JP2013113968A - Curable resin composition containing siloxane compound having glycidyl group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition which allows alkali development, yields a cured product excellent in adhesion and scratch resistance, and is useful as a hard coating material for an image display surface of an image display device.SOLUTION: Provided is a curable resin composition containing (A) a polyvalent alcohol acrylate compound, (B) a compound containing an acrylic group or methacrylic group and a carboxyl group in a molecule, (C) a siloxane compound containing a glycidyl group, and (D) a photo-radical generator. The (C) siloxane compound containing a glycidyl group is preferably a compound represented by the general formula (1) or (2), particularly a siloxane compound containing a 3-glycidoxypropyl group. The general formulas (1) and (2) are as described in the description of the claimed invention.

Description

  The present invention relates to a curable resin composition capable of forming a cured product excellent in transparency and adhesion.

An image display surface in an image display device such as a liquid crystal display, a CRT display, a projection display, a plasma display, or an electroluminescence display is required to be provided with scratch resistance so as not to be damaged during handling.
In order to improve the scratch resistance, a hard coat layer is generally formed on the image display surface. The acrylate compound can be cured in a short time by using a photo radical generator, and a curable composition containing a polyfunctional acrylate as a main component is used as the hard coat material.
Among polyfunctional acrylates, particularly curable compositions mainly composed of dipentaerythritol hexaacrylate (see, for example, Patent Documents 1 and 2) provide a hard coat layer having high surface hardness and excellent scratch resistance. However, the adhesion with glass or the like was insufficient.
A curable composition mainly composed of an acrylate having a hydroxyl group, such as pentaerythritol triacrylate (see, for example, Patent Document 3) has been known as a material having improved adhesion to glass. There was a problem that it was insufficient and easily damaged.
It is also known that a hard coat layer having excellent scratch resistance can be obtained from a curable composition containing a siloxane compound having an epoxycyclohexyl group and a radical curable acrylic resin (see, for example, Patent Document 4). However, the adhesiveness with glass was insufficient.

On the other hand, in order to form a hard coat layer only on the image display surface, it is preferable to use a photoresist. Furthermore, in consideration of the influence on the environment and health, it is preferable to use a photoresist capable of alkali development. .
Photoresists that can be developed with an alkali and that can be used for the hard coat layer are also known (see, for example, Patent Document 5), but these known photoresists have insufficient scratch resistance.

Japanese Patent Laid-Open No. 9-48934 JP 2011-12145 A JP 2000-191710 A JP 2003-292891 A JP 2008-216875 A

  Accordingly, an object of the present invention is to provide a curable resin composition that is capable of alkali development and that provides a cured product having excellent adhesion and scratch resistance, and is useful as a hard coat material for an image display surface of an image display device. There is to do.

As a result of intensive studies, the present inventor blended a siloxane compound having a glycidyl group into a curable resin composition containing a polyfunctional acrylate and a compound having an acrylic group or a methacryl group and a carboxyl group. Thus, it was found that a cured product capable of alkali development, excellent scratch resistance, and excellent adhesion to glass or the like was obtained, and the present invention was completed.
That is, the present invention includes (A) a polyhydric alcohol acrylate compound, (B) a compound having an acrylic group or a methacryl group and a carboxyl group in the molecule, (C) a siloxane compound having a glycidyl group, and (D) a photoradical. A curable resin composition containing a generator is provided.

  The effect of the present invention is to provide a curable resin composition useful as a hard coat material for an image display surface of an image display device, capable of being developed with an alkali, and capable of obtaining a cured product having excellent adhesion and scratch resistance. It is in.

Hereinafter, the present invention will be described in detail.
In the present invention, a compound having an acrylic group or a methacryl group is referred to as an acrylate compound.

  The curable resin composition of the present invention comprises (A) a polyhydric alcohol acrylate compound, (B) a compound having an acrylic group or a methacryl group and a carboxyl group in the molecule, (C) a siloxane compound having a glycidyl group, and (D ) Contains a photoradical generator. First, the polyhydric alcohol acrylate compound as component (A) will be described.

  Examples of the polyhydric alcohol acrylate compound include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and 1,3-butanediol diester. Acrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, isoprene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, octanediol diacrylate, 1,2-cyclohexane Diol diacrylate, 1.4-cyclohexanediol diacrylate, hydrogenated bisphenol A diacrylate, Toxylated bisphenol A diacrylate, propoxylated bisphenol A diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, 1,3- Butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, isoprene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, octanediol dimethacrylate, 1, 2-cyclohexanediol dimethacrylate, 1.4-cyclohexane All dimethacrylate, hydrogenated bisphenol A dimethacrylate, ethoxylated bisphenol A dimethacrylate, acrylate compounds of dihydric alcohols such as propoxylated bisphenol A dimethacrylate;

  Glycerin diacrylate, glycerin triacrylate, trimethylol ethane diacrylate, trimethylol ethane triacrylate, trimethylol propane diacrylate, trimethylol propane triacrylate, tris [acryloxyethyl] isocyanurate, glycerin dimethacrylate, glycerin trimethacrylate, tri Acrylate compounds of trihydric alcohols such as methylolethane dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, tris [methacryloxyethyl] isocyanurate;

  Erythritol triacrylate, erythritol tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, diglycerin triacrylate, diglycerin tetraacrylate, ditrimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, erythritol trimethacrylate, erythritol tetramethacrylate, pentaerythritol Acrylate compounds of tetrahydric alcohols such as trimethacrylate, pentaerythritol tetramethacrylate, diglycerin trimethacrylate, diglycerin tetramethacrylate, ditrimethylolpropane trimethacrylate, ditrimethylolpropane tetramethacrylate;

  Trivalent alcohol acrylate compounds such as triglycerin tetraacrylate, triglycerin pentaacrylate, triglycerin tetramethacrylate, triglycerin pentamethacrylate; dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexa Examples include acrylate compounds of hexahydric alcohols such as methacrylate.

  As the component (A) of the present invention, an acrylate compound of a 4-6 valent alcohol is preferable, an acrylate compound of a 5-6 valent alcohol is more preferable, and dipentaerythritol hexaacrylate is most preferable because of little decrease in scratch resistance. preferable.

