Thermosetting resin compositions, cured products and laminates

Abstract

To provide a thermosetting resin composition which enables formation of a cured film that is excellent in transparency and can maintain good water sliding property over a long period of time.SOLUTION: A thermosetting resin composition contains a polymer (X1) having a polydimethylsiloxane structure and an active hydrogen group in a main chain or a side chain, a compound (Y1) having two or more isocyanate groups that may be blocked in one molecule, and a compound (Z1) having two or more active hydrogen groups in one molecule. A thermosetting resin composition contains a polymer (X1) having a polydimethylsiloxane structure and an active hydrogen group in a main chain or a side chain, and a compound (Y2) having three or more isocyanate groups that may be blocked in one molecule. A thermosetting resin composition contains a polymer (X2) having a polydimethylsiloxane structure and an isocyanate group that may be blocked in a main chain or a side chain, and a compound (Z1) having two or more active hydrogen groups in one molecule.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermosetting resin composition, in particular a thermosetting resin composition capable of forming a cured film with excellent water sliding properties, a cured product of the composition, and a laminate having a layer made of the cured product. [Background technology]

[0002] Resin molded products made from resins such as polymethyl methacrylate resin, polymethacrylimide resin, polycarbonate resin, polystyrene resin, and acrylonitrile-styrene resin are lightweight, have excellent impact resistance, and good transparency, and are therefore used as materials for various automotive lamp lenses, glazing (plastic windows), exteriors, instrument covers, and other components. In recent years, radar devices using various electromagnetic waves, such as millimeter waves, have been installed on the back of emblems or front grilles on the front of vehicles such as automobiles to detect obstacles ahead and measure the distance between vehicles. Because these electromagnetic waves are significantly attenuated by water, the outermost surfaces of emblems, front grilles, etc., through which the electromagnetic waves pass, are required to have water-repellent properties that make it difficult for water droplets to adhere and allow water droplets to slide off easily. To satisfy these requirements, a method is known in which the surface of a resin molded article is coated with a curable composition containing a resin having a polydimethylsiloxane structure to impart water-slip properties.

[0003] For example, Patent Document 1 discloses a method for forming a cured film having water-sliding properties by applying a curable composition containing a monomer having a fluoroalkyl group, a monomer having a polydimethylsiloxane structure, and a copolymer of a polyfunctional unsaturated compound to a substrate and heating the composition. Furthermore, Patent Document 2 discloses a method for forming a cured film having water-sliding properties by curing a thermosetting resin composition containing a copolymer of a monomer having a polydimethylsiloxane structure and a monomer having a hydroxyl group, and a bifunctional isocyanate.

[0004] However, the method described in Patent Document 1 has the problem that defects such as repelling occur in the cured film, which deteriorates the appearance of the cured film and reduces its transparency. Moreover, the method described in Patent Document 2 has the problem that the durability of the cured film is low and the water sliding property is significantly impaired after a wet heat test. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-185072 [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-230060 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a thermosetting resin composition capable of forming a cured film that has excellent transparency and can maintain good water sliding properties for a long period of time, a cured product of the composition, and a laminate having a layer made of the cured product. [Means for solving the problem]

[0007] The gist of the present invention lies in the following [1] to [9]. [1] A thermosetting resin composition comprising: a polymer (X1) having a polydimethylsiloxane structure and an active hydrogen group in the main chain or side chain; a compound (Y1) having two or more optionally blocked isocyanate groups per molecule; and a compound (Z1) having two or more active hydrogen groups per molecule. [2] A thermosetting resin composition comprising a polymer (X1) having a polydimethylsiloxane structure and an active hydrogen group in the main chain or side chain, and a compound (Y2) having three or more optionally blocked isocyanate groups per molecule. [3] A polymer (X2-2) having a polydimethylsiloxane structure and an optionally blocked isocyanate group in the main chain or side chain, and further containing 30% by mass or more of structural units derived from an aromatic vinyl monomer in the main chain. [4] A thermosetting resin composition comprising a polymer (X2) having a polydimethylsiloxane structure and an optionally blocked isocyanate group in the main chain or side chain, and a compound (Z1) having two or more active hydrogen groups per molecule. [5] The thermosetting resin composition according to [4], further comprising a compound (Y1) having two or more optionally blocked isocyanate groups in one molecule. [6] The thermosetting resin composition according to any one of [1], [2], [4] and [5], further comprising inorganic fine particles. [7] The thermosetting resin composition according to [6], wherein the inorganic fine particles are surface-modified with a compound having a functional group selected from the group consisting of a mercapto group, a hydroxyl group, and an isocyanate group. [8] A cured product obtained by curing the thermosetting resin composition according to any one of [1], [2], [4] to [7]. [9] A laminate having a layer made of the cured product of [8] on a substrate. [Effects of the Invention]

[0008] The thermosetting resin composition of the present invention can form a cured film that has excellent transparency and can maintain good water sliding properties for a long period of time. The cured product and laminate of the present invention have excellent transparency and can maintain good water sliding properties for a long period of time. DETAILED DESCRIPTION OF THE INVENTION

[0009] [Composition (A1)] The thermosetting resin composition of the present invention is a thermosetting resin composition [hereinafter referred to as "composition (A1)"] containing a polymer (X1) [hereinafter referred to as "polymer (X1)"] having a polydimethylsiloxane structure and an active hydrogen group in the main chain or side chain, a compound (Y1) [hereinafter referred to as "compound (Y1)"] having two or more optionally blocked isocyanate groups per molecule, and a compound (Z1) [hereinafter referred to as "compound (Z1)"] having two or more active hydrogen groups per molecule.

[0010] <Polymer (X1)> The polymer (X1) is a polymer having a polydimethylsiloxane structure and an active hydrogen group in the main chain or side chain. That is, the polymer (X1) must contain a polydimethylsiloxane structure in either or both of its main chain and side chain, and must contain an active hydrogen group in either or both of its main chain and side chain.

[0011] <Polydimethylsiloxane structure> The polydimethylsiloxane structure contributes to the water-repellent properties of the cured film formed from the composition (A1) containing the polymer (X1).

[0012] Examples of methods for introducing a polydimethylsiloxane structure into the polymer (X1) include: (1) copolymerizing a macromonomer having a polydimethylsiloxane structure and an unsaturated bond [hereinafter referred to as "macromonomer (M1)"] with another monomer; (2) copolymerizing a polydimethylsiloxane having mercapto groups at the α,ω positions with another monomer as a chain transfer agent; (3) copolymerizing an azo compound having a polydimethylsiloxane structure with another monomer; and (4) adding a hydroxyl group of a polydimethylsiloxane having a terminal hydroxyl group to the isocyanate group of a polymer having an optionally blocked isocyanate group.

[0013] Examples of the macromonomer (M1) used in the method (1) include Silaplane (registered trademark) FM-0711 (number average molecular weight listed in the catalog: 1000), Silaplane FM-0721 (number average molecular weight listed in the catalog: 5000), and Silaplane FM-0725 (number average molecular weight listed in the catalog: 10000), all manufactured by JNC; and X-22-174ASX (number average molecular weight listed in the catalog: 900), X-22-174BX (number average molecular weight listed in the catalog: 2300), KF-2012 (number average molecular weight listed in the catalog: 4600), and X-22-2426 (number average molecular weight listed in the catalog: 12000), all manufactured by Shin-Etsu Chemical Co., Ltd. Among these, mono(meth)acryloyloxypropyl-modified polydimethylsiloxanes such as Silaplane FM-072, Silaplane FM-0721, Silaplane FM-0725, X-22-174ASX, X-22-174BX, KF-2012, and X-22-2426 are suitable because they are easily available industrially.

[0014] Examples of polydimethylsiloxanes having mercapto groups at the α- and ω-positions that can be used as chain transfer agents in the method (2) include X-22-167B (number average molecular weight listed in the catalog: 3400) and X-22-167C (number average molecular weight listed in the catalog: 4600) manufactured by Shin-Etsu Chemical Co., Ltd.

[0015] Examples of the azo compound having a polydimethylsiloxane structure used in the method (3) include VPS-0501 (trade name: polydimethylsiloxane-based polymeric azo initiator, polydimethylsiloxane chain length: 5000) and VPS-1001 (trade name: polydimethylsiloxane-based polymeric azo initiator, polydimethylsiloxane chain length: 10000) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0016] As a method for introducing a polydimethylsiloxane structure into the polymer (X1), the above method (1) is preferred from the viewpoint of easy availability of raw materials.

[0017] <Active hydrogen group> The active hydrogen group reacts with the isocyanate group of the compound (Y1), firmly fixing the polymer (X1) to the cured film and contributing to the durability of water sliding property and scratch resistance. The active hydrogen group possessed by the polymer (X1) is, for example, a functional group such as a hydroxyl group, a mercapto group, or an amino group. The active hydrogen group can react with the isocyanate group of the compound (Y1) having the isocyanate group to form a bond such as a urethane bond.

[0018] The hydroxyl group may be primary, secondary, or tertiary, but is preferably primary or secondary. The mercapto group and amino group may also be primary, secondary, or tertiary, but are preferably primary or secondary.

[0019] To introduce an active hydrogen group into the polymer (X1), a preferred method is to copolymerize a monomer having an active hydrogen group [hereinafter referred to as "monomer (M2)"] with the macromonomer (M1) as another monomer in the method (1) for introducing a polydimethylsiloxane structure.

[0020] <Production of Polymer (X1)> Hereinafter, the method (1) for producing the polymer (X1) by copolymerizing the macromonomer (M1) with the monomer (M2) as another monomer will be described.

