JP6889031B2 - A polymerization initiator and a curable composition containing the polymerization initiator. - Google Patents

Description

The present invention relates to a phenolic polymerization initiator and a curable composition containing the polymerization initiator.

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

For example, Patent Documents 1 and 2 below describe curable compositions containing a cationic polymerization initiator.
Further, Patent Document 3 below describes a transparent film containing a phenol compound as an epoxy curing agent.
Further, Non-Patent Document 1 describes cationic polymerization of an epoxy compound using a substituted phenol compound as an initiator, and Non-Patent Document 2 describes polymerization of glycidyl ether initiated in the presence of a fluorine compound. Is described.

Japanese Unexamined Patent Publication No. 2008-189821 Japanese Unexamined Patent Publication No. 2011-219583 Japanese Unexamined Patent Publication No. 2010-168525

Macromolecules Vol. 37, No. 5 P. 1671-1673 JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY 2011, 49, 5210-5216

An object of the present invention is to provide a highly reactive phenolic polymerization initiator and a curable composition containing the phenolic polymerization initiator.

The present invention has achieved the above object by providing a curable composition containing at least one phenol compound substituted with a halogen atom or an alkyl halide group.

The present invention also provides a curable composition containing the above-mentioned polymerization initiator (A) and a polymerizable organic substance (B), and a cured product thereof.

The phenolic polymerization initiator of the present invention has high reactivity, and the curable composition containing the phenolic polymerization initiator has high curability, and is therefore useful in various applications such as adhesives and various coating materials. ..

Hereinafter, the polymerization initiator, the curable composition, and the cured product thereof of the present invention will be described in detail.

The polymerization initiator of the present invention contains at least one phenol compound.

As the above-mentioned phenol compound, a known compound can be used without particular limitation, and examples thereof include those selected from the following group.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴、Ｒ²⁵、Ｒ²⁶、Ｒ²⁷、Ｒ²⁸、Ｒ²⁹、Ｒ³⁰、Ｒ³¹、Ｒ³²、Ｒ³³、Ｒ³⁴、Ｒ³⁵、Ｒ³⁶、Ｒ³⁷、Ｒ³⁸、Ｒ³⁹、Ｒ⁴⁰、Ｒ⁴¹、Ｒ⁴²、Ｒ⁴³、Ｒ⁴⁴、Ｒ⁴⁵、Ｒ⁴⁶、Ｒ⁴⁷、Ｒ⁴⁸、Ｒ⁴⁹、Ｒ⁵⁰、Ｒ⁵¹、Ｒ⁵²、Ｒ⁵³、Ｒ⁵⁴、Ｒ⁵⁵、Ｒ⁵⁶、Ｒ⁵⁷、Ｒ⁵⁸、Ｒ⁵⁹、Ｒ⁶⁰、Ｒ⁶¹、Ｒ⁶²、Ｒ⁶³、Ｒ⁶⁴、Ｒ⁶⁵、Ｒ⁶⁶、Ｒ⁶⁷、Ｒ⁶⁸、Ｒ⁶⁹、Ｒ⁷⁰、Ｒ⁷¹、Ｒ⁷²、Ｒ⁷³、Ｒ⁷⁴、Ｒ⁷⁵、Ｒ⁷⁶、Ｒ⁷⁷、Ｒ⁷⁸、Ｒ⁷⁹、Ｒ⁸⁰、Ｒ⁸¹、Ｒ⁸²、Ｒ⁸³、Ｒ⁸⁴及びＲ⁸⁵は、それぞれ独立に、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環含有基、シアノ基、ニトロ基、カルボキシル基又はハロゲン原子を表し、上記アルキル基及びアリールアルキル基中のアルキレン部分は、不飽和結合、−Ｏ−、−Ｓ−又は−ＣＯ−Ｏ−、−Ｏ−ＣＯ−で置換されている場合もある。）

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , 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 , R ⁴⁹ , R ⁵⁰ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ independently have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon atom number. Represents an arylalkyl group of 7 to 20, a heterocyclic group having 2 to 20 carbon atoms, a cyano group, a nitro group, a carboxyl group or a halogen atom, and the alkylene moiety in the alkyl group and the arylalkyl group is an unsaturated bond. , -O-, -S- or -CO-O-, -O-CO- may be substituted.)