Next, the compound which has an acryl group or a methacryl group and a carboxyl group in the molecule which is the component (B) of the present invention will be described.
In the present invention, the compound having an acrylic group or a methacryl group and a carboxyl group in the molecule means a compound having at least one acrylic group or a methacryl group and at least one carboxyl group in one molecule. . Examples of the compound having an acrylic group or a methacrylic group and a carboxyl group in the molecule include glycidyl-modified acrylate compounds of acrylic acid oligomers, isocyanate-modified acrylate compounds of acrylic acid oligomers, and acid pendane-type epoxy acrylate compounds. However, an acid-pendane-type epoxy acrylate type compound is preferable because of good alkali developability and good adhesion of the cured product. An epoxy acrylate compound is a compound obtained by reacting an epoxy group of an epoxy compound with acrylic acid or methacrylic acid, that is, an epoxy group undergoes a ring-opening reaction with (meth) acrylic acid, and a (meth) acryloyl group and a hydroxyl group In the present invention, an acid pendan-type epoxy acrylate relay compound refers to an acidic partial ester of an epoxy acrylate-compound and a polycarboxylic acid.

（式中、Ｒ⁴はアクリル基又はメタアクリル基を表わし、Ｒ⁵は二塩基酸から１つの水酸基を除いた残基を表わす。） As the component (B) of the present invention, a compound having a partial structure represented by the following general formula (3) is preferable because of excellent adhesion of the cured product and little reduction in scratch resistance.

(In the formula, R ⁴ represents an acrylic group or a methacryl group, and R ⁵ represents a residue obtained by removing one hydroxyl group from a dibasic acid.)

In the general formula (3), R ⁴ represents an acrylic group or a methacryl group, and R ⁵ represents a residue obtained by removing one hydroxyl group from a dibasic acid. Dibasic acids of residues obtained by removing one hydroxyl group from dibasic acids include aliphatic saturated dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid; fumaric acid, maleic acid, itaconic acid Aliphatic unsaturated dibasic acids such as: aromatic dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid; 1,2-cyclohexyl dicarboxylic acid, 1,3-cyclohexyl dicarboxylic acid, 1,4- Examples thereof include alicyclic dibasic acids such as cyclohexyldicarboxylic acid, 1,2,3,6-tetrahydrophthalic acid, and 3,4,5,6-tetrahydrophthalic acid.
Among these dibasic acids, the reactivity of the raw materials is excellent, so succinic acid, maleic acid, phthalic acid, 1,2-cyclohexyldicarboxylic acid, 1,2,3,6-tetrahydrophthalic acid, 3,4 , 5,6-tetrahydrophthalic acid, 3 or 4-methyl-1,2,3,6-tetrahydrophthalic acid, 3 or 4-methyl-1,2-cyclohexyldicarboxylic acid, 3,6-endomethylene-1, 2,3,6-tetrahydrophthalic acid and 3 or 4-3,6-endomethylene-1,2,3,6-tetrahydrophthalic acid are preferable, and a cured product having high hardness can be obtained. Acid, 1,2-cyclohexyl dicarboxylic acid, 1,2,3,6-tetrahydrophthalic acid and 3,4,5,6-tetrahydrophthalic acid are more preferred.

（式中、Ｒ⁶は、酸素原子、硫黄原子、スルフィニル基、スルホン基、炭素数１〜１５の２価の炭化水素基又は直接結合を表わす。） The compound having the partial structure represented by the general formula (3) is an acid pendant type epoxy acrylate compound synthesized from glycidyl ether of a compound having a phenolic hydroxyl group. Preferred compounds having a phenolic hydroxyl group include compounds having at least two phenolic hydroxyl groups in the molecule, such as 1,2-benzenediol, 1,3-benzenediol, 1,4-benzenediol, , 2-naphthalenediol, 1,3-naphthalenediol, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 1,8-naphthalenediol, 2,8 3-naphthalenediol, 2,4-naphthalenediol, 2,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, phenol novolak, naphthol novolak, naphthol-phenol co-condensed novolak, cresol novolak, 4 -Hydroxystyrene Rigomers, compounds represented by the following formula (4), bisphenol compounds represented by the following general formula (5), and the like can be mentioned. Among these, since there is little reduction in scratch resistance, it is represented by the following general formula (5). Bisphenol compounds are preferred.

(In the formula, R ⁶ represents an oxygen atom, a sulfur atom, a sulfinyl group, a sulfone group, a divalent hydrocarbon group having 1 to 15 carbon atoms, or a direct bond.)

In the general formula (5), R ⁶ represents an oxygen atom, a sulfur atom, a sulfinyl group, a sulfone group, a divalent hydrocarbon group having 1 to 15 carbon atoms, or a direct bond. Examples of the divalent hydrocarbon group having 1 to 15 carbon atoms include methylene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, 1-methylpropylidene, 1-methylpentylidene, 1-methyloctylidene, 1-methyldecylidene, Phenylmethylene, cyclohexylidene [following formula (6)], 3,3,5-trimethylcyclohexylidene [following formula (7)], octahydro-4,7-methano-5H-indene-5-ylidene [following formula (8)], 9H-fluorene-9-ylidene [following formula (9)], indan-1-ylidene [following formula (10)], 3-phenylindan-1-ylidene [following formula (11)], phenylene Examples thereof include bis (isopropylidene) [the following formula (12)], a group represented by the following formula (13), and the like.

R ⁶ is preferably a divalent hydrocarbon group having an aromatic ring because of little reduction in scratch resistance, and is preferably 9H-fluorene-9-ylidene, indan-1-ylidene, 3-phenylindane-1-ylidene. And phenylenebis (isopropylidene) are more preferable.

  In the curable resin composition of the present invention, when the content of the component (B) is too small, the alkali developability becomes insufficient, and when it is too large, the scratch resistance is lowered. ) Component content is preferably 1 to 60 parts by mass, more preferably 3 to 30 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (C). Most preferably, it is -18 mass parts.

（式中、Ｒ⁴は前記一般式（３）と同義である。） The compound having the partial structure represented by the general formula (3) is reacted with acrylic acid or methacrylic acid on the epoxy group of the compound having the partial structure represented by the following formula (3a), and the following general formula (3b) It can obtain by making a hydroxyl group of the compound which has a partial structure represented by following General formula (3b) react with a dibasic acid or a dibasic acid anhydride. In the reaction of a compound having a partial structure represented by the following general formula (3b) with a dibasic acid or a dibasic acid anhydride, a dibasic acid anhydride is used because the reaction is possible under relatively mild conditions. It is preferable.

