Thermosetting resin composition, cured product, and laminate

Abstract

This thermosetting resin composition contains a hydroxyl group-containing component and an isocyanate group-containing component. The hydroxyl group-containing component contains (A) a phosphoric acid-modified epoxy polyol and (B) a hydroxyl group-containing resin other than the phosphoric acid-modified epoxy polyol. The isocyanate group-containing component contains (C) polyisocyanate. The phosphoric acid-modified epoxy polyol (A) contains a reaction product of (a1) an epoxy compound having two or more glycidyl groups in one molecule and (a2) a phosphoric acid compound having one or more P-OH bonds in one molecule. The glass transition temperature of the hydroxyl group-containing resin (B) is 45-100°C.

Description

Thermosetting resin compositions, cured products, and laminates

[0001] The present invention relates to thermosetting resin compositions, cured products, and laminates.

[0002] Thermosetting resin compositions containing hydroxyl group-containing resins and curing agents are used in the fields of automotive and home appliance coatings. These thermosetting resin compositions are, for example, applied to a metal substrate, thermosetting, and curing to form a cured product.

[0003] As a thermosetting resin composition, for example, the following electrodeposition coating composition has been proposed. More specifically, the electrodeposition coating composition contains (A) an acrylic resin, (B) an epoxy polyol, (C) a blocked hexamethylene diisocyanate and / or a blocked isophorone diisocyanate, (D) a solvent with a boiling point of 150 to 250°C, and (E) bismuth silicate. The softening point of (A) the acrylic resin is -20 to 60°C, the amino group content of (A) the acrylic resin is 0.4 to 1.0 moles per kg of resin solids, and the hydroxyl group content of (A) the acrylic resin is 0.5 to 3.0 moles per kg of resin solids (see, for example, Patent Document 1).

[0004] Japanese Patent Publication No. 2006-028434

[0005] On the other hand, depending on the application, cured products of thermosetting resin compositions may require both adhesion to metal substrates (hereinafter referred to as "metal adhesion") and transparency.

[0006] The present invention provides a thermosetting resin composition, a cured product, and a laminate that can produce a cured product with relatively good metal adhesion and transparency.

[0007] The present invention [1] comprises a thermosetting resin composition comprising a hydroxyl group-containing component and an isocyanate group-containing component, wherein the hydroxyl group-containing component comprises (A) a phosphoric acid-modified epoxy polyol and (B) a hydroxyl group-containing resin other than the phosphoric acid-modified epoxy polyol, the isocyanate group-containing component comprises (C) a polyisocyanate, (A) the phosphoric acid-modified epoxy polyol comprises a reaction product of (a1) an epoxy compound having two or more glycidyl groups in one molecule and (a2) a phosphoric acid compound having one or more P-OH bonds in one molecule, and (B) the glass transition temperature of the hydroxyl group-containing resin is 45°C or higher and 100°C or lower.

[0008] The present invention [2] comprises (B) the thermosetting resin composition described in [1] above, wherein the hydroxyl group-containing resin contains a hydroxyl group-containing acrylic resin and / or a hydroxyl group-containing polyester resin.

[0009] The present invention [3] includes (B) the thermosetting resin composition described in [1] or [2] above, wherein the hydroxyl value of the hydroxyl group-containing resin is 40 mg KOH / g or more and 110 mg KOH / g or less.

[0010] The present invention [4] includes a thermosetting resin composition according to any one of the above [1] to [3], wherein (B) the glass transition temperature of the hydroxyl group-containing resin is 70°C or more and 100°C or less, and (B) the hydroxyl value of the hydroxyl group-containing resin is 70 mg KOH / g or more and 110 mg KOH / g or less.

[0011] The present invention [5] includes a thermosetting resin composition according to any one of the above [1] to [4], wherein (A) the content of the phosphoric acid-modified epoxy polyol is (B) 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the hydroxyl group-containing resin.

[0012] The present invention [6] includes (a1) a thermosetting resin composition according to any one of the above [1] to [5], wherein the number average molecular weight of the epoxy compound is 100 or more and 1400 or less.

[0013] The present invention [7] includes (a1) a thermosetting resin composition according to any one of the above [1] to [6], wherein the epoxy equivalent of the epoxy compound is 150 g / eq or more and 800 g / eq or less.

[0014] The present invention [8] includes a cured product containing a reaction product of a thermosetting resin composition described in any one of the above items [1] to [7].

[0015] The present invention [9] includes a laminate comprising a substrate and a cured film in contact with at least one part of the substrate, wherein the cured film contains the cured product described in [8] above.

[0016] The present invention

[10] includes the laminate described in [9] above, wherein the base material is made of a metal base material, and the metal base material contains at least one selected from the group consisting of aluminum, aluminum alloys, and stainless steel.

[0017] The thermosetting resin composition of the present invention contains a hydroxyl group-containing component and an isocyanate group-containing component. The hydroxyl group-containing component contains (A) a phosphate-modified epoxy polyol and (B) a hydroxyl group-containing resin other than the phosphate-modified epoxy polyol. The isocyanate group-containing component contains (C) a polyisocyanate. In the above thermosetting resin composition, (A) the phosphate-modified epoxy polyol contains a reaction product of (a1) an epoxy compound having two or more glycidyl groups in one molecule and (a2) a phosphate compound having one or more P-OH bonds in one molecule. Furthermore, in the above thermosetting resin composition, the glass transition temperature of (B) the hydroxyl group-containing resin is within the above predetermined range.

[0018] Therefore, according to the above thermosetting resin composition, a cured product can be obtained that possesses relatively good metal adhesion and transparency.

[0019] The cured product of the present invention contains the reaction product of the above-mentioned thermosetting resin composition. Therefore, the cured product possesses relatively good metal adhesion and transparency.

[0020] The laminate of the present invention comprises a substrate and a cured film in contact with the substrate, wherein the cured film contains the above-mentioned cured product. Therefore, the laminate has excellent adhesion between the substrate and the cured film.

[0021] 1. Thermosetting resin composition The thermosetting resin composition contains a hydroxyl group-containing component and an isocyanate group-containing component as essential components.

[0022] 1) Hydroxyl group-containing component The hydroxyl group-containing component is a component containing a hydroxyl group (OH). The hydroxyl group-containing component contains (A) a phosphoric acid-modified epoxy polyol and (B) a hydroxyl group-containing resin other than the above-mentioned phosphoric acid-modified epoxy polyol (hereinafter sometimes referred to as "other hydroxyl group-containing resin"). Preferably, the hydroxyl group-containing component consists of (A) a phosphoric acid-modified epoxy polyol and (B) other hydroxyl group-containing resin.

[0023] [(A) Phosphate-Modified Epoxy Polyol] (A) Phosphate-Modified epoxy polyol contains a reaction product of (a1) an epoxy compound having two or more glycidyl groups in one molecule (hereinafter referred to as epoxy compound) and (a2) a phosphoric acid compound having one or more P-OH bonds in one molecule (hereinafter referred to as phosphoric acid compound), and preferably consists of a reaction product of (a1) an epoxy compound and (a2) a phosphoric acid compound.

[0024] [(a1) Epoxy Compounds] As described above, (a1) epoxy compounds have two or more glycidyl groups in one molecule. The number of glycidyl groups contained in one molecule of epoxy compound is, for example, 2 to 6, preferably 2 to 4, more preferably 2 to 3, and particularly preferably 2.

[0025] (a1) More specifically, epoxy compounds include glycidyl ether type epoxy compounds, glycidylamine type epoxy compounds, glycidyl ester type epoxy compounds, and alicyclic type epoxy compounds. Examples of glycidyl ether type epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, bisphenol AD ​​type epoxy compounds, cresol novolac type epoxy compounds, phenol novolac type epoxy compounds, α-naphthol novolac type epoxy compounds, bisphenol A type novolac type epoxy compounds, dicyclopentadiene type epoxy compounds, tetrabrombisphenol A type epoxy compounds, brominated phenol novolac type epoxy compounds, tris(glycidyloxyphenyl)methane, and tetrakis(glycidyloxyphenyl)ethane. Examples of glycidylamine type epoxy compounds include tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmetaaminophenol, and tetraglycidylmetaxylylenediamine. Examples of glycidyl ester-type epoxy compounds include diglycidyl phthalate, diglycidyl hexahydrophthalate, and diglycidyl tetrahydrophthalate. Examples of alicyclic epoxy compounds include epoxycyclohexylmethyl-epoxycyclohexanecarboxylate and bis(epoxycyclohexyl)adipate. These can be used alone or in combination of two or more. Preferably, glycidyl ether-type epoxy compounds are used, and more preferably, bisphenol A-type epoxy compounds are used.

[0026] (a1) The epoxy compound may be dissolved and / or dispersed in a solvent, for example. That is, the epoxy compound (a1) may be a solution and / or dispersion. Examples of solvents include the solvent (E) described later.

[0027] (a1) In a solution and / or dispersion of the epoxy compound, the solid content concentration is, for example, 10 to 70% by mass, preferably 30 to 50% by mass.

[0028] (a1) The number-average molecular weight of the epoxy compound is, for example, 100 or more, preferably 300 or more, and more preferably 500 or more, from the viewpoint of transparency and metal adhesion. Also, (a1) the number-average molecular weight of the epoxy compound is, for example, 1400 or less, preferably 1200 or less, and more preferably 1000 or less, from the viewpoint of transparency and metal adhesion. That is, (a1) the number-average molecular weight of the epoxy compound is, for example, 100 to 1400, preferably 300 to 1200, and more preferably 500 to 1000, from the viewpoint of transparency and metal adhesion. The number-average molecular weight is the standard polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC).