[0021] <Macromonomer (M1)> The polydimethylsiloxane structure of the macromonomer (M1) used to produce the polymer (X1) may be either a linear structure or a branched structure. The polydimethylsiloxane structure may have an alkyl group at its terminal or an alkylene group inside. For example, when an unsaturated bond is introduced or a branched chain is formed, an alkylene group having 1 to 6 carbon atoms may be interposed between the polydimethylsiloxane structure and the macromonomer (M1).

[0022] Examples of the unsaturated bond of the macromonomer (M1) include a (meth)acryloyl group, a vinyl group, and a (meth)acrylamide group. Among these, a (meth)acryloyl group is preferred from the viewpoint of ease of copolymerization with other monomers.

[0023] The molecular weight of the macromonomer (M1) is preferably 500 to 40,000, more preferably 700 to 30,000, and even more preferably 800 to 20,000. The smaller the molecular weight, the more compatible the macromonomer (M1) is with other monomers, which tends to facilitate the production of the polymer (X1). Furthermore, the larger the molecular weight, the better the water sliding property of the cured film tends to be.

[0024] The amount of macromonomer (M1) incorporated into polymer (X1) is preferably 5% by mass or more and less than 70% by mass, more preferably 10% by mass or more and less than 60% by mass, and even more preferably 20% by mass or more and less than 50% by mass. The greater the amount incorporated, the better the water sliding properties of the cured film, and the smaller the amount incorporated, the less unpolymerized macromonomer (M1) there is, so the transparency of the cured film tends to be better.

[0025] <Monomer (M2)> The monomer (M2) is used to introduce an active hydrogen group into the polymer (X1). Examples of the monomer (M2) include (meth)acrylic acid esters, N-substituted (meth)acrylamides, and vinyl compounds having a hydroxyl group, a mercapto group, or an amino group. Examples of the monomer (M2) having a hydroxyl group include (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, propylene glycol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, and glycerin mono(meth)acrylate; N-(2-hydroxyethyl)acrylamide, N-(2-hydroxyethyl)methacrylamide, N-(2-hydroxypropyl) ... Examples of N-substituted (meth)acrylamides include N-(1-hydroxypropyl)acrylamide, N-(1-hydroxypropyl)acrylamide, N-(3-hydroxypropyl)acrylamide, N-(3-hydroxypropyl)methacrylamide, N-(2-hydroxybutyl)acrylamide, N-(2-hydroxybutyl)methacrylamide, N-(3-hydroxybutyl)acrylamide, N-(3-hydroxybutyl)methacrylamide, N-(4-hydroxybutyl)acrylamide, and N-(4-hydroxybutyl)methacrylamide. Preferred (meth)acrylic acid esters include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate, and preferred N-substituted (meth)acrylamides include N-(2-hydroxyethyl)acrylamide and N-(2-hydroxyethyl)methacrylamide. Particularly preferred examples of the hydroxyl group-containing monomer (M2) include 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate. The hydroxyl group-containing monomer (M2) may be used alone or in combination of two or more thereof.

[0026] The active hydrogen group can also be introduced by using a chain transfer agent during the production of polymer (X1) by copolymerization. Examples of such a chain transfer agent include mercaptans having a hydroxyl group and mercaptans having an amino group.

[0027] Examples of mercaptans having a hydroxyl group include mercaptoethanol and thioglycerol. Examples of mercaptans having an amino group include 2-aminoethanethiol, 2-aminobenzenethiol, 4-aminobenzenethiol, and L-cysteine, as well as hydrochlorides thereof.

[0028] The amount of active hydrogen groups introduced into the polymer (X1) is preferably 0.1 mmol / g or more and less than 4.0 mmol / g, more preferably 0.2 mmol / g or more and less than 3.5 mmol / g, and even more preferably 0.3 mmol / g or more and less than 3.0 mmol / g. The greater this amount, the more durable the cured film tends to be, while the smaller the amount, the more water slippage of the cured film tends to be.

[0029] <Other monomers> In the production of the polymer (X1), other monomers may be copolymerized in addition to the macromonomer (M1) and the monomer (M2) as long as the performance is not impaired. Other monomers include, for example, aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, vinylbiphenyl, vinylanthracene, and vinylxylene; alkyl (meth)acrylates or alkenyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, behenyl (meth)acrylate, and allyl (meth)acrylate; cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentaerythritol, and the like. (meth)acrylates having an alicyclic structure such as dicyclopentenyl (meth)acrylate and dicyclopentenyl (meth)acrylate; (meth)acrylates having an aromatic ring such as benzyl (meth)acrylate and phenyl (meth)acrylate; (meth)acrylates containing an oxygen atom such as phenoxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate and glycidyl methacrylate; carboxy group-containing methacrylic acid monomers such as (meth)acrylic acid and 2-(meth)acryloyloxyethyl phthalate; N-substituted (meth)acrylamides such as (meth)acrylamide, dimethyl (meth)acrylamide, (meth)acryloylmorpholine, isopropyl (meth)acrylamide and dimethylaminopropyl acrylamide; (meth)acrylates containing a halogen atom such as trifluoroethyl (meth)acrylate and heptadecafluorodecyl (meth)acrylate;Examples of suitable monomers include silicon-containing (meth)acrylates such as trimethylsilyl (meth)acrylate, 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(methyldiethoxy)propyl (meth)acrylate, and 3-(triethoxy)propyl (meth)acrylate; (meth)acrylates having an ultraviolet absorbing group such as 2-(4-benzoxy-3-hydroxyphenoxy)ethyl methacrylate and 2-(2'-hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole; and nitrogen-containing (meth)acrylates such as tetramethylpiperidinyl (meth)acrylate and diethylaminoethyl (meth)acrylate. Other monomers that may be used include vinyl alkanoate compounds and maleic acid-based monomers.

[0030] As the other monomers, those having a glass transition temperature of more than 30°C as a homopolymer are preferred from the viewpoint of improving the hardness of the cured film, and monomers having an aromatic ring or an alicyclic structure are preferred from the viewpoint of water slippage. Among them, aromatic vinyl compounds not containing a carbonyl group are preferred from the viewpoint of improving the water slippage of the cured film because they have low hydrogen bonding properties with water molecules.

[0031] The copolymerization amount of the other monomer in the polymer (X1) is the remainder of the copolymerization amounts of the macromonomer (M1) and the monomer (M2), and is preferably from 20% to less than 90% by mass, more preferably from 25% to less than 85% by mass, and even more preferably from 30% to less than 80% by mass. The higher this copolymerization amount, the better the copolymerization property during copolymerization, and the lower this copolymerization amount, the better the water sliding property tends to be.

[0032] <Initiator> In the production of the polymer (X1), it is preferable to use an initiator when copolymerizing the macromonomer (M1) and the monomer (M2). Various initiators can be used as the initiator. Examples of oil-soluble radical polymerization initiators include azonitrile compounds such as 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 2,2'-azobisisobutyronitrile (V-60, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 2,2'-azobis(2-methylbutyronitrile) (V-59, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); octanoyl peroxide (Perloyl (registered trademark) O, manufactured by NOF Corp.); diacyl peroxides such as lauroyl peroxide (Perloyl L, manufactured by NOF Corp.), stearoyl peroxide (Perloyl S, manufactured by NOF Corp.), succinic acid peroxide (Perloyl SA, manufactured by NOF Corp.), benzoyl peroxide (Niper (registered trademark) BW, manufactured by NOF Corp.), isobutyryl peroxide (Perloyl IB, manufactured by NOF Corp.), 2,4-dichlorobenzoyl peroxide (Niper CS, manufactured by NOF Corp.), and 3,5,5-trimethylhexanoyl peroxide (Perloyl 355, manufactured by NOF Corp.); di-n-propyl peroxide Dicarbonate (Perloyl NPP-50M, NOF Corp.), diisopropyl peroxydicarbonate (Perloyl IPP-50, NOF Corp.), bis(4-t-butylcyclohexyl) peroxydicarbonate (Perloyl TCP, NOF Corp.), di-2-ethoxyethyl peroxydicarbonate (Perloyl EEP, NOF Corp.), di-2-ethoxyhexyl peroxydicarbonate (Perloyl OPP, NOF Corp.), di-2-methoxybutyl peroxydicarbonate (Perloyl MBP, NOF Corp.), di(3-methyl-3-meth) peroxydicarbonates such as tert-butyl)peroxydicarbonate (Peroyl SOP, manufactured by NOF Corp.); hydroperoxides such as t-butyl hydroperoxide (Perbutyl H-69, manufactured by NOF Corp.) and 1,1,3,3-tetramethylbutyl hydroperoxide (Perocta(R) H, manufactured by NOF Corp.); dialkyl peroxides such as di-t-butyl peroxide (Perbutyl(R) D, manufactured by NOF Corp.) and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane (Perhexa(R) 25B, manufactured by NOF Corp.);α,α'-Bis(neodecanoylperoxy)diisopropylbenzene (Diaper (registered trademark) ND, manufactured by NOF Corp.), cumyl peroxy neodecanoate (Percumyl (registered trademark) ND, manufactured by NOF Corp.), 1,1,3,3-tetramethylbutyl peroxy neodecanoate (Perocta ND, manufactured by NOF Corp.), 1-cyclohexyl-1-methylethyl peroxy neodecanoate (Percyclo (registered trademark) ND, manufactured by NOF Corp.), t-hexyl peroxy neodecanoate (Perhexyl (registered trademark) ND, manufactured by NOF Corp.), t-butyl peroxy neodecanoate (Perbutyl ND, manufactured by NOF Corp.), t-hexyl peroxy pivalate (Perhexyl PV, manufactured by NOF Corp.), t-butyl peroxy pivalate (Perbutyl PV, manufactured by NOF Corp.), 1,1,3,3-tetramethylbutyl Examples of suitable initiators include organic peroxides such as peroxyesters such as peroxy-2-ethylhexanoate (Perocta O, manufactured by NOF Corp.), 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane (Perhexa 250, manufactured by NOF Corp.), 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate (Percyclo O, manufactured by NOF Corp.), t-hexylperoxy-2-ethylhexanoate (Perhexyl O, manufactured by NOF Corp.), t-butylperoxy-2-ethylhexanoate (Perbutyl O, manufactured by NOF Corp.), t-butylperoxyisobutyrate (Perbutyl IB, manufactured by NOF Corp.), t-hexylperoxyisopropyl monocarbonate (Perhexyl I, manufactured by NOF Corp.), and t-butylperoxymaleic acid (Perbutyl MA, manufactured by NOF Corp.). The initiator is not limited to these.

