoic acid, and 10-phenyloctadecanoic acid; and hydroxycarboxylic acids such as lactic acid, 3-hydroxybutyric acid, and 3-hydroxy-4-ethoxybenzoic acid. These acid components may be used alone or in combination of two or more.

[0065] As the alcohol component, a polyol having two or more hydroxyl groups in one molecule can be preferably used. Examples of the polyol 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, Diols such as 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, neopentyl glycol hydroxypivalate, hydrogenated bisphenol A, hydrogenated bisphenol F, and dimethylolpropionic acid; polylactone diols formed by adding lactone compounds such as ε-caprolactone to these diols; 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; trivalent or higher alcohols such as glycerol, trimethylolethane, trimethylolpropane, diglycerol, triglycerol, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tris(2-hydroxyethyl)isocyanuric acid, sorbitol, and mannitol; polylactone polyol compounds formed by adding lactone compounds such as ε-caprolactone to these trivalent or higher alcohols; fatty acid esters of glycerol, etc.

[0066] In addition, alcohol components other than the above-mentioned polyols may also be used. Such alcohol components are not particularly limited, and examples thereof include monohydric alcohols such as methanol, ethanol, propanol, butanol, isobutanol, amyl alcohol, 2-ethylhexanol, stearyl alcohol, benzyl alcohol, phenylethyl alcohol, and 2-phenoxyethanol; and alcohol compounds obtained by reacting monoepoxides such as propylene oxide, butylene oxide, and "Cardura E10P" (trade name, manufactured by HEXION, a synthetic glycidyl ester of a highly branched saturated fatty acid) with an acid.

[0067] The method for producing the hydroxyl-containing polyester resin is not particularly limited and can be carried out according to conventional methods. For example, the hydroxyl-containing polyester polyol resin can be produced by heating the acid component and the alcohol component at about 150 to 250° C. for about 5 to 10 hours in a nitrogen stream to cause an esterification reaction or transesterification reaction between the acid component and the alcohol component.

[0068] When subjecting the acid component and the alcohol component to an esterification reaction or transesterification reaction, these components may be added to the reaction vessel all at once, or one or both may be added in multiple additions. Alternatively, the hydroxyl-containing polyester resin may be synthesized first, and then the resulting hydroxyl-containing polyester resin may be reacted with an acid anhydride for semi-esterification to produce a polyester resin containing carboxyl groups and hydroxyl groups. Alternatively, the hydroxyl-containing polyester resin may be synthesized first, and then the alcohol component may be added to produce the hydroxyl-containing polyester resin.

[0069] In the esterification or transesterification reaction, a catalyst known per se, such as dibutyltin oxide, antimony trioxide, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, or tetraisopropyl titanate, can be used as a catalyst for promoting the reaction.

[0070] Furthermore, the aforementioned hydroxyl-containing polyester resin may be modified with fatty acids, monoepoxy compounds, polyisocyanate compounds, or the like during or after the preparation of the resin.

[0071] Examples of the fatty acid include coconut oil fatty acid, cottonseed oil fatty acid, hempseed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, and safflower oil fatty acid. Examples of the monoepoxy compound include "Cardura E10P" (trade name, manufactured by HEXION, a glycidyl ester of a synthetic highly branched saturated fatty acid).

[0072] Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as lysine diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; and alicyclic diisocyanate compounds such as hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 4,4′-methylenebis(cyclohexylisocyanate), 1,3-(isocyanatemethyl)cyclohexane, and 1,4-(isocyanatemethyl)cyclohexane. Aromatic diisocyanate compounds such as toluene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and diphenylmethane diisocyanate; organic polyisocyanates such as trivalent or higher polyisocyanates such as lysine triisocyanate and 4-(isocyanatomethyl)octamethylene diisocyanate; adducts of these organic polyisocyanates with polyols, low molecular weight polyester resins, water, etc.; cyclopolymers (e.g., isocyanurates), biuret-type adducts, and allophanate adducts of these organic polyisocyanates. These polyisocyanate compounds may be used alone or in combination of two or more.

[0073] From the viewpoint of hardness and adhesion of the formed coating film, the hydroxyl value of the hydroxyl-containing polyester resin is preferably within the range of 50 to 800 mgKOH / g, more preferably within the range of 100 to 700 mgKOH / g, and even more preferably within the range of 300 to 600 mgKOH / g.

[0074] In addition, from the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the number average molecular weight of the above-mentioned hydroxyl-containing polyester resin is preferably in the range of 250 to 2500, more preferably in the range of 300 to 1800, and even more preferably in the range of 350 to 1500.

[0075] In addition, from the viewpoint of reducing the VOC content in the obtained coating composition and the hardness, adhesion and color unevenness of the formed coating film, the glass transition temperature (Tg) of the above-mentioned hydroxyl-containing polyester resin is preferably in the range of -80 to 10°C, more preferably in the range of -70 to 5°C, and even more preferably in the range of -60 to 0°C.

[0076] It should be noted that in this specification, the number average molecular weight and weight average molecular weight are values ​​obtained by converting the retention time (retention capacity) measured using a gel permeation chromatograph (GPC) into the molecular weight of polystyrene by comparing the retention time (retention capacity) of a standard polystyrene of known molecular weight measured under the same conditions. Specifically, a "HLC-8120GPC" (trade name, manufactured by Tosoh Corporation) was used as the gel permeation chromatograph, four columns of "TSKgel G4000HXL," "TSKgel G3000HXL," "TSKgel G2500HXL," and "TSKgel G2000HXL" (trade names, all manufactured by Tosoh Corporation) were used as columns, a differential refractometer was used as the detector, and measurements were performed using tetrahydrofuran as the mobile phase, a measurement temperature of 40°C, and a flow rate of 1 mL / min.

[0077] The glass transition temperature can be measured, for example, by using a differential scanning calorimeter "DSC-50Q" (manufactured by Shimadzu Corporation, trade name), placing a sample into a measuring cup, performing vacuum suction to completely remove the solvent, and then measuring the heat change in the range of -100°C to 150°C at a heating rate of 3°C / min. The initial baseline change point on the low temperature side is taken as the static glass transition temperature for measurement.

[0078] When the hydroxyl-containing compound (a11) contains the hydroxyl-containing polyester resin, the content of the hydroxyl-containing polyester resin is preferably in the range of 50 to 100% by mass, more preferably in the range of 60 to 95% by mass, and even more preferably in the range of 70 to 90% by mass, based on the total solid content of the hydroxyl-containing compound (a11), from the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film.

[0079] The hydroxyl-containing polycaprolactone resin can be obtained, for example, by ring-opening polymerization of ε-caprolactone using a divalent to tetravalent polyol as an initiator. Examples of the divalent or higher polyol include ethylene glycol, glycerol, trimethylolethane, trimethylolpropane, diglycerol, di(trimethylol)propane, 1,2,6-hexanetriol, pentaerythritol, tris(2-hydroxyethyl)isocyanurate, and polyol compounds obtained by reacting dimethylolalkanoic acid with a monoepoxide (e.g., "Cardura E10P; a synthetic glycidyl ester of a highly branched saturated fatty acid" manufactured by HEXION Specialty Chemicals). These can be used alone or in combination of two or more.

[0080] In addition, as the above-mentioned hydroxyl group-containing polycaprolactone resin, a commercially available product can be used. Examples of commercially available products include: “PLACCEL 205,” “PLACCEL 205H,” “PLACCEL L205AL,” “PLACCEL 205U,” “PLACCEL 208,” “PLACCEL 210,” “PLACCEL 210N,” “PLACCEL 210CP,” “PLACCEL 212,” “PLACCEL L212AL,” “PLACCEL 220,” “PLACCEL 220N,” “PLACCEL 220CPB,” “PLACCEL 220CPT,” “PLACCEL 220UA,” “PLACCEL 220NP1,” “PLACCEL L220AL,” “PLACCEL 220EB,” “PLACCEL 230,” “PLACCEL 230N,” “PLACCEL 240,” “PLACCEL 303,” “PLACCEL 305,” “PLACCEL 308,” “PLACCEL 309,” “PLACCEL 312,” “PLACCEL 320,” “PLACCEL L320AL", "PLACCEL 410" (above are trade names, manufactured by Daicel), "TONE 0201", "TONE 0230", "TONE 0249", "TONE 0301", "TONE 0305", "TONE 0310", "TONE 1241", "TONE 1278", "TONE 2221" (above are trade names, manufactured by The Dow Chemical Company), "Capa 2043", "Capa 2101", "Capa 2201", "Capa 2205", "Capa 2209", "Capa 2201A", "Capa 2203A", "Capa 7201A", "Capa 7203", "Capa 3031", "Capa 3050J", "Capa 3091", "Capa 4101" (above are trade names, manufactured by Ingevity), etc.

[0081] From the viewpoint of hardness and adhesion of the formed coating film, the hydroxyl value of the hydroxyl-containing polycaprolactone resin is preferably within the range of 50 to 900 mgKOH / g, more preferably within the range of 100 to 750 mgKOH / g, and even more preferably within the range of 130 to 600 mgKOH / g.

[0082] In addition, from the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the number average molecular weight of the above-mentioned hydroxyl-containing polycaprolactone resin is preferably in the range of 250 to 2500, more preferably in the range of 280 to 1500, and even more preferably in the range of 300 to 1000.

[0083] When the hydroxyl-containing compound (a11) contains the hydroxyl-containing polycaprolactone resin, the content of the hydroxyl-containing polycaprolactone resin is preferably in the range of 5 to 100% by mass, more preferably in the range of 10 to 75% by mass, and even more preferably in the range of 10 to 50% by mass, based on the total solid content of the hydroxyl-containing compound (a11), from the viewpoint of reducing the VOC content in the obtained coating composition and the hardness, adhesion and color unevenness of the formed coating film.

[0084] As the hydroxyl-containing polyether resin, alkylene oxide adducts of hydroxyl-containing monomers described below, ring-opening (co)polymers of alkylene oxides or cyclic ethers (tetrahydrofuran, etc.) can be used. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, (block or random) copolymers of ethylene glycol and propylene glycol, polyhexamethylene glycol, and polyoctamethylene glycol.

[0085] The above-mentioned hydroxyl group-containing polyether resins can be used alone or in combination of two or more.

[0086] From the viewpoint of hardness and adhesion of the formed coating film, the hydroxyl value of the hydroxyl-containing polyether resin is preferably within the range of 50 to 600 mgKOH / g, more preferably within the range of 70 to 500 mgKOH / g, and even more preferably within the range of 90 to 400 mgKOH / g.

[0087] From the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion, and color unevenness of the formed coating film, the number average molecular weight of the hydroxyl-containing polyether resin is preferably in the range of 250 to 2500, more preferably in the range of 300 to 1500, and even more preferably in the range of 350 to 1000.

[0088] When the hydroxyl-containing compound (a11) contains the hydroxyl-containing polyether resin, the content of the hydroxyl-containing polyether resin is preferably in the range of 20 to 100% by mass, more preferably in the range of 40 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 hydroxyl-containing compound (a11), from the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film.

[0089] The hydroxyl-containing polycarbonate resin is a compound obtained by polycondensing a known polyol component with a carbonylating agent using a conventional method. Examples of the polyol component include diol components and trivalent or higher alcohol components.

[0090] Examples of the diol component include linear diols such as 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol; and 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, and 2-methyl- Branched diols such as 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, and 2-ethyl-1,3-hexanediol; alicyclic diols such as 1,3-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol; aromatic diols such as p-xylene glycol and p-tetrachloroxylene glycol; ether diols such as diethylene glycol and dipropylene glycol; and polylactone diols obtained by adding lactone compounds such as ε-caprolactone to these diol components. These diol components may be used alone or in combination of two or more.

[0091] Examples of the trivalent or higher alcohol include glycerol, trimethylolethane, trimethylolpropane, trimethylolpropane dimer, pentaerythritol, and polylactone polyols obtained by adding lactone compounds such as ε-caprolactone to these trivalent or higher alcohols. These trivalent or higher alcohols may be used alone or in combination of two or more.

[0092] As the carbonylating agent, known ones can be used. Specifically, for example, alkylene carbonates, dialkyl carbonates, diallyl carbonate, phosgene, etc. can be mentioned. One of these or a combination of two or more can be used. Preferred among these include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, etc.

[0093] From the viewpoint of hardness and adhesion of the formed coating film, the hydroxyl value of the hydroxyl-containing polycarbonate resin is preferably within the range of 50 to 800 mgKOH / g, more preferably within the range of 70 to 700 mgKOH / g, and even more preferably within the range of 90 to 600 mgKOH / g.

[0094] From the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the number average molecular weight of the above-mentioned hydroxyl-containing polycarbonate resin is preferably in the range of 250 to 2500, more preferably in the range of 300 to 1800, and even more preferably in the range of 400 to 1500.

