JP6865614B2 - Curable composition - Google Patents

Description

The present invention relates to a curable composition and a cured product obtained by irradiating or heating the curable composition with energy rays. The curable composition is particularly useful for adhesives.

Curable compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members and the like.

For example, Patent Documents 1 to 4 below disclose an energy ray-curable composition containing a cationically polymerizable component and a radically polymerizable component, or a cured product thereof.

Japanese Unexamined Patent Publication No. 2014-105218 JP 2015-143352 Japanese Unexamined Patent Publication No. 2015-168757 WO2015-194654 Pamphlet

However, conventionally, there is no curable composition that satisfies all of the curability, the adhesion of the cured product, and the heat-resistant adhesion at a high level, and further improvement of the curable composition is required.

An object of the present invention is to provide a curable composition and an adhesive having excellent curability and excellent adhesion and heat-resistant adhesion of a cured product.

As a result of diligent studies to solve the above problems, the present inventors have achieved the above object by providing the following [1] to [5].

[1] Cationicly polymerizable component (A) 10 to 70% by mass, cationic polymerization initiator (B) 1 to 10% by mass, radically polymerizable component (C) 1 to 90% by mass, and radical polymerization initiator (D) 1 A curable composition containing 10% by mass,
The cationically polymerizable component (A) contains a polyfunctional glycidyl compound (A1) having a saturated aliphatic ring.
A curable composition in which the radically polymerizable component (C) contains a (meth) acrylic compound (C1) having a saturated aliphatic ring.

（式中の水素原子は、炭素原子数１〜２０の炭化水素基、複素環を含有する炭素原子数２〜２０の基、又はハロゲン原子で置換される場合があり、
上記炭素原子数１〜２０の炭化水素基又は複素環を含有する炭素原子数２〜２０の基中の水素原子は、更にハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は複素環を含有する炭素原子数２〜２０の基で置換される場合があり、
上記炭素原子数１〜２０の炭化水素基又は複素環を含有する炭素原子数２〜２０の基中のメチレン基は、酸素原子が隣り合わない条件で、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^１−、−ＮＲ^１ＣＯ−、−Ｓ−、−ＣＳ−、−ＳＯ_２−、−ＳＣＯ−、−ＣＯＳ−、−ＯＣＳ−又はＣＳＯ−で置換される場合があり、
Ｒ^１は、水素原子又は炭素原子数１〜２０の炭化水素基を表し、
式中の＊は、式（Ｉ）で表される基が、＊部分で、隣接する基と結合することを意味する。） [2] The curable composition according to [1], wherein the polyfunctional glycidyl compound (A1) having a saturated aliphatic ring is a glycidyl compound having a group represented by the following general formula (I).

(The hydrogen atom in the formula may be substituted with a hydrocarbon group having 1 to 20 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocycle, or a halogen atom.
The hydrogen atom in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocycle further includes a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, and a methacryloyl. It may be substituted with a group having 2 to 20 carbon atoms containing a group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocycle.
The methylene group in the hydrocarbon group having 1 to 20 carbon atoms or the group having 2 to 20 carbon atoms containing a heterocycle is -O-, -CO-, -COO under the condition that oxygen atoms are not adjacent to each other. ^{-, - OCO -, - NR} 1 -, - NR 1 CO -, - S -, - CS -, - SO 2 -, - SCO -, - COS -, - OCS- or CSO- when substituted is in Yes,
R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
* In the formula means that the group represented by the formula (I) is bonded to an adjacent group in the * portion. )

（式中の水素原子は、炭素原子数１〜２０の炭化水素基、複素環を含有する炭素原子数２〜２０の基、又はハロゲン原子で置換される場合があり、
上記炭素原子数１〜２０の炭化水素基又は複素環を含有する炭素原子数２〜２０の基中の水素原子は、更にハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は複素環を含有する炭素原子数２〜２０の基で置換される場合があり、
上記炭素原子数１〜２０の炭化水素基又は複素環を含有する炭素原子数２〜２０の基中のメチレン基は、酸素原子が隣り合わない条件で、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^１１−、−ＮＲ^１１ＣＯ−、−Ｓ−、−ＣＳ−、−ＳＯ_２−、−ＳＣＯ−、−ＣＯＳ−、−ＯＣＳ−又はＣＳＯ−で置換される場合があり、
Ｒ^１１は、水素原子又は炭素原子数１〜２０の炭化水素基を表し、
式中の＊は、式（II）で表される基が、＊部分で、隣接する基と結合することを意味する。） [3] The above-mentioned (1) or [2], wherein the (meth) acrylic compound (C1) having a saturated aliphatic ring is a (meth) acrylic compound having a group represented by the following general formula (II). Curable composition.

(The hydrogen atom in the formula may be substituted with a hydrocarbon group having 1 to 20 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocycle, or a halogen atom.
The hydrogen atom in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocycle further includes a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, and a methacryloyl. It may be substituted with a group having 2 to 20 carbon atoms containing a group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocycle.
The methylene group in the hydrocarbon group having 1 to 20 carbon atoms or the group having 2 to 20 carbon atoms containing a heterocycle is -O-, -CO-, -COO under the condition that oxygen atoms are not adjacent to each other. ^{-, - OCO -, - NR} 11 -, - NR 11 CO -, - S -, - CS -, - SO 2 -, - SCO -, - COS -, - OCS- or CSO- when substituted is in Yes,
R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
* In the formula means that the group represented by the formula (II) is bonded to the adjacent group in the * part. )

[4] A method for curing the curable composition according to any one of [1] to [3] by irradiating it with active energy rays or by heating.

[5] A cured product of the curable composition according to any one of [1] to [3].

The curable composition of the present invention is excellent in curability, and the obtained cured product is excellent in adhesion and heat-resistant adhesion. The curable composition of the present invention is also excellent in chemical resistance of the cured product.

Hereinafter, the curable composition of the present invention will be described in detail.

The cationically polymerizable component (A) used in the present invention is a compound that undergoes a polymerization or cross-linking reaction with a cationic polymerization initiator activated by energy beam irradiation or heating, and is a polyfunctional compound having a saturated aliphatic ring. Glycidyl compound (A1) containing the above glycidyl compound (A1), excluding the glycidyl compound (A1), glycidyl compound, aromatic epoxy compound, other epoxy compound, oxetane compound, alicyclic epoxy compound, vinyl ether, etc. Can be used together. Further, since the cationically polymerizable component (A) used in the present invention is excellent in adhesion, heat adhesion and chemical resistance of the cured product, it is contained in the curable composition of the present invention in an amount of 10 to 70% by mass. It is more preferable that the content is 30 to 60% by mass.

As the glycidyl compound (A1), an epoxy compound obtained by glycidyl etherifying a part or all of the hydroxyl groups of a divalent or higher valent alcohol compound containing a saturated aliphatic ring is preferably mentioned. Examples of the saturated aliphatic ring include a tricyclodecane ring, a cyclohexane ring, an isobolonyl ring, a cycloheptane ring, a cyclobutane ring and the like. The glycidyl compound (A1) may contain only one saturated aliphatic ring, or may contain two or more saturated aliphatic rings. When two or more saturated aliphatic rings are contained, for example, it is preferable that two or more saturated aliphatic rings are bonded to each other by a bonding group. Further, in the glycidyl compound (A1), two or more glycidyl groups may be bonded to one saturated aliphatic ring, or one glycidyl group may be bonded to each of two or more saturated aliphatic rings. .. The glycidyl group is attached to the saturated aliphatic ring either directly or via a binding group. The bonding group of the above, a direct bond, a hydrocarbon group having 1 to 6 carbon atoms, -O -, - CO -, - COO -, - OCO -, - NR 11 -, - NR 11 CO -, - S _{-, - CS -, - SO} 2 -, - SCO -, - COS -, - OCS- or CSO- or group a combination thereof. The above ^{R 11} is the same as ^{R 11} in the general formula (II).
Specific examples of the glycidyl compound of a polyhydric alcohol having a saturated aliphatic ring include dicyclopentadiene dimethanol diglycidyl ether and diglycidyl ether of hydrogenated bisphenol A.