[0033] The amount of initiator added when producing the polymer (X1) is preferably 0.1% by mass or more and less than 10% by mass, more preferably 0.3% by mass or more and less than 6% by mass, and even more preferably 0.5% by mass or more and less than 3% by mass, based on the total amount of the macromonomer (M1), the monomer (M2), and other monomers. The larger the amount of initiator added, the better the coatability, and the smaller the amount, the better the water slipping property.

[0034] The polymer (X1) can be produced by a polymerization method such as solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, etc. The initiator may be used in a manner appropriate for each polymerization method.

[0035] <Molecular weight of polymer (X1)> The weight-average molecular weight of the polymer (X1) is preferably 5,000 to 400,000, more preferably 5,000 to 300,000, and particularly preferably 10,000 to 200,000. The smaller the weight-average molecular weight, the lower the viscosity of the thermosetting resin composition and the better the coatability, while the larger the weight-average molecular weight, the more firmly the polymer (X1) is fixed to the cured film, which tends to improve the water sliding property and scratch resistance.

[0036] The molecular weight of the polymer (X1) is a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) and converted into standard polystyrene.

[0037] <Content of polymer (X1)> The content of polymer (X1) in composition (A1) is preferably 5 to 95 mass%, more preferably 8 to 90 mass%, and even more preferably 10 to 75 mass%, of the total mass of polymer (X1), compound (Y1), and compound (Z1). A higher content tends to improve the water sliding property of the cured film, while a lower content tends to increase the scratch resistance and hardness of the cured film.

[0038] <Compound (Y1)> The compound (Y1) is a compound having two or more optionally blocked isocyanate groups per molecule. When the composition (A1) is cured, the isocyanate groups of the compound (Y1) react with the active hydrogen groups of the polymer (X1) and the active hydrogen groups of the compound (Z1), forming bonds such as urethane bonds between these compounds and the polymer. This increases the crosslink density of the cured product, such as a cured film, which is thought to improve weather resistance and contamination resistance.

[0039] Examples of the compound (Y1) include bifunctional isocyanates such as hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and 4,4-dicyclohexyl diisocyanate, as well as trifunctional or higher isocyanates such as biuret compounds, trimethylolpropane adduct compounds, isocyanurates, and allophanates synthesized using these bifunctional isocyanates as starting materials.

[0040] Examples of the compound (Y1) include a biuret of hexamethylene diisocyanate (trade name: Duranate (registered trademark) 22A-75P), an adduct of hexamethylene diisocyanate (trade name: Duranate P-301-75E), an isocyanurate of hexamethylene diisocyanate (trade name: Duranate TPA-100), a blocked isocyanate (trade name: Duranate MF-K60X), and a trimethylol propionate of 1,3-bis(isocyanatomethyl)cyclohexane (trade name: Duranate MF-K60X) manufactured by Asahi Kasei Chemicals. Examples of such isocyanates include tri- or higher functional isocyanates and blocked isocyanates, such as a trimethylolpropane adduct (trade name: Takenate (registered trademark) D-120N), an isocyanurate of 1,3-bis(isocyanatomethyl)cyclohexane (trade name: Takenate D-127N), a trimethylolpropane adduct of isophorone diisocyanate (trade name: Takenate D-140N), and an allophanate of hexamethylene diisocyanate manufactured by Sumika Covestro Urethane Co., Ltd. (trade name: Desmodur (registered trademark) XP2679).

[0041] As the compound (Y1), a tri- or higher functional isocyanate (hereinafter referred to as "compound (Y2)") is preferred from the viewpoint of improving the crosslink density of the cured film and improving the weather resistance and stain resistance. The compound (Y1) may be used alone or in combination of two or more types.

[0042] The content of compound (Y1) in composition (A1) is preferably 5 to 60 mass%, more preferably 7 to 50 mass%, and even more preferably 10 to 45 mass%, of the total mass of polymer (X1), compound (Y1), and compound (Z1). A higher content tends to improve the scratch resistance and hardness of the cured film, while a lower content tends to improve water sliding properties.

[0043] <Compound (Z1)> The compound (Z1) is a compound having two or more active hydrogen groups in one molecule. The active hydrogen group is, for example, a functional group such as a hydroxyl group, a mercapto group, or an amino group. The active hydrogen group can react with the isocyanate group of the compound (Y1) having an isocyanate group to form a bond such as a urethane bond. The hydroxyl group may be primary, secondary, or tertiary, but is preferably primary or secondary. The mercapto group and amino group may also be primary, secondary, or tertiary, but is preferably primary or secondary.

[0044] The active hydrogen group of the compound (Z1) is most preferably a hydroxyl group, followed by a mercapto group, and then an amino group, from the viewpoints of availability of raw materials and resistance to yellowing of the cured film.

[0045] When the active hydrogen group of the compound (Z1) is a hydroxyl group, any known polyol compound can be used without any particular limitation.

[0046] <Compound (Z1) having two hydroxyl groups per molecule> When the active hydrogen group of the compound (Z1) is a hydroxyl group, any known polyol compound can be used without any particular limitation. Specific examples of the polyol compounds having two hydroxyl groups per molecule include, for example, chain aliphatic glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and bishydroxyethoxybenzene; Examples of suitable polyols include alicyclic glycols such as 4-cyclohexanediol and 1,4-cyclohexanedimethanol; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; polycarbonate diols; dimer acid diols; polyether polyols obtained by addition polymerization of the above glycols with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of a polymerization initiator; and polyester diols obtained by condensing the above glycols with polycarboxylic acids.

[0047] Among compounds having two hydroxyl groups in one molecule, polycarbonate diols with large molecular weights are preferred because they increase the hardness of the cured film. Commercially available polycarbonate diols include, for example, Kuraray Polyol C-1015N, Kuraray Polyol C-1065N (Kuraray carbonate diol: 2-methyl-1,8-octanediol / 1,9-nonanediol, number average molecular weight approximately 1000), Kuraray Polyol C-2015N, Kuraray Polyol C-2065N (Kuraray carbonate diol: 2-methyl-1,8-octanediol / 1,9-nonanediol, number average molecular weight approximately 2000), Kuraray Polyol C-1050, Kuraray Polyol C-1090 (Kuraray carbonate diol: 3-methyl-1,5-pentanediol / 1,6-hexanediol, number average molecular weight approximately 1000), Kuraray Polyol C-2050, Kuraray Polyol C-2090 (Kuraray carbonate diol: 3-methyl-1,5-pentanediol / 1,6-hexanediol, number average molecular weight approximately 2000), DURANOL (registered trademark)-T5650E (Asahi Kasei polycarbonate diol: 1,5-pentanediol / 1,6-hexanediol, number average molecular weight approximately 500), DURANOL-T5651 (Asahi Kasei polycarbonate diol: 1,5-pentanediol / 1,6-hexanediol, number average molecular weight approximately 1000), DURANOL-T5652 (Asahi Kasei polycarbonate diol: 1,5-pentanediol / 1,6-hexanediol, number average molecular weight approximately 2000).

[0048] Of the compounds (Z1), compounds having three or more hydroxyl groups per molecule are preferred because they are more likely to improve the hardness of the cured film than compounds having two hydroxyl groups per molecule. Specific examples of the compound having three or more hydroxyl groups per molecule include trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol, polycaprolactone triol, and polycaprolactone tetraol; polyether polyols obtained by addition polymerization of the trifunctional or tetrafunctional aliphatic alcohols or the like with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of a polymerization initiator; and polyester polyols obtained by condensing the trifunctional or tetrafunctional aliphatic alcohols or the like with polycarboxylic acids.

[0049] Among these compounds having three or more hydroxyl groups per molecule, compounds having five or more hydroxyl groups per molecule and a dendritic branched structure are particularly preferred because they are most effective in improving the hardness and scratch resistance of the cured film. Compounds having five or more hydroxyl groups per molecule and a dendritic branched structure are sometimes called dendrimers or hyperbranched polymers.

[0050] Examples of commercially available dendrimers having a hydroxyl group at the end include Boltorn (registered trademark) H20 (hydroxyl group concentration 8.73 to 9.27 mmol / g, molecular weight 2100 (catalog value)), Boltorn H311 (hydroxyl group concentration 4.10 to 4.63 mmol / g, molecular weight 5300 (catalog value)), Boltorn H2004 (hydroxyl group concentration 2.23 to 2.67 mmol / g, molecular weight 3100 (catalog value)), Boltorn P500 (hydroxyl group concentration 9.98 to 11.23 mmol / g, molecular weight 1800 (catalog value)), Boltorn P1000 (hydroxyl group concentration 7.66 to 11.23 mmol / g, molecular weight 1500 (catalog value)), Boltorn Examples include U3000 (hydroxyl group concentration 0.27 mmol / g, molecular weight 6500 (catalog value)) and Boltorn W3000 (hydroxyl group concentration 0.27 mmol / g, molecular weight 10000 (catalog value)).