(In the formula, R ⁴ has the same meaning as the general formula (3).)

  Reaction of a compound having a partial structure represented by the general formula (3a) with acrylic acid or methacrylic acid, and a compound having a partial structure represented by the general formula (3b) and a dibasic acid or dibasic acid anhydride This reaction may be catalyst-free, but it is preferable to use a catalyst because the reaction proceeds smoothly. Examples of the reaction catalyst include organic phosphorus catalysts such as triphenylphosphine, tributylphosphine, tri (4-methylphenyl) phosphine, tri (nonylphenyl) phosphine; imidazole, 2-methylimidazole, 2,4-dimethylimidazole, 2- Imidazole catalysts such as ethyl-4-methylimidazole and 2-phenylimidazole; tertiary amine catalysts such as triethylamine, triethylenediamine, benzyldimethylamine, 1,8-diazabicyclo [5,4,0] undecene-7, etc. It is preferable to use an organic phosphorus catalyst. The addition amount of the reaction catalyst is preferably 3% by mass or less of the total amount of each raw material, more preferably 0.0001 to 1% by mass, and most preferably 0.001 to 0.1% by mass. The reaction temperature is usually 50 to 150 ° C, preferably 70 to 120 ° C.

Next, the siloxane compound having a glycidyl group as the component (C) of the present invention will be described.
In the present invention, the siloxane compound having a glycidyl group refers to a compound having at least one glycidyl group and at least one siloxane group (Si—O—Si) in one molecule. The glycidyl group may be directly bonded to silicon, or a substituent having a glycidyl group may be bonded to silicon. Examples of the substituent having a glycidyl group include the following formulas (14) to (21). As a substituent having a glycidyl group or a glycidyl group bonded to silicon, the cured product is excellent in adhesion, and therefore, a 3,4-epoxybutyl group [the following formula (14)], a 3-glycidoxypropyl group [the following Formula (19)] and 2-glycidoxycarboxyethyl group [following formula (20)] are preferable, and 3-glycidoxypropyl group is more preferable.

（式中、Ｒ¹は同一でも異なってもよい炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表わし、Ｇはグリシジル基又はグリシジル基を有する置換基を表わし、ａは３〜６の数を表わす。）

（式中、Ｒ²は同一でも異なってもよい炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表わし、Ｒ³は１分子中に２〜４個のビニル基を有し分子量が１０００以下の化合物からビニル基を除いた残基を表わし、Ｇはグリシジル基又はグリシジル基を有する置換基を表わし、ｂは２〜５の数を表わし、ｃは２〜４の数を表わす。）

（式中、Ｒ⁷〜Ｒ¹¹は同一でも異なってもよい炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表わし、Ｇはグリシジル基又はグリシジル基を有する置換基を表わし、Ｘ¹はメチル、グリシジル基又はグリシジル基を有する置換基を表わし、ｄは０〜１００の数を表わし、ｅは０〜１００の数を表わす。但し、ｄが０又は１の場合には、Ｘ¹はグリシジル基又はグリシジル基を有する置換基を表わす。） Examples of the siloxane compound having a glycidyl group include a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (22), and the like. From the viewpoint of adhesion, a compound represented by the following general formula (1) and a compound represented by the following general formula (2) are preferred, and a compound represented by the following general formula (1) is more preferred.

(In the formula, R ¹ represents the same or different alkyl group having 1 to 4 carbon atoms or aryl group having 6 to 10 carbon atoms, G represents a glycidyl group or a substituent having a glycidyl group, and a represents 3 Represents a number of ~ 6)

(In the formula, R ² represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different, and R ³ has 2 to 4 vinyl groups in one molecule. G represents a residue obtained by removing a vinyl group from a compound having a molecular weight of 1000 or less, G represents a glycidyl group or a substituent having a glycidyl group, b represents a number of 2 to 5, and c represents a number of 2 to 4. .)

Wherein R ^{7 to} R ¹¹ represent the same or different alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, G represents a glycidyl group or a substituent having a glycidyl group, X ¹ represents methyl, a glycidyl group or a substituent having a glycidyl group, d represents a number from 0 to 100, and e represents a number from 0 to 100, provided that when d is 0 or 1, ¹ represents a glycidyl group or a substituent having a glycidyl group.)

In the general formula (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, an isobutyl group, and a t-butyl group. Examples of the aryl group having 6 to 10 carbon atoms include phenyl group, ethylphenyl group, tolyl group, cumenyl group, xylyl group, pseudocumenyl group, mesityl group, t-butylphenyl group, and phenethyl group. R ¹ is preferably a methyl group, an ethyl group, and a phenyl group, more preferably a methyl group and a phenyl group, and most preferably a methyl group from the viewpoint of heat resistance. G represents a glycidyl group or a substituent having a glycidyl group. The glycidyl group or the substituent having a glycidyl group is as described for the siloxane compound having a glycidyl group. a represents a number of 3 to 6. From the viewpoint of industrial availability of raw materials, a is preferably a number of 3 to 5, more preferably a number of 3 to 4, and most preferably a number of 4.

In the general formula (2), R ² represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ in the general formula (1). G is the same as in the general formula (1). b represents a number of 2 to 5. In view of industrial availability of raw materials, b is preferably a number of 2 to 4, more preferably a number of 2 to 3, and most preferably a number of 3.

（式中、Ｒ¹²〜Ｒ¹⁴は各々独立して炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表わし、ｆは１〜３の数を表わし、ｇ及びｈは各々独立して０〜６の数を表わす。）

（式中、Ｒ¹⁵〜Ｒ¹⁷は各々独立して炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表わし、ｊは０〜１０の数を表わす。）

（式中、Ｒ¹⁸は各々独立して炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表わし、ｋは３又は４の数を表わす。）

（式中、Ｒ¹⁹及びＲ²⁰は各々独立して炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表わす。）

（式中、ｍは１〜２の数を表わす。）

（式中、ｎは１〜３の数を表わす。）

（式中、Ｒ²¹は炭素数１〜４のアルキル基、炭素数６〜１０のアリール基、グリシジル基又はアリル基を表わす。） In the general formula (2), R ³ represents a residue obtained by removing a vinyl group from a compound having 2 to 4 vinyl groups in one molecule and having a molecular weight of 1000 or less. Examples of the compound having 2 to 4 vinyl groups and a molecular weight of 1000 or less include hydrocarbon compounds having 2 to 4 vinyl groups, silane compounds or siloxane compounds having 2 to 4 vinyl groups, and 2 to 3 And an isocyanurate having a vinyl group. Specific examples of such compounds include compounds represented by the following general formulas (23) to (29). From the viewpoint of heat resistance, compounds represented by the following general formulas (23) to (25) are preferred, From the viewpoint of easy availability, a compound represented by the following general formula (27) is preferred. Since the resist residue of the curable resin composition of the present invention hardly remains, the number of vinyl groups in the compound having 2 to 4 vinyl groups in one molecule is preferably 2.