As the glycidyl compound (A1), a commercially available product can be used, for example, ADEKA REGIN EP-4088S, ADEKA REGIN EP-4088L, EP-4080, EP-4080L (all manufactured by ADEKA), HP-7200L, HP-7200, HP-7200H, HP-7200HH, HP-7200HHH (all manufactured by DIC Corporation) and the like can be mentioned.

Among the glycidyl compounds (A1), the glycidyl compound having a group represented by the general formula (I) is preferable because the curable composition is excellent in curability.

Hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ in the general formula (I) C 1 -C 20 carbon atoms that may replace hydrogen atoms in a hydrocarbon group and the general formula (I) Although not particularly limited, preferably, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and 4 to 20 carbon atoms. Cycloalkylalkyl groups, aryl groups having 6 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, and the like. Since the curable composition has good sensitivity, it has an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 4 to 10 carbon atoms. Cycloalkylalkyl groups, aryl groups having 6 to 10 carbon atoms, arylalkyl groups having 7 to 10 carbon atoms and the like are more preferable.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, and the like. Examples thereof include 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and icosyl. Examples of the alkyl group having 1 to 10 carbon atoms include methyl and ethyl. , Propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, etc. Can be mentioned.

Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-. Heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl, and 4, Examples thereof include 8,12-tetradecatrienylallyl, and examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, and 3-pentenyl. , 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl and the like.

A cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo [1.1.1] pentanyl and tetradecahydroanthrasenyl, etc. Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene and bicyclo. [1.1.1] Pentanyl and the like can be mentioned.

The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which the hydrogen atom of the alkyl group is substituted with the cycloalkyl group. For example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2- Cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-Cyclononylpropyl, 3-cyclodecylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, 4-cycloheptylbutyl, 4-cyclooctylbutyl, 4-cyclononylbutyl, 4-cyclodecyl Examples thereof include butyl, 3-3-adamantylpropyl, decahydronaphthylpropyl and the like, and examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl and cycloheptyl. Methyl, cyclooctylmethyl, cyclononylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3 Examples thereof include −cyclohexylpropyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl and the like.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl, trill, xsilyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl and the like, and one or more substituted with the above alkyl group, the above alkenyl group, the carboxyl group, the halogen atom and the like. Phenyl, biphenylyl, naphthyl, anthryl and the like, for example, 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl and the like, and the above-mentioned carbon atom number 6 Examples of the 10 to 10 aryl groups include, for example, phenyl, trill, xsilyl, ethylphenyl, naphthyl and the like, phenyl, biphenylyl, naphthyl and the like substituted with one or more of the above alkyl group, the above alkenyl group, the carboxyl group, a halogen atom and the like. Anthrill and the like, for example, 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl and the like can be mentioned.

The arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 30 carbon atoms in which the hydrogen atom of the alkyl group is substituted with an aryl group. For example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, naphthylpropyl and the like can be mentioned. The arylalkyl group having 7 to 20 carbon atoms is an aryl group in which the hydrogen atom of the alkyl group is an aryl group. It means a group having 7 to 20 substituted carbon atoms. For example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like can be mentioned.

The group having 2 to 20 carbon atoms containing a heterocycle capable of substituting a hydrogen atom in the above general formula (I) is not particularly limited, and is, for example, pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridazil. , Piperazil, Piperidil, Pyranyl, Pyranylethyl, Pyrazolyl, Triazyl, Triazylmethyl, Pyrrolidil, Kinolyl, Isoquinolyl, Imidazolidine, Benomidazolidine, Triazolyl, Frill, Furanyl, Benzofuranyl, Thienyl, Thiophenyl, Benzothiophenyl, Thiasiazolyl, Thiazolyl, Benthiazolyl, Oxazolidine , Benzoxazolyl, isothiazolidine, isooxazolidine, indrill, morpholinyl, thiomorpholinyl, 2-pyrrolidinone-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidine-3-yl and 2, Examples thereof include 4-dioxyoxazolidine-3-yl and the like, and specific examples including substituents and the like include groups having the following structures.

（上記式中、Ｒはそれぞれ独立して、水素原子又は炭素原子数１〜６のアルキル基を表し、Ｚは直接結合又は炭素原子数１〜６のアルキレン基を表す。尚、式中の＊は、これらの式で表される基が、＊部分で、隣接する基と結合することを意味する。）

(In the above formula, R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z represents a direct bond or an alkylene group having 1 to 6 carbon atoms. Means that the groups represented by these equations are bonded to adjacent groups at the * part.)

Examples of the alkyl group having 1 to 6 carbon atoms represented by R in the above formula include those having 1 to 6 carbon atoms among those exemplified as the above-mentioned alkyl group having 1 to 20 carbon atoms. it can.
Examples of the alkylene group having 1 to 6 carbon atoms represented by Z in the above formula include methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 1,2-dimethylpropylene and 1 , 3-Dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, ethane-1,1 -Diyl, Propane-2,2-Diyl can be mentioned.

As the glycidyl compound of the polyhydric alcohol alkylene oxide adduct, a glycidylated compound of the polyhydric alcohol alkylene oxide adduct containing no saturated aliphatic ring and aromatic ring is preferable.
The glycidyl compound of the polyhydric alcohol alkylene oxide adduct is a polyether polyol obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol such as propylene glycol, trimethylolpropane, or glycerin. Examples thereof include polyglycidyl ethers, polyethylene glycol glycidyls, polypropylene glycol glycidyls and the like.

As the glycidyl product of the polyhydric alcohol alkylene oxide adduct, commercially available products can be used, for example, Denacol EX-145, Denacol EX-171 (all manufactured by Nagase ChemteX Corporation); Epolite 200E, Epolite 400E. , Epolite 70P, Epolite 200P, Epolite 400P (all manufactured by Kyoeisha Kagaku Co., Ltd.) and the like.

The aromatic epoxy compound refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound include polyhydric phenol having at least one aromatic ring such as phenol, cresol, and butylphenol, or Two or more mono / polyglycidyl ethers of the alkylene oxide adduct, such as bisphenol A, bisphenol F, or glycidyl ethers or epoxynovolac resins of compounds further added with alkylene oxide; resorcinol, hydroquinone, catechol, etc. Mono / polyglycidyl etherified product of an aromatic compound having a phenolic hydroxyl group; glycidyl etherified product of an aromatic compound having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol, and phenyldibutanol; phthalic acid, terephthalic acid, Examples thereof include glycidyl ester of a polybasic acid aromatic compound having two or more carboxylic acids such as trimellitic acid, glycidyl ester of benzoic acid, and an epoxidized product of styrene oxide or divinylbenzene.