[0095] When the aforementioned hydroxyl-containing compound (a11) contains the aforementioned hydroxyl-containing polycarbonate resin, from the viewpoint of reducing the VOC content in the obtained coating composition and the hardness, adhesion and color unevenness of the formed coating film, the content of the hydroxyl-containing polycarbonate resin is preferably in the range of 5 to 80 mass %, more preferably in the range of 10 to 50 mass %, and even more preferably in the range of 10 to 40 mass %, based on the total solid content of the hydroxyl-containing compound (a11).

[0096] The hydroxyl-containing acrylic resin can be produced, for example, by copolymerizing a hydroxyl-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers copolymerizable with the hydroxyl-containing polymerizable unsaturated monomer using a known method such as solution polymerization in an organic solvent or emulsion polymerization in water.

[0097] The hydroxyl-containing polymerizable unsaturated monomer is a compound having one or more hydroxyl groups and one or more polymerizable unsaturated bonds per molecule. Examples of the hydroxyl-containing polymerizable unsaturated monomer include monoesters of (meth)acrylic acid with a diol 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; modified ε-caprolactone products of the monoesters of (meth)acrylic acid with a diol having 2 to 8 carbon atoms; N-hydroxymethyl (meth)acrylamide; allyl alcohol; and (meth)acrylates having a polyoxyethylene chain with a hydroxyl group at the molecular end.

[0098] In the present invention, the monomers that meet the following (xvii) polymerizable unsaturated monomers having a UV-absorbing functional group are defined as other polymerizable unsaturated monomers copolymerizable with the above-mentioned hydroxyl-containing polymerizable unsaturated monomers, and are excluded from the hydroxyl-containing polymerizable unsaturated monomers. These monomers may be used alone or in combination of two or more.

[0099] As other polymerizable unsaturated monomers copolymerizable with the above-mentioned hydroxyl group-containing polymerizable unsaturated monomer, for example, the following monomers (i) to (xx) can be used. These polymerizable unsaturated monomers can be used alone or in combination of two or more.

[0100] (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, tert-butylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, tricyclodecyl (meth)acrylate, etc.

[0101] (ii) Polymerizable unsaturated monomer having an isobornyl group: isobornyl (meth)acrylate, etc.

[0102] (iii) Polymerizable unsaturated monomer having an adamantyl group: adamantyl (meth)acrylate, etc.

[0103] (iv) Polymerizable unsaturated monomer having a tricyclodecenyl group: tricyclodecenyl (meth)acrylate, etc.

[0104] (v) Aromatic ring-containing polymerizable unsaturated monomers: benzyl (meth)acrylate, styrene, α-methylstyrene, vinyltoluene, etc.

[0105] (vi) Polymerizable unsaturated monomers having an alkoxysilyl group: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, and the like.

[0106] (vii) Polymerizable unsaturated monomers having a fluorinated alkyl group: perfluoroalkyl (meth)acrylates such as perfluorobutyl ethyl (meth)acrylate and perfluorooctyl ethyl (meth)acrylate; fluoroolefins, etc.

[0107] (viii) A polymerizable unsaturated monomer having a photopolymerizable functional group such as a maleimide group.

[0108] (ix) Vinyl compounds: N-vinyl pyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate, etc.

[0109] (x) Carboxyl group-containing polymerizable unsaturated monomers: (meth)acrylic acid, maleic acid, crotonic acid, β-carboxyethyl (meth)acrylate, etc.

[0110] (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.

[0111] (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.

[0112] (xiii) Epoxy-containing polymerizable unsaturated monomers: glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, 3,4-epoxycyclohexylpropyl (meth)acrylate, allyl glycidyl ether, and the like.

[0113] (xiv) (Meth)acrylates having a polyoxyethylene chain having an alkoxy group at the molecular end.

[0114] (xv) Polymerizable unsaturated monomers having a sulfonic acid group: 2-acrylamide-2-methylpropanesulfonic acid, 2-sulfoethyl (meth)acrylate, allylsulfonic acid, 4-styrenesulfonic acid, etc.; sodium salts and ammonium salts of these sulfonic acids, etc.

[0115] (xvi) Polymerizable unsaturated monomers having a phosphoric acid group: phosphooxyethyl (meth)acrylate, phosphooxypropyl (meth)acrylate, acid phosphooxypoly(oxyethylene) glycol (meth)acrylate, acid phosphooxypoly(oxypropylene) glycol (meth)acrylate, etc.

[0116] (xvii) Polymerizable unsaturated monomers having an ultraviolet-absorbing functional group: 2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropoxy)benzophenone, 2-hydroxy-4-(3-acryloyloxy-2-hydroxypropoxy)benzophenone, 2,2'-dihydroxy-4-(3-methacryloyloxy-2-hydroxypropoxy)benzophenone, 2,2'-dihydroxy-4-(3-acryloyloxy-2-hydroxypropoxy)benzophenone, 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole, etc.

[0117] (xviii) Light-stable polymerizable unsaturated monomers: 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonylamino-2,2,6,6-tetramethylpiperidine, 1-crotonyl-4-crotonyloxy-2,2,6,6-tetramethylpiperidine, etc.

[0118] (xix) Polymerizable unsaturated monomers having a carbonyl group: acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrene, vinyl alkyl ketones having 4 to 7 carbon atoms (e.g., vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), etc.

[0119] (xx) Polymerizable unsaturated monomers having an acid anhydride group: maleic anhydride, itaconic anhydride, citraconic anhydride, etc.

[0120] In this specification, a polymerizable unsaturated group refers to an unsaturated group that can undergo free radical polymerization. Examples of such polymerizable unsaturated groups include vinyl, (meth)acryloyl, (meth)acrylamido, vinyl ether, allyl, propenyl, isopropenyl, and maleimide.

[0121] In this specification, "(meth)acrylate" refers to acrylate and / or methacrylate. "(Meth)acrylic acid" refers to acrylic acid and / or methacrylic acid. "(Meth)acryloyl" refers to acryloyl and / or methacryloyl. "(Meth)acrylamide" refers to acrylamide and / or methacrylamide.

[0122] From the viewpoint of hardness and adhesion of the formed coating film, the hydroxyl value of the hydroxyl-containing acrylic resin is preferably within the range of 5 to 240 mgKOH / g, more preferably within the range of 20 to 220 mgKOH / g, and even more preferably within the range of 25 to 200 mgKOH / g.

[0123] In addition, from the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the number average molecular weight of the above-mentioned hydroxyl-containing acrylic resin is preferably in the range of 250 to 2500, more preferably in the range of 300 to 1800, and even more preferably in the range of 500 to 1500.

[0124] In addition, from the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the glass transition temperature (Tg) of the above-mentioned hydroxyl-containing acrylic resin is preferably in the range of -60 to 80°C, more preferably in the range of -50 to 70°C, and even more preferably in the range of -40 to 60°C.

[0125] In addition, in this specification, the glass transition temperature (Tg) of the said hydroxyl-containing acrylic resin is a value calculated by the following formula.

[0126] 1 / Tg(K)=W1 / T1+W2 / T2+……Wn / Tn

[0127] Tg(℃)=Tg(K)-273

[0128] Wherein, W1, W2, ... Wn are the mass fractions of the monomers, and T1, T2 ... Tn are the glass transition temperatures Tg (K) of the homopolymers of the monomers.

[0129] It should be noted that the glass transition temperature of the homopolymer of each monomer is based on the value obtained in POLYMER HANDBOOK Fourth Edition, edited by J. Brandrup, Eh Immergut, and E.A. Grulke (1999). The glass transition temperature of a monomer not described in this document is the static glass transition temperature when a homopolymer of the monomer is synthesized so as to have a weight-average molecular weight of approximately 50,000.

[0130] When the hydroxyl-containing compound (a11) contains the hydroxyl-containing acrylic resin, the content of the hydroxyl-containing acrylic resin is preferably in the range of 5 to 100% by mass, more preferably in the range of 10 to 75% by mass, and even more preferably in the range of 15 to 50% by mass, based on the total solid content of the hydroxyl-containing compound (a11), from the viewpoints of reducing the VOC content in the resulting coating composition and improving the hardness, adhesion, and color unevenness of the formed coating film.

[0131] Examples of the hydroxyl group-containing compound (a11) 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, tricyclodecane dimethanol, neopentyl glycol hydroxypivalate, hydrogenated bisphenol A, hydrogenated bisphenol F, glycerin, trimethylolethane, trimethylolpropane, diglycerol, triglycerol, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tris(2-hydroxyethyl)isocyanurate, sorbitol, mannitol, hydroxyacetone, 4-(2-hydroxyethyl)morpholine, benzyl alcohol, 2-phenylethanol, 2-phenoxyethanol, 1-naphthol, (1,3-benzodioxol-5-yl)methanol, nonylphenol, dinonylphenol, nonylphenol ethoxylate, monostyrenated phenol, distyrenated phenol, tristyrenated phenol, etc. These can be used alone or in combination of two or more.

[0132] When the hydroxyl-containing compound (a11) contains the hydroxyl-containing monomer, the content of the hydroxyl-containing monomer is preferably in the range of 5 to 100% by mass, more preferably in the range of 5 to 50% by mass, and further preferably in the range of 5 to 30% by mass, based on the total solid content of the hydroxyl-containing compound (a11), from the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film.

[0133] When the isocyanate-reactive group-containing compound (a1) contains the hydroxyl-containing compound (a11), the content of the hydroxyl-containing compound (a11) 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 (a1), from the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film.

[0134] [Amino group-containing compound (a12)]

[0135] The amino group-containing compound (a12) is a compound having at least one primary and / or secondary amino group in its molecule.

[0136] Examples of the amino group-containing compound (a12) include aliphatic polyamines such as ethylenediamine, pentamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, N,N'-bis-(3-aminopropyl)ethylenediamine, and tetraethylenepentamine; and 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4-methyl-1,3-cyclohexanediamine, 2-methyl-1,3-cyclohexanediamine, isophoronediamine, 4,4'-methylenebis(cyclohexylamine), 3,3'-dimethyl-4,4'-methylenebis(cyclohexylamine), N,N'-(isophoronediamine), ... alicyclic polyamines such as 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, norbornanediamine; heterocyclic polyamines such as piperazine and N-(2-aminoethyl)piperazine; 2,4-toluenediamine, 2,6-toluenediamine, 4,4'-diaminodiphenylmethane, diethyltoluenediamine, dimethylthiotoluenediamine, 4,4'-methylenebis[N-(1-methylpropyl)aniline], 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylamine. Aromatic polyamines such as 1,3-diphenylene diphenyl ether, 1,3-bis(3-aminophenoxy)benzene, 4,4'-(1,3-phenylenediisopropylidene)dianiline, 4,4'-(1,4-phenylenediisopropylidene)dianiline, aminobenzylamine, m-phenylenediamine, p-phenylenediamine, and N,N'-di-sec-butyl-p-phenylenediamine; polyether polyamine compounds such as polyoxypropylene diamine, polyoxyethylene diamine, poly(oxyethylene / oxypropylene) diamine, trimethylolpropane poly(oxypropylene) triamine, and glycerol poly(oxypropylene) triamine; tetraethyl N,N'-(2-methylpentane-1,5-diyl)bisaspartate, N,N'-[methylenebis(cyclohexane-4 Polyaspartic acid ester compounds such as tetraethyl bis(1,4-dioxobutane-2-yl)amino]propyl}-ω-{2-[(1,4-diethoxy-1,4-dioxobutane-2-yl)amino]propyloxy}poly[oxy(methylethylene)]; and aminosilane compounds such as N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane, and γ-anilinopropyltrimethoxysilane. These compounds can be used alone or in combination of two or more.

