JP2015157935A - Thermosetting resin composition and set film thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition enabling a high hardness protective film to be formed by thermosetting and a set film formed from the thermosetting resin composition.SOLUTION: There is provided the set film formed by using a thermosetting resin composition containing a copolymer (C) obtained by reacting (A) a macro monomer obtained by reacting a raw material containing (meth)acrylate having 3 or more functionalities (a) and (B) a compound having a polymerizable double bond, or by reacting (A) a macromonomer obtained by reacting the raw material containing trivalent or more (meth)acrylate (a) and (B) the compound having the polymerizable double bond and (a) (meth)acrylate having 3 or more functionalities.

Description

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

  Conventionally, hard coating materials are required for image display devices such as liquid crystal displays, touch panel displays, and organic EL displays in order to prevent damage to the display surface. In recent years, in particular, the market for laptop computers, mobile phones and the like where touch panels are used is increasing.

  With the progress of information terminals and liquid crystal display elements, the development of products such as electronic circuits, displays, and sensors based on organic materials is urgent. Organic materials can be easily adjusted by chemical design or synthesis for electrical properties, processing characteristics, and other characteristics, and can be processed at low temperatures. Advantages include cost reduction by use, and mechanical flexibility and excellent compatibility with flexible substrates.

  Hardened as a hard coat material to prevent scratches on the display surface, color filter protective film, transparent insulating film formed between TFT and alignment film, or between TFT and transparent electrode, when developing organic materials as a base material When the base resin composition is used, it is easy to cure by low temperature (temperature lower than the glass transition temperature of the base material) or light irradiation to prevent deterioration of the base material and avoid overloading. A highly compatible material is desirable. Insufficient curing reduces chemical resistance such as solvent resistance, acid resistance, and alkali resistance during the manufacturing process of the product, causing damage and deterioration of the organic material of the base material. Will also give a big limit.

  So far, photosensitive resin compositions containing polyfunctional (meth) acrylates have been proposed as hard coat materials (see, for example, Patent Documents 1 to 3).

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

  As a method of forming a hard coat layer for improving the surface hardness of a display or the like, there is a wide range of methods in which a polyfunctional acrylate-based active energy ray-curable resin is applied to the surface and cured by irradiation with active energy rays such as ultraviolet rays. It has been adopted. However, since the unreacted photopolymerization initiator remaining in the cured film may have an adverse effect and is inferior in reliability, further improvement is required.

JP 2013-076791 A JP 2004-182765 A JP 2010-027033 A JP2013-083914A

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

Can the inventors obtain a macromonomer (A) obtained by reacting a raw material containing a trifunctional or higher functional (meth) acrylate (a) and a compound (B) having a polymerizable double bond? Or
A macromonomer (A) obtained by reacting a raw material containing a trifunctional or higher functional (meth) acrylate (a), a compound (B) having a polymerizable double bond, and a trifunctional or higher functional (meth) acrylate (a). A protective film using a thermosetting resin composition containing the copolymer (C) obtained by the reaction was found to have high hardness only by thermosetting, and the present invention was completed based on this finding. The present invention includes the following items.

[1] Obtained by reacting a macromonomer (A) obtained by reacting a raw material containing a trifunctional or higher functional (meth) acrylate (a) and a compound (B) having a polymerizable double bond, or
A macromonomer (A) obtained by reacting a raw material containing a trifunctional or higher functional (meth) acrylate (a), a compound (B) having a polymerizable double bond, and a trifunctional or higher functional (meth) acrylate (a). A thermosetting resin composition containing a copolymer (C) obtained by reaction.

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

[3] The item [1] or [2], wherein the compound (B) having a polymerizable double bond is at least one selected from the group of compounds having (meth) acryloyl, α-ethylacryloyl, styryl, or vinyl. ] The thermosetting resin composition of the term.

[4] The compound (B) having a polymerizable double bond is 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxy. The thermosetting resin composition according to item [3], which is at least one selected from silane, p-styryltrimethoxysilane, p-styryltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

（Ｒ^１は水素又はメチルであり、Ｒ^２〜Ｒ^５は炭素数１〜５のアルキルであり、Ｒ^６は炭素数１〜１０のアルキルであり、ｍは１〜１０の整数であり、ｎは１〜１５０の整数である） [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 compounds represented by the following formula (1).

(R ¹ is hydrogen or methyl, R ^{2 to} R ⁵ are alkyl having 1 to ⁵ carbon atoms, R ⁶ is alkyl having 1 to 10 carbon atoms, m is an integer of 1 to 10, and n Is an integer from 1 to 150)

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

[7] The thermosetting resin composition according to any one of [1] to [6], wherein the copolymer (C) has a weight average molecular weight of 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 coat agent comprising the thermosetting resin composition according to any one of [1] to [7].

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

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

  In this specification, in order to show both acrylic acid and methacrylic acid, it may describe as "(meth) acrylic acid". Similarly, in order to indicate one or both of acrylate and methacrylate, it may be expressed as “(meth) acrylate”.

  In the present specification, “alkyl” is linear or branched alkyl, and examples thereof include methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, hexyl and the like.