Commercially available products can be used as the aromatic epoxy compound, for example, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, on-coat. EX-1020, On-Coat EX-1030, On-Coat EX-1040, On-Coat EX-1050, On-Coat EX-1051, On-Coat EX-1010, On-Coat EX-1011, On-Coat 1012 (manufactured by Nagase ChemteX Corporation) Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC); ESN-475V (manufactured by Toto Kasei Co., Ltd.); YX8800 (Made by Mitsubishi Chemical Co., Ltd.); Marproof G-0105SA, Marproof G-0130SP (manufactured by Nippon Oil Co., Ltd.); Epicron N-665, Epicron HP-7200 (manufactured by DIC Corporation); EOCN-1020, EOCN-102S, EOCN- 103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon Kayaku Co., Ltd.); 4100, ADEKA REGIN EP-4901 (manufactured by ADEKA); TECHMORE VG-3101L (manufactured by DIC) and the like.
As the aromatic epoxy compound, a polyfunctional one is preferable because it has excellent curability.

Examples of the other epoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl alcohol glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and glycerol polyglycidyl ether. Examples thereof include trimethylpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether and sorbitol polyglycidyl ether.

Examples of the other epoxy compounds include Denacol EX-111, Denacol EX-121, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, and Denacol. EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-612, Denacol EX-614 and Denacol EX-614B (all manufactured by Nagase ChemteX Corporation) Epolite M-1230, Epolite M- 1500NP, Epolite 80MF, Epoxy 100MF (manufactured by Kyoeisha Chemical Co., Ltd.) Adeka Glycyrole ED-502, Adeka Glycyllol ED-503, Adeka Glycyrrol ED-503G, Adeka Glycyrrol ED-523T, Adeka Glycyrrol ED-505 ADEKA Corporation) and the like.

Examples of the oxetane compound include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, and 1,2-bis [(. 3-Ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, triethylene Glycolbis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycolbis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6 Bifunctional aliphatic oxetane compounds such as −bis (3-ethyl-3-oxetanylmethoxy) hexane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3 Examples thereof include monofunctional oxetane compounds such as -ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, and 3-ethyl-3- (chloromethyl) oxetane. These can be used alone or in combination of two or more, and a polyfunctional oxetane compound is preferable because it enhances the curability and adhesion of the cured product.

As the oxetane compound, commercially available products can be used, for example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.); Aron oxetane OXT-121, Aron oxetane OXT. -221, Aron Oxetane EXOH, Aron Oxetane POX, Aron Oxetane OXA, Aron Oxetane OXT-101, Aron Oxetane OXT-221, Aron Oxetane OXT-212 (manufactured by Toa Synthetic Co., Ltd.), Etanacol OXBP, OXTP (manufactured by Ube Kosan) Can be mentioned.

The alicyclic epoxy compound refers to a compound in which an oxylane ring is directly bonded to a saturated ring without a binding group, and specific examples of the alicyclic epoxy compound include oxidation of a cyclohexene or cyclopentene ring-containing compound. Examples thereof include cyclohexene oxide and cyclopentene oxide-containing compounds obtained by epoxidation with an agent. For example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4 -Epoxy Cyclohexylmethyl-6-Methyl-3,4-Epoxycyclohexanecarboxylate, 3,4-Epoxy-3-methylcyclohexanemethyl-3,4-Epoxy-3-methylcyclohexanecarboxylate, 3,4-Epoxy-5 -Methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxy) Cyclohexane), Propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadiene diepoxyside, ethylenebis (3,4-epoxy) Cyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene Examples thereof include oxidase and limonendioxide.
Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate. It is preferable from the viewpoint of improving adhesion.

As the alicyclic epoxy compound, a commercially available product can be used, and examples thereof include celoxide 2021P, celoxide 2081, celoxide 2000, and celoxide 3000 (manufactured by Daicel).

Examples of the vinyl ether compound include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, and 2-. Examples thereof include hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, and 1,6-cyclohexanedimethanol divinyl ether.

In the cationically polymerizable component (A), the content of the polyfunctional glycidyl compound (A1) having a saturated aliphatic ring is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the cationically polymerizable component (A). Yes, more preferably 30 to 100 parts by mass, and particularly preferably 50 to 100 parts by mass. When the content of the polyfunctional glycisyl compound (A1) having a saturated aliphatic ring is in the above range, the curability is improved, which is preferable.

The cationic polymerization initiator (B) used in the present invention may be any compound capable of releasing a substance that initiates cationic polymerization by irradiation with energy rays or heating, but is preferable. , A double salt, which is an onium salt that releases Lewis acid upon irradiation with energy rays, or a derivative thereof. Further, the cationic polymerization initiator (B) used in the present invention is contained in the curable composition of the present invention in an amount of 1 to 10% by mass.

Typical examples of the cationic polymerization initiator (B) include the following general formulas.
[A] ^{r +} [B] ^r-
Examples of salts of cations and anions represented by.

Here, the cation [A] ^{r +} is preferably onium, and its structure is, for example, the following general formula.
[(R ² ) _a Q] ^{r +}
Can be represented by.

Further, here, R ² is an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms. a is an integer of 1-5. The a R ^2s are independent and may be the same or different. Further, at least one is preferably an organic group as described above having an aromatic ring. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N = N. Further, when the valence of Q in the cation [A] ^{r +} is q, it is necessary that the relationship r = a−q holds (however, N = N is treated as having a valence of 0).

Further, the anion [B] ^r- is preferably a halide complex, and its structure is, for example, the following general formula.
It can be represented by [LY _b ] ^r-.

Further, here, L is a metal or metalloid that is the central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like. Y is a halogen atom. b is an integer of 3 to 7. Further, when the valence of L in the anion [B] ^r- is p, it is necessary that the relationship r = bp is established.

Specific examples of the anion [LY _b ] ^r- of the above general formula include halogen ion, perchlorate ion (ClO ₄ ) ^- , tetrafluoroborate ion (BF ₄ ) ^- , and hexafluorophosphate ion (PF ₆ ). ^-, hexafluoroantimonate (SbF ₆₎ ^-, hexafluoroarsenate (AsF ₆₎ ^-, hexachloroantimonate (SbCl ₆₎ ^- such as an inorganic ion; trifluoromethanesulfonate ion, methanesulfonate ion, butane sulfonic acid ions , Fluorosulfonic acid ion (FSO ₃ ) ^- , benzenesulfonic acid anion, toluenesulfonic acid ion, trinitrobenzenesulfonic acid ion, camphorsulfonic acid ion, nonafluorobutanesulfonic acid ion, hexadecafluorooctanesulfonic acid ion and other sulfonic acids Ions; Tetraaryl sulphonate ion, tetrax (pentafluorophenyl) sulphonic acid ion and other sulphonic acid ions; methanecarboxylic acid ion, ethanecarboxylic acid ion, propanecarboxylic acid ion, butanecarboxylic acid ion, octanecarboxylic acid ion, trifluoromethanecarboxylic acid ion , Benzonic acid ion, carboxylic acid ion such as p-toluene carboxylic acid ion; trifluoromethyl sulfonate (CF ₃ SO ₃ ) ^- , methyl sulfate ion (CH ₃ OSO ₃ ) ^- , bis (trifluoromethanesulfonyl) imide ion, Tris (trifluoromethanesulfonyl) methideion, (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , ((CF ₃ ) ₂₎ C ₆ H ₃ ) In addition to ₄ Ga ⁻ , those selected from the following groups can be mentioned.