[0137] As the amino group-containing compound (a12), a commercially available product can be used. Examples of the trade names of commercially available products include: "Baxxodur EC110", "DETA", "N4 Amine", "Baxxodur EC210", "Baxxodur EC201", "Baxxodur EC330", "Baxxodur EC331", "Baxxodur PC136", "Baxxodur EC130", "Baxxodur EC280", "Baxxodur EC301", "Baxxodur EC302", "Baxxodur EC303", "Baxxodur EC310", and "Baxxodur EC311" (these are trade names, manufactured by BASF), "Clearlink 1000", "Unilink 4200", and "Unilink 4100" (these are trade names, manufactured by DORF KETAL), "JEFFAMINE M-600", "JEFFAMINE M-1000", "JEFFAMINE M-2005", "JEFFAMINE M-2070", and "JEFFAMINE M-3085", "JEFFAMINE D-230", "JEFFAMINE D-400", "JEFFAMINE D-2000", "JEFFAMINE D-4000", "JEFFAMINE ED-600", "JEFFAMINE ED-900", "JEFFAMINE ED-2003", "JEFFAMINE EDR-148", "JEFFAMINE RT-1000", "JEFFAMINE T-403", "JEFFAMINE T-3000", "JEFFAMINE T-5000" (trade names, manufactured by HUNTSMAN Co., Ltd.), "MXDA", "1,3-BAC" (trade names, manufactured by Mitsubishi Gas Chemical Co., Ltd.), "WANAMINE MDA-100H", "ETHACURE 100Plus", "ETHACURE 300", "ETHACURE 420", "Bisaniline-M", "Bisaniline-P" (trade names, manufactured by Mitsui Fine Chemicals Co., Ltd.) Chemicals Co., Ltd.), "VESTAMIN IPD", "VESTAMIN TMD", "VESTAMIN PACM", "ANCAMINE 2049", "AMICURE IC-321", "AMICURE IC-322" (these are trade names, manufactured by EVONIK Industries), "DEH.20", "DEH24", "DEH26", "DEH29", "DEH39", "DEH444", "DEH445", "DEH4042", "DEH4044", "DEH487", "DEH488", "DEH530", "DEH" (the above are trade names, The Dow Chemical Co., Ltd.), "Desmophen NH1220", "Desmophen NH1420", "Desmophen NH1422", "Desmophen NH1423", "Desmophen NH1520", "Desmophen NH1521", "Desmophen NH1523", "Desmophen NH1723LF", "Desmophen NH2885", "Desmophen NH2886" (these are trade names, manufactured by Covestro), "FEISPARTIC F220", "FEISPARTIC F420", "FEISPARTIC F520", "FEISPARTIC F2850", "FEISPARTIC F2872", "FEISPARTIC F221", "FEISPARTIC F321", "FEISPARTIC F525", "FEISPARTIC F421", "FEISPARTIC F524", "FEISPARTIC F330", "FEISPARTIC D2925", "FEISPARTIC D2903" (all trade names, manufactured by Feiyang Protech Co., Ltd.), "TSE-EZASP 7980", "TSE-EZASP 7981", "TSE-EZASP 9033", "TSE-EZASP 8443" (all trade names, manufactured by TSE Industries Co., Ltd.), "Altor 200", "Altor 201", "Altor 202", "Altor 205LV" (all trade names, manufactured by Cargill Co., Ltd.), etc.

[0138] From the viewpoint of reducing the VOC content in the obtained coating composition and the hardness, adhesion and color unevenness of the formed coating film, the above-mentioned amino group-containing compound (a12) preferably contains at least one compound selected from aliphatic polyamines, alicyclic polyamines, polyether polyamine compounds and polyaspartic acid ester compounds, more preferably contains at least one compound selected from alicyclic polyamines and polyaspartic acid esters, and further preferably contains a polyaspartic acid ester compound.

[0139] As the polyaspartic acid ester compound, a commercially available product can be used. Examples of the trade names of commercially available products include: Desmophen NH1220, "Desmophen NH1420," "Desmophen NH1422," "Desmophen NH1423," "Desmophen NH1520," "Desmophen NH1521," "Desmophen NH1523," "Desmophen NH1723LF," "Desmophen NH2885," and "Desmophen NH2886" (these are trade names, manufactured by Covestro), "FEISPARTIC F220," "FEISPARTIC F420," "FEISPARTIC F520," "FEISPARTIC F2850," "FEISPARTIC F2872," "FEISPARTIC F221," "FEISPARTIC F321," and "FEISPARTIC F322." F525", "FEISPARTIC F421", "FEISPARTIC F524", "FEISPARTIC F330", "FEISPARTIC D2925", "FEISPARTIC D2903" (the above are trade names, manufactured by Feiyang Protech Co., Ltd.), "TSE-EZASP 7980", "TSE-EZASP 7981", "TSE-EZASP 9033", "TSE-EZASP 8443" (the above are trade names, manufactured by TSE Industries Co., Ltd.), "Altor200", "Altor 201", "Altor 202", "Altor 205LV" (the above are trade names, manufactured by Cargill Co., Ltd.), etc.

[0140] When the aforementioned isocyanate-reactive group-containing compound (a1) contains the aforementioned amino-containing compound (a12), the content of the amino-containing compound (a12) is preferably in the range of 10 to 100% by mass, more preferably in the range of 40 to 95% by mass, and even more preferably in the range of 50 to 90% by mass, based on the total solid content of the isocyanate-reactive group-containing compound (a1), from the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film.

[0141] [Mercapto group-containing compound (a13)]

[0142] The mercapto group-containing compound (a13) is a compound having at least one mercapto group in one molecule.

[0143] Examples of the mercapto group-containing compound (a13) include pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), tetramethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), trimethylolpropane dipropylene mercaptan, pentaerythritol tripropylene mercaptan, pentaerythritol tetrapropylene mercaptan, 1,4-bis(mercaptomethyl)benzene, pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), tetramethylene glycol bis(3-mercaptobutyrate), tris-[(3-mercaptobutyryloxy)-ethyl]isocyanurate, trimethylolpropane tris(thioglycolate), and pentaerythritol tetrakis(thioglycolate). These compounds can be used alone or in combination of two or more.

[0144] As the mercapto group-containing compound (a13), commercially available products can be used. Examples of the trade names of commercially available products include: "TMMP-LV", "TEMPIC", "PEMP-LV", "DPMP", "EGMP-4", "BDMP", "Multhiol Y-2", "Multhiol Y-3", "Multhiol Y-4", and "PXDT" (trade names, manufactured by SC Organic Chemical Co., Ltd.), "BDTG", "HDTG", "TMTG", "PETG", "EGTP", "BDTP", "TMTP", and "PETP" (trade names, manufactured by Yodo Chemical Co., Ltd.), "Adeka Hardener EH-317" (trade names, manufactured by Adeka Corporation), "Karenz MT PEI", "Karenz MTBDI", "Karenz MT BD1", "Karenz MT TPMB", and "Karenz MT NRI" (trade names, manufactured by Showa Denko K.K.), and "jER Cure QX11" and "jER Cure QX40".

[0145] (the above are trade names, manufactured by Mitsubishi Chemical Corporation) and the like.

[0146] When the aforementioned isocyanate-reactive group-containing compound (a1) contains the aforementioned mercapto group-containing compound (a13), the content of the mercapto group-containing compound (a13) is preferably in the range of 10 to 100% by mass, more preferably in the range of 30 to 95% by mass, and even more preferably in the range of 50 to 90% by mass, based on the total solid content of the isocyanate-reactive group-containing compound (a1), from the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film.

[0147] From the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the content of the isocyanate-reactive group-containing compound (a1) in the above-mentioned main agent (A) is preferably in the range of 30 to 99.5% by mass, more preferably in the range of 50 to 99% by mass, and even more preferably in the range of 70 to 98% by mass, based on the total amount of the main agent (A).

[0148] [Other ingredients]

[0149] The main agent (A) may contain, in addition to the above, an ultraviolet absorber and / or a light stabilizer. Furthermore, as needed, it may contain other additives commonly used in the coating field, such as an internal mold release agent, a solvent (organic solvent, water), a pigment, a catalyst, a dehydrating agent, an antioxidant, a surface conditioner, a defoaming agent, an emulsifier, a surfactant, an antifouling agent, a wetting agent, a thickener, a dye, an abrasion resistance improver, and a gloss modifier.

[0150] UV absorbers

[0151] As the ultraviolet absorber, conventionally known ones can be used, for example, benzotriazole absorbers, triazine absorbers, salicylic acid derivative absorbers, benzophenone absorbers, etc. The ultraviolet absorber may also have a polymerizable unsaturated group.

[0152] Specific examples of the benzotriazole absorbent include: 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, )-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-{2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthalimidomethyl)-5'-methylphenyl}benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, and the like.

[0153] Specific examples of the triazine absorbent 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.

[0154] Specific examples of the salicylic acid derivative absorbent include phenyl salicylate, p-octylphenyl salicylate, and 4-tert-butylphenyl salicylate.

[0155] Specific examples of the benzophenone absorbent include 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, Benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-benzophenone sodium sulfonate, 2,2',4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, resorcinol monobenzoate, 2,4-dibenzoylresorcinol, 4,6-dibenzoylresorcinol, hydroxydodecylbenzophenone, 2,2'-dihydroxy-4-(3-methacryloyloxy-2-hydroxypropoxy)benzophenone, etc.

[0156] Examples of commercially available ultraviolet absorbers include: "TINUVIN 1130", "TINUVIN 900", "TINUVIN 928", "TINUVIN 384-2", "TINUVIN 479", "TINUVIN 477", "TINUVIN 405", and "TINUVIN 400" (trade names manufactured by BASF, TINUVIN is a registered trademark), and "RUVA 93" (trade name manufactured by Otsuka Chemical Co., Ltd.).

[0157] When the main agent (A) contains the ultraviolet absorber, the content of the ultraviolet absorber is preferably in the range of 0.5 to 10% by mass, more preferably in the range of 0.8 to 5.0% by mass, and even more preferably in the range of 1.0 to 4.0% by mass, based on the total amount of the main agent (A), from the viewpoints of weather resistance and adhesion of the formed coating film.

[0158] Light stabilizers

[0159] The light stabilizer is used as a radical chain inhibitor that captures active radical species generated in the deterioration process of the coating film, and examples thereof include light stabilizers of hindered amine compounds.

[0160] Examples of the hindered amine compound include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2',6,6'-tetramethylpiperidine, bis(1,2,2,6,6-pentamethyl-4-piperidyl) malonate {[3,5-bis(1,1-dimethylethyl)-4-piperidyl] Examples include, but are not limited to, monomeric ones such as [[6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)iminoalcohol]}]; and polyester-bonded ones such as a polyester of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol and succinic acid. As the light stabilizer, known polymeric light stabilizers may also be used.

[0161] Examples of commercially available products of the light stabilizer include: "TINUVIN 123," "TINUVIN 152," "TINUVIN 249," and "TINUVIN 292" (trade names of BASF, TINUVIN is a registered trademark), "HOSTAVIN 3058" (trade name of Clariant, Hostavin is a registered trademark), and "ADK STAB LA-82" (trade name of ADEKA Corporation, ADK STAB is a registered trademark).

[0162] When the main agent (A) contains the above-mentioned light stabilizer, the content of the light stabilizer is preferably in the range of 0.5 to 10% by mass, more preferably in the range of 0.8 to 9.0% by mass, and even more preferably in the range of 1.0 to 8.0% by mass, based on the total amount of the main agent (A), from the viewpoints of weather resistance and adhesion of the formed coating film.

[0163] Internal release agent

[0164] When the coating composition of the present invention is used as an in-mold coating composition, the main component (A) preferably contains an internal mold release agent from the viewpoint of the releasability of the formed coating film from the mold.

[0165] Examples of the internal mold release agent include saturated fatty acids such as stearic acid and palmitic acid; saturated fatty acid salts such as zinc stearate, aluminum stearate, magnesium stearate, calcium stearate, sodium stearate, potassium stearate, barium stearate, zinc palmitate, aluminum palmitate, magnesium palmitate, calcium palmitate, and sodium palmitate; 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, and N,N-diethyllauric acid amide. Saturated fatty acid amides such as amine, N,N-diethyl myristamide, N,N-diethyl palmitamide, and N,N-diethyl stearamide; unsaturated fatty acids such as palmitoleic acid and oleic acid; unsaturated fatty acids such as zinc palmitoleate, aluminum palmitoleate, magnesium palmitoleate, calcium palmitoleate, sodium palmitoleate, potassium palmitoleate, barium palmitoleate, zinc oleate, aluminum oleate, magnesium oleate, calcium oleate, sodium oleate, potassium oleate, and barium oleate; palmitoleic acid amide, oleamide, erucic acid amide, behenic acid amide, N-oleyl palmitamide, and N-stearyl erucic acid amide , N, N-dimethyloleamide, N, N-diethyloleamide and other unsaturated fatty acid amides; nonionic surfactants such as polyoxyethylene alkyl ethers and sorbitan alkyl esters; fluorine compounds such as polytetrafluoroethylene, fluoropolyethers, perfluoroalkyl esters and perfluoroalkyl ester salts; phosphate compounds such as phosphate monoesters and / or phosphate diesters with alkyl chains or oxyethylene chains; stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitol ester, stearic acid stearyl ester, palmitic acid monoglyceride, palmitic acid diglyceride, palmitic acid triglyceride, Fatty acid esters such as behenic acid monoglyceride, behenic acid diglyceride, behenic acid triglyceride, behenic acid behenate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, methyl stearate, butyl stearate, methyl laurate, methyl palmitate, isopropyl palmitate, biphenyl biphenyl, sorbitan monostearate, and 2-ethylhexyl stearate; soybean oil lecithin, silicone oil, and fatty acid alcohol dibasic acid esters, which can be used alone or in combination of two or more.

