TWI654213B - Thermosetting resin composition, cured film thereof, thermosetting hard coating agent and display element - Google Patents

Abstract

The present invention is a thermosetting resin composition containing a copolymer (C) and a cured film using the same. The copolymer (C) is a compound (B) having a macromonomer (A) and a polymerizable double bond. ) Reaction, the macromonomer (A) is obtained by reacting a raw material containing (meth) acrylate (a) having three or more functions; or the copolymer (C) is obtained by reacting a macromonomer (A) A compound (B) having a polymerizable double bond is obtained by reacting a trifunctional or higher (meth) acrylate (a). The macromonomer (A) is a compound containing It is obtained by reacting the raw material of the acrylate) acrylate (a). The thermosetting resin composition of the present invention can provide a film with high hardness by thermosetting. This film has excellent characteristics as a protective film.

Description

Thermosetting resin composition, cured film thereof, and thermosetting type hard coating agent And display elements

The present invention relates to a thermosetting resin composition and a cured film obtained by heating and curing the same.

Conventionally, for image display devices such as a liquid crystal display, a touch panel display, and an organic electroluminescence (EL) display, a hard coating material has been required in order to prevent the display surface from being scratched. In recent years, the market for laptop computers, mobile phones, and the like using touch panels has been increasing.

In addition, with the development of information terminals and liquid crystal display elements, there is an urgent need for the development of electronic circuits, displays, sensors and other products based on organic materials. Organic materials can be cited as advantages: electrical properties, processing characteristics, and other characteristics can be easily adjusted by chemical design or synthesis; and low-temperature processing can be achieved by using printing methods such as roll to roll Achieve cost reduction; In addition, it has mechanical flexibility and excellent suitability for flexible substrates.

Promote the development of organic materials as substrates, use hardening resin compositions as hard coating materials for preventing scratches on display surfaces, color filter protective films, thin film transistors (TFTs), and alignment films In the case of a transparent insulating film between the TFT and the transparent electrode, in order to prevent deterioration of the substrate and avoid overload, a low temperature (a temperature lower than the glass transition point temperature of the substrate) or hardening by light irradiation is desired. Highly suitable materials with organic materials. If the hardening is insufficient, the chemical resistance such as solvent resistance, acid resistance, and alkali resistance in the step of manufacturing the product is reduced, which becomes the main cause of the damage and deterioration of the organic material of the base material. limit.

Heretofore, as a hard coating material, a photosensitive resin composition containing a polyfunctional (meth) acrylate has been proposed (for example, refer to Patent Documents 1 to 3).

As a hard coating material, a photosensitive resin composition containing fine particles in order to achieve high hardness has been proposed (for example, refer to Patent Document 4).

As a method for forming a hard coat layer for improving the surface hardness of a display or the like, a method of applying a polyfunctional acrylate-based active energy ray-curable resin to a surface and hardening it by irradiating active energy rays such as ultraviolet rays is widely used. However, the unreacted photopolymerization initiator remaining in the cured film has the possibility of causing adverse effects and the reliability is poor, so further improvement is required.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2013-076791

[Patent Document 2] Japanese Patent Laid-Open No. 2004-182765

[Patent Document 3] Japanese Patent Laid-Open No. 2010-027033

[Patent Document 4] Japanese Patent Laid-Open No. 2013-083914

An object of the present invention is to provide a protective film using a thermosetting resin composition, which becomes high hardness by thermosetting.

The present inventors have discovered that a protective film using a thermosetting resin composition containing a copolymer (C) can be made to have high hardness by only thermosetting, and based on this finding, the present invention has been completed, and the copolymer (C) is It is obtained by reacting a macromonomer (A) and a compound (B) having a polymerizable double bond. The macromonomer (A) comprises a (meth) acrylic acid ester (a ), Or the copolymer (C) is obtained by reacting a macromonomer (A), a compound (B) having a polymerizable double bond, and a trifunctional or higher (meth) acrylate (a). The macromonomer (A) is obtained by reacting a raw material containing a trifunctional or more (meth) acrylate (a). The present invention includes the following items.

[1] A thermosetting resin composition comprising a copolymer (C) which reacts a macromonomer (A) and a compound (B) having a polymerizable double bond and It is obtained that the macromonomer (A) is obtained by reacting a raw material containing a trifunctional or more (meth) acrylate (a); or the copolymer (C) is obtained by reacting a macromonomer (A) Polymerizable double bond The compound (B) is obtained by reacting a trifunctional or higher (meth) acrylate (a), and the macromonomer (A) is a raw material containing a trifunctional or higher (meth) acrylate (a). And get.

[2] The thermosetting resin composition according to the item [1], wherein the total amount of the trifunctional or higher (meth) acrylate (a) and the total amount of the compound (B) having a polymerizable double bond The weight-to-weight ratio is 90.0: 10.0 to 99.9: 0.1.

[3] The thermosetting resin composition according to the item [1] or [2], wherein the compound (B) having a polymerizable double bond is selected from a group having a (meth) acrylfluorenyl group, α -At least one of the group of ethyl acrylofluorenyl, styryl, and vinyl compounds.

[4] The thermosetting resin composition according to item [3], wherein the compound (B) having a polymerizable double bond is selected from the group consisting of 3-methacryloxypropyltrimethoxysilane, 3 -Acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, p-styryltrimethoxysilane At least one of p-styryltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

[5] The thermosetting resin composition according to the item [3], wherein the compound (B) having a polymerizable double bond is at least one selected from the compounds represented by the following formula (1); (R ¹ is hydrogen or methyl, R ² to R ⁵ are alkyl groups having 1 to 5 carbons, R ⁶ is alkyl group having 1 to 10 carbons, m is an integer from 1 to 10, and n is 1 to An integer of 150).

[6] The thermosetting resin composition according to item [5], wherein the compound represented by the formula (1) is α-butyl-ω- (3-methacryloxypropyl) poly Dimethylsilane.

[7] The thermosetting resin composition according to any one of [1] to [6], wherein the weight average molecular weight of the copolymer (C) is 1,000 to 200,000.

[8] A cured film obtained from the thermosetting resin composition according to any one of [1] to [7].