The anion [B] ^r- is the following general formula,
[LY _b-1 (OH)] ^r-
The structure represented by is also preferably used. L, Y, b are the same as above. Other anions that can be used include perchlorate ion (ClO ₄ ) ^- , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonic acid ion (FSO ₃ ) ^- , and toluene sulfonic acid anion. , Trinitrobenzene sulfonic acid anion, camphor sulphonate, nonafluorobutane sulphonate, hexadecafluorooctane sulphonate, tetraaryl borate, tetrakis (pentafluorophenyl) borate and the like.

In the present invention, among such onium salts, it is particularly effective to use the following aromatic onium salts (a) to (c). From these, one of them can be used alone, or two or more of them can be mixed and used.

(A) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate and the like.

(B) Diaryl such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, trilucmil iodonium tetrakis (pentafluorophenyl) borate, etc. Iodonium salt

(C) Sulfonium cations represented by Group I or Group II below and sulfonium salts such as hexafluoroantimon ion, hexafluorophosphate ion, and tetrakis (pentafluorophenyl) borate ion.

Also, those other preferred, (eta ^{5-2,4-cyclopentadiene-1-yl)} [(1,2,3,4,5,6-η) - (1- methylethyl) benzene] - Iron -Iron-allene complexes such as hexafluorophosphate, aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, and tris (salitylaldehidato) aluminum, and silanols such as triphenylsilanol. Mixtures of; salts such as thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, hydrazinium salt; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine; 1,2-diaminocyclohexane, 1,4-diamino Alicyclic polyamines such as -3,6-diethylcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylene diamine, diaminodiphenylmethane and diaminodiphenylsulfone; A polyepoxy addition-modified product produced by reacting with various epoxy resins such as glycidyl ethers such as bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether or glycidyl esters of carboxylic acid by a conventional method; Amidation modified products produced by reacting polyamines with carboxylic acids such as phthalic acid, isophthalic acid, and dimeric acid by a conventional method; the above polyamines and aldehydes such as formaldehyde, and phenol, cresol, xylenol, and the like. Mannig-modified products produced by reacting tributylphenol, resorcin and other phenols having at least one aldehyde reaction-reactive site with a nucleus by a conventional method; polyvalent carboxylic acids (succinic acid, malonic acid, succinic acid). Acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2- Aliphatic dicarboxylic acids such as methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid; phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc. Aromatic dicarboxylic acids; cyclohexanedicarboxylic acid Alicyclic dicarboxylic acids such as acids; tricarboxylic acids such as trimellitic acid, trimesic acid, trimer of castor oil fatty acid; tetracarboxylic acids such as pyromellitic acid) acid anhydrides; dicyandiamides, imidazoles, carboxylic acid esters, Examples thereof include sulfonic acid ester and amineimide.

Among these, from the viewpoint of practical use and improvement of photosensitivity, it is preferable to use an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-alene complex, and an aromatic sulfonium having a structure represented by the following general formula (V). It is more preferable that the salt is contained in an amount of at least 0.1% by mass or more based on 100% by mass of the cationic polymerization initiator (B).

（式中、Ｒ¹⁰¹、Ｒ¹⁰²、Ｒ¹⁰³、Ｒ¹⁰⁴、Ｒ¹⁰⁵、Ｒ¹⁰⁶、Ｒ¹⁰⁷、Ｒ¹⁰⁸、Ｒ¹⁰⁹及びＲ¹¹⁰は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基又は炭素原子数２〜１０のエステル基を表し、Ｒ¹¹¹、Ｒ¹¹²、Ｒ¹¹³及びＲ¹¹⁴は、それぞれ独立に、水素原子、ハロゲン原子又は炭素原子数１〜１０のアルキル基を表し、Ｒ¹¹⁵は、下記（α）〜（γ）より選択されるいずれかの置換基を表し、Ａｎ^ｑ−はｑ価の陰イオンを表し、ｐは電荷を中性にする係数を表す。）

(In the formula, R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ , R ¹⁰⁹ and R ¹¹⁰ are independently hydrogen atoms, halogen atoms, and carbon atoms 1 to 1. It represents an alkyl group of 10 and an alkoxy group having 1 to 10 carbon atoms or an ester group having 2 to 10 carbon atoms, and R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ are independently hydrogen atoms, halogen atoms or It represents an alkyl group having 1 to 10 carbon atoms, R ¹¹⁵ represents any substituent selected from the following (α) to (γ), An ^{q −} represents a q-valent anion, and p represents a q-valent anion. Represents the coefficient that neutralizes the charge.)

（式中、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５、Ｒ^２６、Ｒ^２７、Ｒ^２８、Ｒ^２９、Ｒ^３０、Ｒ^４５、Ｒ^４６、Ｒ^４７、Ｒ^４８及びＲ^４９は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基又は炭素原子数２〜１０のエステル基を表し、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３６、Ｒ^３７、Ｒ^３８、Ｒ^３９、Ｒ^４０、Ｒ^４１、Ｒ^４２、Ｒ^４３及びＲ^４４は、それぞれ独立に、水素原子、ハロゲン原子又は炭素原子数１〜１０のアルキル基を表す。）

(In the formula, R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ are Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an ester group having 2 to 10 carbon atoms, and represents R ³¹ , R ³² , and R ^33. , R ³⁴ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are independently alkyls with hydrogen atoms, halogen atoms or 1 to 10 carbon atoms, respectively. Represents an atom.)

Among the compounds represented by the above general formula (V), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ Examples of the represented halogen atom include fluorine, chlorine, bromine, iodine and the like.
R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ^37. , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ as alkyl groups with 1 to 10 carbon atoms. Methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3- Methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl , Bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tridecafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl , Methoxymethyl, 1,2-epoxyethyl, methoxyethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, t-butylthiomethyl, 4-pentenyloxymethyl, trichloroethoxymethyl, bis (2-chloroethoxy) Methyl, methoxycyclohexyl, 1- (2-chloroethoxy) ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl, trimethylsilylethyl, t-butyldimethylsilyloxymethyl, 2- (trimethylsilyl) ethoxymethyl, t-butoxy Carbonylmethyl, ethyloxycarbonylmethyl, ethylcarbonylmethyl, t-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl, acetylethyl, 2-methoxy-1-propenyl, hydroxymethyl , 2-Hydroxyethyl, 1-Hydroxyethyl, 2-Hydroxypropyl, 3-Hydroxypropyl, 3-Hydroxybutyl, 4-Hide Loxybutyl, 1,2-dihydroxyethyl and the like can be mentioned.
Carbon atoms represented by R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ and R ^49. The alkoxy groups of numbers 1 to 10 include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, s-butyloxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, and cyclohexyl. Methyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethyloxy, 3-methoxypropyloxy, 4-methoxybutyloxy, 2-butoxyethyloxy, methoxyethoxyethyloxy, methoxyethoxyethoxyethyloxy, 3-methoxy Butyloxy, 2-methylthioethyloxy, trifluoromethyloxy and the like can be mentioned.
Carbon atoms represented by R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ and R ^49. The ester groups of the number 2 to 10 include methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy, propionyloxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, and t-butyl. Examples thereof include carbonyloxy, methoxyacetyloxy, and benzoyloxy.

The ratio of the cationic polymerization initiator (B) to the cationically polymerizable component (A) is 0.001 to 15 parts by mass of the cationic polymerization initiator (B) with respect to 100 parts by mass of the cationically polymerizable component (A). It is preferably 0.1 to 10 parts by mass. If it is too small, curing tends to be insufficient, and if it is too large, it may adversely affect various physical properties such as the water absorption rate of the cured product and the strength of the cured product.