[0029] (a1) The epoxy equivalent of the epoxy compound is, for example, 150 g / eq or more, preferably 300 g / eq or more, from the viewpoint of transparency and metal adhesion. Also, the epoxy equivalent of the epoxy compound (a1) is, for example, 800 g / eq or less, preferably 600 g / eq or less, from the viewpoint of transparency and metal adhesion. That is, the epoxy equivalent of the epoxy compound (a1) is, for example, 150 g / eq or more and 800 g / eq or less, preferably 300 g / eq or more and 600 g / eq or less. The epoxy equivalent is calculated from the molecular structure and molecular weight.

[0030] (a1) The softening point of the epoxy compound is, for example, 0°C or higher, preferably 20°C or higher, from the viewpoint of transparency and metal adhesion. Also, from the viewpoint of transparency and metal adhesion, the softening point of the epoxy compound (a1) is, for example, 120°C or lower, preferably 100°C or lower. That is, from the viewpoint of transparency and metal adhesion, the softening point of the epoxy compound (a1) is, for example, 0°C or higher and 120°C or lower, preferably 20°C or higher and 100°C or lower. The softening point is measured by a known ring-and-sphere method.

[0031] (a1) The epoxy compound can be obtained as a commercially available product. Examples of commercially available products include jER1001 (bisphenol A type epoxy compound, number average molecular weight of about 900, epoxy equivalent of 400 to 500 g / eq, softening point of 64 °C, manufactured by Mitsubishi Chemical), jER828 (bisphenol A type epoxy compound, number average molecular weight of about 370, epoxy equivalent of 184 to 194 g / eq, manufactured by Mitsubishi Chemical), and jER1003 (bisphenol A type epoxy compound, number average molecular weight of about 1300, epoxy equivalent of 670 to 770 g / eq, softening point of 89 °C, manufactured by Mitsubishi Chemical).

[0032] [(a2) Phosphoric acid compound] As described above, the (a2) phosphoric acid compound has one or more P-OH bonds in one molecule. The number of P-OH bonds contained in one molecule of the phosphoric acid compound is, for example, 1 or more and 10 or less, preferably 2 or more and 6 or less, more preferably 3 or more and 4 or less, and particularly preferably 3.

[0033] More specifically, examples of the (a2) phosphoric acid compound include phosphoric acid, phosphates, and phosphoric esters. Examples of phosphoric acid include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid, and phosphonic acid. Examples of phosphates include inorganic salts of the above phosphoric acids. Examples of inorganic salts include potassium salts, sodium salts, lithium salts, calcium salts, zinc salts, aluminum salts, tin salts, and barium salts. Examples of phosphoric esters include monobutyl phosphate, monoamyl phosphate, monononyl phosphate, monocetyl phosphate, monophenyl phosphate, and monobenzyl phosphate. In addition, examples of the phosphoric acid compound include hydrates and polycondensates of the above phosphoric acids. These can be used alone or in combination of two or more. Preferably, phosphoric acid is mentioned, and more preferably, orthophosphoric acid is mentioned.

[0034] The (a2) phosphoric acid compound may be dissolved and / or dispersed in a solvent, for example. That is, the (a2) phosphoric acid compound may be a solution and / or a dispersion. Examples of the solvent include the (E) solvent described later.

[0035] In the solution and / or dispersion of the phosphoric acid compound, the solid content concentration is, for example, 10 to 70% by mass, preferably 30 to 50% by mass.

[0036] [Method for producing (A) phosphoric acid-modified epoxy polyol] (A) Phosphoric acid-modified epoxy polyol is produced by reacting (a1) an epoxy compound with (a2) a phosphoric acid compound.

[0037] The method for reacting (a1) an epoxy compound with (a2) a phosphoric acid compound is not particularly limited. For example, (a1) an epoxy compound and (a2) a phosphoric acid compound are blended at a predetermined ratio, and these are heated and mixed.

[0038] The blending ratio of (a1) an epoxy compound and (a2) a phosphoric acid compound is adjusted, for example, based on the equivalent ratio of the hydroxyl group of (a2) the phosphoric acid compound to the glycidyl group of (a1) the epoxy compound (hydroxyl group / glycidyl group). For example, the equivalent ratio of the hydroxyl group of (a2) the phosphoric acid compound to the glycidyl group of (a1) the epoxy compound (hydroxyl group / glycidyl group) is, for example, 0.1 to 3.0, preferably 0.3 to 2.7.

[0039] Also, industrially, the blending ratio of (a1) an epoxy compound and (a2) a phosphoric acid compound can be adjusted on a mass basis. For example, with respect to 100 parts by mass of (a1) an epoxy compound, the blending amount of (a2) the phosphoric acid compound (based on solid content) is, for example, 0.1 to 100 parts by mass, preferably 1 to 10 parts by mass.

[0040] Also, in the reaction of (a1) an epoxy compound and (a2) a phosphoric acid compound, a solvent can be blended as necessary. Examples of the solvent include (E) the solvent described later. The blending amount and blending timing of the solvent are appropriately set according to the purpose and application.

[0041] The reaction conditions of (a1) an epoxy compound and (a2) a phosphoric acid compound are not particularly limited. For example, the reaction temperature is 25°C or higher and 150°C or lower, preferably 50°C or higher and 100°C or lower. The reaction time is, for example, 1 hour or longer and 12 hours or shorter, preferably 2 hours or longer and 6 hours or shorter.

[0042] Through the above reaction, the glycidyl group of the epoxy compound (a1) is opened by the phosphoric acid compound (a2), generating a hydroxyl group, and a phosphoric acid-modified epoxy polyol (A) is obtained.

[0043] In other words, (A) phosphoric acid-modified epoxy polyol is an epoxy polyol obtained by ring-opening the glycidyl group of (a1) epoxy compound with (a2) phosphoric acid compound.

[0044] (A) The phosphoric acid-modified epoxy polyol may be dissolved and / or dispersed in a solvent, for example. That is, (A) the phosphoric acid-modified epoxy polyol may be a solution and / or dispersion. Examples of solvents include the solvent (E) described later.

[0045] (A) In a solution and / or dispersion of a phosphoric acid-modified epoxy polyol, the solid content concentration is, for example, 30 to 90% by mass, preferably 50 to 80% by mass.

[0046] [(A) Physical properties of phosphoric acid-modified epoxy polyol] The number average molecular weight of (A) phosphoric acid-modified epoxy polyol is, for example, 300 or more, preferably 500 or more, and more preferably 700 or more, from the viewpoint of transparency and metal adhesion. Also, the number average molecular weight of (A) phosphoric acid-modified epoxy polyol is, for example, 1600 or less, preferably 1400 or less, and more preferably 1200 or less. That is, the number average molecular weight of (A) phosphoric acid-modified epoxy polyol is, for example, 300 or more and 1600 or less, preferably 500 or more and 1500 or less, and more preferably 700 or more and 1200 or less, from the viewpoint of transparency and metal adhesion. The number average molecular weight is the molecular weight on a standard polystyrene basis measured by gel permeation chromatography.

[0047] (A) The acid value of the phosphoric acid-modified epoxy polyol is, for example, 10 mg KOH / g or more, preferably 20 mg KOH / g or more, from the viewpoint of transparency and metal adhesion. Also, (A) the acid value of the phosphoric acid-modified epoxy polyol is, for example, 100 mg KOH / g or less, preferably 80 mg KOH / g or less, from the viewpoint of transparency and metal adhesion. That is, (A) the acid value of the phosphoric acid-modified epoxy polyol is, for example, 10 mg KOH / g or more and 100 mg KOH / g or less, preferably 20 mg KOH / g or more and 80 mg KOH / g or less. The acid value is measured in accordance with JIS K 1557-5 (2007).

[0048] [(B) Other hydroxyl group-containing resins] (B) Other hydroxyl group-containing resins are resins having two or more hydroxyl groups in one molecule. That is, (B) Other hydroxyl group-containing resins are polyols other than the above (A) phosphoric acid-modified epoxy polyols.

[0049] (B) More specifically, other hydroxyl group-containing resins include, for example, hydroxyl group-containing acrylic resins, hydroxyl group-containing polyester resins, hydroxyl group-containing polyether resins, hydroxyl group-containing polycarbonate resins, and hydroxyl group-containing polyurethane resins. These can be used individually or in combination of two or more types.

[0050] From the viewpoint of balancing transparency, metal adhesion, water resistance, and mechanical properties (particularly hardness), (B) other hydroxyl group-containing resins preferably include hydroxyl group-containing acrylic resins and hydroxyl group-containing polyester resins.

[0051] That is, (B) other hydroxyl group-containing resin preferably contains a hydroxyl group-containing acrylic resin and / or a hydroxyl group-containing polyester resin, and more preferably consists of a hydroxyl group-containing acrylic resin and / or a hydroxyl group-containing polyester resin. Even more preferably, (B) other hydroxyl group-containing resin consists of a hydroxyl group-containing acrylic resin or a hydroxyl group-containing polyester resin.