(Wherein R ^{12 to} R ¹⁴ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, f represents a number of 1 to 3, and g and h are each independently And represents a number from 0 to 6.)

(In the formula, R ^{15 to} R ¹⁷ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and j represents a number from 0 to 10).

(In the formula, each R ¹⁸ independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and k represents a number of 3 or 4.)

(In the formula, R ¹⁹ and R ²⁰ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.)

(In the formula, m represents a number of 1 to 2.)

(In the formula, n represents a number of 1 to 3.)

(In the formula, R ²¹ represents an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, a glycidyl group, or an allyl group.)

The compound represented by the general formula (23) is a compound having 2 to 4 vinyl groups in one molecule. In the general formula (23), R ^{12 to} R ¹⁴ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ in the general formula (1), and since the heat resistance is good, a methyl group, An ethyl group, a propyl group and a phenyl group are preferred, a methyl group, an ethyl group and a phenyl group are more preferred, and a methyl group is most preferred. f represents a number of 1 to 3, and g and h each independently represents a number of 0 to 6.

Among the compounds represented by the general formula (23) in which f is a number of 1, preferred compounds include dimethyldivinylsilane, diethyldivinylsilane, diphenyldivinylsilane, 1,1,3,3-tetramethyl-1 , 3-divinyldisiloxane, 1,1,3,3-tetraethyl-1,3-divinyldisiloxane, 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane, and the like. Of these, dimethyldivinylsilane, diethyldivinylsilane, diphenyldivinylsilane and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane are preferred, and 1,1,3,3-tetramethyl-1,3- More preferred is divinyldisiloxane.
Among the compounds represented by the general formula (23) in which f is a number of 2, preferred compounds include methyltrivinylsilane, ethyltrivinylsilane, phenyltrivinylsilane, 1,1,3,5,5-pentamethyl- 1,3,5-trivinyltrisiloxane, 1,1,5,5-tetramethyl-3-phenyl-1,3,5-trivinyltrisiloxane, tris (dimethylvinylsiloxy) methylsilane, tris (dimethylvinylsiloxy) ) Phenylsilane and the like.
Among the compounds represented by the general formula (23) in which f is a number of 3, preferred compounds include tetravinylsilane, tetrakis (dimethylvinylsiloxy) silane, and the like.

The compound represented by the general formula (24) is a compound having four vinyl groups in one molecule. In the general formula (24), R ^{15 to} R ¹⁷ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ in the general formula (1), and since the heat resistance is good, a methyl group, An ethyl group, a propyl group and a phenyl group are preferred, a methyl group, an ethyl group and a phenyl group are more preferred, and a methyl group is most preferred.
j represents a number from 0 to 10;
Among the compounds represented by the general formula (24), preferred compounds include 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane, 1,3,3,5-tetramethyl- Examples include 1,1,5,5-tetravinyltrisiloxane, 1,5-dimethyl-3,3-diphenyl-1,1,5,5-tetravinyltrisiloxane, and the like.

The compound represented by the general formula (25) is a compound having 3 to 4 vinyl groups in one molecule. In the general formula (25), R ¹⁸ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ in the general formula (1), and since the heat resistance is good, a methyl group, An ethyl group, a propyl group and a phenyl group are preferred, a methyl group, an ethyl group and a phenyl group are more preferred, and a methyl group is most preferred.
k represents a number of 3 or 4, and a number of 4 is preferable from the viewpoint of industrial availability. Among the compounds represented by the general formula (25) in which k is the number 3, a preferred compound is 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 2,4 , 6-triethyl-2,4,6-trivinylcyclotrisiloxane, 2,4,6-triphenyl-2,4,6-trivinylcyclotrisiloxane, 2,4-dimethyl-6-phenyl-2, Examples include 4,6-trivinylcyclotrisiloxane.
Among the compounds represented by the general formula (25) wherein k is a number of 4, preferred compounds include 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotrimethyl. Siloxane, 2,4,6,8-tetraethyl-2,4,6,8-tetravinylcyclotrisiloxane, 2,4,6,8-tetraphenyl-2,4,6,8-tetravinylcyclotrisiloxane 2,4,6-trimethyl-8-phenyl-2,4,6,8-tetravinylcyclotrisiloxane, 2,4-dimethyl-6,8-diphenyl-2,4,6,8-tetravinylcyclotrisiloxane Examples thereof include siloxane.

The compound represented by the general formula (26) is a compound having two vinyl groups in one molecule. In the general formula (26), R ¹⁹ and R ²⁰ each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ in the general formula (1), and since the heat resistance is good, a methyl group, An ethyl group, a propyl group and a phenyl group are preferred, a methyl group, an ethyl group and a phenyl group are more preferred, and a methyl group is most preferred.
Among the compounds represented by the general formula (26), preferred compounds include 1,2-bis (dimethylvinylsilyl) benzene, 1,3-bis (dimethylvinylsilyl) benzene, 1,4-bis ( Dimethylvinylsilyl) benzene, 1,2-bis (diethylvinylsilyl) benzene, 1,3-bis (diethylvinylsilyl) benzene, 1,4-bis (diethylvinylsilyl) benzene and the like. Bis (dimethylvinylsilyl) benzene and 1,4-bis (dimethylvinylsilyl) benzene are preferred, and 1,4-bis (dimethylvinylsilyl) benzene is more preferred.

The compound represented by the general formula (27) is a compound having 2 to 3 vinyl groups in one molecule. In the said General formula (27), m represents the number of 1-2.
Examples of the compound represented by the general formula (27) in which m is the number 1 include 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene.
Examples of the compound represented by the general formula (27) in which m is a number of 2 include 1,2,4-trivinylbenzene and 1,3,5-trivinylbenzene.