[0166] When the main agent (A) contains the internal mold release agent, the content of the internal mold release agent is preferably in the range of 0.4 to 5.0% by mass, more preferably in the range of 0.5 to 4.0% by mass, and even more preferably in the range of 0.5 to 3.0% by mass, based on the total amount of the main agent (A), from the viewpoints of the adhesion of the formed coating film and the releasability of the formed coating film from the mold.

[0167] Solvents

[0168] Examples of the solvent include organic solvents and water. Examples of the organic solvent 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" (a high-boiling-point petroleum solvent manufactured by Cosmo Oil Co., Ltd.); and aliphatic hydrocarbon solvents such as hexane and heptane.

[0169] When the main agent (A) contains the above-mentioned solvent, the content of the solvent is preferably in the range of 0.1 to 5% by mass, more preferably in the range of 0.3 to 4% by mass, and even more preferably in the range of 0.5 to 3% by mass, based on the total amount of the main agent (A), from the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film.

[0170] Catalyst

[0171] As the above-mentioned catalyst, conventionally known ones can be used.

[0172] Examples of the catalyst include tin octylate, dibutyltin diacetate, dibutyltin di(2-ethylhexanoate), dibutyltin dilaurate, dioctyltin diacetate, dioctyltin di(2-ethylhexanoate), dioctyltin dineodecanoate, dioctyltin diversoester carbonate, dibutyltin oxide, dibutyltin sulfide, dioctyltin oxide, dibutyltin fatty acid, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, zinc fatty acids, bismuth octylate, bismuth 2-ethylhexanoate, bismuth oleate, bismuth neodecanoate, bismuth versoester carbonate, bismuth naphthenate, cobalt naphthenate, calcium octylate, copper naphthenate, tetra(2-ethylhexyl) titanate, tetra(n-butyl) titanate, diisopropoxybis(acetylacetonate)titanium, titanium tetraacetylacetonate, diisopropoxybis(ethylacetoacetate)titanium, titanium butoxide dimer. dimer), zirconium tetrapropoxide, zirconium tetrabutoxide, zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate and other organometallic compounds; triethylamine, N,N'-dimethylcyclohexylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyldipropylenetriamine, 1,4-diazabicyclo[2.2.2.]octane (DABCO), 1,8-diazabicyclo[5.4.0.]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0.]-5-nonene (DBN), N- Tertiary amine compounds such as 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; and neutralized salts of such tertiary amine compounds; and quaternary ammonium salts such as carboxylates of tetraalkylammonium, tetraarylammonium, and alkylarylammonium; and halides of tetraalkylammonium, tetraarylammonium, and alkylarylammonium. These can be used alone or in combination of two or more.

[0173] When the main agent (A) contains the catalyst, the amount of the catalyst added is preferably in the range of 0.005 to 5.0% by mass, more preferably in the range of 0.01 to 3.0% by mass, based on the total amount of the main agent (A), from the viewpoint of the hardness and adhesion of the formed coating film.

[0174] In addition, when the coating composition of the present invention contains the above-mentioned catalyst, it may also contain: organic acids such as acetic acid, propionic acid, butyric acid, isovaleric acid, hexanoic acid, 2-ethylbutyric acid, cyclohexaneic acid, octanoic acid, nonanoic acid, decanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, versatic acid, isobutyric anhydride, itaconic anhydride, acetic anhydride, citraconic anhydride, propionic anhydride, maleic anhydride, butyric anhydride, citric anhydride, trimellitic anhydride, pyromellitic anhydride, and phthalic anhydride; inorganic acids such as hydrochloric acid and phosphoric acid; metal coordination compounds such as acetylacetone and imidazole compounds, etc.

[0175] Dehydrating agent

[0176] As the dehydrating agent, conventionally known inorganic dehydrating agents and organic dehydrating agents can be used.

[0177] Examples of the inorganic dehydrating agent include calcium compounds such as calcium hydride, calcium oxide (quicklime), calcium chloride, and calcium sulfate (gypsum); barium compounds such as barium oxide; magnesium compounds such as magnesium sulfate; sodium compounds such as sodium sulfate and sodium carbonate; copper compounds such as copper sulfate; inorganic silicon compounds such as silica gel; and aluminum compounds such as alumina (hydraulic alumina, lithium aluminum hydride, amorphous silica-alumina, and crystalline aluminosilicate (molecular sieves). These can be used alone or in combination of two or more.

[0178] Examples of the organic dehydrating agent include alkyl o-formates, alkyl o-acetates, alkyl o-borates, vinylsilanes, alkoxysilane compounds, monoisocyanate compounds, aliphatic anhydrides such as acetic anhydride, and aromatic anhydrides such as benzoic anhydride. These can be used alone or in combination of two or more.

[0179] When the main agent (A) contains the above-mentioned dehydrating agent, the amount of the dehydrating agent added is preferably in the range of 0.1 to 5.0% by mass, more preferably in the range of 0.3 to 3.0% by mass, based on the total amount of the main agent (A), from the viewpoints of reducing the VOC content in the obtained coating composition and improving the adhesion of the formed coating film.

[0180] The main agent (A) is at a shear rate of 100 sec -1 、Viscosity at 65℃(V A ) is in the range of 20 to 1800 mPa·s.

[0181] From the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the main agent (A) is preferably used at a shear rate of 100 sec -1 、Viscosity at 65℃(V A) is preferably in the range of 50 to 1500 mPa·s, more preferably in the range of 100 to 1000 mPa·s, and even more preferably in the range of 150 to 800 mPa·s.

[0182] From the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the solid content concentration of the above-mentioned main agent (A) is preferably in the range of 95 to 100 mass%, more preferably in the range of 96 to 99.5 mass%, and even more preferably in the range of 97 to 99 mass%.

[0183] From the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion, and color unevenness of the formed coating film, the content of the main agent (A) in the kit and the three-component coating composition of the present invention is preferably in the range of 10 to 70% by mass, more preferably in the range of 15 to 60% by mass, and even more preferably in the range of 25 to 50% by mass, based on the total amount of the three-component coating composition.

[0184] [Curing agent (B)]

[0185] The curing agent (B) contains a polyisocyanate compound (b1).

[0186] [Polyisocyanate compound (b1)]

[0187] The polyisocyanate compound (b1) 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 these polyisocyanates.

[0188] The polyisocyanate compound (b1) preferably contains the aliphatic polyisocyanate from the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion, and color unevenness of the formed coating film.

[0189] Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, 2,6-diisocyanatohexanoic acid methyl ester (common name: lysine diisocyanate), aliphatic diisocyanates such as 2,6-diisocyanatohexanoic acid 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, etc.

[0190] Examples of the alicyclic polyisocyanate include 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(isocyanatemethyl)cyclohexane (common name: hydrogenated xylylene diisocyanate) or its mixture, norbornane diisocyanate and other alicyclic diisocyanates; 1,3,5-triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 2-(3-isocyanatepropyl)-2,5-bis(isocyanatemethyl)-bicyclo(2.2.1)heptane, 2-(3-isocyanatepropyl)-2,5-bis(isocyanatemethyl)-bicyclo(2.2.1)heptane, propyl)-2,6-bis(isocyanate methyl)-bicyclo(2.2.1)heptane, 3-(3-isocyanate propyl)-2,5-bis(isocyanate methyl)-bicyclo(2.2.1)heptane, 5-(2-isocyanate ethyl)-2-isocyanate methyl-3-(3-isocyanate propyl)-bicyclo(2.2.1)heptane, 6-(2-isocyanate ethyl)-2-isocyanate Alicyclic triisocyanates such as ester methyl-3-(3-isocyanate propyl)-bicyclo(2.2.1)heptane, 5-(2-isocyanate ethyl)-2-isocyanate methyl-2-(3-isocyanate propyl)-bicyclo(2.2.1)-heptane, and 6-(2-isocyanate ethyl)-2-isocyanate methyl-2-(3-isocyanate propyl)-bicyclo(2.2.1)heptane.

[0191] Examples of the aromatic aliphatic polyisocyanate include aromatic aliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis(1-isocyanate-1-methylethyl)benzene (commonly known as tetramethylxylylene diisocyanate) or a mixture thereof; and aromatic aliphatic triisocyanates such as 1,3,5-triisocyanate methylbenzene.

[0192] Examples of the aromatic polyisocyanate include aromatic diisocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-toluene diisocyanate or a mixture thereof, 4,4'-toluidine diisocyanate, and 4,4'-diphenyl ether diisocyanate; aromatic triisocyanates such as triphenylmethane-4,4',4"-triisocyanate, 1,3,5-triisocyanatobenzene, and 2,4,6-triisocyanatotoluene; and aromatic tetraisocyanates such as 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate.

[0193] Examples of the derivatives of the polyisocyanate include dimers, trimers, biuret, allophanate, uretdione, uretonimines, isocyanurates, iminooxadiazinediones, polymethylene polyphenyl polyisocyanates (crude MDI, polymeric MDI), and crude TDI of the polyisocyanate compounds. From the standpoint of the hardness and adhesion of the resulting coating, the polyisocyanate preferably contains at least one selected from allophanate, uretdione, and isocyanurate, more preferably contains at least one selected from uretdione and isocyanurate, and even more preferably contains isocyanurate.

[0194] The above-mentioned polyisocyanates and their derivatives can be used alone or in combination of two or more. Among these polyisocyanates, it is preferred to use aliphatic diisocyanates, aliphatic triisocyanates, alicyclic diisocyanates, aromatic aliphatic diisocyanates and their derivatives alone or in combination of two or more.

[0195] Alternatively, the polyisocyanate compound (b1) may be a prepolymer obtained by reacting the polyisocyanate or its derivative with a compound reactive with the polyisocyanate under conditions in which the isocyanate group is in excess. Examples of the compound reactive with the polyisocyanate include compounds having an active hydrogen group such as a hydroxyl group or an amino group. Specifically, polyols, low molecular weight polyester resins, amines, and water may be used.

[0196] As the polyol, the polyols exemplified in the above-mentioned hydroxyl-containing polyester resin can be used.

[0197] From the viewpoint of the hardness and adhesion of the coating film formed, the aforementioned polyisocyanate compound (b1) is preferably used in a manner such that the ratio of the isocyanate group in the polyisocyanate compound (b1) to the isocyanate reactive group in the aforementioned isocyanate reactive group-containing compound (a1) and the isocyanate reactive group in the later-described isocyanate reactive group-containing compound (c1) is within the range of 0.7 to 2.0, and more preferably used in a manner such that the above ratio is within the range of 0.9 to 1.5.

[0198] In addition, from the viewpoint of reducing the VOC content in the obtained coating composition and the hardness, adhesion and color unevenness of the formed coating film, the content of the above-mentioned polyisocyanate compound (b1) in the above-mentioned curing agent (B) is preferably in the range of 30 to 100 mass %, more preferably in the range of 40 to 99.5 mass %, and even more preferably in the range of 50 to 99 mass %, based on the total amount of the curing agent (B).

[0199] [Other ingredients]

[0200] The curing agent (B) may further contain a curing agent other than the polyisocyanate compound (b1) in addition to the above. Furthermore, the curing agent (B) may appropriately contain other additives commonly used in the coating field, such as an ultraviolet absorber, a light stabilizer, an internal mold release agent, a solvent (organic solvent, water), a pigment, a catalyst, a dehydrating agent, an antioxidant, a surface conditioner, a defoaming agent, an emulsifier, a surfactant, an antifouling agent, a wetting agent, a thickener, a dye, an abrasion resistance improver, and a gloss modifier, as needed.

[0201] <Curing agents other than polyisocyanate compound (b1)>

[0202] Examples of curing agents other than the polyisocyanate compound (b1) include carbodiimide group-containing compounds.

[0203] <Carbodiimide group-containing compounds>

[0204] The carbodiimide group-containing compound is a compound having at least one carbodiimide group in one molecule, and for example, a carbodiimide group-containing compound obtained by decarbonation reaction of isocyanate groups of an isocyanate group-containing compound can be used.

[0205] However, in the present invention, the compound having a carbodiimide group and two or more isocyanate groups is not included in the carbodiimide group-containing compound but is included in the polyisocyanate compound (b1).

[0206] As the carbodiimide group-containing compound, a commercially available product can be used. Examples of the trade names of the commercially available products include: "CARBODILITE V-02B," "Elastostab H01," "CARBODILITE V-03," "CARBODILITE V-09," "CARBODILITE V-09GB," "CARBODILITE V-09M," and "CARBODILITE V-04PF" (all trade names, manufactured by Nisshinbo Chemical Co., Ltd.), and "Stabaxol I," "Stabaxol I LF," "Stabaxol P," "Stabaxol P100," and "Stabaxol P200" (all trade names, manufactured by LANXESS).