[0052] [Hydroxygroup-containing acrylic resin] Hydroxylgroup-containing acrylic resin is a copolymer obtained by polymerizing a polymerization component that includes, for example, an alkyl (meth)acrylate and a hydroxygroup-containing acrylic monomer.

[0053] Examples of alkyl (meth)acrylate esters include alkyl (meth)acrylate esters having an alkyl moiety with 1 to 12 carbon atoms. Examples of alkyl (meth)acrylate esters having an alkyl moiety with 1 to 12 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate. (Meth)acrylic acid means methacrylic acid and / or acrylic acid. Alkyl (meth)acrylate esters can be used alone or in combination of two or more types.

[0054] Examples of hydroxyl group-containing acrylic monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. Hydroxyl group-containing acrylic monomers can be used individually or in combination of two or more types.

[0055] Furthermore, the polymerization components may, if necessary, include alkyl (meth)acrylates and copolymerizable vinyl monomers that can copolymerize with hydroxyl group-containing acrylic monomers.

[0056] Examples of copolymerizable vinyl monomers include carboxyl group-containing vinyl monomers, amino group-containing vinyl monomers, glycidyl group-containing vinyl monomers, cyano group-containing vinyl monomers, sulfonic acid group-containing vinyl monomers and their salts, acetoacetoxy group-containing vinyl monomers, phosphate group-containing compounds, amide group-containing vinyl monomers, aromatic vinyl monomers, N-substituted unsaturated carboxylic acid amides, heterocyclic vinyl compounds, vinylidene halogens, α-olefins, and dienes.

[0057] Examples of carboxyl group-containing vinyl monomers include (meth)acrylic acid, maleic anhydride, maleic acid, fumaric acid, itaconic acid, and crotonic acid. Examples of amino group-containing vinyl monomers include 2-aminoethyl (meth)acrylate, 2-(N-methylamino)ethyl (meth)acrylate, and 2-(N,N-dimethylamino)ethyl (meth)acrylate. Examples of glycidyl group-containing vinyl monomers include glycidyl (meth)acrylate. Examples of cyano group-containing vinyl monomers include (meth)acrylonitrile. Examples of sulfonic acid group-containing vinyl monomers include allylsulfonic acid and methallylsulfonic acid. Examples of salts thereof include alkali metal salts (e.g., sodium salts and potassium salts) and ammonium salts of the above sulfonic acid group-containing vinyl monomers. Specifically, examples include sodium allylsulfonate, sodium methallylsulfonate, and ammonium methallylsulfonate. Examples of acetoacetoxy group-containing vinyl monomers include acetoacetoxyethyl (meth)acrylate. Examples of phosphate group-containing compounds include 2-methchloroyloxyethyl acid phosphate. Examples of amide group-containing vinyl monomers include (meth)acrylamide. Examples of aromatic vinyl monomers include styrene, α-methylstyrene, and divinylbenzene. Examples of N-substituted unsaturated carboxylic acid amides include N-methylol(meth)acrylamide. Examples of heterocyclic vinyl compounds include vinylpyrrolidone. Examples of vinylidene halogenated compounds include vinylidene chloride and vinylidene fluoride. Examples of α-olefins include ethylene and propylene. Examples of dienes include butadiene. Copolymerizable vinyl monomers can be used alone or in combination of two or more types.

[0058] The hydroxyl group-containing acrylic resin is obtained by polymerizing (copolymerizing) a polymerization component comprising an alkyl (meth)acrylate, a hydroxyl group-containing acrylic monomer, and a copolymerizable vinyl monomer as needed. The polymerization method is not particularly limited, and known polymerization methods can be employed. Preferably, the polymerization method involves radical polymerization of the polymerization component in a solvent. Examples of solvents include solvent (E) described later.

[0059] More specifically, in this method, the polymerization component and a polymerization initiator are mixed in a solvent, and the polymerization component is polymerized in the solvent. As a result, a hydroxyl group-containing acrylic resin and a solution thereof are obtained. The hydroxyl group-containing acrylic resin is an acrylic polyol.

[0060] The solid content concentration of the hydroxyl group-containing acrylic resin solution is, for example, 10 to 90% by mass, preferably 30 to 70% by mass.

[0061] [Hydroxygroup-containing polyester resins] Examples of hydroxygroup-containing polyester resins include polycondensates of polyhydric alcohols and polybasic acids.

[0062] A polyhydric alcohol is a compound having two or more hydroxyl groups and a number-average molecular weight of 40 or more and less than 400, preferably 300 or less. Dihydric alcohols are preferred as polyhydric alcohols.

[0063] Examples of dihydric alcohols include aliphatic diols, alicyclic diols, and aromatic diols. Examples of aliphatic diols include alkanediols and ether diols. Examples of alkanediols include ethylene glycol, propylene glycol (1,2- or 1,3-propanediol or mixtures thereof), butylene glycol (1,2- or 1,3- or 1,4-butylene glycol or mixtures thereof), 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, and 3,3-dimethylolheptane. Examples of ether diols include diethylene glycol, triethylene glycol, and dipropylene glycol. Examples of alicyclic diols include cyclohexanediol (1,2-, 1,3-, or 1,4-cyclohexanediol or mixtures thereof), cyclohexanedimethanol (1,2-, 1,3-, or 1,4-cyclohexanedimethanol or mixtures thereof), cyclohexanediethanol (1,2-, 1,3-, or 1,4-cyclohexanediethanol or mixtures thereof), and hydrogenated bisphenol A. Examples of aromatic diols include bisphenol A, ethylene oxide adducts of bisphenol A, and propylene oxide adducts of bisphenol A. Polyhydric alcohols can be used alone or in combination of two or more types.

[0064] Examples of polybasic acids include aromatic dibasic acids, alicyclic dibasic acids, and aliphatic dibasic acids. Examples of aromatic dibasic acids include phthalic acids (orthophthalic acid, isophthalic acid, terephthalic acid) and trimellitic acid. Examples of alicyclic dibasic acids include hetic acid and 1,2-hexahydrophthalic acid. Examples of aliphatic dibasic acids include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, hexylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylsuccinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Polybasic acids can be used alone or in combination of two or more types.

[0065] Furthermore, hydroxyl group-containing polyester resins are obtained by reacting a polybasic acid and a polyhydric alcohol (polycondensation reaction) using known methods. In such reactions, the polybasic acid and polyhydric alcohol are blended such that there is an excess of hydroxyl groups in the polyhydric alcohol relative to the carboxyl groups of the polybasic acid. As a result, a hydroxyl group-containing polyester resin having hydroxyl groups at the molecular ends is obtained. Hydroxyl group-containing polyester resins are polyester polyols.

[0066] (B) Other hydroxyl group-containing resins can be used alone or in combination of two or more types.

[0067] From the viewpoint of transparency, metal adhesion, and mechanical properties (particularly hardness), hydroxyl group-containing acrylic resins are preferred. Furthermore, from the viewpoint of metal adhesion and water resistance, hydroxyl group-containing polyester resins are preferred.

[0068] [(B) Physical properties of other hydroxyl group-containing resins] The glass transition temperature of (B) other hydroxyl group-containing resins is 45°C or higher from the viewpoint of transparency and metal adhesion. Also, the glass transition temperature of (B) other hydroxyl group-containing resins is 100°C or lower from the viewpoint of transparency and metal adhesion. In other words, the glass transition temperature of (B) other hydroxyl group-containing resins is 45°C or higher and 100°C or lower.

[0069] Furthermore, from the viewpoint of water resistance, the glass transition temperature of (B) other hydroxyl group-containing resins is preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 70°C or higher. Also, from the viewpoint of transparency, metal adhesion and water resistance, the glass transition temperature of (B) other hydroxyl group-containing resins is preferably 95°C or lower, more preferably 90°C or lower, and even more preferably 80°C or lower. That is, from the viewpoint of transparency, metal adhesion and water resistance, the glass transition temperature of (B) other hydroxyl group-containing resins is preferably 50°C or higher and 100°C or lower, more preferably 60°C or higher and 100°C or lower, more preferably 70°C or higher and 100°C or lower, even more preferably 70°C or higher and 95°C or lower, even more preferably 70°C or higher and 90°C or lower, and particularly preferably 70°C or higher and 80°C or lower. The glass transition temperature can be measured by differential scanning thermal analysis (DSC). Furthermore, if (B) the other hydroxyl group-containing resin is a hydroxyl group-containing acrylic resin, the glass transition temperature can be calculated using the FOX formula.

[0070] Furthermore, when two or more types of (B) other hydroxyl group-containing resins are used in combination, the overall glass transition temperature of the (B) other hydroxyl group-containing resins is within the above range. In such cases, the individual glass transition temperatures of each (B) other hydroxyl group-containing resin may be within the above range, below the lower limit, or above the upper limit.

[0071] Furthermore, when two or more types of (B) other hydroxyl group-containing resins are used in combination, the overall glass transition temperature of the (B) other hydroxyl group-containing resins can be calculated by a known method as the mass-based weighted average of the glass transition temperatures of each (B) other hydroxyl group-containing resin.