The radically polymerizable component (C) used in the present invention is a compound that undergoes a polymerization or cross-linking reaction with a radical polymerization initiator activated by irradiation with energy rays or heating, and has the saturated aliphatic ring (the above-mentioned saturated aliphatic ring). It contains a meta) acrylic compound (C1) [hereinafter, also referred to as a (meth) acrylic compound (C1)], and can be used in combination with known unsaturated ethylenic compounds other than the (meth) acrylic compound (C1). Since the cured product has excellent adhesion, heat adhesion, and chemical resistance, the radical component (C) used in the present invention is contained in the curable composition of the present invention in an amount of 1 to 90% by mass, and is contained in an amount of 30 to 90% by mass. It is more preferably contained in an amount of 90% by mass.

The (meth) acrylic compound (C1) may contain a saturated aliphatic ring and an acrylic group or a methacrylic group in the molecule. The (meth) acrylic compound (C1) may be monofunctional or polyfunctional. Examples of the saturated aliphatic ring include a tricyclodecane ring, a cyclohexane ring, an isobolonyl ring, a cycloheptane ring, a cyclobutane ring and the like. The (meth) acrylic compound (C1) may contain only one saturated aliphatic ring, or may contain two or more saturated aliphatic rings. When two or more saturated aliphatic rings are contained, it is preferable that two or more saturated aliphatic rings are bonded to each other by a bonding group. Further, in the (meth) acrylic compound (C1), two or more acrylic groups or methacrylic groups may be bonded to one saturated aliphatic ring, and one acrylic group or one acrylic group is attached to each of two or more saturated aliphatic rings. A methacrylic group may be bonded. The acrylic or methacrylic group is usually attached to the saturated aliphatic ring either directly or via a binding group. The bonding group of the above, a direct bond, a hydrocarbon group having 1 to 6 carbon atoms, -O -, - CO -, - COO -, - OCO -, - NR 11 -, - NR 11 CO -, - S _{-, - CS -, - SO} 2 -, - SCO -, - COS -, - OCS- or CSO- or group a combination thereof. The above ^{R 11} is the same as ^{R 11} in the general formula (II).
Although not particularly limited, specific examples of the (meth) acrylic compound (C1) include tricyclodecanedimethanol diacrylate, tricyclodecanedimethanol dimethacrylate, 3,3,5-trimethylcyclohexaneacrylate, 3,3,5. -Trimethylcyclohexane methacrylate, isobolonyl acrylate, isobolonyl methacrylate, cyclohexyl methacrylate, cyclohexyl acrylate, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid. Be done.

As the (meth) acrylic compound (C1), a commercially available product can be used, and DCP, A-DCP (above, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) EM70, EM90, EM2104, EM2204, (above, ETERNAL). Light Ester IBX-A, Light Ester IBX-MA, Light Ester CH, Light Ester HO-HH, Light Ester DCP-M, Light Ester DCP-A (above, manufactured by Kyoeisha Chemical Co., Ltd.) Kayarad R-684 (Nippon Kayaku) (Made by Yakusha), etc.

As the (meth) acrylic compound (C1), a compound having a group represented by the general formula (II) is preferable because it has excellent curability.

The hydrocarbon groups having 1 to 20 carbon atoms that can replace the hydrogen atoms in the general formula (II) and the hydrocarbon groups having 1 to 20 carbon atoms represented by ^{R 11 in the general formula (II) are} , hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ in the general formula (I) in 1 to 20 carbon atoms that may replace hydrogen atoms of the hydrocarbon group and the general formula (I) Is the same as each.

The unsaturated ethylenic compound may be any compound having an unsaturated ethylenic group in the molecule, and is not particularly limited, but a monofunctional (meth) acrylic compound or a polyfunctional (meth) acrylic compound is preferable. Can be used.

The monofunctional (meth) acrylic compound may be a compound containing one acrylic group or a methacrylic group in the molecule, and is not particularly limited, but the monofunctional (meth) acrylic compound having a hydroxyl group is a cured product obtained. Is particularly preferable because of its good curability.

Examples of the monofunctional (meth) acrylic compound having a hydroxyl group include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 3-chloro-2-hydroxy-propyl acrylate, and 2-hydroxybutyl acrylate. 6-Hydroxyhexyl methacrylate, 2-hydroxymethyl methacrylate, 2-hydroxypropyl methacrylate, 6-hydroxyhexyl methacrylate, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid and 5,6-dihydroxyhexyl methacrylate. Among the above, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are particularly preferable because they have good adhesion to the cured product.

Examples of the monofunctional (meth) acrylic compound having no hydroxyl group include tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, methoxypolyethylene glycol methacrylate, stearyl methacrylate, isoamyl acrylate, lauryl acrylate, ethoxy-diethylene glycol acrylate, and ethoxy-diethylene glycol acrylate. Examples thereof include methoxy-triethylene glycol acrylate, 2-ethylhexyl-diglucol acrylate, methoxy-polyethylene glycol acrylate, methoxydipropylene glycol acrylate, isobornyl acrylate, and among the above, tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate. A compound having a tetrahydrofurfuryl group such as the above is particularly preferable because the obtained cured product has good adhesion.

As the monofunctional (meth) acrylic compound having no hydroxyl group, commercially available products can also be used. For example, M-90G, M-230G, S, SA (all manufactured by Shin-Nakamura Kogyo) Light Acrylate IAA, L. -A, SA, EC-A, MTG-A, EHDG-AT, 130A, DPM-A, THF-A, THF-MA, IB-X, IB-XA (manufactured by Kyoeisha Chemical Co., Ltd.) and the like. ..

As the monofunctional (meth) acrylic acid ester (C1) having a hydroxyl group, a commercially available product can also be used. For example, light esters HOP-A, HOB-A, HOA-MPE (N) (above, Kyoeisha). (Made by chemicals).

Examples of the polyfunctional (meth) acrylic compound include polyethylene glycol diacrylate, polypropylene glycol diacrylate, propoxylated ethoxylated bisphenol A diacrylate, and 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene. , Tricyclodecanedimethanol diacrylate, 1,10-decanediol diacrylate, 1,9-nonanediol diacrylate, tripropylene glycol diacrylate, polytetramethylene glycol # 650 diacrylate, ethoxylated isocyanuric acid triacrylate, ε -Caprolactone-modified tris- (2-acryroxyethyl) isocyanurate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ditrimethylolpropanetetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc. Can be mentioned.

As the above-mentioned polyfunctional (meth) acrylic compound, commercially available products can also be used, for example, NK ester A-200, NK ester A-400, NK ester A-1000, NK ester A-B1206PE, NK ester ABE. -300, NK Ester A-BPE-10, NK Ester A-BPE-20, NK Ester A-BPE-30, NK Ester A-BPE-4, NK Ester A-BPEF, NK Ester A-DCP, NK Ester A -DOD-N, NK Ester A-NOD-N, NK Ester APG-200, NK Ester APG-400, NK Ester APG-700, NK Ester A-PTMG-65, NK Ester A-9300, NK Ester A-9300S , NK Ester A-9300-1CL, NK Ester A-GLY-9E, NK Ester A-GLY-20E, NK Ester A-TMM-3, NK Ester A-TMM-3L, NK Ester A-TMPT, NK Ester AD -TMP, NK Ester ATM-4E, NK Ester ATM-35E, NK Ester A-TMMT, NK Ester A-DPH (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); Kayarad DPHA, Kayarad DPEA-12, Kayarad DPCA-60, Kayarad PEG400DA, Kayarad THE-330, Kayarad RP-1040, Kayarad PET30, Kayarad R-684 (above, manufactured by Nippon Kayaku); Aronix M-215, Aronix M-350 (above, manufactured by Toa Synthetic); Light acrylate DCP-A , Light acrylate TMP-A, Light acrylate PE-3A, Light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.) SPC-1000, SPC-3000 (manufactured by Showa Denko); and the like.