The compound represented by the general formula (28) is a compound having 2 to 4 vinyl groups in one molecule. In the said General formula (28), n represents the number of 1-3.
Examples of the compound represented by the general formula (28) where n is 1 are 1,2-divinylcyclohexane, 1,3-divinylcyclohexane, and 1,4-divinylcyclohexane.
Examples of the compound represented by the general formula (28) in which n is a number of 2 include 1,2,4-trivinylcyclohexane and 1,3,5-trivinylcyclohexane.
Examples of the compound represented by the general formula (28) in which n is a number of 3 include 1,2,4,5-tetravinylcyclohexane.

The compound represented by the general formula (29) is a compound having 2 to 3 vinyl groups in one molecule. In the general formula (29), R ²¹ represents an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, a glycidyl group, or an allyl group. R ²¹ is preferably a methyl group, an ethyl group, a glycidyl group or an allyl group.
Among the compounds represented by the general formula (29), preferred compounds are 1,3-diallyl-5-methylisocyanurate, 1,3-diallyl-5-ethylisocyanurate, 1,3-diallyl-5. -Glycidyl isocyanurate 1,3,5-triallyl isocyanurate etc. are mentioned.

In the said General formula (2), c represents the number of 2-4. When R ³ is a residue obtained by removing a vinyl group from a compound having two vinyl groups in one molecule and a molecular weight of 1000 or less, c represents a number of 2, and R ³ represents ³ in one molecule. In the case of a residue obtained by removing a vinyl group from a compound having one vinyl group and a molecular weight of 1000 or less, c represents a number of ³ , and R ³ has four vinyl groups in one molecule and has a molecular weight. Is a residue obtained by removing a vinyl group from a compound having 1000 or less, c represents a number of 4.

In the general formula (22), R ⁷ ~R ¹¹ represents an alkyl group or an aryl group having 6 to 10 carbon atoms of 1 to 4 carbon atoms which may be the same or different. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ in the general formula (1). R ^{7 to} R ¹¹ are preferably a methyl group, an ethyl group, a propyl group, and a phenyl group, more preferably a methyl group, an ethyl group, and a phenyl group, and most preferably a methyl group because of good heat resistance. d represents a number from 0 to 100, and e represents a number from 0 to 100. In view of compatibility with the component (A), d + e is preferably from 0 to 100, more preferably from 0 to 30, and most preferably from 0 to 10. G represents a glycidyl group or a substituent having a glycidyl group, X ¹ represents a methyl group, a glycidyl group or a substituent having a glycidyl group, and when d is 0 or 1, X ¹ represents a glycidyl group or a glycidyl group. A substituent having a group is represented. The glycidyl group or the substituent having a glycidyl group is the same as in the general formula (1).

  In the curable resin composition of the present invention, the content of the component (C) is preferably 0.1 to 30 parts by mass, and 0.5 to 20 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is 2-15 mass parts.

（式中、Ｒ¹及びａは前記一般式（１）と同義である。） The compound represented by the general formula (1) is a carbon of a compound having a carbon-carbon double bond having reactivity with the SiH group and a glycidyl group in the SiH group of the compound represented by the following general formula (1a). -It can be obtained by hydrosilylation reaction of a carbon double bond.

(In the formula, R ¹ and a have the same meaning as in the general formula (1).)

As a compound having a carbon-carbon double bond having reactivity with the SiH group and a glycidyl group, for example, when the formulas (14) to (21) are introduced, the following formulas (14a) to ( 21a) may be used.

The hydrosilylation reaction of the compound represented by the following general formula (1a) with a compound having a carbon-carbon double bond having reactivity with SiH group and a glycidyl group can be carried out using a platinum catalyst. Good. Examples of platinum-based catalysts include chloroplatinic acid, complexes of chloroplatinic acid and alcohols, aldehydes, ketones, platinum-olefin complexes, platinum-carbonylvinylmethyl complexes (Ossko catalysts), platinum-divinyltetramethyldisiloxane complexes. (Karstedt catalyst), platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde complex, platinum-phosphine complex (for example, Pt [P (C ₆ H ₅ ) ₃ ] ₄ , PtCl [P (C ₆ H ₅ ) ₃ ] ₃ , Pt [P (C ₄ H ₉ ) ₃ ) ₄ ], platinum-phosphite complex (for example, Pt [P (OC ₆ H ₅ ) ₃ ] ₄ ), Pt [P (OC ₄ H ₉ ) ₃ ] ₄ ), Dicarbonyldichloroplatinum and the like. Examples of the palladium-based catalyst or rhodium-based catalyst include compounds containing a palladium atom or a rhodium atom instead of the platinum atom of the platinum-based catalyst. These may be used alone or in combination of two or more. The hydrosilylation catalyst is preferably a platinum-based catalyst from the viewpoint of reactivity, more preferably a platinum-divinyltetramethyldisiloxane complex and a platinum-carbonylvinylmethyl complex, and most preferably a platinum-carbonylvinylmethyl complex. The addition amount of the catalyst is preferably 5% by mass or less, more preferably 0.0001 to 1% by mass, and most preferably 0.001 to 0.1% by mass of the total amount of each raw material from the viewpoint of reactivity. The reaction conditions for hydrosilylation are not particularly limited, and may be carried out under the conditions known in the art using the above catalyst. From the viewpoint of the reaction rate, it is preferably carried out at room temperature (25 ° C.) to 130 ° C. A conventionally known solvent such as hexane, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate may be used.

（式中、Ｒ²及びｂは前記一般式（２）と同義である。） The compound represented by the general formula (2) is obtained by hydrolyzing a vinyl group of a compound having 2 to 4 vinyl groups and a molecular weight of 1000 or less on one SiH group of the compound represented by the following general formula (2a). After the reaction, the remaining SiH group may be subjected to a hydrosilylation reaction with the carbon-carbon double bond of the compound having a carbon-carbon double bond having reactivity with the SiH group and a glycidyl group.

(In the formula, R ² and b are as defined in the general formula (2).)

  As a compound having a carbon-carbon double bond having reactivity with the SiH group and a glycidyl group, for example, when the formulas (14) to (21) are introduced, the formulas (14a) to (14) (21a) may be used. The conditions for the hydrosilylation reaction may be the same as those for the compound represented by the general formula (1).