[0072] From the viewpoint of water resistance, the hydroxyl value of (B) other hydroxyl group-containing resins is, for example, 40 mg KOH / g or more, preferably 50 mg KOH / g or more, more preferably 60 mg KOH / g or more, and even more preferably 70 mg KOH / g or more. Furthermore, from the viewpoint of transparency and metal adhesion, the hydroxyl value of (B) other hydroxyl group-containing resins is, for example, 110 mg KOH / g or less, preferably 100 mg KOH / g or less, more preferably 95 mg KOH / g or less, and even more preferably 90 mg KOH / g or less. That is, (B) the hydroxyl value of other hydroxyl group-containing resins is, for example, 40 mg KOH / g or more and 110 mg KOH / g or less, preferably 50 mg KOH / g or more and 110 mg KOH / g or less, more preferably 60 mg KOH / g or more and 110 mg KOH / g or less, even more preferably 70 mg KOH / g or more and 110 mg KOH / g or less, even more preferably 70 mg KOH / g or more and 100 mg KOH / g or less, even more preferably 70 mg KOH / g or more and 95 mg KOH / g or less, and particularly preferably 70 mg KOH / g or more and 90 mg KOH / g or less. The hydroxyl value can be measured based on JIS K 0070-1992 (acetylation method).

[0073] Furthermore, when two or more types of (B) other hydroxyl group-containing resins are used in combination, the total hydroxyl value of the (B) other hydroxyl group-containing resins is, for example, within the range described above. In such cases, the hydroxyl value of each (B) other hydroxyl group-containing resin may be within the range described above, below the lower limit, or above the upper limit.

[0074] Furthermore, when two or more types of (B) other hydroxyl group-containing resins are used in combination, the total hydroxyl value of the (B) other hydroxyl group-containing resins can be calculated by a known method as the weighted average value of the hydroxyl values ​​of each (B) other hydroxyl group-containing resin based on mass.

[0075] (B) The weight-average molecular weight of the other hydroxyl group-containing resins is, for example, 10,000 or more, preferably 15,000 or more, more preferably 20,000 or more, even more preferably 25,000 or more, and particularly preferably 30,000 or more. (B) The weight-average molecular weight of the other hydroxyl group-containing resins is, for example, 200,000 or less, preferably 150,000 or less, more preferably 100,000 or less, even more preferably 80,000 or less, and particularly preferably 50,000 or less. That is, (B) the weight-average molecular weight of the other hydroxyl group-containing resin is, for example, 10,000 to 200,000, preferably 15,000 to 150,000, more preferably 20,000 to 100,000, even more preferably 25,000 to 80,000, and particularly preferably 30,000 to 50,000. (B) The weight-average molecular weight of the other hydroxyl group-containing resin is the standard polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC).

[0076] Furthermore, when two or more types of (B) other hydroxyl group-containing resins are used in combination, the overall weight-average molecular weight of the (B) other hydroxyl group-containing resins is, for example, within the range described above. In such cases, the weight-average molecular weight of each (B) other hydroxyl group-containing resin may be within the range described above, below the lower limit, or above the upper limit.

[0077] Furthermore, when two or more types of (B) other hydroxyl group-containing resins are used in combination, the overall weight-average molecular weight of the (B) other hydroxyl group-containing resins can be calculated by known methods as the mass-based weight-average value of the weight-average molecular weights of each (B) other hydroxyl group-containing resin.

[0078] (B) Other hydroxyl group-containing resins may be dissolved and / or dispersed in a solvent. That is, (B) other hydroxyl group-containing resins may be solutions and / or dispersions. Examples of solvents include the solvents described later in (E).

[0079] (B) In solutions and / or dispersions of other hydroxyl group-containing resins, the solid content concentration is, for example, 10 to 80% by mass, preferably 20 to 70% by mass.

[0080] [Content Ratio] In the hydroxyl group-containing components, the content ratio of (A) phosphoric acid-modified epoxy polyol and (B) other hydroxyl group-containing resins are set as appropriate according to the purpose and application.

[0081] For example, the content of (A) phosphoric acid-modified epoxy polyol and (B) other hydroxyl group-containing resins are adjusted within a range in which the desired transparency and metal adhesion can be obtained. Preferably, the content of (A) phosphoric acid-modified epoxy polyol and (B) other hydroxyl group-containing resins are adjusted from the viewpoint of balancing transparency, metal adhesion, water resistance and mechanical properties (particularly hardness).

[0082] For example, the content ratio (on a solid content basis) of (A) phosphate-modified epoxy polyol relative to the total amount of hydroxyl group-containing components (preferably the total amount of (A) phosphate-modified epoxy polyol and (B) other hydroxyl group-containing resins) is, for example, 0.1% by mass or more, preferably 0.3% by mass or more, and more preferably 0.5% by mass or more. Also, the content ratio (on a solid content basis) of (A) phosphate-modified epoxy polyol relative to the total amount of hydroxyl group-containing components (preferably the total amount of (A) phosphate-modified epoxy polyol and (B) other hydroxyl group-containing resins) is, for example, 15.0% by mass or less, preferably 10.0% by mass or less, and more preferably 5.0% by mass or less. In other words, the content ratio (based on solid content) of (A) phosphate-modified epoxy polyol to the total amount of hydroxyl group-containing components (preferably the total amount of (A) phosphate-modified epoxy polyol and (B) other hydroxyl group-containing resins) is, for example, 0.1% by mass or more and 15.0% by mass or less, preferably 0.3% by mass or more and 10.0% by mass or less, and more preferably 0.5% by mass or more and 5.0% by mass or less.

[0083] Furthermore, the content ratio of (B) other hydroxyl group-containing resins (on a solid content basis) relative to the total amount of hydroxyl group-containing components (preferably the total amount of (A) phosphate-modified epoxy polyol and (B) other hydroxyl group-containing resins) is, for example, 85.0% by mass or more, preferably 90.0% by mass or more, and more preferably 95.0% by mass or more. Furthermore, the content ratio of (B) other hydroxyl group-containing resins (on a solid content basis) relative to the total amount of hydroxyl group-containing components (preferably the total amount of (A) phosphate-modified epoxy polyol and (B) other hydroxyl group-containing resins) is, for example, 99.9% by mass or less, preferably 99.7% by mass or less, and more preferably 99.5% by mass or less. In other words, the content ratio (based on solid content) of (B) other hydroxyl group-containing resins relative to the total amount of hydroxyl group-containing components (preferably the total amount of (A) phosphate-modified epoxy polyol and (B) other hydroxyl group-containing resins) is, for example, 85.0% by mass or more and 99.9% by mass or less, preferably 90.0% by mass or more and 99.7% by mass or less, and more preferably 95.0% by mass or more and 99.5% by mass or less.

[0084] Furthermore, for example, the content ratio (based on solid content) of (A) phosphoric acid-modified epoxy polyol per 100 parts by mass of (B) other hydroxyl group-containing resin is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more. Also, the content ratio (based on solid content) of (A) phosphoric acid-modified epoxy polyol per 100 parts by mass of (B) other hydroxyl group-containing resin is, for example, 20 parts by mass or less, preferably 10 parts by mass or less, and more preferably 5 parts by mass or less. That is, the content ratio (based on solid content) of (A) phosphoric acid-modified epoxy polyol per 100 parts by mass of (B) other hydroxyl group-containing resin is, for example, 0.01 parts by mass or more and 20 parts by mass or less, preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.5 parts by mass or more and 5 parts by mass or less.

[0085] Furthermore, in the thermosetting resin composition, the content ratio of (A) phosphoric acid-modified epoxy polyol and (B) other hydroxyl group-containing resins are set appropriately according to the purpose and application.

[0086] For example, the content ratio (based on solid content) of (A) phosphate-modified epoxy polyol relative to the total amount of the thermosetting resin composition is, for example, 0.01% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. Alternatively, the content ratio (based on solid content) of (A) phosphate-modified epoxy polyol relative to the total amount of the thermosetting resin composition is, for example, 0.5% by mass or less, preferably 0.4% by mass or less, and more preferably 0.3% by mass or less. In other words, the content ratio (based on solid content) of (A) phosphate-modified epoxy polyol relative to the total amount of the thermosetting resin composition is, for example, 0.01% by mass or more and 0.5% by mass or less, preferably 0.05% by mass or more and 0.4% by mass or less, and more preferably 0.1% by mass or more and 0.3% by mass or less.

[0087] Furthermore, for example, the content ratio of (B) other hydroxyl group-containing resins (based on solid content) relative to the total amount of the thermosetting resin composition is, for example, 1.0% by mass or more, preferably 5.0% by mass or more, and more preferably 10.0% by mass or more. Also, the content ratio of (B) other hydroxyl group-containing resins (based on solid content) relative to the total amount of the thermosetting resin composition is, for example, 50.0% by mass or less, preferably 40.0% by mass or less, and more preferably 30.0% by mass or less. That is, the content ratio of (B) other hydroxyl group-containing resins (based on solid content) relative to the total amount of the thermosetting resin composition is, for example, 1.0% by mass or more and 50.0% by mass or less, preferably 5.0% by mass or more and 40.0% by mass or less, and more preferably 10.0% by mass or more and 30.0% by mass or less.