[9] A thermosetting hard coating agent comprising the thermosetting resin composition according to any one of [1] to [7].

[10] A display element comprising the cured film according to item [8].

Since the thermosetting resin composition of the present invention has high hardness, it can be used as a surface protective film for an image display element or the like.

In this specification, in order to indicate both acrylic acid and methacrylic acid, Otherwise, it is expressed as "(meth) acrylic acid". Furthermore, similarly, it expresses as "(meth) acrylate" in order to show one or both of an acrylate and a methacrylate.

In the present specification, the "alkyl group" is a linear or branched alkyl group, and examples thereof include methyl, ethyl, propyl, n-butyl, third butyl, pentyl, and hexyl.

<1. Thermosetting resin composition of the present invention>

The thermosetting resin composition of the present invention is characterized by comprising a copolymer (C) obtained by reacting a macromonomer (A) and a compound (B) having a polymerizable double bond, The macromonomer (A) is obtained by reacting a raw material containing a trifunctional or more (meth) acrylate (a); or the copolymer (C) is obtained by reacting a macromonomer (A) with The polymerizable double bond compound (B) is obtained by reacting a trifunctional or higher (meth) acrylate (a), and the macromonomer (A) is a compound containing a trifunctional or higher (meth) acrylate ( a) It is obtained by reacting the raw materials.

<1-1. 3 or more functional (meth) acrylates (a)>

As long as the trifunctional or more (meth) acrylate (a) as a raw material of the macromonomer (A) contained in the thermosetting resin composition of the present invention has three or more polymerizable double bonds in the molecule, It is not particularly limited.

Specific examples of the trifunctional or higher (meth) acrylate (a) are trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, and trimethylol Propane PO modified triacrylate, trimethylolpropane EO modified triacrylate, glycerol tri (meth) acrylate, ethoxylated glycerol tri (meth) acrylate, epichlorohydrin Modified glycerol tri (meth) acrylate, diglycerol EO modified acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythr Tetraol tetra (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate, ethoxylated isocyanurate cyclotri (meth) acrylate, ε-caprolactone modified tri- ( 2-propenyloxyethyl) isocyanurate, propylene oxide modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified trimethylolpropane tri (meth) acrylate , Di-trimethylolpropane tetra (meth) acrylate, isocyanurate EO modified di / triacrylate, pentaerythritol tri / tetraacrylate, dipentaerythritol pentaerythritol pentaerythritol hexaacrylate, diglycerol EO modified acrylate , Ethoxylated isocyanurate triacrylate, tri [(meth) acryloxyethyl] isocyanurate, ethoxylated glycerol triacrylate, and ethoxylated pentaerythritol tetraacrylic acid ester.

Among the compounds, dipentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol

The trifunctional or more (meth) acrylate (a) may be used alone, or two or more kinds may be used in combination.

The polymerization method of the macromonomer (A) obtained by reacting a raw material containing a trifunctional or higher (meth) acrylate (a) is preferably using one or more trifunctional or higher (meth) acrylates (a). Free Radical Polymerization in Solution. The polymerization temperature is not particularly limited as long as it is a temperature at which radicals are sufficiently generated from the polymerization initiator used, and is usually in the range of 50 ° C to 150 ° C. The polymerization time is not particularly limited, but is usually in the range of 1 hour to 24 hours. Further, the polymerization can be performed under any pressure of pressure, reduced pressure, or atmospheric pressure.

The solvent used in the polymerization reaction is preferably a trifunctional or higher-functional (meth) acrylate (a), other monomers used in combination, and the obtained Solvent for macromonomer (A). Specific examples of such a solvent are methanol, ethanol, 1-propanol, 2-propanol, propylene glycol, methyl propylene glycol, acetone, methyl isobutyl ketone, 2-butanone, ethyl acetate, propyl acetate, acetic acid Butyl ester, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, cyclopentanone, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether , Diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, N, N-dimethylformamide, acetic acid , And water. The solvent may be one kind of these solvents, or a mixture of two or more kinds of these solvents.

As the polymerization initiator used in the production of the macromonomer (A), a compound that generates a radical due to heat, an azo initiator such as azobisisobutyronitrile, or a peroxide such as benzamidine peroxide can be used. Species starter. In order to adjust the molecular weight, a chain transfer agent such as thioglycolic acid may be added in an appropriate amount.

Examples of the thermal radical generator include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.) , 2,2'-azobis (2,4-dimethylvaleronitrile) (V-65 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis (isobutyl) Nitrile) (V-60 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis (2-methylbutyronitrile) (V-59 manufactured by Wako Pure Chemical Industries, Ltd.) (Trade name)), 2,2'-azobis [N- (2-propenyl) -2-methylpropanamide] (VF-096 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.) 2,2'-Azobis (N-butyl-2-methylpropanamide) (VAm-110 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-Azobis (Isobutyric acid) dimethyl ester (V-601 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), VPE-0201, VPE-0401, VPE-0601, VPS-1001 (the above are all trade names, Wako Pure Chemical Industries, Ltd.) and so on.

<1-2. Compound (B) having a polymerizable double bond>

The compound (B) having a polymerizable double bond, which is a raw material of the copolymer (C) contained in the thermosetting resin composition of the present invention, is selected from a group having a (meth) acrylfluorenyl group and α-ethylacrylfluorene The group of compounds based on phenyl, styryl, or vinyl is not particularly limited.

As the compound having a (meth) acrylfluorenyl group or an α-ethylacrylfluorenyl group, (meth) acrylic acid, α-ethylacrylic acid, or an ester of these compounds is preferably used.

Examples of the (meth) acrylic acid or α-ethylacrylic acid ester include alkyl esters and haloalkyl esters.