<1. Thermosetting resin composition of the present invention>
The thermosetting resin composition of the present invention reacts a macromonomer (A) obtained by reacting a raw material containing a (meth) acrylate (a) having three or more functional groups and a compound (B) having a polymerizable double bond. Or a macromonomer (A) obtained by reacting a raw material containing a (meth) acrylate (a) having 3 or more functional groups, a compound (B) having a polymerizable double bond, and 3 or more functional ( It comprises a copolymer (C) obtained by reacting a (meth) acrylate (a).

<1-1.3-functional (meth) acrylate (a)>
The trifunctional or higher functional (meth) acrylate (a) which is a raw material of the macromonomer (A) contained in the thermosetting resin composition of the present invention is particularly limited as long as it has three or more polymerizable double bonds in the molecule. It is not something.

  Specific examples of the above-mentioned trifunctional or higher functional (meth) acrylate (a) are trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, trimethylolpropane PO modified triacrylate, trimethylolpropane EO modified triacrylate. Glycerol tri (meth) acrylate, ethoxylated glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate, diglycerin EO modified acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol tetra ( (Meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ethoxylated isocyanuric ring tri (meth) acrylate Ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, propylene oxide modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Isocyanuric acid EO modified di / triacrylate, pentaerythritol tri / tetraacrylate, dipentaerythritol penta / hexaacrylate, diglycerin EO modified acrylate, ethoxylated isocyanuric acid triacrylate, tris [(meth) acryloxyethyl] isocyanurate, ethoxy Glycerol triacrylate and ethoxylated pentaerythritol tetraacrylate.

  Among the above compounds, dipentaerythritol penta / hexaacrylate and pentaerythritol tri / tetraacrylate are preferable from the viewpoint of increasing the hardness of the cured film.

  The trifunctional or higher functional (meth) acrylate (a) may be used alone or in combination of two or more.

  The polymerization method of the macromonomer (A) obtained by reacting a raw material containing a trifunctional or higher functional (meth) acrylate (a) uses one or more trifunctional or higher functional (meth) acrylates (a) in a solution. The radical polymerization at is preferred. The polymerization temperature is not particularly limited as long as radicals are sufficiently generated from the polymerization initiator to be used, but 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 to 24 hours. In addition, the polymerization can be carried out under pressure, reduced pressure, or atmospheric pressure.

  The solvent used in the polymerization reaction is preferably a solvent capable of dissolving the trifunctional or higher functional (meth) acrylate (a) to be used, the other monomer used in combination with this, and the resulting macromonomer (A). Specific examples of such solvents are methanol, ethanol, 1-propanol, 2-propanol, propylene glycol, methylpropylene 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, 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 of these or a mixture of two or more thereof.

  The polymerization initiator used when producing the macromonomer (A) is a compound that generates radicals by heat, an azo initiator such as azobisisobutyronitrile, or a peroxide initiator such as benzoyl peroxide. Can be used. In order to adjust the molecular weight, a suitable amount of a chain transfer agent such as thioglycolic acid may be added.

  As the thermal radical generator, 2,2′-Azobis (4-methoxy-2,4-dimethylvaleronitile) (V-70 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-Azobis (2 , 4-dimethylvalerontrile (V-65 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), 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-methylpropionamide] VF-096 (trade name) manufactured by Kojun Pharmaceutical Co., Ltd.), 2,2'-Azobis N-butyl-2-methylpropionamide (VAm-110 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), Dimethyl 2,2′-Azobis (isobutyrate) (V-601 manufactured by Wako Pure Chemical Industries, Ltd.) Name)), VPE-0201, VPE-0401, VPE-0601, VPS-1001 (all are trade names, Wako Pure Chemical Industries, Ltd.) and the like.

<1-2. Compound (B) having 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, contains (meth) acryloyl, α-ethylacryloyl, styryl, or vinyl. As long as it is selected from the group of compounds having, it is not particularly limited.

  As the compound having (meth) acryloyl or α-ethylacryloyl, it is preferable to use (meth) acrylic acid, α-ethylacrylic acid or an ester thereof.

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

Here, examples of the “alkyl” include linear alkyl having 1 to 20 carbons, branched alkyl having 1 to 20 carbons and cyclic alkyl having 3 to 12 carbons. The linear alkyl having 1 to 20 carbon atoms and the branched alkyl having 1 to 20 carbon atoms may be an alkoxyalkyl in which any —CH ₂ — in the alkyl chain is replaced by —O—, and ethyleneoxy is continuous. It may have a polyethylene glycol (PEG) structure. The straight chain alkyl having 1 to 20 carbon atoms and the branched alkyl having 1 to 20 carbon atoms are ester bonds in which any —CH ₂ — in the alkyl chain is replaced with —CO—O— and / or O—CO—. You may have. The linear alkyl having 1 to 20 carbon atoms and the branched alkyl having 1 to 20 carbon atoms may have an azaalkyl structure in which any —CH ₂ — in the alkyl chain is replaced with —NH—. The hydrogen of —NH— may be replaced by a linear alkyl having 1 to 6 carbon atoms, a branched alkyl having 1 to 6 carbon atoms, or a cyclic alkyl having 3 to 6 carbon atoms. A cyclic alkyl having 5 to 12 carbon atoms has a structure of a cyclic ether such as tetrahydrofuran, 1,3-dioxane, 1,4-dioxane in which any —CH ₂ — of the ring is replaced by —O—. It can also be taken. The linear alkyl having 1 to 20 carbon atoms and the branched alkyl having 1 to 20 carbon atoms may have a structure in which any —CH ₂ — in the alkyl chain is replaced by a cyclic alkyl having 3 to 6 carbon atoms. Good. The cyclic alkyl having 5 or 6 carbon atoms has a structure of a cyclic ether such as tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, in which any —CH ₂ — of the ring is replaced by —O—. It can also be taken. Moreover, arbitrary hydrogen of a C1-C20 linear alkyl and a C1-C20 branched alkyl is substituted by the C3-C12 cyclic alkyl or the C6-C24 aromatic group. These cyclic alkyl and aromatic groups may have a substituent.