[0088] Furthermore, the content ratio (based on solid content) of the total amount of hydroxyl group-containing components (preferably the total amount of (A) phosphoric acid-modified epoxy polyol and (B) other hydroxyl group-containing resins) relative to the total amount of the thermosetting resin composition is, for example, 1.0% by mass or more, preferably 5.0% by mass or more, and more preferably 10.0% by mass or more. Also, the content ratio (based on solid content) of the total amount of hydroxyl group-containing components (preferably the total amount of (A) phosphoric acid-modified epoxy polyol and (B) other hydroxyl group-containing resins) relative to the total amount of the thermosetting resin composition is, for example, 50.0% by mass or less, preferably 40.0% by mass or less, and more preferably 30.0% by mass or less. In other words, the content ratio (based on solid content) of the total amount of hydroxyl group-containing components (preferably the total amount of (A) phosphoric acid-modified epoxy polyol and (B) other hydroxyl group-containing resins) relative to the total amount of the thermosetting resin composition is, for example, 1.0% by mass or more and 50.0% by mass or less, preferably 5.0% by mass or more and 40.0% by mass or less, and more preferably 10.0% by mass or more and 30.0% by mass or less.

[0089] 2) Isocyanate group-containing component The isocyanate group-containing component contains (C) polyisocyanate. Preferably, the isocyanate group-containing component consists of (C) polyisocyanate.

[0090] [(C) Polyisocyanate] (C) polyisocyanate has two or more isocyanate groups in one molecule. The number of isocyanate groups contained in one molecule of (C) polyisocyanate is, for example, 2 to 6, preferably 2 to 4, and more preferably 2 to 3.

[0091] (C) More specifically, polyisocyanates include, for example, polyisocyanate monomers and polyisocyanate derivatives.

[0092] Examples of polyisocyanate monomers include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates.

[0093] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 1,2-propane diisocyanate, 1,2-butane diisocyanate, 2,3-butane diisocyanate, 1,3-butane diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methyl caproate. These can be used individually or in combination of two or more.

[0094] Examples of alicyclic polyisocyanates include isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), and methylenebis(cyclohexyl isocyanate) (H １２ MDI), and bis(isocyanatomethyl)cyclohexane (H ６ Examples include XDI. These can be used individually or in combination of two or more types.

[0095] Examples of aromatic polyisocyanates include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), toluidine diisocyanate (TODI), paraphenylenedi diisocyanate, and naphthalene diisocyanate (NDI). These can be used individually or in combination of two or more types.

[0096] Examples of aromatic aliphatic polyisocyanates include xylylene diisocyanate (XDI) and tetramethyl xylylene diisocyanate (TMXDI). These can be used individually or in combination of two or more types.

[0097] These polyisocyanate monomers can be used individually or in combination of two or more types.

[0098] Examples of polyisocyanate derivatives include modified products obtained by modifying the above-mentioned polyisocyanate monomer by known methods. More specifically, examples of polyisocyanate derivatives include polymers, isocyanurate modified products, allophanate modified products, polyol modified products (e.g., trimethylolpropane adducts), biuret modified products, urea modified products, oxadiazinetrione modified products, and carbodiimide modified products. Polymethylene polyphenylene polyisocyanate is also an example of a polyisocyanate derivative.

[0099] These polyisocyanate derivatives can be used individually or in combination of two or more types.

[0100] Furthermore, in (C) polyisocyanate, the isocyanate group may be a free isocyanate group or may be blocked by a blocking agent. That is, the isocyanate group may be a free isocyanate group or a blocked isocyanate group.

[0101] Blocking agents are compounds having an active group (hereinafter referred to as a blocking group) that reacts with an isocyanate group. Examples of blocking agents include active methylene compounds, active methine compounds, imidazole compounds, imidazoline compounds, pyrimidine compounds, guanidine compounds, alcohol compounds, phenolic compounds, amine compounds, imine compounds, oxime compounds, carbamic acid compounds, urea compounds, acid amide compounds, lactam compounds, acid imide compounds, triazole compounds, pyrazole compounds, mercaptan compounds, and bisulfites. These can be used alone or in combination of two or more. Preferably, blocking agents include imidazole compounds, imidazoline compounds, oxime compounds, and pyrazole compounds.

[0102] The method for obtaining (C) polyisocyanate having blocked isocyanate groups is not particularly limited. For example, (C) polyisocyanate having blocked isocyanate groups can be produced by reacting (C) polyisocyanate having free isocyanate groups with the blocking agent. The method for reacting (C) polyisocyanate having free isocyanate groups with the blocking agent is not particularly limited and can be appropriately determined according to the purpose and application.

[0103] (C) Polyisocyanates can be used alone or in combination of two or more types.

[0104] From the viewpoint of balancing transparency, metal adhesion, water resistance, and mechanical properties (particularly hardness), (C) polyisocyanate is preferably aliphatic polyisocyanate and its derivatives, more preferably hexamethylene diisocyanate and its derivatives, and even more preferably isocyanurate derivatives of hexamethylene diisocyanate.

[0105] Furthermore, from the viewpoint of mechanical properties (particularly hardness), (C) polyisocyanate is preferably an aromatic aliphatic polyisocyanate and its derivatives, more preferably a xylylene diisocyanate and its derivatives, and even more preferably a polyol modified form of xylylene diisocyanate (for example, a trimethylolpropane adduct).

[0106] (C) Polyisocyanate may be dissolved and / or dispersed in a solvent, for example. That is, (C) polyisocyanate may be a solution and / or dispersion. Examples of solvents include known solvents that are inert to isocyanate groups. Examples of solvents include solvent (E) described later.

[0107] (C) In a solution and / or dispersion of polyisocyanate, the solid content concentration is, for example, 10 to 80% by mass, preferably 20 to 70% by mass.

[0108] [Physical Properties of (C) Polyisocyanate] The average number of functional groups (average number of isocyanate groups) of (C) polyisocyanate is, for example, 2 or more, preferably 2.5 or more. Also, the average number of functional groups (average number of isocyanate groups) of (C) polyisocyanate is, for example, 6 or less, preferably 4 or less. That is, the average number of functional groups (average number of isocyanate groups) of (C) polyisocyanate is, for example, 2 or more and 6 or less, preferably 2.5 or more and 4 or less. The average number of functional groups (average number of isocyanate groups) can be calculated by known methods based on the isocyanate group content (mass%) and molecular weight (the same applies hereinafter).

[0109] The isocyanate group content of (C) polyisocyanate is, for example, 15% by mass or more, preferably 18% by mass or more. Also, the isocyanate group content of (C) polyisocyanate is, for example, 30% by mass or less, preferably 25% by mass or less. The isocyanate group content of (C) polyisocyanate is, for example, 15% by mass or more and 30% by mass or less, preferably 18% by mass or more and 25% by mass or less. The isocyanate group content (by mass%) can be determined by method A or method B of JIS K 1603-1 (2007) (the same applies hereinafter).

[0110] [Content Ratio] In the isocyanate group-containing components, the content ratio of (C) polyisocyanate is set appropriately according to the purpose and application. For example, the content ratio of (C) polyisocyanate relative to the total amount of isocyanate group-containing components is, for example, 100% by mass.

[0111] Furthermore, in the thermosetting resin composition, the content ratio of (C) polyisocyanate is set appropriately according to the purpose and application.

[0112] For example, the content of (C) polyisocyanate is adjusted within a range where the desired transparency and metal adhesion are obtained. Preferably, the content of (C) polyisocyanate is adjusted from the viewpoint of balancing transparency, metal adhesion, water resistance and mechanical properties (particularly hardness).

[0113] For example, the content of (C) polyisocyanate (based on solid content) relative to the total amount of the thermosetting resin composition is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more. Alternatively, the content of (C) polyisocyanate (based on solid content) relative to the total amount of the thermosetting resin composition is, for example, 15% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less. In other words, the content of (C) polyisocyanate (based on solid content) relative to the total amount of the thermosetting resin composition is, for example, 0.1% by mass or more and 15% by mass or less, preferably 0.5% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 5% by mass or less.

[0114] 3) Other components The thermosetting resin composition may contain other components as optional components. Examples of other components include (D) curing accelerators, (E) solvents, and (F) additives.

[0115] [(D) Curing accelerator] Examples of curing accelerators include urethane catalysts. Examples of urethane catalysts include organometallic compounds and amines.

[0116] Examples of organometallic compounds include organotin compounds, organolead compounds, organonickel compounds, organocobalto compounds, organocoupramide compounds, and organobismuth compounds. Examples of organotin compounds include tin acetate, tin octoate (stannous octoate), tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurylate, and dibutyltin dichloride. Examples of organocobalto compounds include lead octanoate and lead naphthenate. Examples of organonickel compounds include nickel naphthenate. Examples of organocobalto compounds include cobalt naphthenate. Examples of organocoupramide compounds include copper octnate. Examples of organic bismuth compounds include bismuth octanoate (bismuth octylate) and bismuth neodecanoate. These can be used individually or in combination of two or more.

[0117] Examples of amines include tertiary amines, quaternary ammonium salts, and imidazoles. Examples of tertiary amines include triethylamine, triethylenediamine, bis-(2-dimethylaminoethyl) ether, and N-methylmorpholine. An example of a quaternary ammonium salt is tetraethylhydroxylammonium. Examples of imidazoles include imidazole and 2-ethyl-4-methylimidazole. These can be used individually or in combination of two or more types.

[0118] (D) The curing accelerator can be used alone or in combination of two or more types.

[0119] (D) Preferably, the hardening accelerator is an organometallic compound, more preferably an organotin compound, and even more preferably dibutyltin dilaurate (DBTDL).

[0120] If the thermosetting resin composition contains (D) a curing accelerator, the proportion of (D) the curing accelerator is set appropriately according to the purpose and application.