Here, "alkyl" includes a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and a cyclic alkyl group having 3 to 12 carbon atoms. The linear alkyl group having 1 to 20 carbon atoms and the branching alkyl group having 1 to 20 carbon atoms may be any -CH ₂ -alkoxyalkyl group substituted with -O- in the alkyl chain, or It may have a polyethylene glycol (PEG) structure with continuous ethyleneoxy groups. The linear alkyl group having 1 to 20 carbon atoms and the branched alkyl group having 1 to 20 carbon atoms may have any -CH ₂ -via -CO-O- and / or -O-CO- Substituted ester bonds. The linear alkyl group having 1 to 20 carbon atoms and the branched alkyl group having 1 to 20 carbon atoms may have an azaalkyl structure in which any -CH ₂ -substituted with -NH- of the alkyl chain is substituted. The -NH- hydrogen may also be substituted with a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms. The cyclic alkyl group having 5 to 12 carbon atoms may also be substituted with any -CH ₂ -substituted with -O-, such as tetrahydrofuran, 1,3-dioxane, and 1,4-dioxane. Cyclic ether structure. The linear alkyl group having 1 to 20 carbon atoms and the branched alkyl group having 1 to 20 carbon atoms may further have any -CH _{2 of the} alkyl chain substituted with a cyclic alkyl group having 3 to 6 carbon atoms. Into the structure. Among them, the cyclic alkyl group having 5 or 6 carbon atoms may also be substituted by any -CH ₂ -substituted with -O- such as tetrahydrofuran, 1,3-dioxane, and 1,4-dioxane. The structure of such a cyclic ether. In addition, any hydrogen of a linear alkyl group having 1 to 20 carbon atoms and a branched alkyl group having 1 to 20 carbon atoms may be passed through a cyclic alkyl group having 3 to 12 carbon atoms or 6 to 24 carbon atoms. These cyclic alkyl groups and aromatic groups may further have a substituent.

The so-called "haloalkyl group" is an arbitrary hydrogen atom of the linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and a cyclic alkyl group having 3 to 12 carbon atoms. Substituted alkyl. Halogen is fluorine, chlorine, bromine, or iodine, and fluorine is preferred.

The "alkyl" may also have various functional groups. Examples of the functional group include a hydroxyl group, a carboxyl group, an epoxy group, an oxetanyl group, an amine group, an alkoxysilyl group, and a polyorganosiloxane. Regarding the linear, branched, or cyclic alkyl groups having these functional groups, the principle of substitution using -O-, -NH-, and the like described above is similarly applied.

The structure having a "carboxyl group" may be a structure in which -COOH is connected to the alkyl chain, and one of the carboxyl groups of the dicarboxylic acid such as succinic acid or hexahydrophthalic acid and the alkyl chain may be preferably used. Structure that forms an ester bond.

Examples of the structure having an "epoxy group" include glycidyl, 3,4-epoxycyclohexyl, and the like.

Examples of the structure having "oxetanyl" include 3-methyloxetane-3- Group, 3-ethyloxetane-3-yl, and the like.

Examples of the structure having an "amine group" include a structure having an amine group substituted with an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, or third butyl, and methyl and ethyl are preferred.

Examples of the alkoxy group having the "structure having an alkoxysilyl group" include alkoxysilyl groups having 1 to 4 carbon atoms. The so-called alkoxy group having 1 to 4 carbon atoms is methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, third butoxy, Preferred are methoxy and ethoxy. The silicon of the alkoxysilyl group may be bonded to the carbon of the alkyl group or the nitrogen of the azaalkyl group to make the compound a ring structure.

The “polyorganosiloxane structure” refers to a structure in which an alkyl chain having an m of about 1 to 10 is connected to a linear polysiloxane chain having an n of about 1 to 150 in the following formula (1 ′).

(R ² to R ⁵ are alkyl groups having 1 to 5 carbons, R ⁶ is alkyl groups having 1 to 10 carbons, m is an integer of 1 to 10, and n is an integer of 1 to 150)

The compound (B) having a polymerizable double bond having each of the structures will be specifically described.

Examples of (meth) acrylic acid, α-ethylacrylic acid, and esters of these compounds include acrylic acid, methacrylic acid, α-ethylacrylic acid, methyl (meth) acrylate, and (meth) acrylic acid. Ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate (n-BMA), isobutyl (meth) acrylate, (meth) acrylic acid Second butyl ester, third butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, (meth) ) Isooctyl acrylate, nonyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate Trialkyl ester, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, isomethacrylate Bornyl ester, phenoxy polyethylene glycol (meth) acrylate, benzyl (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate Ester, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol Alcohol (meth) acrylate, phenoxyethyl (meth) acrylate, (Meth) acrylic acid-1,2,2,6,6-pentamethyl-4-amidinyl ester, (meth) acrylic acid-2,2,6,6-tetramethyl-4-amidinoyl Ester, trifluoroethyl (meth) acrylate, -1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, -2, 2, 3, 3, (meth) acrylic acid, 4,4,4-Heptafluorobutyl ester, (meth) acrylic acid-2,2,3,3,3-pentafluoropropyl ester, (meth) acrylic acid-2,2,3,4,4,4- Hexafluorobutyl, -2,2,2-trifluoroethyl (meth) acrylate, -2,2,3,3-tetrafluoropropyl (meth) acrylate, 2-hydroxy (meth) acrylate Ethyl ester (HEMA), 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (methyl) Acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, 4-hydroxybutyl (meth) acrylate Ester glycidyl ether, 1,4-cyclohexanedimethanol mono (meth) acrylate, (meth) acrylic acid 4-hydroxyphenyl ester, 2- (meth) acryloxyethyl succinic acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acrylic acid Oxyethyl phthalic acid, glycidyl (meth) acrylate (GMA), methyl glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, -3,4 (meth) acrylic acid -Epoxycyclohexyl ester, -3,4-epoxycyclohexyl methyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate ( OXE-10, OXE-30), 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyloxy Cyclobutane, 3-methyl-3- (meth) acryloxyethyloxetane, 3-ethyl-3- (meth) acryloxyethyloxetane , 2- (dimethylamino) ethyl methacrylate (DMAEMA), 2- (diethylamino) ethyl methacrylate, third butylaminoethyl methacrylate, 3- Methacryloxypropyltrimethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane (KBE-503), 3-propene Methoxypropyltri Oxysilane, ((meth) acryloxymethyl) triethoxysilane, ((meth) acryloxymethyl) trimethoxysilane, 3- (meth) acryloxypropyl Methylmethyldimethoxysilane, ((meth) acryloxymethyl) methyldiethoxysilane, ((meth) acryloxymethyl) methyldimethoxysilane, ( (Meth) acryloxypropylmethyldiethoxysilane, (meth) acryloxypropylmethyldimethoxysilane, (meth) acryloxypropyldimethylethoxy Silane, (meth) acryloxypropyl dimethylmethoxysilane, (meth) acryloxy undecyltrimethoxysilane, having a structure represented by the following formula (1) Compounds etc.