In the radically polymerizable component (C), the proportion of (C1) is preferably 30% by mass or more because the curability is good.

Examples of the radical initiator (D) include a photoradical polymerization initiator and a thermal radical polymerization initiator, and a photoradical polymerization initiator is more preferable because of its high reactivity. Further, the radical polymerization initiator (D) used in the present invention is contained in the curable composition of the present invention in an amount of 1 to 10% by mass.

The photoradical polymerization initiator is not particularly limited as long as it generates a radical by light irradiation, and conventionally known compounds can be used. For example, an acetophenone compound, a benzyl compound, a benzophenone compound, and a thioxanthone can be used. A system compound, an oxime ester system compound, and the like can be exemplified as preferable ones.

Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, and 2-hydroxymethyl-2. -Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetonone, p-tershalibutyldichloroacetophenone, p-tershaributyltrichloroacetophenone, p-azidobenzal Acetphenone, 1-Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2- Examples thereof include methyl-1-propane-1-one.

Examples of the benzyl compound include benzyl and the like.

Examples of benzophenone compounds include benzophenone, methyl o-benzoyl benzoate, Michler ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 4-benzoyl-4'-methyldiphenylsulfide and the like. ..

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

Examples of the oxime ester compound include the compound No. 1 shown below. Examples thereof include D1 to D15.

Other radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pill-1). -Il)] Titanocene compounds such as titanium can be mentioned.

Commercially available radical initiators include ADEKA PUTMER N-1414, N-1717, N-1919, ADEKA ARCULUS NCI-831, NCI-930 (all manufactured by ADEKA); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE ORE. 01, IRGACURE OXE 02, IRGACURE784 (above, manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (above, manufactured by Trony); and the like.

The thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and conventionally known compounds can be used. For example, azo compounds, peroxides, persulfates and the like are preferable. It can be exemplified as a thing.

Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, and 1,1'-. Azobis (1-acetoxy-1-phenylethane) and the like can be mentioned.

Examples of the peroxide include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butylperoxypivalate and di (4-t-butylcyclohexyl) peroxydicarbonate.

Examples of the persulfate include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.

In the curable composition of the present invention, preferably, the total of the cationically polymerizable component (A), the cationic polymerization initiator (B), the radically polymerizable component (C), and the radical polymerization initiator (D) is 100% by mass. 15 to 85 parts by mass of the cationically polymerizable component (A), 1 to 10 parts by mass of the cationic polymerization initiator (B), and 15 to 85 parts by mass of the radically polymerizable component (C). The radical polymerization initiator (D) is 1 to 10 parts by mass. If the mixing ratio is other than the above, the curability and adhesion of the cured product may deteriorate.

A sensitizer and / or a sensitizer aid can be further used in the curable composition of the present invention, if necessary. The sensitizer is a compound that exhibits maximum absorption at a wavelength longer than the maximum absorption wavelength indicated by the cationic polymerization initiator (B) and promotes the polymerization initiation reaction by the cationic polymerization initiator (B). The sensitizer is a compound that further promotes the action of the sensitizer.

Examples of the sensitizer and the sensitizer aid include anthracene compounds and naphthalene compounds.

Examples of the anthracene-based compound include those represented by the following formula (IIIa).

（式中、Ｒ^９及びＲ^１０は、各々独立に水素原子、炭素原子数１〜６のアルキル基又は炭素原子数２〜１２のアルコキシアルキル基を表し、Ｒ^１１は水素原子又は炭素原子数１〜６のアルキル基を表す。）

(In the formula, R ⁹ and R ¹⁰ independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 12 carbon atoms, and R ¹¹ is a hydrogen atom or 1 carbon atom. Represents an alkyl group of ~ 6)

Specific examples of the anthracene-based compound represented by the above formula (IIIa) include the following compounds.

9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentyloxyanthracene, 9, 10-Dihexyloxyanthracene, 9,10-bis (2-methoxyethoxy) anthracene, 9,10-bis (2-ethoxyethoxy) anthracene, 9,10-bis (2-butoxyethoxy) anthracene, 9,10-bis (3-Butoxypropoxy) anthracene, 2-methyl- or 2-ethyl-9,10-dimethoxyanthracene, 2-methyl- or 2-ethyl-9,10-diethoxyanthracene, 2-methyl- or 2-ethyl- 9,10-dipropoxyanthracene, 2-methyl- or 2-ethyl-9,10-diisopropoxyanthracene, 2-methyl- or 2-ethyl-9,10-dibutoxyanthracene, 2-methyl- or 2- Examples thereof include ethyl-9,10-dipentyloxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene.

Examples of the naphthalene compound include those represented by the following formula (IIIb).

（式中、Ｒ^１２及びＲ^１３は各々独立に炭素原子数１〜６のアルキル基を表す）

(In the formula, R ¹² and R ¹³ each independently represent an alkyl group having 1 to 6 carbon atoms).

Specific examples of the naphthalene-based compound represented by the above formula (IIIb) include the following compounds.

4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyloxy-1-naphthol, 1,4-dimethoxynaphthalene, 1- Examples thereof include ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene and 1,4-dibutoxynaphthalene.

The ratio of the sensitizer and the sensitizer to the cationically polymerizable component (A) is not particularly limited, and the sensitizer and the sensitizer may be used at a generally normal ratio as long as the object of the present invention is not impaired. From the viewpoint of improving curability, it is preferable that the sensitizer and the sensitizer aid are each 0.1 to 3 parts by mass or more with respect to 100 parts by weight of the cationically polymerizable component (A).

A silane coupling agent can be used in the curable composition of the present invention, if necessary.
Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkenyl-functional alkoxysilanes such as alkyl-functional alkoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane, 3-methacryloxybropyrriethoxysilane, 3-methacryloxybropyrtrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and other epoxy-functional alkoxysilanes, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl Amino-functional alkoxysilanes such as −γ-aminopropyltrimethoxysilane, mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, titanium alkoxides such as titaniumtetraisopropoxide, titaniumtetranormalbutoxide, and titanium diocties. Titanium chelates such as loxybis (octylene glycolate) and titanium diisopropoxybis (ethylacetoacetate), zirconium chelates such as zirconium tetraacetylacetonate, zirconiumtributoxymonoacetylacetonate, zirconiumtributoxymono Zirconyl acylates such as stearate, isocyanate silanes such as methyltriisocyanate silane, and the like can be used.

The amount of the silane coupling agent used is not particularly limited, but is usually in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of solids in the curable composition.

The properties of the cured product can also be improved by using a thermoplastic organic polymer in the curable composition of the present invention, if necessary. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate ethyl acrylate copolymer, methyl methacrylate glycidyl methacrylate copolymer, poly (meth) acrylic acid, and styrene- (meth) acrylic acid copolymer. , (Meta) acrylic acid-methyl methacrylate copolymer, glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester and the like.