  The “haloalkyl” is an alkyl in which any hydrogen of the above-mentioned straight chain alkyl having 1 to 20 carbon atoms, branched alkyl having 1 to 20 carbon atoms and cyclic alkyl having 3 to 12 carbon atoms is replaced with halogen. Halogen is fluorine, chlorine, bromine or iodine, with fluorine being preferred.

  The “alkyl” may have various functional groups. Examples of the functional group include hydroxy, carboxyl, epoxy, oxetanyl, amino, alkoxysilyl, polyorganosiloxane, and the like. The above-described principle of replacement with —O—, —NH—, etc. is similarly applied to linear, branched or cyclic alkyl having these functional groups.

  The structure having “carboxyl” may be a structure in which —COOH is linked to the alkyl chain, but a structure in which one carboxyl of the dicarboxylic acid such as succinic acid or hexahydrophthalic acid is ester-bonded is also preferably used. It is done.

  Examples of the structure having “epoxy” include glycidyl and 3,4-epoxycyclohexyl.

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

  Examples of the structure having “amino” include a structure having amino substituted with alkyl having 1 to 4 carbon atoms. C1-C4 alkyl is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, and tertiary butyl, and methyl and ethyl are preferred.

  Examples of the alkoxy of “structure having alkoxysilyl” include alkoxysilyl having 1 to 4 carbon atoms. C1-C4 alkoxy is methoxy, ethoxy, propoxy, isopropyloxy, butoxy, isobutyloxy, secondary butyloxy, tertiary butyloxy, and methoxy and ethoxy are preferable. The silicon of alkoxysilyl may be bonded to the alkyl carbon or azaalkyl nitrogen linked to form a ring structure of the compound.

（Ｒ^２〜Ｒ^５は炭素数１〜５のアルキルであり、Ｒ^６は炭素数１〜１０のアルキルであり、ｍは１〜１０の整数であり、ｎは１〜１５０の整数である） The “polyorganosiloxane structure” represents a structure in which an alkyl chain having an m of about 1 to 10 is linked to a linear polysiloxane chain of the following formula (1 ′) having an n of about 1 to 150.

(R ^{2 to} R ⁵ are alkyl having 1 to ⁵ carbon atoms, R ⁶ is alkyl having 1 to 10 carbon atoms, 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 the above-described structures will be specifically described.

  Examples of (meth) acrylic acid, α-ethylacrylic acid and esters thereof include acrylic acid, methacrylic acid, α-ethylacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl ( (Meth) acrylate, n-butyl (meth) acrylate (n-BMA), isobutyl (meth) acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, Heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate Relate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, benzyl (Meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, methoxy Polyethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, 1,2,2,6,6, -pentamethyl-4-piperidyl (Meth) acrylate, 2,2,6,6, -tetramethyl-4-piperidyl (meth) acrylate, trifluoroethyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl ( (Meth) acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2,2,3 4,4,4-hexafluorobutyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylate (HEMA), 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Chill (meth) acrylate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 1 , 4-cyclohexanedimethanol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- ( (Meth) acryloyloxyethyl phthalic acid, glycidyl (meth) acrylate (GMA), methyl glycidyl (meth) acrylate, α-ethyl acrylate glycidyl ester, 3,4-epoxy Hexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate (OXE-10, OXE-30), 3-methyl-3- ( (Meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, methacryl 2- (dimethylamino) ethyl acid (DMAEMA), 2- (diethylamino) ethyl methacrylate, tertiary butylaminoethyl methacrylate, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxy Propyl triet Xylsilane (KBE-503), 3-acryloxypropyltriethoxysilane, ((meth) acryloxymethyl) triethoxysilane, ((meth) acryloxymethyl) trimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxy Silane, ((meth) acryloxymethyl) methyldiethoxysilane, ((meth) acryloxymethyl) methyldimethoxysilane, (meth) acryloxypropylmethyldiethoxysilane, (meth) acryloxypropylmethyldimethoxysilane, (meta ) Acryloxypropyldimethylethoxysilane, (meth) acryloxypropyldimethylmethoxysilane, (meth) acryloxyundecyltrimethoxysilane, and a compound having a structure represented by the following formula (1).