[0051] Examples of commercially available hyperbranched polymers with terminal hydroxyl groups include BASF's Basonol (registered trademark) HPE 1170B (hydroxyl group concentration 4.99 mmol / g, molecular weight 1800 (catalog value)) and Basonol HPE 021 (hydroxyl group concentration 3.39 mmol / g, molecular weight 1400 (catalog value)).

[0052] Specific examples of the compound (Z1) having two mercapto groups per molecule include 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexaneedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, bis(mercaptomethyl)sulfide, bis(mercaptoethyl)sulfide, bis(mercaptomethyl)ether, bis(mercaptoethyl)ether, bis(mercaptomethyl)amine, and bis(mercaptoethyl)amine.

[0053] Specific examples of the compound (Z1) having three or more mercapto groups per molecule include trimethylolpropane tris(3-mercaptopropionate), tris[(3-mercaptopropionyloxy)-ethyl]isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(2-(3-sulfanylbutanoyloxy)ethyl)-1,3,5-triazinane-2,4,6-trione, and trimethylolpropane tris(3-mercaptobutyrate).

[0054] Specific examples of the compound (Z1) having two amino groups per molecule include low molecular weight diamines in which the alcoholic hydroxyl group of the above-mentioned low molecular weight diol is substituted with an amino group, such as ethylenediamine and propylenediamine; polyether diamines such as polyoxypropylenediamine and polyoxyethylenediamine; menthenediamine, isophoronediamine, norbornenediamine, bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiro(5,5 alicyclic diamines such as m-xylenediamine, α-(m / p-aminophenyl)ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldimethyldiphenylmethane, diaminodiethyldiphenylmethane, dimethylthiotoluenediamine, diethyltoluenediamine, α,α'-bis(4-aminophenyl)-p-diisopropylbenzene, and the like; hydrazine; and dicarboxylic acid dihydrazide compounds, which are compounds of hydrazine with the dicarboxylic acids exemplified in the polycarboxylic acids used in the polyester polyols.

[0055] Among the compounds (Z1), examples of compounds having three or more amino groups in one molecule include aliphatic amines such as triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

[0056] As the compound (Z1), a single compound may be used, or two or more compounds may be used in combination.

[0057] The molecular weight of compound (Z1) is preferably 150 to 30,000, more preferably 600 to 10,000, and even more preferably 800 to 5,000. The higher the molecular weight, the higher the hardness of the cured film, and the lower the molecular weight, the better the appearance of the cured film. Here, the molecular weight is the weight-average molecular weight (Mw) measured by gel permeation chromatography (GPC) and converted into standard polystyrene.

[0058] The active hydrogen group concentration of the compound (Z1) is preferably 0.35 to 18.0 mmol / g, more preferably 0.90 to 12.0 mmol / g. The higher the hydroxyl group concentration, the higher the hardness of the cured film tends to be, and the lower the hydroxyl group concentration, the better the solubility of the compound (Z1) in the composition (A1).

[0059] The content of compound (Z1) in composition (A1) is preferably 3 to 60 mass%, more preferably 5 to 50 mass%, and even more preferably 10 to 45 mass%, of the total mass of polymer (X1), compound (Y1), and compound (Z1). The higher this content, the higher the scratch resistance and hardness of the cured film tend to be, and the lower the content, the higher the water slippage of the cured film tends to be.

[0060] <Compounds having only one optionally blocked isocyanate group per molecule> Composition (A1) may contain a compound having only one optionally blocked isocyanate group per molecule. Examples of the compound having only one optionally blocked isocyanate group per molecule include 2-isocyanatopropane, 2-isocyanato-2-methylpropane, isocyanatocyclohexane, 1-isocyanato-4-isopropenyl-1-methyl-cyclohexane, 4-(1-isocyanato-1-methylethyl)-1-methyl-1-cyclohexene, 1,3-dimethyl-5-isocyanatoadamantane, and 1-(1-isocyanato-1-methylethyl)-3-isopropenylbenzene.

[0061] The content of the compound having only one optionally blocked isocyanate group per molecule in composition (A1) is preferably less than 8 mass %, more preferably less than 4 mass %, and particularly preferably less than 2 mass %.

[0062] <Compounds with only one active hydrogen group per molecule> The composition (A1) may contain a compound having only one active hydrogen group per molecule. Examples of the compound having only one blocked active hydrogen group per molecule include alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, palmitoleic alcohol, heptadecanol, and stearyl alcohol (including isomers), as well as monofunctional thiols and monoamines.

[0063] The content of the compound having only one optionally blocked active hydrogen group per molecule in composition (A1) is preferably less than 8 mass %, more preferably less than 4 mass %, and particularly preferably less than 2 mass %.

[0064] <Inorganic fine particles> The composition (A1) may contain inorganic fine particles such as silica fine particles. The inorganic fine particles contribute to improving the scratch resistance of the cured film. Since this further improves scratch resistance, the inorganic fine particles preferably have functional groups on their surfaces that can react with the active hydrogen groups of the polymer (X1) or the compound (Z1) or the isocyanate groups of the compound (Y1) to form bonds such as urethane bonds. Examples of such functional groups include mercapto groups, isocyanate groups, epoxy groups, hydroxyl groups, amino groups, and carbamoyl groups. Mercapto groups, isocyanate groups, and epoxy groups are preferred because of their high reactivity with active hydrogen groups or isocyanate groups.

[0065] As the inorganic fine particles to which the functional groups are introduced, silica fine particles are preferred in terms of ease of introduction. As a method for introducing the functional groups onto the surface of silica fine particles, for example, a method of treating by reacting the silanol groups on the surface of the silica fine particles with a silane coupling agent having the desired functional group can be mentioned.

[0066] The inorganic fine particles are preferably blended in the form of a dispersion. Specific examples of commercially available dispersions of silica fine particles include SIRMEK20WT%-M70, SIRMEK50WT%-E86, SIRMIBK15WT%-M96, and SIRMIBK30WT%-S39 manufactured by CIK Nanotech, and MEK-EC-2130Y, MEK-EC-6150P, and MEK-EC-7150P manufactured by Nissan Chemical Industries, Ltd. The inorganic fine particles may be used alone or in combination of two or more types.

[0067] The average particle size of the inorganic fine particles is preferably 300 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less, from the viewpoint of transparency of the cured film. Furthermore, from the viewpoint of improving scratch resistance, the average particle size is preferably 2 nm or more, more preferably 4 nm or more. The average particle size is a value converted from the specific surface area measured by the BET adsorption method (in accordance with JIS Z8830).

[0068] The content of the inorganic fine particles is preferably 1 to 60 mass %, more preferably 3 to 50 mass %, and even more preferably 5 to 45 mass %. The greater the amount of inorganic fine particles added, the better the hardness of the cured film.

[0069] <Curing accelerating catalyst> Composition (A1) can be cured at room temperature or by heating, and may contain a curing-accelerating catalyst, if necessary. Examples of curing-accelerating catalysts include triethylamine, tetra(2-ethylhexyl) titanate, di-n-butyltin dilaurate, and 1,4-diazabicyclo[2.2.2]octane. The curing-accelerating catalysts may be used alone or in combination of two or more. The content of the curing-accelerating catalyst in composition (A1) is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.1 to 1 part by mass, per 100 parts by mass of isocyanate.

[0070] <Organic solvents> Composition (A1) may optionally contain an organic solvent. Examples of organic solvents include alcohol-based solvents such as methanol, isopropyl alcohol, n-butanol, diacetone alcohol, 2-methoxyethanol (methyl cellosolve), 2-ethoxyethanol (ethyl cellosolve), 2-butoxyethanol (butyl cellosolve), and tertiary amyl alcohol; carboxylic acid ester-based solvents such as ethyl acetate, n-propyl acetate, butyl acetate, and butyl formate; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone, and cyclohexanone; amide-based solvents such as dimethylformamide and dimethylacetamide; ether-based solvents such as diethyl ether, methoxytoluene, 1,2-dimethoxyethane, 1,2-dibutoxyethane, 1,1-dimethoxymethane, 1,1-dimethoxyethane, 1,4-dioxane, and tetrahydrofuran; and aliphatic and aromatic hydrocarbon-based solvents such as hexane, pentane, xylene, toluene, and benzene. These solvents may be used alone or in combination.

[0071] <UV absorbers, light stabilizers> Composition (A1) may contain a weather resistance imparting agent such as an ultraviolet absorber or a light stabilizer to impart weather resistance to the cured film. As the weather resistance imparting agent, an ultraviolet absorber having a maximum absorption spectrum in the ultraviolet wavelength region that accelerates substrate deterioration is preferred.

[0072] The ultraviolet absorber is preferably a compound derived from a triazine-based, benzophenone-based, benzotriazole-based, phenyl salicylate-based, or phenyl benzoate-based compound, with benzophenone-based compounds being preferred because they can be contained in large amounts in the composition, and triazine-based and benzotriazole-based compounds being preferred because they can prevent yellowing of substrates such as polycarbonate. The ultraviolet absorber is more preferably one having a maximum absorption wavelength in the range of 240 to 380 nm.

[0073] Examples of the ultraviolet absorber include a mixture of 2-[4-(2-hydroxy-3-dodecyloxy-propyl)oxy-2-hydroxyphenyl]-4,6-[bis(2,4-dimethylphenyl)-1,3,5-triazine] and 2-[4-(2-hydroxy-3-tridecyloxy-propyl)oxy-2-hydroxyphenyl]-4,6-[bis(2,4-dimethylphenyl)-1,3,5-triazine] (trade name "Tinuvin (registered trademark) 400") manufactured by BASF; [2,4,6-[2-{4-(octyl-2-methylethanoate)oxy-2-hydroxyphenyl}]-1,3,5-triazine] {trade name: "Tinuvin 479"}, tris[2,4,6-[2-{4-(octyl-2-methylethanoate)oxy-2-hydroxyphenyl}]-1,3,5-triazine] {trade name: "Tinuvin 777"}, and other commercially available products such as 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and -Hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, phenyl salicylate, p-tert-butylphenyl salicylate, p-(1,1,3,3-tetramethylbutyl)phenyl salicylate, 3-hydroxyphenyl benzoate, phenylene-1,3-dibenzoate, 2- Examples of the benzotriazole include (2-hydroxy-5'-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octylphenyl)benzotriazole, and 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole. These may be used alone or in combination of two or more.