[0207] From the viewpoints of reducing the VOC content in the obtained coating composition and improving the adhesion and color unevenness of the formed coating film, the carbodiimide group-containing compound preferably contains a solvent-free carbodiimide group-containing compound.

[0208] As the solvent-free carbodiimide group-containing compound, a commercially available product can be used, and examples of the commercially available product include "CARBODILITE V-02B," "Elastostab H01," and "CARBODILITE V-04PF" (all manufactured by Nisshinbo Chemical Co., Ltd.).

[0209] In addition, from the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the number average molecular weight of the aforementioned carbodiimide group-containing compound is preferably in the range of 500 to 5000, more preferably in the range of 600 to 3000, and even more preferably in the range of 700 to 1500.

[0210] When the curing agent (B) contains the carbodiimide group-containing compound, the content of the carbodiimide group-containing compound is preferably within a range of 0.5 to 5.0% by mass, more preferably within a range of 0.8 to 4.0% by mass, and even more preferably within a range of 1.0 to 3.0% by mass, based on the total amount of the curing agent (B), from the viewpoints of reducing the VOC content in the resulting coating composition and improving the hardness, adhesion, and color unevenness of the formed coating film.

[0211] Solvents

[0212] As the solvent, for example, the solvents exemplified in the above-mentioned main agent (A) can be used.

[0213] When the curing agent (B) contains the above-mentioned solvent, the content of the solvent is preferably in the range of 0.1 to 5% by mass, more preferably in the range of 0.2 to 4% by mass, and even more preferably in the range of 0.3 to 3% by mass, based on the total amount of the curing agent (B), from the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion, and color unevenness of the formed coating film.

[0214] Dehydrating agent

[0215] As the dehydrating agent, for example, the dehydrating agents exemplified in the main agent (A) can be used.

[0216] When the curing agent (B) contains the dehydrating agent, the amount of the dehydrating agent blended is preferably within a range of 0.1 to 5% by mass, more preferably within a range of 0.3 to 3% by mass, based on the total amount of the curing agent (B), from the viewpoints of hardness and adhesion of the resulting coating film.

[0217] The curing agent (B) is heated at a shear rate of 100 sec -1 、Viscosity at 65℃(V B ) is in the range of 20 to 1800 mPa·s.

[0218] From the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the curing agent (B) is preferably used at a shear rate of 100 sec -1 、Viscosity at 65℃(V B ) is preferably in the range of 50 to 1500 mPa·s, more preferably in the range of 100 to 1000 mPa·s, and even more preferably in the range of 150 to 600 mPa·s.

[0219] From the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the solid content concentration of the curing agent (B) is preferably in the range of 95 to 100% by mass, more preferably in the range of 96 to 100% by mass, and even more preferably in the range of 97 to 100% by mass.

[0220] From the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion, and color unevenness of the formed coating film, the content of the curing agent (B) in the kit of the present invention and the three-component coating composition of the present invention is preferably in the range of 20 to 80% by mass, more preferably in the range of 30 to 75% by mass, and even more preferably in the range of 40 to 70% by mass, based on the total amount of the three-component coating composition.

[0221] [Pigment slurry (C)]

[0222] The pigment slurry (C) contains an isocyanate-reactive group-containing compound (c1) and a pigment (C2).

[0223] [Isocyanate-reactive group-containing compound (c1)]

[0224] The isocyanate-reactive group-containing compound (c1) is a compound having at least one isocyanate-reactive group in one molecule.

[0225] From the viewpoint of reducing the VOC content in the obtained coating composition and the hardness, adhesion and color unevenness of the formed coating film, the above-mentioned isocyanate-reactive group-containing compound (c1) preferably contains an isocyanate-reactive group-containing compound with a number average molecular weight in the range of 250 to 2500, more preferably contains an isocyanate-reactive group-containing compound with a number average molecular weight in the range of 300 to 1800, and further preferably contains an isocyanate-reactive group-containing compound with a number average molecular weight in the range of 300 to 1500.

[0226] The isocyanate-reactive group is not particularly limited as long as it is a group reactive toward an isocyanate group. Examples of the isocyanate-reactive group include a hydroxyl group, an amino group, and a thiol group. From the perspectives of the hardness, adhesion, and color unevenness of the resulting coating film, the isocyanate-reactive group preferably contains at least one selected from a hydroxyl group and an amino group, and more preferably contains a hydroxyl group.

[0227] Therefore, as the above-mentioned isocyanate-reactive group-containing compound (c1), hydroxyl-containing compounds (c11), amino-containing compounds (c12), mercapto-containing compounds (c13) and the like can be listed. From the viewpoint of the hardness, adhesion and color unevenness of the coating film formed, it is preferred to contain at least one compound selected from the hydroxyl-containing compound (c11) and the amino-containing compound (c12), and it is more preferred to contain the hydroxyl-containing compound (c11).

[0228] [Hydroxy-containing compound (c11)]

[0229] The hydroxyl-containing compound (c11) is a compound having at least one hydroxyl group in one molecule. As the hydroxyl-containing compound (c11), regarding hydroxyl-containing oligomers and hydroxyl-containing polymers, for example, hydroxyl-containing polyester resins, hydroxyl-containing polycaprolactone resins, hydroxyl-containing polyether resins, hydroxyl-containing polycarbonate resins, hydroxyl-containing acrylic resins, hydroxyl-containing polyurethane resins, hydroxyl-containing epoxy resins, hydroxyl-containing alkyd resins, etc. can be listed. Among them, from the perspectives of reducing the VOC content in the obtained coating composition and the hardness, adhesion and color unevenness of the formed coating film, it is preferred to contain at least one resin selected from hydroxyl-containing polyester resins, hydroxyl-containing polycaprolactone resins and hydroxyl-containing polyether resins, and more preferably contain at least one resin selected from hydroxyl-containing polyester resins and hydroxyl-containing polycaprolactone resins. They can be used alone or in combination of two or more.

[0230] As the hydroxyl-containing polyester resin, for example, the hydroxyl-containing polyester resins exemplified in the main component (A) can be used.

[0231] From the viewpoint of hardness and adhesion of the formed coating film, the hydroxyl value of the hydroxyl-containing polyester resin is preferably within the range of 50 to 800 mgKOH / g, more preferably within the range of 100 to 700 mgKOH / g, and even more preferably within the range of 300 to 600 mgKOH / g.

[0232] In addition, from the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the number average molecular weight of the above-mentioned hydroxyl-containing polyester resin is preferably in the range of 250 to 2500, more preferably in the range of 300 to 1800, and even more preferably in the range of 350 to 1500.

[0233] In addition, from the viewpoint of reducing the VOC content in the obtained coating composition and the hardness, adhesion and color unevenness of the formed coating film, the glass transition temperature (Tg) of the above-mentioned hydroxyl-containing polyester resin is preferably in the range of -80 to 10°C, more preferably in the range of -70 to 5°C, and even more preferably in the range of -60 to 0°C.

[0234] When the hydroxyl-containing polyester resin is contained as the hydroxyl-containing compound (c11), the content of the hydroxyl-containing polyester resin is preferably in the range of 50 to 100 mass %, more preferably in the range of 60 to 95 mass %, and even more preferably in the range of 75 to 90 mass %, based on the total solid content of the hydroxyl-containing compound (c11), from the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film.

[0235] As the hydroxyl group-containing polycaprolactone resin, for example, the hydroxyl group-containing polycaprolactone resins exemplified in the main component (A) can be used.

[0236] From the viewpoint of hardness and adhesion of the formed coating film, the hydroxyl value of the hydroxyl-containing polycaprolactone resin is preferably within the range of 50 to 900 mgKOH / g, more preferably within the range of 100 to 750 mgKOH / g, and even more preferably within the range of 130 to 600 mgKOH / g.

[0237] In addition, from the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the number average molecular weight of the above-mentioned hydroxyl-containing polycaprolactone resin is preferably in the range of 250 to 2500, more preferably in the range of 280 to 1500, and even more preferably in the range of 300 to 1000.

[0238] When the hydroxyl-containing compound (c11) contains the hydroxyl-containing polycaprolactone resin, the content of the hydroxyl-containing polycaprolactone resin is preferably in the range of 5 to 100% by mass, more preferably in the range of 10 to 75% by mass, and even more preferably in the range of 10 to 50% by mass, based on the total solid content of the hydroxyl-containing compound (c11), from the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film.

[0239] As the hydroxyl group-containing polyether resin, for example, the polyether resins exemplified in the main component (A) can be used.

[0240] From the viewpoint of hardness and adhesion of the formed coating film, the hydroxyl value of the hydroxyl-containing polyether resin is preferably within the range of 50 to 600 mgKOH / g, more preferably within the range of 70 to 500 mgKOH / g, and even more preferably within the range of 90 to 400 mgKOH / g.

[0241] From the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion, and color unevenness of the formed coating film, the number average molecular weight of the hydroxyl-containing polyether resin is preferably in the range of 250 to 2500, more preferably in the range of 300 to 1500, and even more preferably in the range of 350 to 1000.

[0242] When the aforementioned hydroxyl-containing compound (c11) contains the aforementioned hydroxyl-containing polyether resin, from the viewpoint of reducing the VOC content in the obtained coating composition and the hardness, adhesion and color unevenness of the formed coating film, the content of the hydroxyl-containing polyether resin is preferably in the range of 20 to 100 mass %, more preferably in the range of 40 to 100 mass %, and even more preferably in the range of 50 to 100 mass %, based on the total solid content of the hydroxyl-containing compound (c11).

[0243] As the hydroxyl group-containing polycarbonate resin, for example, the polycarbonate resins exemplified in the main component (A) can be used.

[0244] From the viewpoint of hardness and adhesion of the formed coating film, the hydroxyl value of the hydroxyl-containing polycarbonate resin is preferably within the range of 50 to 800 mgKOH / g, more preferably within the range of 70 to 700 mgKOH / g, and even more preferably within the range of 90 to 600 mgKOH / g.

[0245] From the viewpoint of reducing the VOC content in the obtained coating composition and improving the adhesion and color unevenness of the formed coating film, the number average molecular weight of the above-mentioned hydroxyl-containing polycarbonate resin is preferably in the range of 250 to 2500, more preferably in the range of 300 to 1800, and even more preferably in the range of 400 to 1500.

[0246] When the hydroxyl-containing compound (C11) contains the hydroxyl-containing polycarbonate resin, the content of the hydroxyl-containing polycarbonate resin is preferably in the range of 5 to 80% by mass, more preferably in the range of 10 to 50% by mass, and even more preferably in the range of 10 to 40% by mass, based on the total solid content of the hydroxyl-containing compound (c11), from the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film.

[0247] As the hydroxyl group-containing acrylic resin, for example, the acrylic resins exemplified in the main component (A) can be used.

[0248] From the viewpoint of hardness and adhesion of the formed coating film, the hydroxyl value of the hydroxyl-containing acrylic resin is preferably within the range of 5 to 240 mgKOH / g, more preferably within the range of 20 to 220 mgKOH / g, and even more preferably within the range of 25 to 200 mgKOH / g.

[0249] In addition, from the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the number average molecular weight of the above-mentioned hydroxyl-containing acrylic resin is preferably in the range of 250 to 2500, more preferably in the range of 300 to 1800, and even more preferably in the range of 500 to 1500.

[0250] In addition, from the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the glass transition temperature (Tg) of the above-mentioned hydroxyl-containing acrylic resin is preferably in the range of -60 to 80°C, more preferably in the range of -50 to 70°C, and even more preferably in the range of -40 to 60°C.

[0251] When the hydroxyl-containing compound (c11) contains the hydroxyl-containing acrylic resin, the content of the hydroxyl-containing acrylic resin is preferably in the range of 5 to 100% by mass, more preferably in the range of 10 to 75% by mass, and even more preferably in the range of 15 to 50% by mass, based on the total solid content of the hydroxyl-containing compound (c11), from the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film.

[0252] As the hydroxyl group-containing compound (c11), for example, the hydroxyl group-containing monomers exemplified in the main component (A) can be used.

[0253] When the above-mentioned hydroxyl-containing compound (c11) contains the above-mentioned hydroxyl-containing monomer, the content of the hydroxyl-containing monomer is preferably in the range of 5 to 100 mass %, more preferably in the range of 5 to 50 mass %, and further preferably in the range of 5 to 30 mass %, based on the total solid content of the hydroxyl-containing compound (c11), from the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film.

[0254] When the aforementioned isocyanate-reactive group-containing compound (c1) contains the aforementioned hydroxyl-containing compound (c11), the content of the hydroxyl-containing compound (c11) is preferably in the range of 50 to 100% by mass, more preferably in the range of 60 to 100% by mass, and still more preferably in the range of 70 to 100% by mass, based on the total solid content of the isocyanate-reactive group-containing compound (c1), from the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film.