[0121] For example, the proportion of (D) curing accelerator (based on solid content) relative to the total amount of the thermosetting resin composition is, for example, 1.0 × 10 －５ Mass% or more 5.0 x 10 －２ Mass% or less, preferably 1.0 × 10 －４ Mass% or more 1.0×10 －２ It is less than or equal to a mass percent.

[0122] Furthermore, for example, the content ratio (based on solid content) of (D) curing accelerator per 100 parts by mass of the total amount of hydroxyl group-containing components and isocyanate group-containing components is, for example, 0.001 parts by mass or more and 1.0 parts by mass or less, preferably 0.005 parts by mass or more and 0.1 parts by mass or less.

[0123] [(E) Solvent] Examples of (E) solvents include alcohols, alkylbenzenes, and acetate esters. Examples of alcohols include methanol, ethanol, isopropanol, isobutanol, and n-butanol. Examples of alkylbenzenes include benzene, toluene, and xylene. Examples of acetate esters include ethyl acetate, propyl acetate, butyl acetate, and amyl acetate. In addition to the above, examples of solvents include tetrahydrofuran, methyl ethyl ketone, and methyl isobutyl ketone. These can be used alone or in combination of two or more. Preferably, alcohols and acetate esters are used, and more preferably, isobutanol and ethyl acetate are used in combination.

[0124] If the thermosetting resin composition contains solvent (E), the proportion of solvent (E) is not particularly limited and is set as appropriate depending on the purpose and application.

[0125] For example, the proportion of solvent (E) relative to the total amount of the thermosetting resin composition is, for example, 30% by mass or more and 99% by mass or less, preferably 50% by mass or more and 90% by mass or less.

[0126] [(F) Additives] Examples of (F) additives include pigments, dyes, leveling agents, stabilizers, foam inhibitors, weather resistance enhancers, anti-wrinkle agents, antioxidants, dispersants, wetting agents, thixotropes, and ultraviolet absorbers. These can be used individually or in combination of two or more types.

[0127] If the thermosetting resin composition contains additive (F), the proportion of additive (F) is set appropriately according to the purpose and application.

[0128] 6) Method for producing a thermosetting resin composition A thermosetting resin composition is produced by mixing the above-mentioned hydroxyl group-containing component and the above-mentioned isocyanate group-containing component in the above-mentioned proportions. More specifically, a thermosetting resin composition is produced as a mixed composition by mixing the above-mentioned (A) phosphoric acid-modified epoxy polyol and the above-mentioned (B) other hydroxyl group-containing resin and the above-mentioned (C) polyisocyanate in the above-mentioned proportions.

[0129] Furthermore, the mixing ratio of the hydroxyl group-containing component and the isocyanate group-containing component can be adjusted based on the equivalent ratio (NCO / OH) of the isocyanate groups of the isocyanate group-containing component to the hydroxyl groups of the hydroxyl group-containing component.

[0130] The equivalent ratio (NCO / OH) of the isocyanate group in the isocyanate group-containing component to the hydroxyl group in the hydroxyl group-containing component is, for example, 0.7 or more and 1.5 or less, preferably 0.8 or more and 1.4 or less.

[0131] The mixing conditions are not particularly limited, as long as they do not cause a urethane reaction between the hydroxyl group-containing component and the isocyanate group-containing component.

[0132] More specifically, the mixing temperature is, for example, 0°C to 60°C, preferably 10°C to 50°C. The mixing time is, for example, 0.1 hours to 6 hours, preferably 0.2 hours to 5 hours.

[0133] The above mixing yields a thermosetting resin composition. The thermosetting resin composition contains hydroxyl group-containing components and isocyanate group-containing components that have not undergone the urethane reaction (i.e., are in an unreacted state). In other words, the thermosetting resin composition is a thermosetting polyurethane resin composition.

[0134] In the above method, other components may be mixed as needed. More specifically, in the above mixture, the curing accelerator (D), the solvent (E), and / or the additive (F) may be mixed in the above proportions as needed.

[0135] Preferably, the above mixture includes the curing accelerator (D) and the solvent (E). That is, the thermosetting resin composition preferably contains the curing accelerator (D) and the solvent (E). In other words, the thermosetting resin composition more preferably contains an unreacted hydroxyl group-containing component, an unreacted isocyanate group-containing component, the curing accelerator, and the solvent.

[0136] Particularly preferably, the thermosetting resin composition comprises an unreacted hydroxyl group-containing component, an unreacted isocyanate group-containing component, the above-mentioned curing accelerator, and the above-mentioned solvent.

[0137] The timing for mixing other components is set appropriately according to the purpose and application. For example, other components can be mixed together with the hydroxyl group-containing component and the isocyanate group-containing component at the same time. Alternatively, other components can be mixed in advance with the hydroxyl group-containing component and / or the isocyanate group-containing component. Alternatively, other components can be mixed into a mixed composition of the hydroxyl group-containing component and the isocyanate group-containing component.

[0138] Furthermore, according to the above thermosetting resin composition, a cured product can be obtained that possesses relatively good metal adhesion and transparency.

[0139] 2. The cured product and the laminated cured product contain the reaction products of the thermosetting resin composition described above. Preferably, the cured product consists of the reaction products of the thermosetting resin composition described above.

[0140] More specifically, a cured product can be a cured film. The method for obtaining the cured film is not particularly limited, and known methods can be employed.

[0141] For example, to obtain a cured film, first, the thermosetting resin composition described above is applied to one side of a substrate using a known coating method to obtain a coating film.

[0142] From the viewpoint of industrial availability, resins and metals can be used as substrates. Examples of resins include polystyrene resin, (meth)acrylic resin (including acrylic resin and / or methacrylic resin), polyolefin resin, polycarbonate resin, polyamide resin, polyimide resin, acrylonitrile-styrene-butadiene copolymer resin (ABS resin), polystyrene resin, polyvinylidene chloride, styrene-acrylonitrile copolymer resin, and cellulose acetate. Examples of polystyrene resins include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate. Examples of (meth)acrylic resins include polymethyl methacrylate resin (PMMA). Examples of polyolefin resins include polyethylene resin and polypropylene resin. Examples of metals include iron, aluminum, magnesium, and zinc. In addition, alloys can also be used as metals. Examples of alloys include iron alloys (e.g., stainless steel), aluminum alloys, magnesium alloys, and zinc alloys. These can be used individually or in combination of two or more types.

[0143] Preferably, the base material is a metal base material. In other words, the base material is preferably a metal base material.

[0144] Preferably, the metal in the metal substrate is aluminum, aluminum alloy, and stainless steel. In other words, the metal substrate preferably contains at least one selected from the group consisting of aluminum, aluminum alloy, and stainless steel, and more preferably consists of at least one selected from the group consisting of aluminum, aluminum alloy, and stainless steel.

[0145] The thickness of the substrate is not particularly limited and can be set as appropriate depending on the purpose and application.

[0146] Examples of coating methods include spray coating, dip coating, roll coating, gravure coating, spin coating, bar coating, and doctor blade coating. The bar coating method is preferred as the coating method.

[0147] Next, in this method, the coating film of the thermosetting resin composition is heated and heat-cured. The heating conditions are set appropriately according to the types and amounts of various components contained in the thermosetting resin composition.

[0148] More specifically, the heating temperature is, for example, 50°C to 130°C, preferably 60°C to 120°C. The heating time is, for example, 0.1 hours to 5 hours, preferably 0.2 hours to 4 hours.

[0149] The heating described above causes the hydroxyl group-containing component and the isocyanate group-containing component to react, yielding a cured product. More specifically, a cured film containing the cured product is formed by the method described above. The above reaction is a urethane reaction between the hydroxyl groups in the hydroxyl group-containing component and the isocyanate groups in the isocyanate group-containing component, and the cured product (cured film) is a polyurethane resin.

[0150] Furthermore, by the above method, a laminate is obtained comprising a substrate and a cured film in contact with at least a portion of one side of the substrate. More specifically, a laminate is obtained comprising a substrate and a cured film disposed on at least a portion of one side surface of the substrate. Preferably, the cured film is disposed on the substrate and the entire one side surface of the substrate and in contact with the entire one side surface of the substrate.

[0151] The thickness of the cured product (cured film) is, for example, 1 μm to 50 μm, preferably 3 μm to 20 μm. The thickness of the laminate is not particularly limited and can be set appropriately according to the thickness of the substrate and the thickness of the cured product.

[0152] 3) Effects The above thermosetting resin composition contains a hydroxyl group-containing component and an isocyanate group-containing component. The hydroxyl group-containing component contains (A) a phosphate-modified epoxy polyol and (B) a hydroxyl group-containing resin other than the phosphate-modified epoxy polyol. The isocyanate group-containing component contains (C) polyisocyanate. In the above thermosetting resin composition, (A) the phosphate-modified epoxy polyol contains a reaction product of (a1) an epoxy compound and (a2) a phosphate compound. Furthermore, in the above thermosetting resin composition, the glass transition temperature of (B) the hydroxyl group-containing resin is within the above predetermined range.

[0153] In other words, the above thermosetting resin composition uses a combination of a predetermined (A) phosphoric acid-modified epoxy polyol and a predetermined (B) hydroxyl group-containing resin as hydroxyl group-containing components.

[0154] Therefore, according to the above thermosetting resin composition, a cured product can be obtained that possesses relatively good metal adhesion and transparency.

[0155] Furthermore, the cured product contains the reaction product of the thermosetting resin composition described above. Therefore, the cured product possesses relatively good metal adhesion and transparency.