[0074] <Other components of composition (A1)> Composition (A1) may contain, as needed, components such as antioxidants, anti-yellowing agents, bluing agents, pigments, leveling agents, antifoaming agents, thickeners, anti-settling agents, antistatic agents, and anti-fogging agents.

[0075] [Composition (A2)] The thermosetting resin composition of the present invention is a thermosetting resin composition [hereinafter referred to as "composition (A2)"] that contains a polymer (X1) having a polydimethylsiloxane structure and an active hydrogen group in the main chain or side chain, and a compound (Y2) having three or more optionally blocked isocyanate groups per molecule.

[0076] <Polymer (X1)> The polymer (X1) having a polydimethylsiloxane structure and an active hydrogen group in the main chain or side chain, which is a component of the composition (A2), is the same as the polymer (X1) in the composition (A1).

[0077] The content of polymer (X1) in composition (A2) is preferably 5 to 95 mass%, more preferably 8 to 90 mass%, and even more preferably 10 to 75 mass%, of the total mass of polymer (X1) and compound (Y2). A higher content tends to improve the water sliding property of the cured film, while a lower content tends to increase the scratch resistance and hardness of the cured film.

[0078] <Compound (Y2)> Compound (Y2) is a compound having three or more optionally blocked isocyanate groups per molecule. When composition (A2) is cured, the isocyanate groups of compound (Y2) react with the active hydrogen groups of the polymer (X1), forming bonds such as urethane bonds between these compounds and the polymer. This increases the crosslink density of the cured product, such as a cured film, and is thought to improve weather resistance and stain resistance. Compound (Y2) is a compound of compound (Y1), a component of composition (A1), having three or more optionally blocked isocyanate groups per molecule, so a detailed description is omitted.

[0079] The content of compound (Y2) in composition (A2) is preferably 10 to 99 mass%, more preferably 20 to 97 mass%, and even more preferably 95 to 30 mass%, of the total mass of polymer (X1) and compound (Y2). A higher content tends to improve the scratch resistance and hardness of the cured film, while a lower content tends to improve the water sliding properties of the cured film.

[0080] <Inorganic fine particles> The composition (A2) may contain the same inorganic fine particles such as silica fine particles as those in the composition (A1) in the same amount and for the same purpose.

[0081] <Other components of composition (A2)> Composition (A2) may contain components other than polymer (X1) and compound (Y2). Examples of such components include compound (Y1) other than compound (Y2) described in composition (A1), compound (Z1), a compound having only one optionally blocked isocyanate group per molecule, a compound having only one active hydrogen group per molecule, a curing accelerator, an organic solvent, an ultraviolet absorber, a light stabilizer, an antioxidant, an anti-yellowing agent, a bluing agent, a pigment, a leveling agent, an antifoaming agent, a thickener, an anti-settling agent, an antistatic agent, and an anti-fogging agent.

[0082] [Composition (A3)] The thermosetting resin composition of the present invention is a thermosetting resin composition containing a polymer (X2) [hereinafter referred to as "polymer (X2)"] having a polydimethylsiloxane structure and an optionally blocked isocyanate group in the main chain or side chain, and a compound (Z1) having two or more active hydrogen groups per molecule.

[0083] <Polymer (X2)> The polymer (X2) is a polymer having a polydimethylsiloxane structure and optionally blocked isocyanate groups in its main chain or side chain. That is, the polymer (X2) must contain a polydimethylsiloxane structure in either or both of its main chain and side chain, and must contain an isocyanate group in either or both of its main chain and side chain.

[0084] <Polydimethylsiloxane structure> The polydimethylsiloxane structure contributes to the water-repellent properties of the cured film formed from the composition (A3) containing the polymer (X2). The isocyanate group reacts with the active hydrogen group of the compound (Z1) to firmly fix the polymer (X2) to the cured film, contributing to the durability of the water-repellent properties and scratch resistance.

[0085] Methods for introducing a polydimethylsiloxane structure into polymer (X2) include, as explained for polymer (X1), (1) a method of copolymerizing macromonomer (M1) with another monomer, (2) a method of copolymerizing polydimethylsiloxane having mercapto groups at the α- and ω-positions with another monomer as a chain transfer agent, (3) a method of copolymerizing an azo compound having a polydimethylsiloxane structure with another monomer, and (4) a method of adding a hydroxyl group of a polydimethylsiloxane having a terminal hydroxyl group to the isocyanate group of a polymer having an optionally blocked isocyanate group.

[0086] <Optionally blocked isocyanate group> The isocyanate group which may be blocked in the polymer (X2) can be appropriately deblocked to react with the active hydrogen group of the compound (Z1) having the active hydrogen group to form a bond such as a urethane bond.

[0087] To introduce an optionally blocked isocyanate group into polymer (X2), a preferred method is to copolymerize a monomer having an optionally blocked isocyanate group [hereinafter referred to as "monomer (M3)] with macromonomer (M1) as another monomer in the method (1) for introducing a polydimethylsiloxane structure. The blocked isocyanate group may be obtained by copolymerizing a monomer having an isocyanate group and then blocking the isocyanate group of the resulting copolymer by a known method.

[0088] <Production of Polymer (X2)> Hereinafter, the method (1) for producing the polymer (X2) by copolymerizing the macromonomer (M1) with the monomer (M3) as another monomer will be described.

[0089] <Macromonomer (M1)> The macromonomer (M1) used to produce the polymer (X2) is the same as that described for the polymer (X1). It is similar to the above.

[0090] The amount of macromonomer (M1) incorporated into polymer (X2) is preferably 5% by mass or more and less than 70% by mass, more preferably 10% by mass or more and less than 60% by mass, and even more preferably 20% by mass or more and less than 50% by mass. The greater the amount incorporated, the better the water sliding properties of the cured film, and the smaller the amount incorporated, the less unpolymerized macromonomer (M1) there is, so the transparency of the cured film tends to be better.

[0091] <Monomer (M3)> Monomer (M3) is used to introduce an isocyanate group into polymer (X2). Examples of monomer (M3) include 2-isocyanatoethyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, and methacryloyloxyethoxyethyl isocyanate. The isocyanate group contained in these monomers may be blocked with a blocking agent such as alcohol, phenols, lactam, oxime, alkyl acetoacetate, alkyl malonate, phthalimide, imidazole, hydrogen chloride, hydrogen cyanide, or sodium hydrogen sulfite.

[0092] Specific examples of blocking agents include alcohols such as methanol, ethanol, and benzyl alcohol; phenols such as phenol and cresol; lactams such as caprolactam and butyrolactam; and oximes such as cyclohexanone, oxime, and methyl ethyl ketoxime.

[0093] The amount of isocyanate groups introduced into the polymer (X2) is preferably 0.1 mmol / g or more and less than 4.0 mmol / g, more preferably 0.2 mmol / g or more and less than 3.5 mmol / g, and more preferably 0.3 mmol / g or more and less than 3.0 mmol / g. The greater the amount introduced, the better the durability of the cured film tends to be, while the smaller the amount introduced, the better the water slipping property tends to be. In the case of a blocked isocyanate, the amount introduced of the isocyanate group refers to the amount introduced after deblocking.

[0094] <Other monomers> In the production of polymer (X2), other monomers can be copolymerized in addition to macromonomer (M1) and monomer (M3) as long as the copolymerization does not impair performance. Examples of other monomers include the same as those other than macromonomer (M1) and monomer (M2) described for polymer (X1). Among these, aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, vinylbiphenyl, vinylanthracene, and vinylxylene can be included as monomers constituting polymer (X2), thereby exhibiting particularly good water-slip properties. The aromatic vinyl monomer-derived structural units are preferably contained in polymer (X2) in an amount of 30% by mass or more (hereinafter referred to as "polymer (X2-2)").

[0095] <Initiator> In the production of the polymer (X2), it is preferable to use an initiator when copolymerizing the macromonomer (M1) and the monomer (M3). Examples of the initiator include the same initiators as those described for the polymer (X1).

[0096] The amount of initiator added when producing the polymer (X2) is preferably 0.1% by mass or more and less than 10% by mass, more preferably 0.3% by mass or more and less than 6% by mass, and even more preferably 0.5% by mass or more and less than 3% by mass, based on the total amount of the macromonomer (M1), the monomer (M3), and other monomers. The higher the amount of initiator added, the better the coatability, and the lower the amount, the better the water slipping property.

[0097] The polymer (X2) can be produced by, for example, a polymerization method such as solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization. An initiator may be used in a manner appropriate for each polymerization method.

[0098] <Molecular weight of polymer (X2)> The weight-average molecular weight of polymer (X2) is preferably 5,000 to 400,000, more preferably 5,000 to 300,000, and particularly preferably 10,000 to 200,000. When the weight-average molecular weight is less than 400,000, the viscosity of the thermosetting resin composition decreases, improving coatability. When the weight-average molecular weight is more than 1,000, polymer (X2) is firmly fixed to the cured film, improving water sliding properties and scratch resistance. The molecular weight of polymer (X2) is the weight-average molecular weight (Mw) measured by gel permeation chromatography (GPC) in terms of standard polystyrene.