(R ¹ is hydrogen or methyl, R ² to R ⁵ are alkyl groups having 1 to 5 carbons, R ⁶ is alkyl group having 1 to 10 carbons, m is an integer from 1 to 10, and n is 1 to An integer of 150)

A specific example of the compound represented by the formula (1) is α-butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane (FM-0711).

The compound having a styryl group is preferably a compound having a functional group such as an alkoxysilyl group bonded to the para position of styrene directly or via an alkylene group or the like.

Examples of the compound having a styryl group and an alkoxysilyl group include p-styryltrimethoxysilane, p-styryltriethoxysilane, styrylethyltrimethoxysilane, and the like.

As the compound having a vinyl group, a compound having a functional group such as an alkoxysilyl group bonded to the vinyl group directly or via an alkylene group or the like is preferably used.

Examples of the compound having a vinyl group and an alkoxysilyl group include vinyltrimethoxysilane (VTMS), vinyltriethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, and ethylene. Tris (2-methoxyethoxy) silane, butenyltriethoxysilane, (divinylmethylsilylethyl) triethoxysilane, behenyltriethoxysilane , Cetylfluorododec-11-alkenyl-1-trimethoxysilane, hexenyltriethoxysilane, 7-octenyltrimethoxysilane, 10-undecenyltrimethoxysilane, ethylene Tris-butoxysilane, vinyltris (methoxypropoxy) silane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, ethyl Alkenyl dimethyl ethoxysilane, vinyl dimethyl methoxy silane, trivinyl methoxy silane, bis (triethoxy silane ethyl) vinyl methyl silane, triethoxy ( 1-phenylvinyl) silane, 3- (N-allylamino) propyltrimethoxysilane, N-allyl-aza-2,2-dimethoxysilane ( N-allyl-aza-2, 2-dimethoxysilacyclopentane) and the like.

Examples of the compound having a functional group other than a vinyl group and an alkoxysilyl group include N-vinylphthalimide and the like.

The compound (B) having a polymerizable double bond may be used alone or as a mixture of two or more kinds.

Among the compounds, if 3-methacryloxypropyltrimethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane are used , 3-propenyloxypropyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, α -Butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane, or a mixture of these, the coating property of the thermosetting film on the substrate and the sliding property of the coating film surface It is preferable because it becomes better.

<1-3. Polymerization method of copolymer (C)>

The polymerization method of the copolymer (C) contained in the thermosetting resin composition of the present invention is to add the compound (B) having a polymerizable double bond to the macromonomer (A) previously polymerized, and further It is obtained by polymerization. In addition, a predetermined amount of a trifunctional or more (meth) acrylate (a) may be divided into two parts, one part of which is to produce a macromonomer (A), and the other part of the compound (B) having a polymerizable double bond (B ) Mix and react with (A). These polymerizations are preferably free radical polymerizations in solution. The polymerization temperature is not particularly limited as long as it is a temperature at which radicals are sufficiently generated by the polymerization initiator used, and is usually in the range of 50 ° C to 150 ° C. The polymerization time is not particularly limited, but is usually in the range of 1 hour to 24 hours. Further, the polymerization can be performed under any pressure of pressure, reduced pressure, or atmospheric pressure.

The solvent used in the polymerization reaction is preferably a solvent capable of dissolving the macromonomer (A) used, the compound (B) having a polymerizable double bond, and a trifunctional or higher (meth) acrylate (a). . As a specific example of such a solvent, the solvent used at the time of manufacturing the said macromonomer (A) is mentioned preferably. That is, it is methanol, ethanol, 1-propanol, 2-propanol, propylene glycol, methyl propylene glycol, acetone, methyl isobutyl ketone, 2-butanone, ethyl acetate, propyl acetate, butyl acetate, Tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, cyclopentanone, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethyl ether Glycol ethyl methyl ether, diethylene glycol monoethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, N, N-dimethylformamide, acetic acid, and water . The solvent may be one of these, or a mixture of two or more of these.

The polymerization initiator used to polymerize the copolymer (C) is the same as that used in the production of the macromonomer (A), and a compound that generates a radical due to heat, azobisisobutyronitrile, can be used. Isoazo-based initiators, or peroxide-based initiators such as benzamidine peroxide. In order to adjust the molecular weight, a chain transfer agent such as thioglycolic acid may be added in an appropriate amount.

Examples of the thermal radical generator include 2,2'-azobis (4-methoxy-2,4-dimethyl Valeronitrile) (V-70 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) V-65 (trade name)), 2,2'-azobis (isobutyronitrile) (V-60 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis (2-methylbutyronitrile) (V-59 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [N- (2-propenyl) -2-methylpropane Fluoramine] (VF-096 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis (N-butyl-2-methylpropanamide) (Wako Pure Chemical Industries, Ltd. Co., Ltd.'s VAm-110 (trade name)), 2,2'-azobis (isobutyric acid) dimethyl (V-601 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), VPE- 0201, VPE-0401, VPE-0601, VPS-1001 (the above are all trade names, Wako Pure Chemical Industries, Ltd.) and so on.

As for the copolymer (C), from the viewpoint of the hardness of the thermosetting film and the coatability on the substrate, the total amount of the trifunctional or more (meth) acrylate (a) is preferably based on the total weight of the raw materials. The amount is 90.0% by weight to 99.9% by weight, and the total amount of the compound (B) having a polymerizable double bond is 0.1% by weight to 10.0% by weight, and the total amount of the trifunctional or higher (meth) acrylate (a) is more preferable. It is 95.0% by weight to 99.9% by weight, and the total amount of the compound (B) having a polymerizable double bond is 0.1% by weight to 5.0% by weight.