（式中、Ｒ⁷〜Ｒ¹¹、ｄ及びｅは前記一般式（３）と同義であり、Ｘ²はメチル又は水素原子を表わす。但し、ｄが０又は１の場合には、Ｘ²は水素原子を表わす。） The compound represented by the general formula (22) is a carbon of a compound having a carbon-carbon double bond having reactivity with the SiH group and a glycidyl group in the SiH group of the compound represented by the following general formula (22a). -A carbon double bond may be hydrosilylated.

(In the formula, R ^{7 to} R ¹¹ , d and e are as defined in the general formula (3), and X ² represents a methyl or hydrogen atom. However, when d is 0 or 1, X ² is Represents a hydrogen atom.)

  As a compound having a carbon-carbon double bond having reactivity with the SiH group and a glycidyl group, for example, when the formulas (14) to (21) are introduced, the formulas (14a) to (14) 21a) may be used. The conditions for the hydrosilylation reaction may be the same as those for the compound represented by the general formula (1).

  Next, the photo radical generator that is the component (D) of the present invention will be described. In the present invention, the photo radical generator refers to a compound that generates radicals by irradiation with gamma rays, X rays, ultraviolet rays, visible rays, electron beams, or the like.

  Examples of the photo radical generator include acetophenone photo radical generator, benzyl photo radical generator, benzophenone photo radical generator, thioxanthone photo radical generator, acyl phosphine oxide photo radical generator, oxime light. A radical generator etc. are mentioned.

  Examples of the acetophenone photoradical generator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 2 -Hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiarybutyldichloroacetophenone, p-tertiarybutyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butano -1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, 2-hydroxy-2-methyl-1- [4-vinyl- (1-methylvinyl) phenyl] Examples include propanone oligomers.

  Examples of the benzyl photo radical generator include diphenyl diketone (also referred to as benzyl), bis (4-methoxyphenyl) diketone (also referred to as anisyl), and the like.

  Examples of the benzophenone-based photo radical generator include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide. Etc.

  Examples of the thioxanthone photoradical generator include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and the like.

  Examples of the acylphosphine oxide photo radical generator include 2-methylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester. Monoacylphosphine oxide photoradical generators such as bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxy) And bisacylphosphine oxide photo radical generators such as benzoyl) -2,4,4-trimethylpentylphosphine oxide.

  Examples of the oxime photo radical generator include 1-{(4-phenylthio) phenyl} -1,2-butanedione-2- (O-benzoyloxime), 1-{(4-phenylthio) phenyl} -1 , 2-octanedione-2- (O-benzoyloxime), 1-{(4-phenylthio) phenyl} -1-octanone-1- (O-acetyloxime), 1- {4- (2-hydroxyethoxyphenyl) Thio) phenyl} -1,2-propanedione-2- (O-acetyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- ( O-acetyloxime), (9-ethyl-6-nitro-9H-carbazol-3-yl) {4- (2-methoxy) -1-methylethoxy} -2-methylphenol Le} methanone (O-acetyl oxime), and the like.

  As the photoradical generator, an oxime photoradical generator is preferred because the reactivity of the curable resin composition of the present invention is good, and 1-{(4-phenylthio) phenyl} -1,2- Octanedione-2- (O-benzoyloxime) and 1- {4- (2-hydroxyethoxyphenylthio) phenyl} -1,2-propanedione-2- (O-acetyloxime) are more preferred. -{4- (2-hydroxyethoxyphenylthio) phenyl} -1,2-propanedione-2- (O-acetyloxime) is most preferred. Only one type of photo radical generator may be used, or two or more types may be used in combination.

  In the curable resin composition of the present invention, if the content of the component (D) is too small, curing may be insufficient, and if it is too large, the physical properties of the cured product may be adversely affected. Therefore, the content of the component (D) is preferably 0.3 to 20 parts by mass with respect to 100 parts by mass (excluding the organic solvent) of the curable resin composition of the present invention. More preferably, it is 5 parts by mass.

（式中、Ｒ²³はアクリル基又はメタアクリル基を表わし、Ｒ²⁴は炭素数２〜４のアルキレン基を表わし、ｐは１〜３の数を表わす。） It is preferable that the curable resin composition of the present invention further contains (E) a phosphoric acid acrylate compound because the adhesiveness is further improved. In the present invention, the phosphate acrylate compound refers to a phosphate compound having an acrylic group or a methacryl group in the molecule. As the phosphoric acid acrylate compound, a compound represented by the following general formula (30) is preferable because the adhesion improving effect is large.

(In the formula, R ²³ represents an acrylic group or a methacryl group, R ²⁴ represents an alkylene group having 2 to 4 carbon atoms, and p represents a number of 1 to 3).

R ²³ represents an acryl group or a methacryl group, and R ²⁴ represents an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include ethylene group, trimethylene group, tetramethylene group, 1-methylethylene group, 2-methylethylene group, 1-ethylethylene group, and 2-ethylethylene group. R ²⁴ is preferably an ethylene group, a 1-methylethylene group or a 2-methylethylene group, and more preferably an ethylene group. p represents a number of 1 to 3. p is preferably a number of 1 or 2 because the effect of improving adhesion is large. In this case, p may be a compound having a number of 1 and a mixture of a compound having a number of p of 2.

  In the curable resin composition of the present invention, when the content of the component (E) is too small, the adhesion is not improved, and when it is too large, the storage stability of the curable resin composition of the present invention Since the water resistance of the cured product is adversely affected, the content of the component (E) is preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the component (A), and 1 to 8 parts by mass. More preferably.

  The curable resin composition of the present invention may contain an organic solvent (F) as necessary, in addition to the components (A) to (E). The organic solvent dissolves the curable resin composition of the present invention and has a viscosity suitable for various coating methods such as spin coating, dip coating, knife coating, roll coating, spray coating, and slit coating. It is a component mix | blended so that it may become.

  Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol and isopropyl alcohol; esters such as ethyl acetate and butyl acetate; ethers such as 1,4-dioxane and tetrahydrofuran; methyl ethyl ketone and methyl Ketones such as isobutyl ketone; glycol derivatives such as cellosolve, butyl cellosolve and cellosolve acetate; alicyclic hydrocarbons such as cyclohexanone and cyclohexanol; and petroleum solvents such as petroleum ether and petroleum naphtha.