[0156] Furthermore, the above-described laminate comprises a substrate and a cured film in contact with the substrate, and the cured film contains the above-described cured material. Therefore, the above-described laminate has excellent adhesion between the substrate and the cured film.

[0157] Therefore, thermosetting resin compositions, cured products, and laminates are suitably used in the field of metal coatings. More specifically, thermosetting resin compositions, cured products, and laminates are particularly suitably used in the fields of automotive coatings and home appliance coatings.

[0158] Next, the present invention will be described based on synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, "parts" and "%" are based on mass. Furthermore, specific numerical values ​​such as blending ratios (content), physical properties, and parameters used in the following description may be replaced with the corresponding upper limits (numerical values ​​defined as "less than or equal to" or "less than") or lower limits (numerical values ​​defined as "greater than or equal to" or "greater than") of the blending ratios (content), physical properties, and parameters described in the "Modes for Carrying Out the Invention" above.

[0159] 1. (A) Phosphate-modified epoxy polyol [Preparation example (A-1)] In a nitrogen-purged 3 L four-necked flask, jER1001 (trade name, bisphenol A type epoxy compound, number average molecular weight approximately 900, epoxy equivalent 450-500 g / eq, softening point 64°C, manufactured by Mitsubishi Chemical Corporation) was charged as (a1) epoxy compound. In addition, n-butanol and cyclohexanone were charged into the same flask as solvents. The contents of the flask were then heated to 80°C while stirring. The amount of (a1) epoxy compound was 475.8 g, the amount of n-butanol was 654.6 g, and the amount of cyclohexanone was 241.5 g.

[0160] Next, (a2) a solution of orthophosphoric acid as a phosphate compound (n-butanol solution, solid content concentration 85% by mass) was added to the flask over 1 hour. The amount of phosphate solution added was 28.4 g, and the solid content mass of orthophosphoric acid was 24.2 g.

[0161] Furthermore, the equivalent ratio (hydroxyl group / glycidyl group) of the hydroxyl group of the phosphoric acid compound (a2) to the glycidyl group of the epoxy compound (a1) was 0.7.

[0162] Next, the contents of the flask were heated to 90°C and stirred at 90°C for 3 hours to react (a1) the epoxy compound with (a2) the phosphoric acid compound to obtain phosphoric acid-modified epoxy polyol (A-1).

[0163] Subsequently, 104.0 g of isopropyl alcohol was added to the obtained phosphate-modified epoxy polyol (A-1), and the phosphate-modified epoxy polyol (A-1) was dissolved in the isopropyl alcohol. A solution of phosphate-modified epoxy polyol (A-1) was thus obtained.

[0164] The solid content concentration of the phosphate-modified epoxy polyol (A-1) was 50% by mass, and the acid value (according to JIS K 1557-5 (2007) (hereinafter the same)) was 30 mg KOH / g.

[0165] [Preparation Example (A-2)] (a1) As the epoxy compound, jER828 (trade name, bisphenol A type epoxy compound, number average molecular weight approximately 370, epoxy equivalent 184-194 g / eq, manufactured by Mitsubishi Chemical Corporation) was used. In addition, the amount of epoxy compound (a1) was changed to 424.0 g, the amount of n-butanol was changed to 356.0 g, and the amount of cyclohexanone was changed to 117.2 g. In addition, the amount of orthophosphoric acid solution (85% by mass) was changed to 89.1 g, and the amount of isopropyl alcohol was changed to 13.6 g. The solid content mass of orthophosphoric acid was 75.7 g.

[0166] Furthermore, the equivalent ratio (hydroxyl group / glycidyl group) of the hydroxyl group of the phosphoric acid compound (a2) to the glycidyl group of the epoxy compound (a1) was 1.0.

[0167] Aside from these, the phosphoric acid-modified epoxy polyol (A-2) and its solution were obtained using the same method as in preparation example (A-1).

[0168] The solid content concentration of the phosphate-modified epoxy polyol (A-2) was 50% by mass, and the acid value was 75 mg KOH / g.

[0169] [Preparation Example (A-3)] (a1) As the epoxy compound, jER1003 (trade name, bisphenol A type epoxy compound, number average molecular weight approximately 1300, epoxy equivalent weight 670-770 g / eq, softening point 89°C, manufactured by Mitsubishi Chemical Corporation) was used. In addition, the amount of epoxy compound (a1) was changed to 451.3 g, the amount of n-butanol was changed to 359.6 g, and the amount of cyclohexanone was changed to 118.4 g. In addition, the amount of orthophosphoric acid solution (85% by mass) was changed to 56.9 g, and the amount of isopropyl alcohol was changed to 13.8 g. The solid content mass of orthophosphoric acid was 48.4 g.

[0170] Furthermore, the equivalent ratio (hydroxyl group / glycidyl group) of the hydroxyl group of the phosphoric acid compound (a2) to the glycidyl group of the epoxy compound (a1) was 2.4.

[0171] Apart from these, the phosphoric acid-modified epoxy polyol (A-3) was obtained using the same method as in preparation example (A-1).

[0172] The solid content concentration of the phosphate-modified epoxy polyol (A-3) was 50% by mass, and the acid value was 20 mg KOH / g.

[0173] 2. (B) Other hydroxyl group-containing resins [Preparation example (B-1)] 20 g of ethyl acetate (solvent) and 80 g of n-butyl acetate (solvent) were charged into a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube. The contents of the flask were heated to 100°C while degassing with nitrogen.

[0174] On the other hand, 30.0 g of methyl methacrylate, 35.0 g of styrene, 3.0 g of ethyl acrylate, 18.1 g of n-butyl acrylate, and 13.9 g of 2-hydroxyethyl methacrylate were mixed as polymerization components. Furthermore, 1.2 g of perbutyl O (trade name, abbreviation PBO, tert-butyl=2-ethylperoxyhexanoate, manufactured by NOF Corporation) was mixed with the above polymerization components as a polymerization initiator to obtain a mixture.

[0175] The above mixture was added dropwise to a flask over 4 hours for polymerization. Also, the content of the flask was aged for 1 hour. As a result, a solution of the hydroxyl group-containing acrylic resin (B-1) was obtained. The solid content concentration was 50% by mass.

[0176] [Preparation Examples (B-2) to (B-6) and Comparative Preparation Examples (B'-1) to (B'-3)] Solutions of hydroxyl group-containing acrylic resins (B-2) to (B-6) and (B'-1) to (B'-3) were obtained in the same manner as in Preparation Example (B-1), except that the formulations shown in Table 1 were changed. The solid content concentration was 50% by mass.

[0177] [Physical Property Measurement] (1) Glass transition temperature The glass transition temperature of the hydroxyl group-containing acrylic resin was calculated by the FOX equation represented by the following formula (1). The results are shown in Table 1.

[0178] 1 / Tg = W １ / Tg １ +W ２ / Tg ２ +···+W ｎ / Tg ｎ (1)

[0179] In the above formula (1), Tg is the glass transition temperature (K) of n types of polymerization components (monomers), and W １ , W ２ , W ｎ are the mass fractions of each monomer, and W １ +W ２ +···+W ｎ = 1. Also, Tg １ , Tg ２ , Tg ｎ are the glass transition temperatures (K) of the homopolymers of each monomer.

[0180] Also, the glass transition temperatures of the homopolymers of the monomers were referred to the Acrylic Ester Catalog (1997 edition) of Mitsubishi Rayon Co., Ltd., and "New Polymer Library 7 Introduction to Synthetic Resins for Paints" written by Kyozo Kitaoka, published by Kobunshi Kankokai, pages 168 to 169.

[0181] (2) Hydroxyl value The hydroxyl value of the hydroxyl group-containing acrylic resin was measured based on JIS K 0070-1992 (acetylation method). The results are shown in Table 1.

[0182] (3) Weight-average molecular weight The weight-average molecular weight of each hydroxyl group-containing acrylic resin was measured by GPC under the following measurement conditions. The results are shown in Table 1. Detector: Differential refractometer (RI) Column: TSKgel G7000 x 1, TSKgel G4000 x 2, TSKgel G2000 x 1 (all manufactured by Tosoh Corporation) Mobile phase: Tetrahydrofuran (THF) Column temperature: 25°C Flow rate: 0.6 ml / min Sample concentration: 20 mg / mL (tetrahydrofuran solution) Injection volume: 10 μl

[0183] The weight-average molecular weight was calculated using a calibration curve created from monodisperse standard polystyrene.

[0184] [Preparation Example (B-7)] A hydroxyl group-containing polyester resin (B-7) was produced by the following method.

[0185] Trimethylolpropane: 10.0% by mass Neopentyl glycol: 35.0% by mass Adipic acid: 18.5% by mass Phthalic anhydride: 19.0% by mass Isophthalic acid: 20.0% by mass

[0186] The above compounds were placed in a flask in the above proportions, and the contents of the flask were heated while nitrogen was flowed into the flask. The contents of the flask were then stirred once it became possible to stir them.

[0187] Next, under temperature conditions of 100°C or below, DBTO (di-n-butyl oxide) was added as a polymerization catalyst in an amount of 0.05% by mass relative to the contents of the flask. Then, the contents of the flask were heated from 140°C to 230°C over 3 to 10 hours while stirring, and the above compound was reacted.