The weight average molecular weight of the copolymer (C) is preferably 1,000 to 200,000, and from the viewpoint of film-forming properties, it is more preferably 10,000 to 100,000.

The weight average molecular weight in this specification is a polystyrene conversion value calculated | required by GPC method (column temperature: 35 degreeC, flow rate: 1 mL / min). standard Polystyrene with a molecular weight of 645 ~ 132,900 (for example, Agilent S-M2-10 polystyrene calibration kit PL2010-0102 (trade name, Agilent Technologies Co., Ltd.)), and column using PLgel MIXED-D (Trade name, Agilent Technologies Co., Ltd.). The mobile phase was measured using THF. In addition, the weight average molecular weight of a commercial item in this specification is a catalogue value.

<1-4. Other ingredients>

From the viewpoint of adding further characteristics, the thermosetting resin composition of the present invention may contain other components than those described above as necessary. Examples of such other components include solvents and additives.

<1-4-1. Solvents>

A solvent may be added to the thermosetting resin composition of the present invention. The solvent that can be optionally added to the thermosetting resin composition of the present invention is preferably a solvent that can dissolve the polymer and other additives. Specific examples of the solvent that can be added are water, acetone, methyl isobutyl ketone, methanol, ethanol, 1-propanol, 2-propanol, 2-butanone, ethyl acetate, propyl acetate, butyl acetate, Butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxylate Methyl acetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-methyl Methyloxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxo Methyl-2-methylpropanoate, ethyl 2-oxy-2-methylpropanoate, 2-methoxy-2-methyl Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, 2- Methyl oxobutanoate, ethyl 2-oxobutanoate, tetrahydrofuran, acetonitrile, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, methyl propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate , Ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol mono Diethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, toluene , Xylene, γ-butyrolactone, N, N-dimethylacetamide, and N, N-dimethylformamide. These may be used alone or in combination of two or more.

If the solvent is selected from propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, Ethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, ethyl lactate, and acetic acid At least one kind of butyl ester is more preferable from the viewpoint of improving the coating uniformity of the thermosetting resin composition of the present invention. In addition, if it is selected from propylene glycol, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol ethyl methyl ether, ethyl lactate, And at least one of butyl acetate is more preferable from the viewpoint of improving the coating uniformity of the thermosetting resin composition of the present invention and the viewpoint of safety to the human body.

The solvent is preferably blended in the thermosetting resin composition of the present invention such that the total amount of the solid copolymer (C) and other additives becomes 5 to 90% by weight.

<1-4-2. Additives>

The thermosetting resin composition of the present invention may further contain an additive. The additives arbitrarily added to the thermosetting resin composition of the present invention are added from the viewpoint of improving the characteristics of the thermosetting resin composition of the present invention such as coating uniformity, adhesion, and stability. Examples of the additives include polymerization inhibitors, acrylic, styrenic, polyethyleneimine, or urethane-based polymer dispersants, anionic, cationic, nonionic, or fluorine-based surfactants, silicon Ketone resin coating improver, adhesion improver such as silane coupling agent, anti-agglomerating agent such as sodium polyacrylate, thermal cross-linking agent such as epoxy compound, melamine compound or diazide compound, and antioxidant such as hindered phenol , Imidazole or polyfunctional acrylate hardening accelerator.

A surfactant and a coating property improving agent may be added to the thermosetting resin composition of the present invention. The surfactant and the coating property improving agent are used to improve the wettability, leveling property, or coating property of the base substrate. The surfactant optionally added to the thermosetting resin composition of the present invention includes Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, and Polyflow No. 95 ( The above are trade names, Kyoeisha Chemical Industry Co., Ltd.), BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346 (the above are all trade names, Japan Becker Chemical Co., Ltd.), KP-341, KP -358, KP-368, KF-96-50CS, KF-50-100CS (to The above are trade names, Shin-Etsu Chemical Industry Co., Ltd.), Surflon SC-101, Surflon KH-40, Surflon S611 (both are trade names, AGC Tsingmei Chemical Co., Ltd.), Vogel ( Ftergent) 222F, Ftergent 208G, Ftergent 251, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 602A, Ftergent 650A, FTX-218 (the above are all trade names, Neos Corporation), AI ETOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (the above are all trade names, Mitsubishi Materials Corporation), Megafac F- 171, Megafac F-177, Megafac F-410, Megafac F-430, Megafac F-444, Megafac F-472SF, Megafac F-475, Megafac F-477, Megafac F-552, Megafac F-553, Megafac F- 554, Megafac F-555, Megafac F-556, Megafac F-558, Megafac R-30, Megafac R-94, Megafac RS-75, Megafac RS-72-K, Megafac RS-76-NS (The above are all products Name, Di Edison (DIC) Co., Ltd.), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2250N (all above are trade names, Evonik degussa japan Co., Ltd.), fluoroalkylbenzene sulfonate, fluoroalkylcarboxylic acid Salt, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetra (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium Salt, fluoroalkylamino sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether , Polyoxyethylene tridecyl ether, polyoxyethylene whale Wax ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan Sugar anhydride palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan Palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, or alkyl diphenyl ether disulfonic acid Salt, etc. It is preferable to use at least one selected from these additives.

In these surfactants, if selected from the group consisting of fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, and fluoroalkane Sulfonate, diglycerol tetra (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl amino sulfonate, Megafac R-08, Megafac R-30, Megafac F-477, At least one of fluorosurfactants such as Megafac F-556, Megafac F-554, and other silicone resin-based coating improvers such as BYK306, BYK342, BYK344, BYK346, KP-341, KP-358, or KP-368 From the viewpoint of improving the coating uniformity of the thermosetting resin composition of the present invention, it is preferably used.

The content of the surfactant and the coating enhancer in the thermosetting resin composition of the present invention is preferably 0.001% to 0.1% by weight with respect to the total amount of the composition.