（Ｒ^１は水素又はメチルであり、Ｒ^２〜Ｒ^５は炭素数１〜５のアルキルであり、Ｒ^６は炭素数１〜１０のアルキルであり、ｍは１〜１０の整数であり、ｎは１〜１５０の整数である）

(R ¹ is hydrogen or methyl, R ^{2 to} R ⁵ are alkyl having 1 to ⁵ carbon atoms, R ⁶ is alkyl having 1 to 10 carbon atoms, m is an integer of 1 to 10, and n Is an integer from 1 to 150)

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

  As the compound having styryl, a compound in which a functional group such as alkoxysilyl is linked directly or via alkylene or the like to the para-position of styrene is preferably used.

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

  As the compound having vinyl, a compound in which a functional group such as alkoxysilyl is linked to vinyl directly or via alkylene is preferably used.

  Examples of the compound having vinyl and alkoxysilyl include vinyltrimethoxysilane (VTMS), vinyltriethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, vinyltris (2-methoxyethoxy) silane, butenyltriethoxysilane, ( Divinylmethylsilylethyl) triethoxysilane, dococenyltriethoxysilane, hexadecafluorododeca-11-enyl-1-trimethoxysilane, hexenyltriethoxysilane, 7-octenyltrimethoxysilane, 10-undecenyltrimethoxysilane , Vinyl tritertiary butoxysilane, vinyltris (methoxypropoxy) silane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyldimethylethoxysilane, vinyl Dimethylmethoxysilane, trivinylmethoxysilane, bis (triethoxysilylethyl) vinylmethylsilane, triethoxy (1-phenylethenyl) silane, 3- (N-allylamino) propyltrimethoxysilane, N-allyl-aza-2, Examples include 2-dimethoxysilacyclopentane.

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

  The compound (B) having a polymerizable double bond may be used alone or in combination of two or more.

  Among the above compounds, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, p-styryltrimethoxysilane, p -When styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, α-butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane, or a mixture thereof is used, the thermosetting film is applied to the substrate. And slip properties on the surface of the coating film are preferable.

<1-3. Polymerization method of copolymer (C)>
In the polymerization method of the copolymer (C) contained in the thermosetting resin composition of the present invention, a compound (B) having a polymerizable double bond is added to the macromonomer (A) polymerized in advance. Further, it can be obtained by polymerization. Further, a predetermined amount of tri- or higher functional (meth) acrylate (a) is divided into two parts, on the other hand, the macromonomer (A) is produced, and the other is mixed with the compound (B) having a polymerizable double bond. And may be reacted with (A). These polymerizations are preferably radical polymerization in solution. The polymerization temperature is not particularly limited as long as radicals are sufficiently generated from the polymerization initiator to be used. The polymerization time is not particularly limited, but is usually in the range of 1 to 24 hours. In addition, the polymerization can be carried out under pressure, reduced pressure, or atmospheric pressure.

  The solvent used in the polymerization reaction is preferably a solvent that can dissolve the macromonomer (A) to be used, the compound (B) having a polymerizable double bond, and a tri- or higher functional (meth) acrylate (a). A specific example of such a solvent is preferably a solvent used in producing the above-mentioned macromonomer (A). That 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, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, With N, N-dimethylformamide, acetic acid, and water That. The solvent may be one of these or a mixture of two or more thereof.

  The polymerization initiator used when polymerizing the copolymer (C) is the same as that used when producing the macromonomer (A), a compound that generates radicals by heat, azobisisobutyronitrile, etc. Azo initiators and peroxide initiators such as benzoyl peroxide can be used. In order to adjust the molecular weight, a suitable amount of a chain transfer agent such as thioglycolic acid may be added.

  As the thermal radical generator, 2,2′-Azobis (4-methoxy-2,4-dimethylvaleronitile) (V-70 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-Azobis (2 , 4-dimethylvalerontrile (V-65 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), 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-methylpropionamide] VF-096 (trade name) manufactured by Kojun Pharmaceutical Co., Ltd.), 2,2'-Azobis N-butyl-2-methylpropionamide (VAm-110 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), Dimethyl 2,2′-Azobis (isobutyrate) (V-601 manufactured by Wako Pure Chemical Industries, Ltd.) Name)), VPE-0201, VPE-0401, VPE-0601, VPS-1001 (all are trade names, Wako Pure Chemical Industries, Ltd.) and the like.

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

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

  The weight average molecular weight in the present specification is a value in terms of polystyrene determined by GPC method (column temperature: 35 ° C., flow rate: 1 mL / min). Standard polystyrene has a molecular weight of 645-132,900 (for example, Agilent S-M2-10 polystyrene calibration kit PL2010-0102 (trade name, Agilent Technologies)), and column has PLgel MIXED-D (product) Name, Agilent Technology Co., Ltd.), and using THF as the mobile phase. In addition, the weight average molecular weight of the commercial item in this specification is a catalog publication value.

<1-4. Other ingredients>
The thermosetting resin composition of the present invention may contain other components other than the above as necessary from the viewpoint of adding further properties. Examples of such other components include solvents and additives.