[0099] <Content of polymer (X2)> The content of polymer (X2) in composition (A3) is preferably 5 to 95 mass%, more preferably 8 to 90 mass%, and even more preferably 10 to 75 mass%, of the total mass of polymer (X2) and compound (Z1). A higher content tends to improve the water sliding property of the cured film, while a lower content tends to increase the scratch resistance and hardness of the cured film.

[0100] <Compound (Z1)> The compound (Z1) having two or more active hydrogen groups in one molecule is the same as the compound (Z1) in the composition (A1), and therefore a detailed description thereof will be omitted.

[0101] The content of compound (Z1) in composition (A2) is preferably 3 to 60 mass%, more preferably 5 to 50 mass%, and even more preferably 10 to 45 mass%, of the total mass of polymer (X1) and compound (Z1). A higher content tends to improve the scratch resistance and hardness of the cured film, while a lower content tends to improve the water sliding properties of the cured film.

[0102] <Inorganic fine particles> The composition (A3) may contain inorganic fine particles such as silica fine particles in the same amount as in the composition (A1) for the same purpose.

[0103] <Other components of composition (A3)> Composition (A3) may contain components other than polymer (X2) and compound (Z1), such as compound (Y1) described in composition (A1), a compound having only one optionally blocked isocyanate group per molecule, a compound having only one active hydrogen group per molecule, a curing accelerator, an organic solvent, an ultraviolet absorber, a light stabilizer, an antioxidant, an anti-yellowing agent, a bluing agent, a pigment, a leveling agent, an antifoaming agent, a thickener, an anti-settling agent, an antistatic agent, and an anti-fogging agent.

[0104] [Composition (A4)] The thermosetting resin composition of the present invention is a thermosetting resin composition comprising a polymer (X2) [hereinafter referred to as "polymer (X2)"] having a polydimethylsiloxane structure and an optionally blocked isocyanate group in the main chain or side chain, a compound (Z1) having two or more active hydrogen groups per molecule, and a compound (Y1) having two or more optionally blocked isocyanate groups per molecule.

[0105] <Polymer (X2)> The polymer (X2) having a polydimethylsiloxane structure and an active hydrogen group in the main chain or side chain, which is a component of the composition (A4), is the same as the polymer (X2) in the composition (A3). Therefore, detailed description will be omitted.

[0106] The content of polymer (X2) in composition (A4) is preferably 5 to 95 mass%, more preferably 8 to 90 mass%, and even more preferably 10 to 75 mass%, of the total mass of polymer (X2), compound (Z1), and compound (Y1). A higher content tends to improve the water sliding property of the cured film, while a lower content tends to increase the scratch resistance and hardness of the cured film.

[0107] <Compound (Z1)> The compound (Z1) having two or more active hydrogen groups in one molecule is the same as the compound (Z1) in the composition (A1), and therefore a detailed description thereof will be omitted.

[0108] The content of compound (Z1) in composition (A4) is preferably 5 to 95 mass%, more preferably 10 to 80 mass%, and even more preferably 15 to 50 mass%, of the total mass of polymer (X2), compound (Z1), and compound (Y1). A higher content tends to improve the scratch resistance and hardness of the cured film, while a lower content tends to improve the water sliding properties of the cured film.

[0109] <Compound (Y1)> The compound (Y1) having two or more optionally blocked isocyanate groups in one molecule is the same as the compound (Y1) in the composition (A1), and therefore a detailed description thereof will be omitted.

[0110] The content of compound (Y1) in composition (A4) is preferably 5 to 95 mass%, more preferably 10 to 80 mass%, and even more preferably 15 to 50 mass%, of the total mass of polymer (X2), compound (Z1), and compound (Y1). A higher content tends to improve the scratch resistance and hardness of the cured film, while a lower content tends to improve the water sliding properties of the cured film.

[0111] <Inorganic fine particles> The composition (A4) may contain inorganic fine particles such as silica fine particles in the same amount as in the composition (A1) for the same purpose.

[0112] <Other components of composition (A4)> Composition (A4) may contain components other than polymer (X2) and compounds (Z1) and (Y1), such as a compound having only one optionally blocked isocyanate group per molecule, a compound having only one active hydrogen group per molecule, a curing accelerator, an organic solvent, an ultraviolet absorber, a light stabilizer, an antioxidant, an anti-yellowing agent, a bluing agent, a pigment, a leveling agent, an antifoaming agent, a thickener, an anti-settling agent, an antistatic agent, and an anti-fogging agent.

[0113] [Cured product] The cured product obtained by curing the thermosetting resin composition of the present invention can be obtained, for example, by applying the thermosetting resin composition to a substrate by a known method.

[0114] <Base material> Examples of the substrate include metals such as zinc-plated steel sheet, zinc alloy-plated steel sheet, stainless steel sheet, and tin-plated steel sheet, polymethyl methacrylate resin, polycarbonate resin, polyester resin, polystyrene resin, ABS resin, AS resin, polyamide resin, polyarylate resin, polymethacrylimide resin, and polyallyl diglycol carbonate resin. It is particularly effective in improving the scratch resistance of the surfaces of polymethyl methacrylate resin, polycarbonate resin, polystyrene resin and polymethacrylimide resin.

[0115] <Coating method> The coating onto the substrate can be carried out by a known method such as brush coating, gravure coating, die coating, bar coating, spray coating, dip coating, spin coating, curtain coating, etc. If necessary, the thermosetting resin composition can be applied multiple times.

[0116] <Curing method> The temperature for curing the coating composition of the present invention may be appropriately set taking into consideration the heat resistance and thermal deformation properties of the substrate, but is preferably from 20° C. to 200° C., more preferably from 60° C. to 150° C. The curing time is preferably from several minutes to several hours.

[0117] <Thickness of the cured film> The thickness of the cured film obtained by curing the thermosetting resin composition of the present invention is preferably 1 to 50 μm, preferably 1 μm or more in terms of obtaining the effects of the coating composition of the present invention, and preferably 50 μm or less in terms of reducing cracks.

[0118] [Laminate] The laminate of the present invention is a laminate having a substrate and a layer made of a cured film obtained by curing the thermosetting resin composition of the present invention. The laminate of the present invention has excellent water sliding properties and transparency, and is therefore suitable for various lamp lenses and glazing for automobiles, as well as radome parts such as emblems and front grilles on the front of electromagnetic wave radar devices, and is particularly suitable for use in millimeter wave radar covers. [Example]

[0119] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these. In the explanations, "parts" means "parts by mass." Measurements and evaluations were carried out using the following methods.

[0120] [Measurement and evaluation method] <Molecular weight> The molecular weight of the polymer produced in the present invention is a weight average molecular weight (Mw) calculated in terms of standard polystyrene, measured by gel permeation chromatography (GPC) under the following conditions. Equipment: Waters "e2695" Column: Tosoh "TSKgel Super H3000+H4000+H6000" Detector: Differential refractive index detector (RI detector / built-in), Solvent: tetrahydrofuran, Temperature: 40℃, Flow rate: 0.5mL / min, Injection volume: 10μL, Concentration: 0.2% by mass, Calibration sample: monodisperse polystyrene, Calibration method: Polystyrene equivalent

[0121] <Evaluation sample> The thermosetting resin composition was applied to the PMMA side of a two-layer laminate sheet of polymethyl methacrylate (PMMA) and polycarbonate (ShineTech (registered trademark) AW-10U, total thickness 1.0 mm, PMMA layer 60 μm) using a bar coater (#30) so that the cured coating would be 7 μm thick. This was then heat-treated at 110°C for 30 minutes to produce a laminate in which a cured film of the thermosetting resin composition was formed on the substrate. This was used as an evaluation sample and evaluated as follows.

[0122] <Transparency> The transparency of the evaluation sample was evaluated by measuring the total light transmittance and diffuse transmittance (haze value) using a haze meter (SH 7000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7136: 2000. The transparency evaluation criteria are as follows: ·Judgment criteria 3: Haze value is less than 1%. 2: Haze value is 1% or more and less than 5%. 1: Haze value is 5% or more.

[0123] <Initial hydrophobicity> The initial water slide property of the evaluation sample was evaluated by measuring the sliding angle of 20 μL of water using a contact angle meter (DM-500, manufactured by Kyowa Interface Science Co., Ltd.) by the sliding method. The evaluation criteria for the initial water slide property are as follows: ·Judgment criteria 5: The sliding angle of 20 μL of water is greater than 1° and less than 20°. 4: The sliding angle of 20 μL of water is greater than 20° and less than 50°. 3: The sliding angle of 20 μL of water is greater than 50° and less than 70°. 2: The sliding angle of 20 μL of water is greater than 70° and less than 80°. 1: The sliding angle of 20 μL of water is greater than 80°.

[0124] <Water slippage after wet heat test> The evaluation sample was left to stand at 50°C and 99% humidity for 24 hours, then removed and water droplets adhering to the surface of the evaluation sample were removed, and the water slippage after the moist heat test was evaluated by measuring the sliding angle of 20 μL of water in the same manner as in the evaluation of initial water slippage. The evaluation criteria for water slippage after the moist heat test are as follows: ·Judgment criteria 5: The sliding angle of 20 μL of water is greater than 1° and less than 20°. 4: The sliding angle of 20 μL of water is greater than 20° and less than 50°. 3: The sliding angle of 20 μL of water is greater than 50° and less than 70°. 2: The sliding angle of 20 μL of water is greater than 70° and less than 80°. 1: The sliding angle of 20 μL of water is greater than 80°.