A hardening accelerator may be added to the thermosetting resin composition of the present invention. The hardening accelerator is used to promote the hardening reaction of the thermosetting resin composition and improve the hardness, heat resistance, and chemical resistance of the cured film. Thermosetting property of the present invention The hardening accelerators arbitrarily added to the resin composition are trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, and trimethylolpropane PO modified triacrylic acid. Ester, trimethylolpropane EO modified triacrylate, glycerol tri (meth) acrylate, ethoxylated glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri ( (Meth) acrylate, diglycerol EO modified acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, alkyl modified dipentaerythritol tri ( (Meth) acrylate, ethoxylated isocyanurate cyclotri (meth) acrylate, ε-caprolactone modified tri- (2-propenyloxyethyl) isocyanurate, propylene oxide Modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified trimethylolpropane tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, isocyanide Uric acid EO modified di / triacrylate, pentaerythritol tri / tetraacrylate, dipentaerythritol pentaerythritol five / hexaacrylate, diglycerol EO modified acrylate, ethyl Triacylated isocyanurate triacrylate, tri [(meth) acryloxyethyl] isocyanurate, ethoxylated glycerol triacrylate, ethoxylated pentaerythritol tetraacrylate, 2- Undecyl imidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzene And imidazole.

The hardening accelerator may be used alone or in combination of two or more.

Among hardening accelerators, dipentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol pentaerythritol

An adhesion improver may be added to the thermosetting resin composition of the present invention. The adhesion improving agent is used to improve the adhesion between the thermosetting resin composition and the substrate. Adhesiveness improver arbitrarily added to the thermosetting resin composition of the present invention A coupling agent can be suitably used. The adhesiveness improving agent may be one type or two or more types. As the coupling agent, silane-based, aluminum-based, or titanate-based compounds can be used. Examples of such coupling agents include 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, and 3-glycidyloxypropyltrimethoxy Silyl, ethanoyl alkoxy aluminum diisopropoxide, and tetraisopropyl bis (dioctyl phosphite) titanate. Among these, 3-glycidoxypropyltrimethoxysilane has a large effect of improving adhesion, and is therefore preferably used.

An anticoagulant may be added to the thermosetting resin composition of the present invention. The anticoagulant can be fused with a solvent to prevent aggregation. Specific examples of the anticoagulant added arbitrarily to the thermosetting resin composition of the present invention are DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK- 182, DISPERBYK-184, DISPERBYK-185, DISPERBYK-2163, DISPERBYK-2164, BYK-220S, DISPERBYK-191, DISPERBYK-199, DISPERBYK-2015 (all product names, Japan Biochem Co., Ltd.), FTX- 218, Ftergent 710FM, Ftergent 710FS (both trade names, Neos Co., Ltd.), FLOWLEN G-600, FLOWLEN G-700 (both trade names, Kyoeisha Chemical Industry Co., Ltd. Ltd.).

An antioxidant may be added to the thermosetting resin composition of the present invention. As the antioxidant, hindered phenols, hindered amines, phosphorus, and sulfur compounds can be suitably used. The antioxidant may be used alone or in combination of two or more. Self-weathering From a viewpoint, it is preferable that the antioxidant is an antioxidant which is a hindered phenol compound.

As the antioxidant optionally added to the thermosetting resin composition of the present invention, hindered amines, hindered phenols, and the like can be used. Specific examples include IRGAFOS XP40, IRGAFOS XP60, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 1520L (all product names, manufactured by BASF Corporation of Japan) , ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80 (trade name, ADEKA) Co., Ltd. . Among these, IRGANOX 1010 and ADK STAB AO-60 are more preferable from the viewpoint of suppressing discoloration of the thermosetting resin composition of the present invention.

From the viewpoint of further improving heat resistance, chemical resistance, in-plane uniformity, flexibility, flexibility, and elasticity, the thermosetting resin composition of the present invention may optionally include a crosslinking agent.

Specific examples of the thermal crosslinking agent arbitrarily added to the thermosetting resin composition of the present invention include jER807, jER815, jER825, jER827, jER828, jER190P, and jER191P (all are trade names, Mitsubishi Chemical Corporation), jER1004 , JER1256, YX8000 (all are trade names, Mitsubishi Chemical Corporation), Araldite CY177, Araldite CY184 (both trade names, Japan Huntsman Corporation), Celloxide 2021P, EHPE-3150 ( (Both trade names, Daicel Chemical Industry Co., Ltd.), Tecmoa VG3101L (trade name, Prtec Corporation), NIKALAC MW-30HM, NIKALAC MW-100LM, NIKALAC MW-270, NIKALAC MW-280, NIKALAC MW-290, NIKALAC MW-390, NIKALAC MW-750LM (all are trade names, Sanwa Chemical Co., Ltd.).

<1-5. Preservation of thermosetting resin composition>

If the thermosetting resin composition of the present invention is stored in a light-shielded state in a temperature range of -30 ° C to 25 ° C, the stability of the composition over time is improved, which is preferable. If the storage temperature is -20 ° C to 10 ° C, there are no precipitates and it is more preferable.

<2. A cured film obtained from a thermosetting resin composition>

The thermosetting resin composition of the present invention may include a copolymer (C). Depending on the target characteristics, a solvent, a coupling agent, a surfactant, an antioxidant, and other additives may be further added as needed, and these may be mixed and dissolved uniformly. obtain.

When the thermosetting resin of the present invention or a thermosetting composition using the same (after being dissolved in a solvent in a solid state without a solvent) is applied to the surface of a substrate, the solvent is removed by, for example, heating or the like. , It can form a coating film.

The coating method of the thermosetting resin composition of the present invention can be formed by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, a slit coating method, an inkjet method, a flexographic printing method, and a gravure printing method. Coating film.

Examples of the substrate used in film formation include plastics, glass, and glass with transparent electrodes such as FTO or ITO. Specific examples of the plastic include polycarbonate, poly (meth) acrylate, polyurethane, polyethylene terephthalate, and triethyl cellulose.

This coating film can be heated (pre-baked) using a hot plate or an oven. heating The conditions vary depending on the type of each component and the blending ratio, usually 70 ° C to 110 ° C, 5 minutes to 15 minutes in an oven, and 1 minute to 5 minutes in a hot plate. Thereafter, in order to harden the coating film, heat treatment is performed at 100 ° C. to 150 ° C., preferably 120 ° C. to 150 ° C. for 30 minutes to 90 minutes in an oven, and 5 minutes to 30 minutes for a hot plate. Heat treatment (post-baking), whereby a cured film can be obtained.