<1-4-1. Solvent>
A solvent may be added to the thermosetting resin composition of the present invention. The solvent arbitrarily added to the thermosetting resin composition of the present invention is preferably a solvent capable of dissolving the polymer and other additives. Specific examples of the solvent that can be added include water, acetone, methyl isobutyl ketone, methanol, ethanol, 1-propanol, 2-propanol, 2-butanone, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, ethyl lactate, and oxyacetic acid. Methyl, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, 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-methoxypropionic acid Chill, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2-methylpropionic acid Ethyl, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-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 monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Cole 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.

  The solvent is propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, It is more preferable that it is at least one selected from diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, ethyl lactate and butyl acetate from the viewpoint of improving the coating uniformity of the thermosetting resin composition of the present invention. Furthermore, the heat of the present invention is at least one selected from propylene glycol, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol ethyl methyl ether, ethyl lactate, and butyl acetate. It is more preferable from the viewpoint of enhancing the application uniformity of the curable resin composition and from the viewpoint of safety to the human body.

  In the thermosetting resin composition of the present invention, the solvent is preferably blended so that the copolymer (C), which is a solid content, and other additives are 5 to 90% by weight in total.

<1-4-2. Additives>
An additive may be contained in the thermosetting resin composition of the present invention. Additives optionally added to the thermosetting resin composition of the present invention are added from the viewpoint of improving the properties of the thermosetting resin composition of the present invention, such as coating uniformity, adhesion, and stability. . Additives include, for example, polymerization inhibitors, acrylic-based, styrene-based, polyethyleneimine-based or urethane-based polymer dispersants, anionic, cationic, nonionic or fluorine-based surfactants, and improved silicone resin coating properties. Agents, adhesion improvers such as silane coupling agents, aggregation inhibitors such as sodium polyacrylate, thermal crosslinking agents such as epoxy compounds, melamine compounds or bisazide compounds, antioxidants such as hindered phenols, imidazole and Examples include polyfunctional acrylate-based curing accelerators.

  A surfactant and a coating property improver may be added to the thermosetting resin composition of the present invention. The surfactant and the coating property improver are used for improving wettability, leveling property, or coating property to the base substrate. The surfactant optionally added to the thermosetting resin composition of the present invention is Polyflow No. 45, polyflow KL-245, polyflow no. 75, Polyflow No. 90, polyflow no. 95 (all are trade names, Kyoeisha Chemical Industry Co., Ltd.), BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346 (all are trade names, BYK Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (all are trade names, Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40, Surflon S611 (all are trade names, AGC Seimi Chemical Co., Ltd.), Aftergent 222F, Aftergent 208G, Aftergent 251, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 601AD, Aftergent 602A, Aftergent 50A, FTX-218 (all are trade names, Neos Corporation), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 Inc.), Megafuck F-171, Megafuck F-177, Megafuck F-410, Megafuck F-430, Megafuck F-444, Megafuck F-472SF, Megafuck F-475, Megafuck F- 477, Megafuck F-552, Megafuck F-553, Megafuck F-554, Megafuck F-555, Megafuck F-556, Megafuck F-558, Megafuck R-30, Megafuck R-94, Megafuck RS-75, Megafuck RS-72 K, Megafuck RS-76-NS (all are trade names, DIC Corporation), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2200N Rad 2250N (all are trade names, Evonik Degussa Japan Co., Ltd.), fluoroalkylbenzene sulfonate, fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylsulfonate , Diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyltrimethylan Nium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene Oxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate , Sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan pal Examples include mitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, or alkyl diphenyl ether disulfonate. It is preferable to use at least one selected from these as additives.

  Among these surfactants, fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyalkylene) Oxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, megafac R-08, megafac R-30, megafaq F-477, megafaq F-556, megafaq F-554, etc. Selected from silicone surfactants such as BYK306, BYK342, BYK344, BYK346, KP-341, KP-358, or KP-368 That if at least one is added, from the viewpoint of enhancing coating uniformity of the thermosetting resin composition of the present invention.

  The content of the surfactant and the coating improver 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 curing accelerator may be added to the thermosetting resin composition of the present invention. It is used for accelerating the curing reaction of the thermosetting resin composition and improving the hardness, heat resistance, and chemical resistance of the cured film. The curing accelerator optionally added to the thermosetting resin composition of the present invention is trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, trimethylolpropane 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 dipentaerythritol Tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ethoxylated isocyanuric ring tri (meth) acrylate , Ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, propylene oxide modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate Isocyanuric acid EO modified di / triacrylate, pentaerythritol tri / tetraacrylate, dipentaerythritol penta / hexaacrylate, diglycerin EO modified acrylate, ethoxylated isocyanuric acid triacrylate, tris [(meth) acryloxyethyl] isocyanurate, Ethoxylated glycerol triacrylate, ethoxylated pentaerythritol tetraacrylate, 2-undecylimidazole, 2-hept Tadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, and the like.

  A hardening accelerator may be used independently and may mix and use 2 or more.

  Among the curing accelerators, dipentaerythritol penta / hexaacrylate and pentaerythritol tri / tetraacrylate are more preferable from the viewpoint of increasing the hardness of the cured film.