[0125] <Scratch resistance> The evaluation sample was subjected to a flat abrasion test using a KASAI scratch tester. Steel wool #000 was placed on the evaluation sample, and 250 g / 1.1 cm 2 After 20 reciprocating rubs using a rubbing tester under a load of 1000 kJ / min, the diffuse transmittance (haze value) was measured using a haze meter (SH 7000, manufactured by Nippon Denshoku Industries Co., Ltd.). Scratch resistance was evaluated based on the value obtained by subtracting the initial haze value from the measured haze value (increased haze value (Δ haze value)). The evaluation criteria for scratch resistance are as follows: ·Judgment criteria 3: Increased haze value is less than 25%. 2: Increased haze value is 25% or more but less than 40%. 1: Increased haze value is 40% or more.

[0126] <Pencil hardness> The pencil hardness of the evaluation samples was evaluated in accordance with ISO / DIS 15184. After the test, the highest hardness that did not cause any scratches was adopted as the pencil hardness of the cured film. The evaluation criteria for pencil hardness are as follows: ·Judgment criteria 3: F or higher. 2:B~HB. Less than 1:B.

[0127] [Polymer preparation] The methods for preparing the polymers used in the examples and comparative examples of the present invention are described below. Polymers (1-1) to (1-4) prepared in the following examples correspond to polymer (X1), polymers (2-1) to (2-5) correspond to polymer (X2), and of these, polymers (2-1) to (2-4) correspond to polymer (X2-2). Furthermore, polymer (3-1) prepared in the following examples is a polymer that does not have a polydimethylsiloxane structure and does not correspond to either polymer (X1) or polymer (X2).

[0128] <Preparation of Polymer (1-1)> A 300 ml five-neck separable flask equipped with a stirrer, a dropping funnel, a cooling condenser, and a thermometer was charged with 18 g of toluene, 18.5 g of propylene glycol monomethyl ether acetate, 31.25 g of styrene, 0.75 g of acrylic acid, 3.0 g of 2-hydroxyethyl methacrylate, 20.0 g of polydimethylsiloxane having a methacryloyl group at one end (manufactured by JNC, Silaplane FM-0721), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxylate (manufactured by NOF Corporation, Perocta O). Furthermore, 18 g of toluene, 18.5 g of propylene glycol monomethyl ether acetate, 31.25 g of styrene, 0.75 g of acrylic acid, 3.0 g of 2-hydroxyethyl methacrylate, 10.0 g of polydimethylsiloxane having a methacryloyl group at one end (manufactured by JNC, Silaplane FM-0721), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxyate (manufactured by NOF Corp., Perocta O) were placed into the dropping funnel. Next, the flask was placed in an oil bath, stirring was started under a nitrogen atmosphere, and the internal temperature was raised to 85°C. Thirty minutes after the internal temperature reached 85°C, the raw materials from the dropping funnel were added dropwise over 2 hours, and the mixture was maintained for 1 hour. Then, 0.1 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxyate (NOF Corp., Perocta O) was added. Another 0.1 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxyate (NOF Corp., Perocta O) was added 1 hour later. The mixture was allowed to react for 5 hours, and then cooled to prepare a polymer (1-1) solution. The solid content and solids ratio of the resulting solution, as well as the weight-average molecular weight (Mw) and active hydrogen group (hydroxyl group) concentration of polymer (1-1), are shown in Table 1.

[0129] <Preparation of Polymer (1-2)> A 300 ml five-neck separable flask equipped with a stirrer, a dropping funnel, a cooling condenser, and a thermometer was charged with 36.5 g of methyl isobutyl ketone, 28.25 g of styrene, 0.75 g of acrylic acid, 6.0 g of 2-hydroxyethyl methacrylate, 20.0 g of polydimethylsiloxane having a methacryloyl group at one end (manufactured by JNC, Silaplane FM-0721), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxylate (manufactured by NOF Corp., Perocta O). The dropping funnel was charged with 36.5 g of methyl isobutyl ketone, 28.25 g of styrene, 0.75 g of acrylic acid, 6.0 g of 2-hydroxyethyl methacrylate, 10.0 g of polydimethylsiloxane having a methacryloyl group at one end (Silaplane FM-0721, manufactured by JNC), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxyate (Perocta O, manufactured by NOF Corp.). Polymer (1-2) was prepared in the same manner as in the preparation of polymer (1-1). The solid content and solids ratio of the resulting solution, as well as the weight-average molecular weight (Mw) and active hydrogen group (hydroxyl group) concentration of polymer (1-2), are shown in Table 1.

[0130] <Preparation of Polymer (1-3)> A 300 ml five-neck separable flask equipped with a stirrer, a dropping funnel, a cooling condenser, and a thermometer was charged with 36.5 g of methyl isobutyl ketone, 28.25 g of styrene, 0.75 g of acrylic acid, 6.0 g of 2-hydroxyethyl methacrylate, 20.0 g of polydimethylsiloxane having a methacryloyl group at one end (manufactured by JNC, Silaplane FM-0711), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxylate (manufactured by NOF Corp., Perocta O). The dropping funnel was charged with 36.5 g of methyl isobutyl ketone, 28.25 g of styrene, 0.75 g of acrylic acid, 6.0 g of 2-hydroxyethyl methacrylate, 10.0 g of polydimethylsiloxane having a methacryloyl group at one end (Silaplane FM-0711, manufactured by JNC), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxylate (Perocta O, manufactured by NOF Corp.). Polymer (1-3) was prepared in the same manner as in the preparation of polymer (1-1). The solid content and solids ratio of the resulting solution, as well as the weight-average molecular weight (Mw) and active hydrogen group (hydroxyl group) concentration of polymer (1-3), are shown in Table 1.

[0131] <Preparation of Polymer (1-4)> A 300 ml five-neck separable flask equipped with a stirrer, a dropping funnel, a cooling condenser, and a thermometer was charged with 36.5 g of methyl isobutyl ketone, 28.25 g of styrene, 0.75 g of acrylic acid, 6.0 g of 4-hydroxybutyl acrylate, 20.0 g of polydimethylsiloxane having a methacryloyl group at one end (manufactured by JNC, Silaplane FM-0721), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxyate (manufactured by NOF Corp., Perocta O). The dropping funnel was charged with 36.5 g of methyl isobutyl ketone, 28.25 g of styrene, 0.75 g of acrylic acid, 6.0 g of 4-hydroxybutyl acrylate, 10.0 g of polydimethylsiloxane having a methacryloyl group at one end (Silaplane FM-0721, manufactured by JNC), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxylate (Perocta O, manufactured by NOF Corp.). Polymer (1-4) was prepared in the same manner as in the preparation of polymer (1-1). The solid content and solids ratio of the resulting solution, as well as the weight-average molecular weight (Mw) and active hydrogen group (hydroxyl group) concentration of polymer (1-4), are shown in Table 1.

[0132] <Preparation of Polymer (2-1)> A 300 ml five-neck separable flask equipped with a stirrer, a dropping funnel, a cooling condenser, and a thermometer was charged with 36.5 g of toluene, 29.0 g of styrene, 20.0 g of polydimethylsiloxane having a methacryloyl group at one end (manufactured by JNC, Silaplane FM-0721), 6.0 g of 2-(acryloyloxy)ethyl isocyanate (manufactured by Showa Denko, Karenz (registered trademark) AOI), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxyate (manufactured by NOF Corp., Perocta O). The dropping funnel was charged with 36.5 g of toluene, 29.0 g of styrene, 10.0 g of polydimethylsiloxane having a methacryloyl group at one end (Silaplane FM-0721, manufactured by JNC), 6.0 g of 2-(acryloyloxy)ethyl isocyanate (Karenz AOI, manufactured by Showa Denko), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxyate (Perocta O, manufactured by NOF Corp.). Polymer (2-1) was prepared in the same manner as in the preparation of polymer (1-1), except for the above. The solid content and solid content ratio of the resulting solution, as well as the weight-average molecular weight (Mw) and isocyanate group concentration of polymer (2-1), are shown in Table 1.

[0133] <Preparation of Polymer (2-2)> A 300 ml five-neck separable flask equipped with a stirrer, a dropping funnel, a cooling condenser, and a thermometer was charged with 37.0 g of toluene, 29.0 g of styrene, 20.0 g of polydimethylsiloxane having a methacryloyl group at one end (manufactured by JNC, Silaplane FM-0721), 6.0 g of 2-(acryloyloxy)ethyl isocyanate (manufactured by Showa Denko, Karenz AOI), and 0.5 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxylate (manufactured by NOF Corp., Perocta O). The dropping funnel was charged with 37.0 g of toluene, 29.0 g of styrene, 10.0 g of polydimethylsiloxane having a methacryloyl group at one end (Silaplane FM-0721, manufactured by JNC), 6.0 g of 2-(acryloyloxy)ethyl isocyanate (Karenz AOI, manufactured by Showa Denko), and 0.5 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxyate (Perocta O, manufactured by NOF Corp.). Polymer (2-2) was prepared in the same manner as in the preparation of polymer (1-1), except for the above. The solid content and solid content ratio of the resulting solution, as well as the weight-average molecular weight (Mw) and isocyanate group concentration of polymer (2-2) are shown in Table 1.

[0134] <Preparation of Polymer (2-3)> A 300 ml five-neck separable flask equipped with a stirrer, a dropping funnel, a cooling condenser, and a thermometer was charged with 36.5 g of toluene, 42.0 g of styrene, 7.0 g of polydimethylsiloxane having a methacryloyl group at one end (manufactured by JNC, Silaplane FM-0721), 6.0 g of 2-(acryloyloxy)ethyl isocyanate (manufactured by Showa Denko, Karenz AOI), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxylate (manufactured by NOF Corp., Perocta O). The dropping funnel was charged with 36.5 g of toluene, 42.0 g of styrene, 3.0 g of polydimethylsiloxane having a methacryloyl group at one end (Silaplane FM-0721, manufactured by JNC), 6.0 g of 2-(acryloyloxy)ethyl isocyanate (Karenz AOI, manufactured by Showa Denko), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxyate (Perocta O, manufactured by NOF Corp.). Polymer (2-3) was prepared in the same manner as in the preparation of polymer (1-1), except for the above. The solid content and solid content ratio of the resulting solution, as well as the weight-average molecular weight (Mw) and isocyanate group concentration of polymer (2-3), are shown in Table 1.