  The component (F) is not particularly limited as long as it can dissolve the components (A) to (E) uniformly. However, a glycol derivative is preferable because there is little decrease in scratch resistance. Although content of (F) component is not specifically limited, 30-300 mass parts is preferable with respect to 100 mass parts of total amounts of (A)-(E) component.

  If necessary, various additives such as fillers such as talc, barium sulfate, silica and clay; thixotropic agents such as aerosil; colorants such as phthalocyanine blue, phthalocyanine green and titanium oxide; silicones and fluorines Leveling agents and antifoaming agents; polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether can be added.

  The curable resin composition of the present invention is cured by active energy rays such as visible light, ultraviolet rays, and X-rays after being applied to the target material. Examples of the coating method include known methods such as spin coating, dip coating, knife coating, roll coating, spray coating, and slit coating. The thickness of the coating film of the curable resin composition of the present invention varies depending on the purpose of use, but when used as a hard coat material for an image display surface of an image display device, the film thickness after curing is 0.1 to 0.1. The thickness is preferably 30 μm. When the curable resin composition of this invention contains the (F) organic solvent, it is preferable to harden | cure after apply | coating the curable resin composition of this invention after application | coating. The pre-baking is performed in a range of 50 to 150 ° C. for 30 seconds to 30 minutes using a heating device such as a hot plate or an oven.

  When the coating film of the curable resin composition of the present invention is cured, examples of the light source for active energy rays such as ultraviolet rays include ultrahigh pressure mercury lamps, deep UV lamps, high pressure mercury lamps, low pressure mercury lamps, metal halide lamps, and excimer lasers. These light sources are appropriately selected according to the photosensitive wavelength of the photo radical generator or sensitizer. The irradiation energy of the active energy ray is appropriately selected depending on the layer thickness of the curable resin composition, the type and amount of the photo radical generator.

  The coating film obtained from the curable resin composition of the present invention can be used for photolithography and can be used as a negative photoresist capable of alkali development. When using as a negative photoresist, when irradiating active energy rays to the coating film formed from the curable resin composition of the present invention, after coating with a photomask and selectively irradiating active energy rays Then, a light-shielded portion (uncured portion) is dissolved and dispersed in an alkaline developer and removed (sometimes referred to as development), whereby a patterned cured film can be formed. The alkaline developer is obtained by blending an aqueous solution of an alkaline compound with a water-soluble organic solvent, a surfactant or the like, if necessary. Examples of the alkaline compound in the alkaline developer include inorganic alkali compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine, and triethanolamine. , Pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, etc. Examples include cyclic tertiary amines, amines such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and ammonium compounds.

  Post-baking is preferred because the hardness of the cured film is further improved after development. Post bake is preferably performed at 160 ° C. to 250 ° C. for 5 minutes to 3 hours using a heating device such as a hot plate or oven.

  The cured film obtained by the curable resin composition of the present invention is excellent in transparency, heat resistance, weather resistance, chemical resistance, and scratch resistance. Useful for applications such as membranes. In addition to these, the curable resin composition of the present invention is useful as a hard coating material for plastic members, and in particular, lighting members such as lighting covers and decorative materials, automotive members such as headlamp components and instrument panel components, and automotive painting. It is useful as a hard coat material.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further, this invention is not limited by these Examples. Unless otherwise specified, “parts” and “%” in the examples are based on mass. The mass average molecular weight was defined as a polystyrene-reduced mass average molecular weight when GPC (Gel Permeation Chromatography) analysis was performed using tetrahydrofuran as a solvent. Moreover, the epoxy equivalent was measured based on JIS K-7236 (how to obtain an epoxy resin).

[Production Example 1: Production of siloxane compound C1]
In a glass reaction vessel equipped with a thermometer and a stirrer, 240 g (1 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, 456 g of allyl glycidyl ether (4 mol), 300 g of toluene as a solvent, platinum as a catalyst -15 mg of divinyltetramethyldisiloxane complex (Karstedt catalyst) was added and reacted at 50-60 ° C for 15 hours with stirring. The solvent was distilled off from this reaction solution under reduced pressure at 60 ° C. to obtain the following siloxane compound C1. The siloxane compound C1 is a compound in which R ¹ is a methyl group, G is a 3-glycidyloxypropylene group, and a is a number 4 in the general formula (1).

[Production Example 2: Production of siloxane compound C2]
In Production Example 1, 512 g (4 mol) of 2,3-epoxypropyl acrylate was used instead of 456 g (4 mol) of allyl glycidyl ether, and 0.05 g of p-methoxyphenol was added as a polymerization inhibitor to react. Performed the same operation as in Production Example 1 to obtain the following siloxane compound C2. The siloxane compound C2 is a compound in which R ¹ is a methyl group, G is a 3-glycidylcarbonyloxypropyl group, and a is a number 4 in the general formula (1).

[Production Example 3: Production of siloxane compound C3]
In a glass reaction vessel equipped with a thermometer and a stirrer, 240 g (1, 1 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-vinyldisiloxane 96 g (0.5 mol), 300 g of toluene as a solvent, and 15 mg of a platinum-divinyltetramethyldisiloxane complex (Karsttedt catalyst) as a catalyst were added and reacted at 50 to 60 ° C. for 3 hours with stirring. Furthermore, 342 g (3 mol) of allyl glycidyl ether was added and reacted at 50 to 60 ° C. for 15 hours with stirring. The solvent was distilled off from this reaction solution under reduced pressure at 60 ° C. to obtain the following siloxane compound C3. In the general formula (2), R ¹ is a methyl group, a is a number of 4, and R ³ is 1,1,3,3-tetramethyl-1,3-vinyldisiloxane to vinyl group. It is a compound that is a residue excluding.

[Production Example 4: Production of siloxane compound C4]
In Production Example 3, 65 g (0.5 mol) of 1,4-divinylbenzene was used instead of 96 g (0.5 mol) of 1,1,3,3-tetramethyl-1,3-vinyldisiloxane. The following siloxane compound C4 was obtained by performing the same operation as in Production Example 3 except that 0.05 g of p-methoxyphenol was added as a polymerization inhibitor and reacted. In the general formula (2), R ¹ is methyl, a is a number 4, and R ³ is a residue obtained by removing a vinyl group from divinylbenzene (that is, a 1,4-phenylene group). A compound.