[0255] [Amino group-containing compound (c12)]

[0256] As the amino group-containing compound (c12), for example, the amino group-containing compound (c12) exemplified in the main agent (A) can be used.

[0257] When the aforementioned isocyanate-reactive group-containing compound (c1) contains the aforementioned amino-containing compound (c12), the content of the amino-containing compound (c12) is preferably in the range of 10 to 100% by mass, more preferably in the range of 40 to 95% by mass, and even more preferably in the range of 50 to 90% by mass, based on the total solid content of the isocyanate-reactive group-containing compound (c1), from the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film.

[0258] [Mercapto group-containing compound (c13)]

[0259] As the mercapto group-containing compound (c13), for example, the mercapto group-containing compound (c13) exemplified in the main agent (A) can be used.

[0260] When the aforementioned isocyanate-reactive group-containing compound (c1) contains the aforementioned mercapto group-containing compound (c13), the content of the mercapto group-containing compound (c13) is preferably in the range of 10 to 100% by mass, more preferably in the range of 30 to 95% by mass, and even more preferably in the range of 50 to 90% by mass, based on the total solid content of the isocyanate-reactive group-containing compound (c1), from the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film.

[0261] From the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the content of the above-mentioned isocyanate-reactive group-containing compound (c1) in the above-mentioned pigment slurry (C) is preferably in the range of 10 to 99 mass %, more preferably in the range of 15 to 90 mass %, and even more preferably in the range of 20 to 80 mass %, based on the total amount of the pigment slurry (C).

[0262] [Pigment (c2)]

[0263] Examples of the pigment (c2) include bright pigments, coloring pigments, and extender pigments. These pigments can be used alone or in combination of two or more.

[0264] Examples of the bright pigment 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.

[0265] Examples of the coloring pigments include titanium oxide, zinc oxide, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, anthracene pigments, perylene pigments, dioxazine pigments, diketopyrrolopyrrole pigments, and heat-insulating pigments.

[0266] Examples of the extender pigment include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and aluminum white.

[0267] From the viewpoint of reducing the VOC content in the obtained coating composition and improving the hardness and color unevenness of the formed coating film, the content of the pigment (c2) in the pigment slurry (C) is preferably in the range of 1.0 to 70% by mass, more preferably in the range of 1.0 to 65% by mass, further preferably in the range of 2.0 to 64% by mass, and even more preferably in the range of 3.0 to 62% by mass, based on the total amount of the pigment slurry (C).

[0268] [Other ingredients]

[0269] The pigment slurry (C) may further contain an ultraviolet absorber and / or a light stabilizer in addition to the above-mentioned ingredients. Furthermore, as needed, it may appropriately contain other additives commonly used in the coating field, such as an internal release agent, a solvent (organic solvent, water), a pigment, a catalyst, a dehydrating agent, an antioxidant, a surface conditioner, a defoaming agent, an emulsifier, a surfactant, an antifouling agent, a wetting agent, a thickener, a dye, an abrasion resistance improver, and a gloss modifier.

[0270] UV absorbers

[0271] As the ultraviolet absorber, for example, the ultraviolet absorbers exemplified in the main component (A) can be used.

[0272] When the pigment slurry (C) contains the ultraviolet absorber, the content of the ultraviolet absorber is preferably in the range of 0.5 to 10% by mass, more preferably in the range of 0.8 to 5.0% by mass, and even more preferably in the range of 1.0 to 4.0% by mass, based on the total amount of the pigment slurry (C) coating composition, from the viewpoints of weather resistance and adhesion of the formed coating film.

[0273] Light stabilizers

[0274] As the light stabilizer, for example, the light stabilizers exemplified in the main component (A) can be used.

[0275] When the pigment slurry (C) contains the above-mentioned light stabilizer, the content of the light stabilizer is preferably in the range of 0.5 to 10% by mass, more preferably in the range of 0.8 to 9.0% by mass, and even more preferably in the range of 1.0 to 8.0% by mass, based on the total amount of the pigment slurry (C), from the viewpoints of weather resistance and adhesion of the formed coating film.

[0276] Internal release agent

[0277] When the coating composition of the present invention is used as an in-mold coating composition, the pigment slurry (C) may contain an internal mold release agent from the viewpoint of the releasability of the formed coating film from the mold.

[0278] As the internal mold release agent, for example, the internal mold release agents exemplified in the main agent (A) can be used.

[0279] When the pigment slurry (C) contains the internal release agent, the content of the internal release agent is preferably in the range of 0.4 to 8.0% by mass, more preferably in the range of 0.5 to 7.0% by mass, and even more preferably in the range of 0.5 to 6.0% by mass, based on the total amount of the pigment slurry (C), from the viewpoints of the adhesion of the formed coating film and the releasability of the formed coating film from the mold.

[0280] Solvents

[0281] As the solvent, for example, the solvents exemplified in the above-mentioned main agent (A) can be used.

[0282] When the pigment slurry (C) contains the above-mentioned solvent, the content of the solvent is preferably in the range of 2 to 15% by mass, more preferably in the range of 2 to 13% by mass, and even more preferably in the range of 2 to 10% by mass, based on the total amount of the pigment slurry (C), from the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film.

[0283] Catalyst

[0284] As the catalyst, for example, the catalysts exemplified in the main component (A) can be used.

[0285] When the pigment slurry (C) contains the catalyst, the amount of the catalyst blended is preferably in the range of 0.01 to 5.0% by mass, more preferably in the range of 0.1 to 3.0% by mass, based on the total amount of the pigment slurry (C), from the viewpoints of hardness and adhesion of the formed coating film.

[0286] Dehydrating agent

[0287] As the dehydrating agent, for example, the dehydrating agents exemplified in the main agent (A) can be used.

[0288] When the pigment slurry (C) contains the dehydrating agent, the amount of the dehydrating agent blended is preferably in the range of 0.1 to 5.0% by mass, more preferably in the range of 0.3 to 3.0% by mass, based on the total amount of the pigment slurry (C), from the viewpoints of hardness and adhesion of the formed coating film.

[0289] The pigment slurry (C) is subjected to a shear rate of 100 sec -1 、Viscosity at 65℃(V C ) is in the range of 20 to 1800 mPa·s.

[0290] From the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion and color unevenness of the formed coating film, the pigment slurry (C) is subjected to a shear rate of 100 sec -1 、Viscosity at 65℃(V C ) is preferably in the range of 50 to 1500 mPa·s, more preferably in the range of 100 to 1000 mPa·s, and even more preferably in the range of 150 to 800 mPa·s.

[0291] From the viewpoint of reducing the VOC content in the obtained coating composition and improving the adhesion and color unevenness of the formed coating film, the solid content concentration of the above-mentioned pigment slurry (C) is preferably in the range of 84 to 99 mass%, more preferably in the range of 85 to 98 mass%, further preferably in the range of 87 to 98 mass%, and even more preferably in the range of 90 to 98 mass%.

[0292] From the viewpoints of reducing the VOC content in the obtained coating composition and improving the hardness, adhesion, and color unevenness of the formed coating film, the content of the pigment slurry (C) in the kit of the present invention and the three-component coating composition of the present invention is preferably in the range of 3 to 50% by mass, more preferably in the range of 4 to 40% by mass, and even more preferably in the range of 5 to 30% by mass, based on the total amount of the three-component coating composition.

[0293] <Coating film formation method using a kit and a three-component coating composition>

[0294] The kit and the three-component coating composition of the present invention are applied to a substrate to form a wet coating film (uncured coating film), and then the wet coating film is cured to form a target coating film.

[0295] From the viewpoint of adhesion of the formed coating film, etc., the substrate is preferably a resin material.

[0296] Examples of the resin material include acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polyethylene 1,4-cyclohexanedimethyl terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, and polybutylene terephthalate, and Epikote (trade name: YukaShell). Epoxy resins represented by commercially available products such as Epoxy Co., Ltd., polycarbonate resins, polyimide resins, novolac resins, phenol resins, acrylonitrile-butadiene-styrene (ABS) resins, acrylonitrile-ethylene-styrene (AES) resins, acrylonitrile-styrene-acrylate (ASA) resins, vinyl chloride resins, vinylidene chloride resins, polyurethane resins, cellulose ester resins (e.g., cellulose triacetate, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamide resins, polystyrene resins (e.g., syndiotactic polystyrene), polyolefin resins (e.g., polypropylene, polyethylene, polymethylpentene), polysulfone resins, polyethersulfone resins, polyarylate resins, polyetherimide resins, polyetherketone resins, various fiber reinforced plastic materials (hereinafter sometimes referred to as FRP materials or simply FRP), and polymer alloys thereof.

[0297] Furthermore, the substrate may be one on which a primer, a mid-coat, a topcoat, or the like is preliminarily formed by coating the resin material with a primer, a mid-coat, a topcoat, or the like.

[0298] The substrate may be treated (physical treatment) by at least one physical method selected from the group consisting of plasma treatment, corona discharge treatment, active energy ray treatment, flame treatment, sandblasting treatment, and polishing treatment.

[0299] It should be noted that the three-component coating composition formed from the kit of the present invention and the three-component coating composition of the present invention are preferably applied directly on a substrate.

[0300] Furthermore, the applications of the three-component coating composition formed from the kit of the present invention and the objects to be coated with the three-component coating composition of the present invention are not particularly limited, and examples thereof include: exterior panels of automobile bodies such as passenger cars, trucks, motorcycles, and buses; automotive interior and exterior parts such as bumpers, center pillars, rearview mirrors, door handles, instrument panels, door trims, and center consoles; furniture and building material-related parts such as chairs, vanity mirrors, window frames, and gates; and exterior panels of household appliances such as mobile phones and audio equipment.

[0301] The method for applying the three-component coating composition formed from the kit of the present invention, or the three-component coating composition of the present invention, to a substrate is not particularly limited. For example, application can be by air spray, airless spray, rotary atomizer, dip coating, film applicator, brush, roller, in-mold coating, or the like. Electrostatic application may also be employed during coating.

[0302] The coating film thickness is preferably within a range of 5 to 2000 μm, more preferably within a range of 10 to 1500 μm, and even more preferably within a range of 15 to 1000 μm in terms of cured film thickness.

[0303] The three-component coating composition formed from the kit of the present invention and the three-component coating composition of the present invention can be cured by heating the three-component coating composition.

[0304] <Heating>

[0305] Heating can be performed using any method known in the art. Specifically, for example, hot air, hot gas, infrared heaters, IR radiators, ovens, heated rollers, hot presses, and microwaves can be used. In the present invention, heating using hot air, infrared heaters, hot presses, and the like is preferred from the perspective of ease of operation.

[0306] From the viewpoints of productivity, workability, and thermal stability of the substrate, the heating temperature is preferably within a range of 30 to 200°C, more preferably within a range of 50 to 180°C, and even more preferably within a range of 70 to 160°C.

[0307] The heating time is preferably within a range of 20 seconds to 60 minutes, more preferably within a range of 40 seconds to 10 minutes.

[0308] Furthermore, the three-component coating composition of the present invention is preferably used for coating using the in-mold coating method. This in-mold coating method generally allows the use of coating compositions with low VOC content and reduces air conditioning energy consumption during coating, thereby reducing environmental impact.

[0309] <In-mold coating method>

[0310] The in-mold coating method of the present invention comprises the following steps: injecting the coating composition of the present invention (hereinafter, when the coating composition of the present invention is used in the in-mold coating method, it is referred to as the in-mold coating composition) between the molded substrate and the inner wall of the mold, curing the in-mold coating composition, and then removing the coated molded object from the mold.

[0311] As the in-mold coating method, any conventional method of forming and coating in a mold can be used without particular limitation. Specifically, for example, the method described in Japanese Patent Application Laid-Open No. 2000-141407 and Japanese Translation of National Publication No. 2008-525212 can be used.

[0312] It should be noted that the resin molding die used when molding the resin material and the in-mold coating die used when in-mold coating the coating composition may be the same or different.

[0313] 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 can be injected between the resin molding die having the shape of the target molded article. The resin material is cooled and pressurized within the resin molding die to form a molded article. The resin molding die is then separated from the surface of the resin molding article. An in-mold coating composition is then prepared by mixing the main agent (A), the curing agent (B), and the pigment slurry (C). A gap sufficient for injecting the in-mold coating composition is provided between the surface of the resin molding article and the in-mold coating die. The in-mold coating composition is injected between the surface of the resin molding article and the inner wall of the in-mold coating die. The in-mold coating die is closed to form an uncured in-mold coating film on the resin molding article. The uncured in-mold coating film formed on the resin molding article is then heated and molded into the target shape, thereby obtaining an in-mold coating molded article having a cured in-mold coating film formed on the resin molding article.