The thermosetting resin composition of the present invention can be thermally cured to obtain a cured film even at a low temperature at which the coating film is cured at a low temperature of 120 ° C to 150 ° C. Therefore, if a thermosetting resin composition of the present invention is applied to a substrate having a low glass transition point, such as plastic, a cured film can be obtained without causing degradation or damage to the substrate.

[Example]

Hereinafter, the present invention is further described by examples, but the present invention is not limited by these examples. The evaluation method of the thermosetting resin composition of this invention is shown below.

[Evaluation method of thermosetting resin composition]

1) Film thickness

Spin on a glass substrate (EagleXG (trade name), Corning Co., Ltd., 40mm × 40mm × 0.7mm) or PET film (COSMOSHINE A4300 (trade name), 210mm × 297mm × 0.25mm, manufactured by Toyobo Co., Ltd.) at 700 rpm. The thermosetting resin composition was applied for 10 seconds, and dried on a hot plate at 80 ° C for 3 minutes. This substrate was post-baked in an oven at 120 ° C. in the case of a PET film and 150 ° C. in the case of a glass substrate, and the film thickness was measured. membrane Thickness is measured using a step, surface roughness, and fine shape measuring device (P-16 + (trade name), KLA-Tencor Japan Co., Ltd.), and the average value of the three measurements is taken as Film thickness.

2) Coating

The formed cured film was visually observed, and the case where there was no unevenness was regarded as ￮, the case where unevenness occurred was Δ, and the case where shrinkage occurred and the film was not sufficiently formed on the substrate was ×.

3) Pencil hardness

It is performed in accordance with JIS-K5600. Samples that did not form a sufficient film and could not be measured for pencil hardness are indicated as "-".

4) Transparency

In the obtained glass substrate with a cured film, a light transmittance at a wavelength of 400 nm of only the light of the cured film was measured with an ultraviolet-visible near-infrared spectrophotometer (trade name: V-670, Japan Spectroscopy Corporation). If the light transmittance is 95% or more, it is determined that the transparency is good. A sample which cannot be sufficiently formed and whose transmittance cannot be measured is indicated as "-".

[Example 1]

In a four-necked flask equipped with a stirrer, 20.0 g of diethylene glycol ethyl methyl ether as a polymerization solvent and Aronix M-402 (trade name, Toa Synthetic Co., Ltd.) as a monomer were charged while bubbling with nitrogen. Co., Ltd.) 9.9g, 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent 2.00g, V-65 (trade name, Wako Pure Chemical Industries, Ltd. as a polymerization initiator) Company) 0.5g, heating at 80 ° C for 0.5 hour Instead, polymerization was performed. Next, a solution of 0.1 g of Silaplane FM-0711 (trade name, JNC Co., Ltd.) dissolved in 20.0 g of diethylene glycol ethyl methyl ether as a monomer was added dropwise to the polymerization solution over 0.5 hours. Polymerization was performed by heating at 80 ° C for 1.5 hours.

The polymerization solution was cooled to room temperature to obtain a copolymer (A1). A part of the polymerization solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 24,000.

Using this polymerization solution, a film was formed on a glass substrate and a PET substrate, respectively, and the evaluation was performed.

[Example 2 to Example 11]

As shown in Table 1, the copolymer was obtained in the same manner as in Example 1 except that the types of the trifunctional or higher (meth) acrylate (a) and the compound (B) having a polymerizable double bond were changed. A2) to copolymer (A11). Using these polymerization solutions, the same evaluation as in Example 1 was performed.

[Example 12]

In a four-necked flask equipped with a stirrer, 20.0 g of diethylene glycol ethyl methyl ether as a polymerization solvent and Aronix M-402 (trade name, Toa Synthetic Co., Ltd.) as a monomer were charged while bubbling with nitrogen. Co., Ltd.) 8.9 g, 2.00 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and V-65 (trade name, Wako Pure Chemical Industries, Ltd.) as a polymerization initiator Co., Ltd.) 0.5 g, and polymerized by heating at 80 ° C for 0.5 hour. Next, Silaplane FM-0711 (trade name, A solution of 0.1 g of JNC Co., Ltd. and 1.0 g of Aronix M-402 (trade name, East Asia Synthetic Co., Ltd.) was further polymerized by heating at 80 ° C for 1.5 hours.

The polymerization solution was cooled to room temperature to obtain a copolymer (A12). A part of the polymerization solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 24,000. Using this polymerization solution, the same evaluation as in Example 1 was performed.

M-402: Aronix M-402 (trade name, East Asia Synthesis Co., Ltd.)

M-305: Aronix M-305 (trade name, East Asia Synthesis Co., Ltd.)

FM-0711: Silaplane FM-0711 (trade name, JNC Corporation)

Blemmer GH: glycidyl methacrylate (trade name, Japan Oil Corporation)

n-BMA: butyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

OXE-30: (3-ethyloxetane-3-yl) methacrylate (trade name, large (Han Organic Chemical Industry Co., Ltd.)

VTMS: vinyltrimethoxysilane

DMAEMA: 2- (dimethylamino) ethyl methacrylate

KBE-503: 3-methacryloxypropyltriethoxysilane (trade name, Shin-Etsu Chemical School Industry Co., Ltd.)

[Comparative Example 1]

In a four-necked flask equipped with a stirrer, 20.0 g of diethylene glycol ethyl methyl ether as a polymerization solvent and Light acrylate 1,6HX-A (trade name, Kyoeisha Chemical Co., Ltd.) 9.9g, 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent 2.00g, V-65 (trade name, and Kwang Chun Pharmaceutical Co., Ltd.) 0.5 g, and was polymerized by heating at 80 ° C for 0.5 hour. Next, a solution of 0.1 g of Silaplane FM-0711 (trade name, JNC Co., Ltd.) dissolved in 20.0 g of diethylene glycol ethyl methyl ether as a monomer was added dropwise to the polymerization solution over 0.5 hours. Polymerization was performed by heating at 80 ° C for 1.5 hours.