For the curable composition of the present invention, a solvent capable of dissolving or dispersing each of the above-mentioned components (A), (B), (C) and (D), which is not particularly limited and is usually used, can be used, for example. , Methyl ethyl ketone, Methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and other ketones; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxy Ether-based solvents such as ethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol, etc. Ester solvent; Cellosolve solvent such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol solvent such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; Ethylene glycol monomethyl acetate , Ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ether ester solvents such as ethoxyethyl propionate; benzene, toluene , BTX-based solvent such as xylene; aliphatic hydrocarbon-based solvent such as hexane, heptane, octane, cyclohexane; terpene-based hydrocarbon oil such as terepine oil, D-lymonen, pinen; mineral spirit, swazole # 310 (Cosmo Matsuyama Petroleum) , Solvento # 100 (Exxon Chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane; halogenated fragrances such as chlorobenzene Group hydrocarbon solvents; propylene carbonate, carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, Examples thereof include water, and these solvents can be used as one kind or a mixed solvent of two or more kinds.

Since the curable composition of the present invention improves curability, adhesiveness, and liquid storage stability, the water content is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. Too much water is not preferable because it may cause cloudiness or precipitation of components.

In the curable composition of the present invention, if necessary, the protective group is further desorbed and activated by an ultraviolet absorber, an inactive material at room temperature, heating to a predetermined temperature, light irradiation, acid, or the like. It is also possible to use a compound that exhibits an ultraviolet absorbing ability.

Further, as long as the effects of the present invention are not impaired, colorants such as polyols, inorganic fillers, organic fillers, pigments and dyes, antifoaming agents, thickeners, surfactants, leveling agents and difficulties are required. Various resin additives such as flame retardants, tinctures, diluents, plasticizers, stabilizers, polymerization inhibitors, UV absorbers, antioxidants, antistatic agents, flow conditioners, and adhesion promoters can be added. it can.

The curable composition of the present invention is applied onto a support substrate by known means such as a roll coater, a curtain coater, various types of printing, and immersion. Further, once applied on a support substrate such as a film, it can be transferred onto another support substrate, and there is no limitation on the application method.

The material of the support substrate is not particularly limited, and a commonly used material can be used. For example, an inorganic material such as glass; diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl, etc. can be used. Cellulose esters such as cellulose and nitrocellulose; polyamide; polyimide; polyurethane; epoxy resin; polycarbonate; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxy Polyesters such as ethane-4,4'-dicarboxylate, polybutylene terephthalate; polystyrene; polyolefins such as polyethylene, polypropylene, polymethylpentene; vinyl compounds such as polyvinyl acetate, polyvinyl chloride, polyvinyl fluoride; polymethylmethacrylate , Polyacrylate and other acrylic resins; Polyethylene; Polysulfone; Polyether sulfone; Polyether ketone; Polyetherimide; Polyoxyethylene, Norbornen resin, Cycloolefin polymer (COP) and other polymer materials.
The support substrate may be subjected to surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.

In the method of curing the curable composition of the present invention by irradiation with active energy rays, examples of the active energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies, and ultraviolet rays are the most economically preferable. .. Examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.

The conditions in the method of curing the curable composition of the present invention by heating are 70 to 250 ° C. for 1 to 100 minutes. It may be pre-baked (PAB) and then pressurized to post-bake (PEB), or it may be baked at several different temperatures.
The heating conditions vary depending on the type and blending ratio of each component, but are, for example, 70 to 180 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Then, a cured film can be obtained by heat-treating the coating film at 180 to 250 ° C., preferably 200 to 250 ° C. for 30 to 90 minutes in an oven and 5 to 30 minutes in a hot plate.

Specific applications of the curable composition of the present invention or a cured product thereof include adhesives, glasses, optical materials typified by imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, and printing. Plates, color TVs, PC monitors, mobile information terminals, digital cameras, organic EL, display elements such as touch panels, insulating varnish, insulating sheets, laminated boards, printed boards, semiconductor devices, LED packages, liquid crystal inlets, organic Encapsulants for EL, optical elements, electrical insulation, electronic parts, separation films, etc., molding materials, putty, glass fiber impregnants, sealants, passivation films for semiconductors, solar cells, etc., layers Insulating film, protective film, prism lens sheet used for backlight of liquid crystal display device, Frenel lens sheet used for screen of projection TV, lens part of lens sheet such as lenticular lens sheet, or such sheet Examples thereof include the used backlight and the like, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, casting agents for optical modeling, and the like.

The display device of the present invention includes a transparent support, an undercoat layer, an antireflection layer, a polarizing element layer, a retardation layer, a birefringence layer, a light scattering layer, a hard coat layer, a lubricating layer, and a protective layer, if necessary. For example, a film made of the cured product of the present invention can be used for each layer.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited to these Examples.

Hereinafter, the curable composition of the present invention and the cured product obtained by curing the curable composition will be specifically described with reference to Examples, Evaluation Examples and Comparative Examples. In the examples and comparative examples, the part means a mass part.

[Preparation of curable composition: Examples 1-29, Comparative Examples 1-7]
Each component was sufficiently mixed with the formulations shown in [Table 1] to [Table 5] below to obtain carried out curable compositions 1 to 29 and comparative curable compositions 1 to 7, respectively. The unit of numbers in [Table 1] to [Table 5] is the mass part.

The following compound was used as the cationically polymerizable component (A).
A1-1: Compound A1-1 [Component (A1); structural formula is described below]
A1-2: Adecaledin EP-4080
[(A1) component; manufactured by ADEKA Corporation]
A2-1: Adecaledin EP-4000
[Component (A) that does not belong to component (A1); manufactured by ADEKA Corporation]
A2-2: Adecaledin EP-4005
[Component (A) that does not belong to component (A1); manufactured by ADEKA Corporation]
A2-3: Adeka Glycyrol ED-523T
[Component (A) that does not belong to component (A1); manufactured by ADEKA Corporation]
A2-4: Denacol EX-201
[Component (A) that does not belong to component (A1); manufactured by Nagase ChemteX Corporation]
A2-5: Compound A2-5
[Component (A) that does not belong to component (A1); the structural formula is described below]
A2-6: Serokiside 2021P
[Component (A) that does not belong to component (A1); manufactured by Daicel Corporation]
A2-7: Aron Oxetane OXT-221
[Component (A) that does not belong to component (A1); manufactured by Toagosei Co., Ltd.]

The following compounds were used as the cationic polymerization initiator (B).
B-1: A 50% by mass solution of propylene carbonate, which is a mixture of the compound represented by the following formula (a) and the compound represented by the following formula (b).

The following compounds were used as the radically polymerizable component (C).
C1-1: R-684 [(C1) component; manufactured by Nippon Kayaku Co., Ltd.]
C1-2: Light ester IB-X [(C1) component; manufactured by Kyoeisha Chemical Co., Ltd.]
C1-3: Light ester IB-XA
[(C1) component; manufactured by Kyoeisha Chemical Co., Ltd.]
C2-1: Tetrahydrofurfuryl acrylate
[Component (C) that does not belong to component (C1)]
C2-2: 4-hydroxybutyl acrylate
[Component (C) that does not belong to component (C1)]
C2-3: 1,6-hexanediol diacrylate
[Component (C) that does not belong to component (C1)]
C2-4: A-9300S [(C1) component that does not belong to (C1) component; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]
C2-5: Trimethylolpropane triacrylate
[Component (C) that does not belong to component (C1)]
C2-6: Kayarad DPHA
[Component (C) that does not belong to component (C1); manufactured by Nippon Kayaku Co., Ltd.]