[0314] When the resin molding die and the in-mold coating die are separate, for example, a resin material heated and melted in an injection cylinder can be injected between the resin molding dies having the shape of the target molded article. The resin material can be cooled and pressurized within the resin molding dies to form a molded article. The resin molding dies can then be separated and removed from the surface of the resin molding. An in-mold coating composition can then be prepared by mixing the main agent (A), the curing agent (B), and the pigment slurry (C). The in-mold coating die can be brought close to the surface of the resin molding. A gap sufficient for injecting the in-mold coating composition can be provided between the surface of the resin molding and the in-mold coating die. The in-mold coating composition can then be injected between the surface of the resin molding and the inner wall of the in-mold coating die. The in-mold coating die can then be closed to form an uncured in-mold coating film on the resin molding. Next, the uncured in-mold coating film formed on the molded object of the resin material is heated and molded into a target shape, thereby obtaining an in-mold-coated molded object having a cured in-mold coating film formed on the molded object of the resin material.

[0315] In addition, from the perspective of the releasability of the in-mold coating molded product from the in-mold coating mold, an external release agent can be applied to the mold. As the external release agent, for example, fluorine-based, silicone-based, surfactant-based, and wax-based external release agents can be used.

[0316] The heating temperature when melting the resin in the injection cylinder is arbitrarily determined according to the type of resin material, etc., and is preferably 80 to 300° C. The mold temperature when injecting the resin material is arbitrarily determined according to the molding time, the type of resin material, etc., and is preferably 30 to 120° C.

[0317] When the in-mold coating composition is prepared by mixing the main agent (A), the curing agent (B), and the pigment slurry (C), it is preferred that the main agent (A), the curing agent (B), and the pigment slurry (C) are heated separately before mixing from the viewpoints of hardness, adhesion, and color unevenness of the resulting coating film.

[0318] When the main agent (A), the curing agent (B) and the pigment slurry (C) are heated separately and then mixed, the temperature is preferably in the range of 30 to 100° C., more preferably in the range of 40 to 90° C., and even more preferably in the range of 50 to 80° C., from the viewpoint of the hardness, adhesion and color unevenness of the coating film formed.

[0319] In addition, since the main agent (A), the curing agent (B) and the pigment slurry (C) are heated when mixed, the flash point of the main agent (A) is preferably above 70°C, more preferably above 100°C, the flash point of the curing agent (B) is preferably above 70°C, more preferably above 100°C, and the flash point of the pigment slurry (C) is preferably above 70°C, more preferably above 100°C.

[0320] The molding time of the resin material may be until the resin material is completely cured, but it only needs to be cured to a strength that does not damage the molded shape when the in-mold coating composition is injected. Generally, it is preferably about 20 seconds to 60 minutes.

[0321] The injection amount of the in-mold coating composition is an amount sufficient to obtain a desired film thickness, preferably an amount sufficient to obtain a cured film thickness of 15 to 2000 μm.

[0322] The heating temperature when heating the uncured in-mold coating film is preferably in the range of 20 to 160°C, more preferably in the range of 40 to 150°C, and even more preferably in the range of 60 to 140°C.

[0323] The heating time when heating the uncured in-mold coating film is preferably in the range of 20 seconds to 10 minutes, more preferably in the range of 30 seconds to 5 minutes, and even more preferably in the range of 40 seconds to 4 minutes.

[0324] When the uncured in-mold coating film is heated and cured, it is preferably pressurized.

[0325] When the pressurization is performed, the pressure is preferably within a range of 2 to 14 MPa from the viewpoints of hardness and adhesion of the coating film to be formed.

[0326] [Example]

[0327] The present invention is described in more detail below using preparation examples, embodiments, and comparative examples. These preparation examples, embodiments, and comparative examples are provided for illustrative purposes only and are not intended to limit the scope of the present invention. In the preparation examples, embodiments, and comparative examples, "parts" and "%" are based on mass unless otherwise specified. Furthermore, the film thickness of the coating film is based on the cured coating film.

[0328] The components used in the following examples are as follows.

[0329] <Preparation of main agent (A)>

[0330] Production Example 1

[0331] In a container equipped with a stirring device, 80.0 parts of "Desmophen XP2488" (trade name, manufactured by Covestro, a hydroxyl-containing polyester resin containing 26% of a hydroxyl-containing monomer, number average molecular weight 500, solid content concentration 100%), 20.0 parts of "PLACCEL 303" (trade name, manufactured by Daicel, a hydroxyl-containing polycaprolactone resin, number average molecular weight 310, solid content concentration 100%), 1.7 parts of "Moldwiz INT-120IMC" (trade name, manufactured by AXEL PLASTICS, a mixture containing tertiary dimethyl amides of fatty acids, solid content concentration 100%), 0.2 parts of "BYK-333" (trade name, manufactured by BYK-Chemie, a surface conditioner (polyether-modified polydimethylsiloxane), solid content concentration 100%), and 0.2 parts of "TINUVIN" (trade name, manufactured by BYK-Chemie, a surface conditioner (polyether-modified polydimethylsiloxane), solid content concentration 100%) were added. 2.9 parts of "TINUVIN 400" (trade name, manufactured by BASF, a triazine-based UV absorber with a solid content of 85%), 5.7 parts of "TINUVIN 292" (trade name, manufactured by BASF, a hindered amine compound light stabilizer with a solid content of 100%), and 1.7 parts of "Neostann U-830" (trade name, manufactured by Nitto Kasei Co., Ltd., dioctyltin ditert-carbonate with a solid content of 100%) were mixed uniformly to obtain a main agent (A-1) with a solid content of 98.5%.

[0332] Production Examples 2 to 11

[0333] In Production Example 1, except that the compounding composition was as shown in the following Table 1, the same method as in Production Example 1 was carried out to obtain main components (A-1) to (A-11).

[0334] <Main agent (A) at shear rate 100sec -1 、Viscosity at 65℃(V A ) determination>

[0335] The shear rate of the main agents (A-1) to (A-11) obtained in Preparation Examples 1 to 11 was measured by the following method for 100 sec. -1 、Viscosity at 65℃(V A The results are recorded in Table 1.

[0336] At a shear rate of 100 sec -1 The temperature was raised from 20°C to 80°C at a rate of 5°C / min, and the shear rate was measured using a cone & plate viscometer "MCR-302e" (trade name, manufactured by Anton Paar, with a diameter of 25 mm and a 2° inclined cone & plate) for 100 sec. -1 、Viscosity at 65℃(V A ).

[0337] [Table 1]

[0338] Table 1

[0339]

[0340] In addition, each component described in the table is as follows.

[0341] (Note 1) "Desmophen VPLS2249 / 1": Trade name, manufactured by Covestro, a hydroxyl-containing polyester resin containing 44% of a hydroxyl-containing monomer, number average molecular weight 1008, solid content 100%,

[0342] (Note 2) "ETERNACOL PH-300": manufactured by UBE, a hydroxyl-containing polycarbonate resin with a number average molecular weight of 3000 and a solid content of 100%.

[0343] (Note 3) "Desmophen NH1220": Trade name, manufactured by Covestro, N,N'-(2-methylpentane-1,5-diyl)bis(aspartic acid) tetraethyl ester, number average molecular weight 461, solid content 100%,

[0344] (Note 4) "Desmophen NH1423": Trade name, manufactured by Covestro, N,N'-[methylenebis(cyclohexane-4,1-diyl)]bis(aspartic acid) tetraethyl ester, number average molecular weight 551, solid content 100%,

[0345] (Note 5) "TMMP-LV": Trade name, manufactured by SC Organic Chemical Co., Ltd., trimethylolpropane tris(3-mercaptopropionate), number average molecular weight 399, solid content 100%,

[0346] (Note 6) "TEMPIC": Trade name, manufactured by SC Organic Chemical Co., Ltd., tris-[(3-mercaptopropionyloxy)-ethyl] isocyanurate, number average molecular weight 526, solid content concentration 100%,

[0347] (Note 7) “PEMP-LV”: Trade name, manufactured by SC Organic Chemical Co., Ltd., pentaerythritol tetrakis(3-mercaptopropionate), number average molecular weight 489, solid content 100%.

[0348] <Preparation of Curing Agent (B)>

[0349] Production Example 12

[0350] In a container equipped with a stirring device, 40.0 parts of "Desmodur N3900" (trade name, manufactured by Sumika Covestro Urethane Co., Ltd., iminooxadiazinedione of hexamethylene diisocyanate, solid content concentration 100%), 20.0 parts of "Desmodur N3400" (trade name, manufactured by Sumika Covestro Urethane Co., Ltd., a mixture of uretdione of hexamethylene diisocyanate and isocyanurate, solid content concentration 100%), 40.0 parts of "Desmodur NZ200" (trade name, manufactured by Sumika Covestro Urethane Co., Ltd., a mixture of isocyanurate of hexamethylene diisocyanate and isocyanurate of isophorone diisocyanate, solid content concentration 100%), and "CARBODILITE V-05" (trade name, manufactured by Nisshinbo 2.3 parts of a carbodiimide-containing compound having an aromatic ring structure and two isocyanate groups, manufactured by a Chemical company, with a carbodiimide equivalent of 262 based on solid content, a number average molecular weight of 800, and a solid content concentration of 100%) were added and uniformly mixed to obtain a curing agent (B-1) with a solid content concentration of 100.0%.

[0351] Production Examples 13 to 19

[0352] In Production Example 12, except that the compounding composition was as shown in Table 2 below, a curing agent (B-2) and a curing agent (B-8) were obtained in the same manner as in Production Example 12.

[0353] <Curing agent (B) at shear rate 100sec -1 、Viscosity at 65℃(V B ) determination>

[0354] For the curing agents (B-1) to (B-8) obtained in Production Examples 12 to 19, the shear rate was measured according to the following method for 100 sec. -1 、Viscosity at 65℃(V B The results are also recorded in Table 2.

[0355] At a shear rate of 100 sec -1 The temperature was raised from 20°C to 80°C at 5°C / min, and the shear rate was measured for 100 sec using a cone & plate viscometer "MCR-302e" (trade name, manufactured by Anton Paar, with a diameter of 25 mm and a 2° inclined cone & plate). -1 、Viscosity at 65℃(V B ).

[0356] [Table 2]

[0357] Table 2

[0358]

[0359] In addition, each component described in the table is as follows.

[0360] (Note 8) "Desmodur N3600": Trade name, manufactured by Sumika Covestro Urethane Co., Ltd., isocyanurate of hexamethylene diisocyanate, solid content concentration 100%.

[0361] (Note 9) "Desmodur N3500": Trade name, manufactured by Sumika Covestro Urethane Co., Ltd., allophanate of hexamethylene diisocyanate, solid content concentration 100%.

[0362] <Preparation of Pigment Slurry (C)>

[0363] Production Example 20

[0364] In a container equipped with a stirring device, 80.0 parts of "Desmophen XP2488" (trade name, manufactured by Covestro, a hydroxyl-containing polyester resin containing 26% of a hydroxyl-containing monomer, number average molecular weight 500, solid content concentration 100%), 20.0 parts of "PLACCEL 303" (trade name, manufactured by Daicel, a hydroxyl-containing polycaprolactone resin, number average molecular weight 310, solid content concentration 100%), 4.8 parts of "Raven 5000 ULTRA II POWDER" (trade name, manufactured by Birla Carbon, carbon black pigment, solid content concentration 100%), 0.5 parts of "SOLSPERSE 5000S" (trade name, manufactured by Lubrisol, a phthalocyanine pigment derivative, solid content concentration 100%), 2.4 parts of "DISPERBYK-2013" (trade name, manufactured by BYK-Chemie, a dispersant, solid content concentration 100%), and "Moldwiz" were added. 1.7 parts of "INT-120IMC" (trade name, manufactured by AXEL PLASTICS, a mixture containing tertiary dimethyl amides of fatty acids, solid content concentration 100%), 0.2 parts of "BYK-333" (trade name, manufactured by BYK-Chemie, a surface conditioner (polyether-modified polydimethylsiloxane), solid content concentration 100%), 2.9 parts of "TINUVIN 400" (trade name, manufactured by BASF, a triazine-based UV absorber, solid content concentration 85%), 5.7 parts of "TINUVIN 292" (trade name, manufactured by BASF, a hindered amine compound light stabilizer, solid content concentration 100%), 1.7 parts of "Neostann U-830" (trade name, manufactured by Nitto Kasei Co., Ltd., dioctyltin ditert-carbonate, solid content concentration 100%), and 8.7 parts of butyl acetate were mixed uniformly. The obtained mixed solution was then placed in a wide-mouthed glass bottle, glass beads with a diameter of about 1.3 mm were added as a dispersion medium, and the bottle was sealed. The mixture was then dispersed using a paint shaker for 3 hours to obtain a pigment slurry (C-1) having a solid content concentration of 92.0%.

[0365] Production Examples 21 to 81

[0366] In Production Example 20, except that the compounding compositions were as shown in Table 3 below, pigment slurries (C-2) to (C-62) were obtained in the same manner as in Production Example 20.