  An adhesion improver may be added to the thermosetting resin composition of the present invention. The adhesion improver is used to improve the adhesion between the thermosetting resin composition and the substrate. As the adhesion improver that is optionally added to the thermosetting resin composition of the present invention, a coupling agent can be suitably used. The adhesion improver may be one type or two or more types. As the coupling agent, a silane-based, aluminum-based or titanate-based compound can be used. Examples of such coupling agents include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, acetoalkoxyaluminum diisopropylate, and tetra And isopropyl bis (dioctyl phosphite) titanate. Among these, 3-glycidoxypropyltrimethoxysilane is preferable because it has a large effect of improving adhesion.

  An anti-aggregation agent may be added to the thermosetting resin composition of the present invention. The agglomeration inhibitor is used to blend with the solvent and prevent agglomeration. Specific examples of the aggregation inhibitor optionally added to the thermosetting resin composition of the present invention include 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 trade names, Big Chemie Japan, Inc.), FTX-218, footent 710FM, footer Gento 710FS (both trade names, Neos Co., Ltd.), Floren G-600, Floren G-700 (both trade names, Sakaesha is a Chemical Industry Co., Ltd.).

  An antioxidant may be added to the thermosetting resin composition of the present invention. As the antioxidant, hindered phenol compounds, hindered amine compounds, phosphorus compounds, and sulfur compounds can be preferably used. An antioxidant may be used independently and may mix and use 2 or more. It is preferable from the viewpoint of weather resistance that the antioxidant is an antioxidant of 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. Specifically, IRGAFOS XP40, IRGAFOS XP60, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 1520L (all trade names, manufactured by BASF Japan Ltd.), ADK STAB AO-20, ADK STA AB , ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, and ADK STAB AO-80 (trade name, ADEKA Corporation). 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.

  The thermosetting resin composition of the present invention may optionally contain a crosslinking agent from the viewpoint of further improving heat resistance, chemical resistance, in-film uniformity, flexibility, flexibility, and elasticity.

  Specific examples of the thermal crosslinking agent optionally added to the thermosetting resin composition of the present invention include jER807, jER815, jER825, jER827, jER828, jER190P, and jER191P (all trade names, Mitsubishi Chemical Corporation), jER1004, jER1256, YX8000 (all trade names, Mitsubishi Chemical Corporation), Araldite CY177, Araldite CY184 (all trade names, Huntsman Japan), Celoxide 2021P, EHPE-3150 (all trade names, Daicel) Chemical Industry Co., Ltd.), Techmore VG3101L (trade name, Printec Co., Ltd.), Nicarak MW-30HM, Nicarak MW-100LM, Nicarak MW-270, Nicarac MW-280, Nicarac MW-290, Nicarac MW- 90, NIKALACK MW-750LM, (all trade names, Ltd. Sanwa Chemical) and the like can be mentioned.

<1-5. Storage of thermosetting resin composition>
The thermosetting resin composition of the present invention is preferably stored in the temperature range of −30 ° C. to 25 ° C. in a light-shielded state because the composition is stable over time. A storage temperature of −20 ° C. to 10 ° C. is more preferable because there is no precipitate.

<2. Cured film obtained from thermosetting resin composition>
The thermosetting resin composition of the present invention contains a copolymer (C) and, depending on the intended properties, further selects a solvent, a coupling agent, a surfactant, an antioxidant and other additives as necessary. And then uniformly mixing and dissolving them.
The thermosetting resin of the present invention or a thermosetting composition using the same (after dissolving in a solvent in the case of a solid state without a solvent) is applied to the substrate surface, and the solvent is removed, for example, by heating. Then, a coating film can be formed.

  The coating method of the thermosetting resin composition of the present invention is to form a coating film by a conventionally known method such as spin coating method, roll coating method, dipping method, slit coating method, ink jet method, flexographic printing method and gravure printing method. can do.

  As a base material used at the time of film-forming, base materials, such as plastic, glass, glass with transparent electrodes, such as FTO and ITO, are mentioned. Specific examples of the plastic include polycarbonate, poly (meth) acrylate, polyurethane, polyethylene terephthalate, and triacetyl cellulose.

  This coating film is heated (prebaked) with a hot plate or an oven. The heating conditions vary depending on the type and mixing ratio of each component, but are usually 70 to 110 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Thereafter, a cured film is obtained by heat treatment (post-bake) at 100 to 150 ° C., preferably 120 to 150 ° C. for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate in order to cure the coating film. Can do.

  The thermosetting resin composition of the present invention can be cured by heating at a low temperature of 120 to 150 ° C. as a temperature for curing the coating film to obtain a cured film. For this reason, if the thermosetting resin composition of the present invention is applied to a base material having a low glass transition point, such as plastic, a cured film can be obtained without causing deterioration or breakage of the base material.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these. The evaluation method of the thermosetting resin composition of the present invention is shown below.