The polymerization solution was cooled to room temperature to obtain a copolymer (B1). A part of the polymerization solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 3,600.

Using this polymerization solution, the same evaluation as in Example 1 was performed.

[Comparative Example 2]

In a four-necked flask equipped with a stirrer, 20.0 g of diethylene glycol ethyl methyl ether as a polymerization solvent and Aronix M-402 (trade name, Toa Synthetic Co., Ltd.) as a monomer were charged while bubbling with nitrogen. Co., Ltd.) 9.9g, 2,4-diphenyl-4-methyl-1-pentene 2.0g as a chain transfer agent, V-65 (trade name, Wako Pure Chemical Industries, Ltd.) as a polymerization initiator Co., Ltd.) was 0.5 g and polymerized by heating at a polymerization temperature of 80 ° C for 0.5 hour. Next, a solution in which 0.1 g of Aronix M-402 as a monomer was dissolved in 20.0 g of diethylene glycol ethyl methyl ether was added dropwise to the polymerization solution over 0.5 hours, and the solution was heated at 80 ° C. for 1.5 hours. polymerization.

The polymerization solution was cooled to room temperature to obtain a copolymer (B2). A part of the polymerization solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 74,000.

Using this polymerization solution, the same evaluation as in Example 1 was performed.

[Comparative Example 3]

In a four-necked flask equipped with a stirrer, 20.0 g of diethylene glycol ethyl methyl ether as a polymerization solvent and Aronix M-402 (trade name, Toa Synthetic Co., Ltd.) as a monomer were charged while bubbling with nitrogen. Co., Ltd.) 8.5g, 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent 2.00g, V-65 (trade name, Wako Pure Chemical Industries, Ltd. as a polymerization initiator) Co., Ltd.) 0.5 g, and polymerized by heating at 80 ° C for 0.5 hour. Next, a solution of 1.5 g of Silaplane FM-0711 (trade name, JNC Co., Ltd.) dissolved in 20.0 g of diethylene glycol ethyl methyl ether as a monomer was added dropwise to the polymerization solution over 0.5 hours. Heating at 80 ° C for 1.5 hours and Polymerize.

The polymerization solution was cooled to room temperature to obtain a copolymer (B3). A part of the polymerization solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 60,000.

Using this polymerization solution, the same evaluation as in Example 1 was performed.

The thermosetting resin compositions of Examples 1 to 12 and Comparative Examples 1 to 3 are shown in Table 2 with the results obtained by the above-mentioned evaluation methods.

From the results in Table 2, it was found that the thermosetting composition containing the copolymers of Examples 1 to 12 was excellent in coatability, and the film formed using the composition exhibited characteristics of excellent hardness and transparency.

Comparative Example 1 used a bifunctional acrylate in a copolymer monomer. Comparing In Example 1, a film could not be formed, and a cured film having a high hardness was obtained in Examples 1 to 12. This shows that the method using a trifunctional or higher-functional acrylate (a) in the copolymer monomer is useful.

Comparative Example 2 used only 6-functional acrylate in the copolymer monomer. Comparative Example 2 is inferior in coating properties and hardness compared to Examples 1 to 12, and therefore shows that in Example 1 to Example 9, the compound (B) having a polymerizable double bond was used as a copolymer monomer. Method is useful.

Comparative Example 3 increased the content of the compound (B) having a polymerizable double bond in the monomer in the copolymer, but failed to form a film. Therefore, a method showing that the content of the monomer in the copolymer is appropriately controlled is useful.

Examples 1 to 12 show that it is also useful for a substrate (PET) having a low glass transition point such as plastic.

[Industrial availability]

The thermosetting resin composition and the cured film obtained in the present invention can be applied to the production of a cured film having a high hardness. For example, it is useful as a material for protecting a surface.

Claims (10)

A thermosetting resin composition comprising a copolymer (C) obtained by reacting a macromonomer (A) and a compound (B) having a polymerizable double bond. The macromonomer (A) is obtained by reacting a raw material containing a trifunctional or more (meth) acrylate (a); or the copolymer (C) is obtained by polymerizing the macromonomer (A) A compound (B) having a double bond and a trifunctional or higher (meth) acrylate (a) are obtained by reacting the macromonomer (A) with a trifunctional or higher (meth) acrylate (a) ). The thermosetting resin composition according to item 1 of the scope of patent application, wherein the total amount of the trifunctional or more (meth) acrylate (a) and the total amount of the compound (B) having a polymerizable double bond are The weight ratio is 90.0: 10.0 to 99.9: 0.1. The thermosetting resin composition according to claim 1 or claim 2, wherein the compound (B) having a polymerizable double bond is selected from the group consisting of (meth) acrylfluorenyl and α-ethylpropylene At least one of the group of a fluorenyl, styryl, or vinyl compound. The thermosetting resin composition according to claim 3, wherein the compound (B) having a polymerizable double bond is selected from the group consisting of 3-methacryloxypropyltrimethoxysilane and 3-propene Ethoxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-propenyloxypropyltriethoxysilane, p-styryltrimethoxysilane, At least one type of styryltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. The thermosetting resin composition according to claim 3, wherein the compound (B) having a polymerizable double bond is at least one selected from the compounds represented by the following formula (1); R ¹ is hydrogen or methyl, R ² to R ⁵ are alkyl groups having 1 to 5 carbons, R ⁶ is alkyl group having 1 to 10 carbons, m is an integer from 1 to 10, and n is 1 to 150 Integer. The thermosetting resin composition according to item 5 of the scope of patent application, wherein the compound represented by the formula (1) is α-butyl-ω- (3-methacryloxypropyl) polydimethylene Siloxane. The thermosetting resin composition according to claim 1 or claim 2, wherein the copolymer (C) has a weight average molecular weight of 1,000 to 200,000. A cured film, which is obtained from the thermosetting resin composition according to any one of claims 1 to 7 of the scope of patent application. A thermosetting hard coating agent, comprising the thermosetting resin composition according to any one of claims 1 to 7 of the scope of patent application. A display element comprising a cured film as described in item 8 of the scope of patent application.