[0367] Pigment slurry (C) at a shear rate of 100 sec -1 、Viscosity at 65℃(V C ) determination>

[0368] For the pigment slurries (C-1) to (C-62) obtained in Production Examples 20 to 81, the shear rate was measured according to the following method for 100 sec. -1 、Viscosity at 65℃ (V C The results are summarized in Table 3.

[0369] At a shear rate of 100 sec -1 The temperature was raised from 20°C to 80°C at a rate of 5°C / min, and the shear rate was measured using a cone & plate viscometer "MCR-302e" (trade name, manufactured by Anton Paar, with a diameter of 25 mm and a 2° inclined cone & plate) for 100 sec. -1 、Viscosity at 65℃ (V B ).

[0370] [Table 3]

[0371] Table 3

[0372]

[0373] [Table 4]

[0374] Table 3 (Continued-1)

[0375]

[0376] [Table 5]

[0377] Table 3 (Continued-2)

[0378]

[0379] [Table 6]

[0380] Table 3 (Continued-3)

[0381]

[0382] [Table 7]

[0383] Table 3 (Continued-4)

[0384]

[0385] [Table 8]

[0386] Table 3 (Continued-5)

[0387]

[0388] In addition, each component described in the table is as follows.

[0389] (Note 10) "PTMG-2000": Trade name, manufactured by Mitsubishi Chemical Corporation, polytetramethylene glycol, number average molecular weight 2000, solid content concentration 100%,

[0390] (Note 11) "PTMG-3000": Trade name, manufactured by Mitsubishi Chemical Corporation, polytetramethylene glycol, number average molecular weight 3000, solid content concentration 100%,

[0391] (Note 12) "TIPAQUE CR-95": Trade name, manufactured by Ishihara Sangyo Co., Ltd., titanium oxide, solid content concentration 100%,

[0392] (Note 13) "Chlorinated cyanine blue G-314": Trade name, manufactured by Sanyo Pigment Co., Ltd., phthalocyanine blue pigment, solid content concentration 100%,

[0393] (Note 14) "YELLOW 2GLMA": Trade name, manufactured by Dominion Colour Corporation, bismuth vanadate yellow pigment, solid content concentration 100%,

[0394] (Note 15) "Irgazin Rubine L4025": Trade name, manufactured by BASF, diketopyrrolopyrrole red pigment, solid content concentration 100%,

[0395] (Note 16) "ELgee neo BLUE #325": Trade name, manufactured by Oike Metallic Design Co., Ltd., vapor-deposited aluminum pigment, solid content concentration 100%,

[0396] (Note 17) "ELgee neo RED #325": Trade name, manufactured by Oike Metallic Design Co., Ltd., vapor-deposited aluminum pigment, solid content concentration 100%,

[0397] (Note 18) "Xirallic T60-23 WNT Galaxy Blue": Trade name, manufactured by Merck, titanium oxide-coated aluminum oxide flake pigment, solid content concentration 100%,

[0398] (Note 19) "Xirallic F60-51 SW RADIENT RED": Trade name, manufactured by Merck, iron oxide-coated aluminum oxide flake pigment, solid content 100%,

[0399] (Note 20) "DISPERBYK-111": Trade name, manufactured by BYK-Chemie, dispersant, solid content concentration 100%,

[0400] (Note 21) "Borchi Gen 1757": Trade name, manufactured by Borchers Americas, dispersant, solid content concentration 100%.

[0401] <Production of in-mold coating molded products>

[0402] Example 1

[0403] (Production of In-Mold Coating Molded Product (M1))

[0404] First, an injection molding cylinder was filled with "Dialac TW20" (trade name, manufactured by Techno-UMG, acrylonitrile-styrene-acrylate resin (ASA resin)) and heated and melted at 230°C. The mixture was then injected between a resin molding die at 60°C, where the pressure was maintained for 30 seconds and cooled to obtain a 100 mm × 100 mm × 2 mm flat plate-shaped "Dialac TW20" molded article.

[0405] Next, a set containing the main agent (A-1) obtained in Production Example 1, the curing agent (B-1) obtained in Production Example 12, and the pigment slurry (C-1) obtained in Production Example 20 was prepared and heated to 65°C. The main agent (A-1), the curing agent (B-1), and the pigment slurry (C-1) were then mixed in a container equipped with a stirring device at a mass ratio of (A-1) / (B-1) / (C-1) of 30.3 / 62.1 / 7.6, and uniformly mixed to obtain an in-mold coating composition No. 1 having a solids concentration of 98.9%.

[0406] Next, the resin molding die was opened, and the in-mold coating composition No. 1 was injected between the obtained flat-plate "Dialac TW20" molded product and the coating film coating mold. The coating film coating mold was heated to 80°C, and pressurized at a molding pressure of 5 MPa while maintaining the temperature for 1 minute. After that, the pressure was reduced, and the coating film coating mold was opened. In this way, an in-mold-coated molded product (M1-1) was produced, in which a coating film with a cured film thickness of 200 μm was applied to the flat-plate "Dialac TW20" molded product.

[0407] (Production of In-Mold Coating Molded Product (M2))

[0408] First, an injection molding cylinder was filled with "Makroblend UT235M" (a polymer alloy of polyethylene terephthalate resin and polycarbonate resin, manufactured by Covestro) and heated to 270°C to melt. The mixture was then injected between a resin molding die at 70°C, where the pressure was maintained for 30 seconds and then cooled to produce a 100 mm x 100 mm x 2 mm flat-plate "Makroblend UT235M" molded article.

[0409] Next, the main agent (A-1) obtained in Production Example 1, the curing agent (B-1) obtained in Production Example 12, and the pigment slurry (C-1) obtained in Production Example 20 were each heated to 65° C. The main agent (A-1), the curing agent (B-1), and the pigment slurry (C-1) were then mixed in a container equipped with a stirring device at a mass ratio of (A-1) / (B-1) / (C-1) of 30.3 / 62.1 / 7.6, and the mixture was uniformly mixed to obtain an in-mold coating composition No. 1 having a solids concentration of 98.9%.

[0410] Next, the resin molding die was opened, and the in-mold coating composition No. 1 was injected between the obtained flat-plate "Makroblend UT235M" molded product and the coating film coating mold. The inside of the coating film coating mold was heated to 80°C, and pressurized at a molding pressure of 5 MPa while maintaining the temperature for 1 minute. After that, the pressure was reduced, and the coating film coating mold was opened. Thus, an in-mold coated molded product (M2-1) was produced in which a coating with a cured film thickness of 200 μm was applied to the flat-plate "Makroblend UT235M" molded product.

[0411] Examples 2 to 59, Comparative Examples 1 to 26

[0412] In-mold molded articles (M1-2) to (M1-85) and (M2-2) to (M2-85) were produced in the same manner as in Example 1 except that the compounding compositions were as shown in Table 4 below.

[0413] <Evaluation of in-mold coating molded products>

[0414] The cured coating films of the obtained in-mold coating molded products were evaluated for color unevenness, hardness, and adhesion. The evaluation results are shown in Table 4.

[0415] (Uneven color)

[0416] The surfaces of the in-mold coated molded articles obtained in Examples 1 to 59 and Comparative Examples 1 to 26 were visually observed, and the degree of color unevenness was evaluated based on the following criteria: ◎ and ○ were considered acceptable.

[0417] ◎: Almost no color unevenness was observed.

[0418] ○: Color unevenness was slightly observed.

[0419] Δ: Color unevenness was observed.

[0420] ×: Color unevenness was clearly observed.

[0421] (hardness)

[0422] The Martens hardness (N / mm) of the cured coating film of each in-mold coating molded product obtained in Examples 1 to 59 and Comparative Examples 1 to 26 was measured using "Fischerscope (registered trademark) HM2000S" (trade name, manufactured by Fischer Instruments Co., Ltd.). 2 ) and evaluated based on the following criteria. The measurement conditions were: indenter: quadrangular pyramid Vickers indenter (material: diamond, opposite angle: 136°), maximum test load: 20 mN, indentation speed: 20 mN / 25 seconds, temperature: 21±2°C, humidity: 50±5% relative humidity. ◎ and ○ indicate passing.

[0423] ◎: Martens hardness is 110N / mm 2 above,

[0424] ○: Martens hardness is 100N / mm 2 Above and less than 110N / mm 2 ,

[0425] Δ: Martens hardness is 75N / mm 2 Above and less than 100N / mm 2 ,

[0426] ×: Martens hardness less than 75N / mm 2 .

[0427] (Adhesion)

[0428] The coating films of each in-mold-coated article obtained in Examples 1-59 and Comparative Examples 1-26 were cut in a grid pattern using a cutter, reaching the substrate to create 100 2 mm x 2 mm checkered patterns. An adhesive cellophane tape was then applied to the surface of each in-mold-coated article. The tape was then rapidly peeled off at a temperature of 23 ± 2°C and a relative humidity of 50 ± 5%. The remaining state of the checkered pattern coating after peeling was observed, and the adhesion was evaluated based on the following criteria. A score of ◎ or ○ indicated acceptable.

[0429] ◎: 100 checkered patterns of coating remain, and no small edge defects or lifting of the coating occur at the cutter's cutting edge.

[0430] ○: 100 checkered patterns of the coating film remained, and small edge defects and lifting of the coating film occurred at the cutting edge of the cutter.

[0431] Δ: 90 to 99 checkerboard coatings remain.

[0432] ×: The number of remaining checkered coating films was 89 or less.

[0433] [Table 9]

[0434] Table 4

[0435]

[0436] [Table 10]

[0437] Table 4 (Continued-1)

[0438]

[0439] [Table 11]

[0440] Table 4 (Continued-2)

[0441]

[0442] [Table 12]

[0443] Table 4 (Continued-3)

[0444]

[0445] [Table 13]

[0446] Table 4 (Continued-4)

[0447]

[0448] [Table 14]

[0449] Table 4 (Continued-5)

[0450]

[0451] [Table 15]

[0452] Table 4 (Continued-6)

[0453]

[0454] [Table 16]

[0455] Table 4 (Continued-7)

[0456]

Claims

1. A kit for a three-component coating composition, comprising: A main agent (A) containing a compound (a1) containing an isocyanate-reactive group, A curing agent (B) containing a polyisocyanate compound (b1), and A pigment paste (C) containing an isocyanate-reactive group-containing compound (c1) and a pigment (c2), The main agent (A) is at a shear rate of 100 sec -1 、Viscosity at 65℃(V A ) is in the range of 20 to 1800 mPa·s, The curing agent (B) is heated at a shear rate of 100 sec -1 、Viscosity at 65℃ (V B ) is in the range of 20 to 1800 mPa·s, The pigment slurry (C) is heated at a shear rate of 100 sec -1 、Viscosity at 65℃(V C ) is in the range of 20 to 1800 mPa·s.

2. The set according to claim 1, wherein: The three-component coating composition formed from the kit has a solid content concentration of 95% by mass or more.

3. The set according to claim 1 or 2, wherein: The solid content concentration of the pigment slurry (C) is within a range of 85 to 98% by mass.

4. The set according to any one of claims 1 to 3, wherein: The isocyanate-reactive group-containing compound (c1) includes an isocyanate-reactive group-containing compound having a number average molecular weight within a range of 250 to 2,500.

5. The set according to any one of claims 1 to 4, wherein: The content of the pigment (c2) is within a range of 1.0 to 65% by mass based on the total amount of the pigment slurry (C).

6. The set according to any one of claims 1 to 5, wherein: The (V A ), said (V B ) and (V C ) satisfies the following formulas (1) and (2): 0.4≤(V B ) / (V A )≤2.5 Formula (1) 0.3≤(V C ) / (V A )≤3.0Formula (2).

7. A three-liquid coating composition comprising: A main agent (A) containing a compound (a1) containing an isocyanate-reactive group, A curing agent (B) containing a polyisocyanate compound (b1), and A pigment paste (C) containing an isocyanate-reactive group-containing compound (c1) and a pigment (c2), The main agent (A) is at a shear rate of 100 sec -1 、Viscosity at 65℃ (V A ) is in the range of 20 to 1800 mPa·s, The curing agent (B) is heated at a shear rate of 100 sec -1 、Viscosity at 65℃ (V B ) is in the range of 20 to 1800 mPa·s, The pigment slurry (C) is heated at a shear rate of 100 sec -1 、Viscosity at 65℃ (V C ) is in the range of 20 to 1800 mPa·s.

8. An in-mold coating method comprising: The process of injecting an in-mold coating composition between the molded substrate and the inner wall of the mold, curing the in-mold coating composition, and then removing the coated molded object from the mold. The in-mold coating composition is a three-component coating composition formed from the kit according to any one of claims 1 to 6 or the three-component coating composition according to claim 7.

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