The following D-1 was used as the radical polymerization initiator (D).
D-1: IRGACURE184 (manufactured by BASF)

[Evaluation of curable composition and cured product: Examples 1-29, Comparative Examples 1-7]
A curability test, an adhesion test, a chemical resistance test and a heat adhesion test were carried out according to the following evaluation methods. The evaluation results are also shown in [Table 1] to [Table 5].

(Curing test)
The curability test was carried out by the following method.
The implementation compositions 1 to 29 obtained above and the comparative compositions 1 to 7 were applied to a COP (cycloolefin polymer, manufactured by Nippon Zeon: product number Zeonoa film 14-060) film subjected to a corona discharge treatment, respectively. A corona-treated TAC film (triacetyl cellulose, TD80ULM manufactured by Fuji Film Co., Ltd.) and a laminator are used to bond them together, and a metal halide lamp (400 mW / cm ² ) is used to emit ^{ultraviolet rays equivalent to 400 mJ / cm 2} through the COP film. Exposed. Immediately after the exposure, the COP film was peeled off, and the case where there was no tack was evaluated as ◯, and the case where there was tack was evaluated as ×. When the evaluation is 〇, the curability is high and it is useful as an adhesive.

(Adhesion)
The adhesion test was carried out by the following method.
Each of the above-mentioned implementation compositions 1 to 29 and the comparative compositions 1 to 7 is applied to one PET film (Toyobo Co., Ltd .: product number Kosshine A4300), and then another corona discharge treatment is performed. COP (cycloolefin polymer, manufactured by Nippon Zeon: Part No. Zeonoa Film 14-060) film and laminator were used to bond them together, and an electrodeless ultraviolet lamp was used to irradiate light equivalent to ^{1000 mJ / cm 2 through the COP film.} And adhered to obtain a test piece. The obtained test piece was subjected to a 90-degree peel test using FTN-13A / 500 manufactured by AIKOH, and evaluated according to the following criteria.
Adhesion is 2.0 N / cm or more: ◎
Adhesion is 1.0 N / cm or more and less than 2.0 N / cm: 〇 Adhesion is less than 1.0 N / cm: ×
Those having an evaluation of adhesion of ⊚ can be used particularly preferably as an adhesive, those of ◯ can be preferably used as an adhesive, and those of × cannot be used as an adhesive.

(Chemical resistance test)
The chemical resistance test was carried out by the following method.
Each of the implementation compositions 1 to 29 and the comparative compositions 1 to 7 obtained above was applied to silver cardboard No. 6 using bar coater # 14, and then using a metal halide lamp (380 mW / cm ² ). And irradiated with ultraviolet rays (400 mJ / cm ² × 2 Pass) to obtain an evaluation sample. The obtained evaluation sample was rubbed with a cotton swab moistened with MEK, and the number of times until the cured film was peeled off was compared.
Those with more than 150 round trips until peeling were marked with ⊚, those with 100 round trips or more and less than 150 round trips were marked with 〇, those with 50 round trips or more and less than 100 round trips were marked with Δ, and those with less than 50 round trips were marked with ×.
Those with a chemical resistance test evaluation of ◎ can be used particularly preferably as an adhesive, those with a ◯ can be preferably used as an adhesive, those with a △ have few applicable adhesive applications, and those with a × have few uses. , Cannot be used as an adhesive.

(Heat resistance)
The heat-resistant adhesion test was carried out by the following method.
After applying each of the implementation compositions 1 to 29 and the comparative compositions 1 to 7 obtained above to Eagle XG (Corning Inc.) using bar coater # 14, a metal halide lamp (400 mW / cm ² ) was applied. It was irradiated with ultraviolet rays (870 mJ / cm ² × 3 Pass) to obtain an evaluation sample. After baking the obtained evaluation sample at 200 ° C. for 3 hours, 100 squares of 10 × 10 were cross-cut at 1 mm intervals, and 100 squares were attempted to be peeled off with cellophane tape. As a result, those without peeling were marked with ⊚, those with peeling of 1 to 10 squares were marked with 〇, and those with peeling of 11 squares or more were marked with x. Those having an evaluation of ⊚ can be particularly preferably used as an adhesive, and those having an evaluation of ◯ can be preferably used as an adhesive.

From [Table 1] to [Table 5], it is clear that the curable composition of the present invention is excellent in curability, adhesion, chemical resistance and heat-resistant adhesion of the cured product. Further, the curable composition of the present invention is particularly useful as an adhesive.

Claims (4)

Cationic Polymerization Initiator (A) (1000/111) -100 % by mass, Cationic Polymerization Initiator Selected from Aromatic Iodonium Salt, Aromatic Sulfonium Salt and Iron- Alane Complex (B) (100/111) -10% by Mass , A curable composition containing 1 to (9000/111) mass% of the radically polymerizable component (C) and 10% by mass of the radical polymerization initiator (D) (100/111).
The cationically polymerizable component (A) contains (1000/111) by mass or more of the polyfunctional glycidyl compound (A1) having a saturated aliphatic ring in the curable composition.
The polyfunctional glycidyl compound (A1) having a saturated aliphatic ring contains a glycidyl compound having a group represented by the following general formula (I).

(The hydrogen atom in the formula may be substituted with a hydrocarbon group having 1 to 20 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocycle, or a halogen atom.
The hydrogen atom in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocycle further includes a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, and a methacryloyl. It may be substituted with a group having 2 to 20 carbon atoms containing a group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocycle.
The methylene group in the hydrocarbon group having 1 to 20 carbon atoms or the group having 2 to 20 carbon atoms containing a heterocycle is -O-, -CO-, -COO under the condition that oxygen atoms are not adjacent to each other. ^{-, - OCO -, - NR} 1 -, - NR 1 CO -, - S -, - CS -, - SO 2 -, - SCO -, - COS -, - OCS- or CSO- when substituted is in Yes,
R ¹ represents a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms.
* In the formula means that the group represented by the formula (I) is bonded to an adjacent group in the * portion. )
A curable composition in which the radically polymerizable component (C) contains (1500/111) by mass or more of a (meth) acrylic compound (C1) having a saturated aliphatic ring in the curable composition. The curable composition according to claim 1 , wherein the (meth) acrylic compound (C1) having a saturated aliphatic ring is a (meth) acrylic compound having a group represented by the following general formula (II).

(The hydrogen atom in the formula may be substituted with a hydrocarbon group having 1 to 20 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocycle, or a halogen atom.
The hydrogen atom in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocycle further includes a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, and a methacryloyl. It may be substituted with a group having 2 to 20 carbon atoms containing a group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocycle.
The methylene group in the hydrocarbon group having 1 to 20 carbon atoms or the group having 2 to 20 carbon atoms containing a heterocycle is -O-, -CO-, -COO under the condition that oxygen atoms are not adjacent to each other. ^{-, - OCO -, - NR} 11 -, - NR 11 CO -, - S -, - CS -, - SO 2 -, - SCO -, - COS -, - OCS- or CSO- when substituted is in Yes,
R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
* In the formula means that the group represented by the formula (II) is bonded to the adjacent group in the * part. ) A method for curing the curable composition according to claim 1 or 2 by irradiating it with active energy rays or by heating it. A cured product of the curable composition according to claim 1 or 2.