[0188] Next, when the acid value of the contents of the flask (hereinafter referred to as the reaction product) fell to 5.0 mg KOH / g or less, heating was stopped and the reaction product was cooled. As a result, a hydroxyl group-containing polyester resin (B-7) was obtained.

[0189] Subsequently, a solvent (product name Solvesso 100, high-boiling point hydrocarbon solvent, manufactured by Ando Parachemy Co., Ltd.) was added to the hydroxyl group-containing polyester resin (B-7) to obtain a solution of the hydroxyl group-containing polyester resin (B-7) (solid content: 50% by mass).

[0190] The weight-average molecular weight of the hydroxyl group-containing polyester resin (B-7) measured by the above method was 51,000. The hydroxyl value of the hydroxyl group-containing polyester resin (B-7), also measured by the above method, was 52 mgKOH / g. The glass transition temperature of the hydroxyl group-containing polyester resin (B-7), measured by differential scanning thermal analysis (DSC), was 45°C.

[0191] 3. (C) Polyisocyanate [Preparation Example (C-1)] Takenate D-170N (trade name, isocyanurate derivative of hexamethylene diisocyanate, isocyanate group concentration 20.9% by mass, solid content concentration 100% by mass, manufactured by Mitsui Chemicals) was prepared as polyisocyanate (C-1).

[0192] [Preparation Example (C-2)] Takenate D-110N (trade name, trimethylolpropane adduct of m-xylylene diisocyanate, isocyanate group concentration 11.5% by mass, solid content concentration 75% by mass, manufactured by Mitsui Chemicals) was prepared as polyisocyanate (C-2).

[0193] 4. Other components [Preparation example (D-1)] Dibutyltin dilaurate (abbreviated DBTDL, urethane catalyst) was prepared as a curing accelerator (D-1).

[0194] [Preparation Example (E-1)] A mixed solvent of ethyl acetate and isobutanol was prepared as solvent (E-1). The volume ratio of ethyl acetate to isobutanol (ethyl acetate / isobutanol) was adjusted to 90 / 10.

[0195] [Preparation Example (F-1)] As additive (F-1), an epoxy compound (trade name jER1001, bisphenol A type epoxy compound, number average molecular weight approximately 900, epoxy equivalent 450-500 g / eq, softening point 64°C, manufactured by Mitsubishi Chemical Corporation) was prepared.

[0196] [Preparation Example (F-2)] Orthophosphoric acid (100% solids) was prepared as additive (F-2).

[0197] 5. Thermosetting resin compositions, cured products, and laminates [Examples 1-14 and Comparative Examples 1-7] According to the formulations shown in Tables 2-4, (A) phosphoric acid-modified epoxy polyol, (B) other hydroxyl group-containing resin, (C) polyisocyanate, (D) curing accelerator, and (E) solvent were mixed at 20°C for 1 hour. A thermosetting resin composition was obtained as a result.

[0198] In each example and comparative example, the equivalent ratio (NCO / OH) of isocyanate groups in the isocyanate group-containing component (i.e., (C) polyisocyanate) to the hydroxyl groups in the hydroxyl group-containing component (i.e., (A) phosphoric acid-modified epoxy polyol and (B) other hydroxyl group-containing resins) was 1.2.

[0199] In Comparative Example 1, (B) other hydroxyl group-containing resins were not included. Also, in Comparative Example 2, (A) phosphate-modified epoxy polyol was not included.

[0200] In Comparative Examples 3 and 4, an epoxy compound (additive (F-1)) was added instead of (A) the phosphate-modified epoxy polyol.

[0201] In Comparative Example 4, instead of (A) the phosphate-modified epoxy polyol, an epoxy compound (additive (F-1)) and orthophosphoric acid (additive (F-2)) were blended.

[0202] In addition, comparative examples 5 to 7 incorporated hydroxyl group-containing acrylic resins (B'-1) to (B'-3).

[0203] Next, the thermosetting resin composition was applied to a glass plate, a stainless steel plate (SUS304, manufactured by Testpiece Co., Ltd.), or an aluminum plate (A1050P, manufactured by Testpiece Co., Ltd.) using a bar coater #50.

[0204] Next, the coating film of the thermosetting resin composition was heated at 80°C for 0.5 hours to cure the thermosetting resin composition. A cured product (cured film) of the thermosetting resin composition was obtained. A laminate comprising the above cured film was also obtained. The thickness of the cured product was 10 μm.

[0205] 6. Evaluation [Transparency] The transparency of the cured material was evaluated using the following method. Specifically, the haze of the cured material formed on a glass plate was measured using a haze meter (NDH-4000 model, manufactured by Nippon Denshoku Industries Co., Ltd.) and evaluated according to the following criteria. The results are shown in Tables 2 to 4.

[0206] A: Haze value between 0% and 1.0% B: Haze value exceeding 1.0% and 5.0% or less C: Haze value exceeding 5.0%

[0207] [Metal Adhesion] The metal adhesion of the hardened material was evaluated in accordance with JIS K5400 8.5.2 (1990) using the following method. Specifically, a grid pattern of 1 mm wide cuts was made in the hardened material formed on a stainless steel plate or aluminum plate, so that the knife could reach the plate. Then, cellophane adhesive tape was applied to the surface of the hardened material and immediately peeled off. After that, the state of the hardened material was evaluated according to the following criteria. The results are shown in Tables 2 to 4.

[0208] A: No delamination was observed. B: Delamination was observed on some surfaces. C: Delamination was observed on the entire surface.

[0209] [Water Resistance] The water resistance of the cured material was evaluated using the following method. Specifically, the cured material formed on a stainless steel plate was immersed in boiling water for 30 minutes, and then dried at room temperature for 1 hour. After that, the metal adhesion of the cured material to the stainless steel plate was evaluated as water resistance according to the following criteria. The results are shown in Tables 2 to 4.

[0210] A: No peeling was observed after the water resistance test. B: Peeling was observed on some surfaces after the water resistance test. C: Peeling was observed on the entire surface after the water resistance test.

[0211] [Hardness] The hardness of the hardened material was evaluated in accordance with JIS K 5600-5-4 (1999) using the following method. Specifically, a pencil lead was applied to the hardened material at an angle of approximately 45°. Then, the lead was moved forward at a uniform speed of approximately 10 mm while pressing it against the hardened material with just enough force to prevent the lead from breaking. The hardness of the hardest pencil among those that did not damage the hardened material was defined as the pencil hardness and evaluated according to the following criteria. The results are shown in Tables 2 to 4.

[0212] S: H or more A: F B: B or more, HB or less C: 2B or less

[0213]

[0214]

[0215]

[0216]

[0217] Details of the abbreviations in the table are as follows: PBO: Trade name Perbutyl O, tert-butyl=2-ethylperoxyhexanoate, manufactured by NOF Corporation DBTDL: Dibutyltin dilaurate, urethane catalyst SUS304: Stainless steel plate A1050P: Aluminum plate

[0218] The above invention is provided as an illustrative embodiment of the present invention, but this is merely illustrative and should not be interpreted restrictively. Modifications of the present invention that are obvious to those skilled in the art are included in the claims below.

[0219] The thermosetting resin composition, cured product, and laminate of the present invention are suitably used in the field of metal coatings.

Claims

1. A thermosetting resin composition comprising a hydroxyl group-containing component and an isocyanate group-containing component, wherein the hydroxyl group-containing component comprises (A) a phosphoric acid-modified epoxy polyol and (B) a hydroxyl group-containing resin other than the phosphoric acid-modified epoxy polyol, the isocyanate group-containing component comprises (C) a polyisocyanate, (A) the phosphoric acid-modified epoxy polyol comprises (a1) a reaction product of an epoxy compound having two or more glycidyl groups in one molecule and (a2) a phosphoric acid compound having one or more P-OH bonds in one molecule, and (B) the glass transition temperature of the hydroxyl group-containing resin is 45°C or higher and 100°C or lower.

2. (B) The thermosetting resin composition according to claim 1, wherein the hydroxyl group-containing resin contains a hydroxyl group-containing acrylic resin and / or a hydroxyl group-containing polyester resin.

3. (B) The thermosetting resin composition according to claim 1, wherein the hydroxyl value of the hydroxyl group-containing resin is 40 mg KOH / g or more and 110 mg KOH / g or less.

4. (B) The thermosetting resin composition according to claim 1, wherein the glass transition temperature of the hydroxyl group-containing resin is 70°C or higher and 100°C or lower, and (B) the hydroxyl value of the hydroxyl group-containing resin is 70 mg KOH / g or higher and 110 mg KOH / g or lower.

5. The thermosetting resin composition according to claim 1, wherein the content of (A) the phosphoric acid-modified epoxy polyol is 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of (B) the hydroxyl group-containing resin.

6. (a1) The thermosetting resin composition according to claim 1, wherein the number average molecular weight of the epoxy compound is 100 or more and 1400 or less.

7. (a1) The thermosetting resin composition according to claim 1, wherein the epoxy equivalent of the epoxy compound is 150 g / eq or more and 800 g / eq or less.

8. A cured product containing a reaction product of the thermosetting resin composition according to any one of claims 1 to 7.

9. A laminate comprising a substrate and a cured film in contact with at least one part of the substrate, wherein the cured film contains the cured product described in claim 8.

10. The laminate according to claim 9, wherein the substrate is made of a metal substrate, and the metal substrate contains at least one selected from the group consisting of aluminum, aluminum alloy, and stainless steel.

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