[Method for evaluating thermosetting resin composition]
1) Film thickness On a glass substrate (Corning Co., Ltd. EagleXG (trade name), 40 mm x 40 mm x 0.7 mm) or PET film (Toyobo Cosmo Shine A4300 (trade name), 210 mm x 297 mm x 0.25 mm) The thermosetting resin composition was spin-coated at 700 rpm for 10 seconds and dried on an 80 ° C. hot plate for 3 minutes. This substrate was post-baked in an oven at 120 ° C. for a PET film and 150 ° C. for a glass substrate for 30 minutes, and the film thickness was measured. The film thickness was measured using a step / surface roughness / fine shape measuring device (P-16 + (trade name), KLA-Tencor Japan Co., Ltd.), and the average value of the measurements at three locations was taken as the film thickness.
2) Applicability When the formed cured film is visually observed, ◯ indicates a good case without unevenness, Δ indicates a case where unevenness occurs, and × indicates a case where the film is not sufficiently formed on the substrate due to repelling. did.
3) Pencil hardness It carried out based on JIS-K5600. A sample that could not be sufficiently deposited and whose pencil hardness could not be measured was indicated as “−”.
4) Transparency In the obtained glass substrate with a cured film, the light transmittance at a wavelength of 400 nm of only the cured film was measured with an ultraviolet-visible near-infrared spectrophotometer (trade name; manufactured by V-670 JASCO Corporation). Was measured. If the light transmittance was 95% or more, it was judged that the transparency was good. Samples that could not be sufficiently deposited and whose light transmittance could not be measured were indicated as “−”.

[Example 1]
In a four-necked flask equipped with a stirrer, while bubbling nitrogen, 20.0 g of diethylene glycol ethyl methyl ether as a polymerization solvent, 9.9 g of Aronix M-402 (trade name, Toagosei Co., Ltd.) as a monomer, and 2, as a chain transfer agent 2.00 g of 4-diphenyl-4-methyl-1-pentene and 0.5 g of V-65 (trade name, Wako Pure Chemical Industries, Ltd.) as a polymerization initiator are charged and heated at 80 ° C. for 0.5 hours for polymerization. Was done. Subsequently, a solution prepared by dissolving 0.1 g of Silaplane FM-0711 (trade name, JNC Co., Ltd.) as a monomer in 20.0 g of diethylene glycol ethyl methyl ether was added dropwise to this polymerization solution over 0.5 hours, and the temperature was 80 ° C. For 1.5 hours to conduct polymerization.

  The polymerization liquid 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.

Each film was formed on a glass substrate and a PET substrate using this polymerization solution, and the above evaluation was performed.
[Examples 2 to 11]
As shown in Table 1, a copolymer is produced in the same manner as in Example 1 except that the type of the trifunctional or higher (meth) acrylate (a) and the compound (B) having a polymerizable double bond is changed. (A2) to (A11) were obtained. Evaluation similar to Example 1 was performed using these polymerization liquids.

[Example 12]
In a four-necked flask equipped with a stirrer, 20.0 g of diethylene glycol ethyl methyl ether as a polymerization solvent while bubbling nitrogen, 8.9 g of Aronix M-402 (trade name, Toagosei Co., Ltd.) as a monomer, and 2, as a chain transfer agent 2.00 g of 4-diphenyl-4-methyl-1-pentene and 0.5 g of V-65 (trade name, Wako Pure Chemical Industries, Ltd.) as a polymerization initiator are charged and heated at 80 ° C. for 0.5 hours for polymerization. Was done. Subsequently, a solution in which 0.1 g of Silaplane FM-0711 (trade name, JNC Corporation) and 1.0 g of Aronix M-402 (same as above) were dissolved in 20.0 g of diethylene glycol ethyl methyl ether as a monomer in this polymerization solution. The solution was added dropwise over 0.5 hours, and further polymerized by heating at 80 ° C. for 1.5 hours.

  The polymerization liquid 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. Evaluation similar to Example 1 was performed using this polymerization liquid.

M-402: Aronix M-402 (trade name, Toagosei Co., Ltd.)
M-305: Aronix M-305 (trade name, Toagosei Co., Ltd.)
FM-0711: Silaplane FM-0711 (trade name, JNC Corporation)
BLEMMER GH: Glycidyl methacrylate (trade name, NOF Corporation)
n-BMA: Butyl methacrylate HEMA: Methacrylate 2-hydroxyethyl OXE-30: (3-Ethyloxetane-3-yl) methyl methacrylate (trade name, Osaka Organic Chemical Industry Co., Ltd.)
VTMS: Vinyltrimethoxysilane DMAEMA: 2- (dimethylamino) ethyl methacrylate KBE-503: 3-methacryloxypropyltriethoxysilane (trade name, Shin-Etsu Chemical Co., Ltd.)

[Comparative Example 1]
In a four-necked flask with a stirrer, 20.0 g of diethylene glycol ethyl methyl ether as a polymerization solvent while bubbling nitrogen, 9.9 g of light acrylate 1,6HX-A (trade name, Kyoeisha Chemical Co., Ltd.) as a monomer, a chain transfer agent 2,4-diphenyl-4-methyl-1-pentene 2.00 g, V-65 (trade name, Wako Pure Chemical Industries, Ltd.) 0.5 g as a polymerization initiator, and heated at 80 ° C. for 0.5 hours Polymerization was carried out. Subsequently, a solution prepared by dissolving 0.1 g of Silaplane FM-0711 (trade name, JNC Co., Ltd.) as a monomer in 20.0 g of diethylene glycol ethyl methyl ether was added dropwise to this polymerization solution over 0.5 hours, and the temperature was 80 ° C. For 1.5 hours to conduct polymerization.