[0135] <Preparation of Polymer (2-4)> A 300 ml five-neck separable flask equipped with a stirrer, a dropping funnel, a cooling condenser, and a thermometer was charged with 36.5 g of toluene, 34.0 g of styrene, 20.0 g of polydimethylsiloxane having a methacryloyl group at one end (manufactured by JNC, Silaplane FM-0721), 1.0 g of 2-(acryloyloxy)ethyl isocyanate (manufactured by Showa Denko, Karenz AOI), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxylate (manufactured by NOF Corp., Perocta O). The dropping funnel was charged with 36.5 g of toluene, 34.0 g of styrene, 10.0 g of polydimethylsiloxane having a methacryloyl group at one end (Silaplane FM-0721, manufactured by JNC), 1.0 g of 2-(acryloyloxy)ethyl isocyanate (Karenz AOI, manufactured by Showa Denko), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxyate (Perocta O, manufactured by NOF Corp.). Polymer (2-4) was prepared in the same manner as in the preparation of polymer (1-1). The solid content and solid content ratio of the resulting solution, as well as the weight-average molecular weight (Mw) and isocyanate group concentration of polymer (2-4), are shown in Table 1.

[0136] <Preparation of Polymer (2-5)> A 300 ml five-neck separable flask equipped with a stirrer, dropping funnel, cooling condenser, and thermometer was charged with 36.5 g of toluene, 29.0 g of isobornyl methacrylate, 20.0 g of polydimethylsiloxane having a methacryloyl group at one end (JNC, Silaplane FM-0721), 6.0 g of 2-(acryloyloxy)ethyl isocyanate (Showa Denko, Karenz AOI), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxylate (NOF, Perocta O). The dropping funnel was charged with 36.5 g of toluene, 29.0 g of isobornyl methacrylate, 10.0 g of polydimethylsiloxane having a methacryloyl group at one end (JNC, Silaplane FM-0721), and 2-(acryloyloxy)ethyl isocyanate (Showa Denko, Karenz A 6.0 g of 2-ethylhexaneperoxyacid (OI) and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxyate (NOF Corp., Perocta O) were added. Other operations were the same as in the preparation of polymer (1-1), to prepare polymer (2-5). The solid content and solid content ratio of the obtained solution, as well as the weight average molecular weight (Mw) and isocyanate group concentration of polymer (2-5) are shown in Table 1.

[0137] <Preparation of Polymer (3-1)> A 300 ml five-neck separable flask equipped with a stirrer, dropping funnel, cooling condenser, and thermometer was charged with 36.5 g of toluene, 49.0 g of styrene, 6.0 g of 2-(acryloyloxy)ethyl isocyanate (Showa Denko K.K., Karenz AOI), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxyate (NOF K.K., Perocta O). The dropping funnel was also charged with 36.5 g of toluene, 39.0 g of styrene, 6.0 g of 2-(acryloyloxy)ethyl isocyanate (Showa Denko K.K., Karenz AOI), and 0.25 g of 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxyate (NOF K.K., Perocta O). Polymer (3-1) was prepared in the same manner as in the preparation of polymer (1-1). Table 1 shows the solid content and solid content ratio of the obtained solution, as well as the weight average molecular weight (Mw) and isocyanate group concentration of the polymer (3-1).

[0138] [Table 1]

[0139] The abbreviations in Table 1 are as follows: FM-0721: JNC Silaplane FM-0721 (catalog number listed average molecular weight 5000) FM-0711: JNC Silaplane FM-0711 (catalog number-average molecular weight: 1000) HEMA: 2-hydroxyethyl methacrylate 4-HBA: 4-hydroxybutyl acrylate AOI: Showa Denko Karenz AOI (2-isocyanatoethyl acrylate) St: styrene IBXMA: Isobornyl methacrylate AA: acrylic acid Perocta O: NOF Corp. Perocta O (1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxylate)

[0140] [Preparation of inorganic fine particles] <Preparation of inorganic fine particles (C-1) having mercapto groups> A flask equipped with a stirrer was charged with 12 g of 3-mercaptopropyltrimethoxysilane manufactured by Tokyo Chemical Industry Co., Ltd., 6 g of distilled water, and 21 g of tetrahydrofuran, and the mixture was stirred at 30°C for 3 hours to carry out a hydrolysis reaction. Next, this reaction liquid (silanol solution) was transferred to a dropping funnel. Next, the dropping funnel was attached to a 2000 ml five-neck separable flask equipped with a stirrer, cooling condenser, and thermometer, and 1000 g of methyl isobutyl ketone-dispersed silica sol (trade name: "MIBK-ST", solvent: methyl isobutyl ketone, solids concentration: 30 mass%, average particle size: 15 nm) manufactured by Nissan Chemical Industries, Ltd. was charged into the flask and heated to 70° C. The reaction liquid (silanol solution) in the dropping funnel was added dropwise over 2 hours, and the reaction was continued for another hour after the end of the addition to obtain a dispersion of inorganic fine particles (C-1) having mercapto groups.

[0141] [Example 1] Polymer (X1) was polymer (1-1) 158.6 g (solid content 92.0 g), compound (Y2) having three or more optionally blocked isocyanate groups per molecule Duranate 22A-75P (Asahi Kasei) 10.67 g (solid content 8.0 g), catalyst dibutyltin dilaurate 0.05 g, organic solvent cyclohexanone and methyl isobutyl ketone mixed in a mass ratio of 60:40 330.9 g was blended to prepare a thermosetting resin composition with a solid content concentration of 20 mass%. Using the obtained thermosetting resin composition, evaluation samples (laminates) were prepared by the above method, and the evaluation results are shown in Table 2.

[0142] [Examples 2 to 14, Comparative Examples 1 to 3] Thermosetting resin compositions were prepared and evaluated in the same manner as in Example 1, except that the raw materials were mixed so as to obtain the solid content mass ratios shown in Tables 2 to 4. The evaluation results are shown in Tables 2 to 4.

[0143] [Table 2]

[0144] The abbreviations in Table 2 are as follows: Functional group concentration: Concentration of hydroxyl or isocyanate groups Amount of mixture: Solid content if solvent is included 22A-75P: Asahi Kasei Duranate 22A-75P HDI: Hexamethylene diisocyanate DBTDL: Dibutyltin dilaurate Overall evaluation: Total value of the evaluations of transparency, initial water slippage, water slippage after moist heat test, pencil hardness, and scratch resistance

[0145] [Table 3]

[0146] The abbreviations in Table 3 are as follows: Functional group concentration: Concentration of hydroxyl or isocyanate groups Amount of mixture: Solid content if solvent is included C-1090: Kuraray Polyol C-1090 manufactured by Kuraray HPE 1170B:Basonol HPE 1170B manufactured by BASF DBTDL: Dibutyltin dilaurate Overall evaluation: Total value of the evaluations of transparency, initial water slippage, water slippage after moist heat test, pencil hardness, and scratch resistance

[0147] [Table 4]

[0148] The abbreviations in Table 4 are as follows: Functional group concentration: Concentration of hydroxyl or isocyanate groups Amount of mixture: Solid content if solvent is included C-1090: Kuraray Polyol C-1090 manufactured by Kuraray HPE 1170B:Basonol HPE 1170B manufactured by BASF 22A-75P: Asahi Kasei Duranate 22A-75P DBTDL: Dibutyltin dilaurate Tinuvin 400: BASF Tinuvin 400 Tinuvin 123: BASF Tinuvin 123

[0149] The evaluation results in Tables 2 to 4 show that the cured films obtained from the thermosetting resin compositions of the examples had excellent transparency and good water sliding properties both initially and after the wet heat test. In contrast, the cured film obtained from the thermosetting resin composition of Comparative Example 1 had good initial water sliding property, but the water sliding property after the moist heat test was low. The cured film obtained from the thermosetting resin composition of Comparative Example 2 did not exhibit water sliding property because a polymer not containing a polydimethylsiloxane structure was used. The thermosetting resin composition of Comparative Example 3 did not contain polymer (X2), so the cured film of this composition did not exhibit water sliding property. [Industrial Applicability]

[0150] The thermosetting resin composition of the present invention has excellent water sliding properties and transparency, and is therefore suitable for hard coatings on the surfaces of various lamp lenses and glazing for automobiles, as well as radome parts such as emblems and front grilles on the front surfaces of electromagnetic wave radar devices, and is particularly suitable for use as hard coatings on millimeter wave radar covers.

Claims

1. The polymer (X1) has a polydimethylsiloxane structure and an active hydrogen group in the main chain or a side chain, a compound (Y1) has two or more optionally blocked isocyanate groups in one molecule, and a compound (Z) has five or more hydroxyl groups in one molecule and has a dendritic branched structure, The thermosetting resin composition, wherein the polymer (X1) is a polymer obtained by copolymerizing at least a macromonomer having a polydimethylsiloxane structure and an unsaturated bond, and a monomer having a hydroxyl group.

2. The thermosetting resin composition according to claim 1, further comprising inorganic fine particles.

3. 3. The thermosetting resin composition according to claim 2, wherein the inorganic fine particles are surface-modified with a compound having a functional group selected from the group consisting of a mercapto group, a hydroxyl group, and an isocyanate group.

4. A cured product obtained by curing the thermosetting resin composition according to any one of claims 1 to 3.

5. A laminate having a layer comprising the cured product of claim 4 on a substrate.

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