[Examples 1-8 and Comparative Examples 1-9: Production and Evaluation of the Present Invention and Comparative Curable Resin Composition]
(A) Component A1 and A2 below, Component (B) B1 and B2 below, Component (C) C1 to C4 obtained in Production Examples 1 to 4 or C′1 to C′3 below (D) ) The following D1 as the component, the following E1 as the (E) component, and the following F1 as the (F) component, blended in the proportions shown in the following [Table 1], filtered, and Examples 1-8 and Comparative Example 1 -9 curable compositions were prepared.

Ｂ２：

（Ｃ’）成分（比較用）
Ｃ’１：

Ｃ’２：

Ｃ’３：フェノ−ルノボラック型エポキシ樹脂（ＤＩＣ社製、商品名：ＥＰＩＣＬＯＮ Ｎ−７３０Ａ、エポキシ当量：１７５）
（Ｄ）成分
Ｄ１：１−｛４−（２−ヒドロキシエトキシフェニルチオ）フェニル｝−１，２−プロパンジオン−２−（Ｏ−アセチルオキシム）
（Ｅ）成分
Ｅ１：２−メタクリロキシエチルホスフェートとビス（２−メタクリロキシエチル）ホスフェートの等モル混合物
（Ｆ）成分
Ｆ１：プロピレングリコールモノメチルエーテルアセテート (A) Component A1: Dipentaerythritol hexaacrylate A2: Pentaerythritol triacrylate (B) Component B1:

B2:

(C ′) component (for comparison)
C'1:

C'2:

C'3: Pheno-novolak type epoxy resin (manufactured by DIC, trade name: EPICLON N-730A, epoxy equivalent: 175)
(D) Component D1: 1- {4- (2-hydroxyethoxyphenylthio) phenyl} -1,2-propanedione-2- (O-acetyloxime)
(E) Component E1: Equimolar mixture of 2-methacryloxyethyl phosphate and bis (2-methacryloxyethyl) phosphate (F) Component F1: Propylene glycol monomethyl ether acetate

<Adhesion test, scratch resistance test>
Spin the curable compositions of Examples 1 to 8 and Comparative Examples 1 to 9 on a 10 cm square glass substrate or ITO vapor-deposited glass substrate (ITO substrate) so that the thickness after solvent evaporation is 5 μm. After coating by coating and volatilizing the solvent, prebaking was performed at 90 ° C. for 1 minute. Next, it was cured by post-baking at 230 ° C. for 30 minutes after irradiating ultraviolet rays of 120 mJ / cm ² (wavelength 365 nm exposure conversion) with a high-pressure mercury lamp. Using these test pieces, an adhesion test (a heat-resistant adhesion test and a moisture-resistant adhesion test) and a scratch resistance test were performed by the methods shown below. The results are shown in [Table 2].

1. Adhesion test In accordance with JIS K5600-5-6 (General coating test method-Part 5: Mechanical properties of coating film-Section 6: Adhesion (cross-cut method)), adhesion of cured film to substrate Evaluated. The cut interval was 1 mm. Moreover, an evaluation result is six steps of 0-5, and it shows that it is excellent in adhesiveness, so that a number is small.

1-1. Heat-resistant adhesion test The test piece of the glass substrate and the test piece of the ITO substrate were heated in a thermostatic bath at 230 ° C. for 2 hours, and then the adhesion was evaluated by the method 1 described above.

1-2. Moisture resistance adhesion test After placing a glass substrate test piece and an ITO substrate test piece in a high-pressure, constant-humidity bath at 121 ° C., 2 atm and 100% relative humidity for 3 hours, the adhesion was evaluated by the method described in 1 above. did.

2. Scratch resistance test Specimens for glass substrates were cured in accordance with JIS K5600-5-4 (General coating test methods-Part 5: Mechanical properties of coating films-Section 4: Scratch hardness (pencil method)). The scratch hardness of the film was measured. In addition, an evaluation result shows that it is excellent in abrasion resistance in order of 6H, 5H, 4H, 3H, 2H, and H.

<Developability test>
The curable compositions of Examples 1 to 8 and Comparative Examples 1 to 9 were applied to a 10 cm square glass substrate by spin coating so that the thickness after solvent evaporation was 5 μm, and the solvent was volatilized. Pre-baked at 1 ° C. for 1 minute. Photomasks (10 lines each) with line widths of 20 μm, 25 μm, 30 μm, 35 μm, and 40 μm were installed and irradiated with ultraviolet rays of 120 mJ / cm 2 (wavelength 365 nm exposure equivalent) with a high-pressure mercury lamp. Thereafter, the film was developed by being immersed in 2.38% tetraethylammonium hydroxide for 30 seconds. After development, it was rinsed pure and post-baked at 230 ° C. for 30 minutes. The minimum line width at which a pattern without cutting was formed was taken as the resolution. The results are shown in [Table 2].

  As is clear from the results of [Table 2] above, the cured film obtained from the curable resin composition of the present invention has excellent adhesion to the glass substrate and the ITO vapor-deposited glass group, and high scratch resistance. You can see that

Claims (4)

  (A) a polyhydric alcohol acrylate compound, (B) a compound having an acrylic group or a methacryl group and a carboxyl group in the molecule, (C) a siloxane compound having a glycidyl group, and (D) a curing containing a photoradical generator. Resin composition. The curable resin composition according to claim 1, wherein the (C) siloxane compound having a glycidyl group is a compound represented by the following general formula (1) or a compound represented by the following general formula (2).

(In the formula, R ¹ represents the same or different alkyl group having 1 to 4 carbon atoms or aryl group having 6 to 10 carbon atoms, G represents a glycidyl group or a substituent having a glycidyl group, and a represents 3 Represents a number of ~ 6)

(In the formula, R ² represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different, and R ³ has 2 to 4 vinyl groups in one molecule. G represents a residue obtained by removing a vinyl group from a compound having a molecular weight of 1000 or less, G represents a glycidyl group or a substituent having a glycidyl group, b represents a number of 2 to 5, and c represents a number of 2 to 4. .)   The curable resin composition according to claim 1 or 2, wherein the (C) siloxane compound having a glycidyl group is a siloxane compound having a 3-glycidoxypropyl group.   Furthermore, (E) The curable resin composition of any one of Claims 1-3 containing a phosphoric acid acrylate compound.