  The polymerization liquid 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.

  Evaluation similar to Example 1 was performed using this polymerization liquid.

[Comparative Example 2]
While bubbling nitrogen through a four-necked flask equipped with a stirrer, 20.0 g of diethylene glycol ethyl methyl ether as a polymerization solvent, 9.9 g of Aronix M-402 (trade name, Toagosei Co., Ltd.) as a monomer, and 2,4 as a chain transfer agent -2.0 g of diphenyl-4-methyl-1-pentene and 0.5 g of V-65 (trade name, Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were charged and heated at a polymerization temperature of 80 ° C for 0.5 hours. Polymerization was performed. Subsequently, a solution prepared by dissolving 0.1 g of Aronix M-402 as a monomer in 20.0 g of diethylene glycol ethyl methyl ether was added dropwise to this polymerization solution over 0.5 hours, and the mixture was heated at 80 ° C. for 1.5 hours to polymerize. Was done.

  The polymerization liquid 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.

  Evaluation similar to Example 1 was performed using this polymerization liquid.

[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 while bubbling nitrogen, 8.5 g of Aronix M-402 (trade name, Toagosei Co., Ltd.) as a monomer, and 2, as a chain transfer agent 2.00 g of 4-diphenyl-4-methyl-1-pentene and 0.5 g of V-65 (trade name, Wako Pure Chemical Industries, Ltd.) as a polymerization initiator are charged and heated at 80 ° C. for 0.5 hours for polymerization. Was done. Subsequently, a solution prepared by dissolving 1.5 g of Silaplane FM-0711 (trade name, JNC Co., Ltd.) as a monomer in 20.0 g of diethylene glycol ethyl methyl ether was added dropwise to the polymerization solution over 0.5 hours, and the temperature was 80 ° C. For 1.5 hours to conduct polymerization.

  The polymerization liquid 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.

  Evaluation similar to Example 1 was performed using this polymerization liquid.

  About the thermosetting resin composition of Examples 1-12 and Comparative Examples 1-3, the result obtained by said evaluation method is shown in Table 2.

  As is clear from the results in Table 2, the thermosetting compositions containing the copolymers of Examples 1 to 12 were excellent in coatability, and the film formed using this composition was excellent in hardness and transparency. The characteristics are shown.

  Comparative Example 1 uses a bifunctional acrylate as a copolymer monomer. In Comparative Example 1, it was impossible to form a film, and in Examples 1 to 12, a hardened cured film was obtained. Therefore, it is useful to use a trifunctional or higher functional acrylate (a) as a copolymer monomer. It is shown that.

  Comparative Example 2 uses only hexafunctional acrylate as a copolymer monomer. Since Comparative Example 2 is inferior in coating properties and hardness as compared with Examples 1 to 12, in Examples 1 to 9, it is useful to use a compound (B) having a polymerizable double bond as a copolymer monomer. Show.

  In Comparative Example 3, the content of the compound (B) having a polymerizable double bond in the monomer in the copolymer was increased, but no film could be formed. For this reason, it has shown that it is useful to appropriately control the monomer content in the copolymer.

  In Examples 1-12, it has shown that it is useful also with respect to the base material (PET) with a low glass transition point like a plastics.

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

Claims (10)

Obtained by reacting a compound (B) having a polymerizable double bond with a macromonomer (A) obtained by reacting a raw material containing a tri- or higher functional (meth) acrylate (a), or
A macromonomer (A) obtained by reacting a raw material containing a trifunctional or higher functional (meth) acrylate (a), a compound (B) having a polymerizable double bond, and a trifunctional or higher functional (meth) acrylate (a). A thermosetting resin composition containing a copolymer (C) obtained by reaction.   The weight ratio of the total amount of the trifunctional or higher (meth) acrylate (a) and the total amount of the compound (B) having a polymerizable double bond is 90.0: 10.0 to 99.9: 0.1. Item 2. The thermosetting resin composition according to Item 1.   The thermosetting according to claim 1 or 2, wherein the compound (B) having a polymerizable double bond is at least one selected from the group of compounds having (meth) acryloyl, α-ethylacryloyl, styryl, or vinyl. Resin composition.   The compound (B) having a polymerizable double bond is 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, p The thermosetting resin composition according to claim 3, which is at least one selected from -styryltrimethoxysilane, p-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 compounds represented by the following formula (1).

(R ¹ is hydrogen or methyl, R ^{2 to} R ⁵ are alkyl having 1 to ⁵ carbon atoms, R ⁶ is alkyl having 1 to 10 carbon atoms, m is an integer of 1 to 10, and n Is an integer from 1 to 150)   The thermosetting resin composition according to claim 5, wherein the compound represented by the formula (1) is α-butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane.   The thermosetting resin composition according to any one of claims 1 to 6, wherein the copolymer (C) has a weight average molecular weight of 1,000 to 200,000.   The cured film obtained from the thermosetting resin composition of any one of Claims 1-7.   A thermosetting hard coat agent comprising the thermosetting resin composition according to claim 1.   A display element comprising the cured film according to claim 8.