（式中、Ｒ⁸⁸、Ｒ⁸⁹、Ｒ⁹⁰、Ｒ⁹¹、Ｒ⁹²、Ｒ⁹³、Ｒ⁹⁴、Ｒ⁹⁵、Ｒ⁹⁶、Ｒ⁹⁷、Ｒ⁹⁸、Ｒ⁹⁹、Ｒ¹³³、Ｒ¹³⁴、Ｒ¹³⁵、Ｒ¹³⁶、Ｒ¹³⁷、Ｒ¹³⁸、Ｒ¹³⁹、Ｒ¹⁴⁰、Ｒ¹⁴¹、Ｒ¹⁴²、Ｒ¹⁴³、Ｒ¹⁴⁴、Ｒ¹⁴⁵、Ｒ¹⁴⁶、Ｒ¹⁴⁷、Ｒ¹⁴⁸、Ｒ¹⁴⁹、Ｒ¹⁵⁰、Ｒ¹⁵¹、Ｒ¹⁵²、Ｒ¹⁵³、Ｒ¹⁵⁴、Ｒ¹⁵⁵、Ｒ¹⁵⁶、Ｒ¹⁵⁷、Ｒ¹⁵⁸、Ｒ¹⁵⁹、Ｒ¹⁶⁰、Ｒ¹⁶¹、Ｒ¹⁶²、Ｒ¹⁶³、Ｒ¹⁶⁴、Ｒ¹⁶⁵、Ｒ¹⁶⁶、Ｒ¹⁶⁷、Ｒ¹⁶⁸、Ｒ¹⁶⁹、Ｒ¹⁷⁰、Ｒ¹⁷¹、Ｒ¹⁷²、Ｒ¹⁷³、Ｒ¹⁷⁴、Ｒ¹⁷⁵、Ｒ¹⁷⁶、Ｒ¹⁷⁷、Ｒ¹⁷⁸、Ｒ¹⁷⁹、Ｒ¹⁸⁰、Ｒ¹⁸¹、Ｒ¹⁸²、Ｒ¹⁸³、Ｒ¹⁸⁴、Ｒ¹⁸⁵、Ｒ¹⁸⁶、Ｒ¹⁸⁷、Ｒ¹⁸⁸、Ｒ¹⁸⁹及びＲ¹⁹⁰は、それぞれ独立に、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環含有基、シアノ基、ニトロ基、カルボキシル基又はハロゲン原子を表し、上記アルキル基及びアリールアルキル基中のアルキレン部分は、不飽和結合、−Ｏ−、−Ｓ−又は−ＣＯ−Ｏ−、−Ｏ−ＣＯ−で置換されている場合もあり、Ｒ¹⁹¹、Ｒ¹⁹²及びＲ¹⁹³は、それぞれ独立に、水素原子又は炭素原子数１〜４のアルキル基を表し、Ｍ^１、Ｍ^２、Ｍ^３及びＭ^４は、それぞれ独立に、直接結合、メチレン基、炭素原子数１〜４のアルキリデン基、脂環式炭化水素基、Ｏ、Ｓ、ＳＯ_２、ＳＳ、ＳＯ、ＣＯ、ＯＣＯ、下記式（Ｖ−１）、（Ｖ−２）あるいは（Ｖ−３）で表される群から選ばれる置換基を表す。）

(In the formula, R ⁸⁸ , R ⁸⁹ , R ⁹⁰ , R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ , R ⁹⁵ , R ⁹⁶ , R ⁹⁷ , R ⁹⁸ , R ⁹⁹ , R ¹³³ , R ¹³⁴ , R ¹³⁵ , R ¹³⁶ , R ¹³⁷ , R ¹³⁸ , R ¹³⁹ , R ¹⁴⁰ , R ¹⁴¹ , R ¹⁴² , R ¹⁴³ , R ¹⁴⁴ , R ¹⁴⁵ , R ¹⁴⁶ , R ¹⁴⁷ , R ¹⁴⁸ , R ¹⁴⁹ , R ¹⁵⁰ , R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ , R ¹⁵⁶ , R ¹⁵⁷ , R ¹⁵⁸ , R ¹⁵⁹ , R ¹⁶⁰ , R ¹⁶¹ , R ¹⁶² , R ¹⁶³ , R ¹⁶⁴ , R ¹⁶⁵ , R ¹⁶⁶ , R ¹⁶⁷ , R ¹⁶⁸ , R ^169. , R ¹⁷⁰ , R ¹⁷¹ , R ¹⁷² , R ¹⁷³ , R ¹⁷⁴ , R ¹⁷⁵ , R ¹⁷⁶ , R ¹⁷⁷ , R ¹⁷⁸ , R ¹⁷⁹ , R ¹⁸⁰ , R ¹⁸¹ , R ¹⁸² , R ¹⁸³ , R ¹⁸⁴ , R ¹⁸⁵ , R ¹⁸⁶ , R ¹⁸⁷ , R ¹⁸⁸ , R ¹⁸⁹ and R ¹⁹⁰ are independently hydrogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 10 carbon atoms, and aryl having 6 to 20 carbon atoms, respectively. Represents a group, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group containing 2 to 20 carbon atoms, a cyano group, a nitro group, a carboxyl group or a halogen atom, and an alkylene moiety in the above alkyl group and arylalkyl group. May be substituted with an unsaturated bond, -O-, -S- or -CO-O-, -O-CO-, where R ¹⁹¹ , R ¹⁹² and R ¹⁹³ are independent hydrogen atoms, respectively. Alternatively, it represents an alkyl group having 1 to 4 carbon atoms, and M ¹ , M ² , M ³ and M ⁴ are independently bonded, methylene group, alkylidene group having 1 to 4 carbon atoms, and alicyclic carbonization. It represents a hydrogen group, O, S, SO ₂ , SS, SO, CO, OCO, a substituent selected from the group represented by the following formulas (V-1), (V-2) or (V-3). )

（Ｒ¹⁰⁹、Ｒ¹¹⁰、Ｒ¹¹¹、Ｒ¹¹²、Ｒ¹¹³、Ｒ¹¹⁴、Ｒ¹¹⁵、Ｒ¹¹⁶、Ｒ¹¹⁷、Ｒ¹¹⁸、Ｒ¹¹⁹、Ｒ¹²⁰、Ｒ¹²¹、Ｒ¹²²、Ｒ¹²³、Ｒ¹²⁴、Ｒ¹²⁵、Ｒ¹²⁶、Ｒ¹²⁷、Ｒ¹²⁸、Ｒ¹²⁹、Ｒ¹³⁰、Ｒ¹³¹及びＲ¹³²は、それぞれ独立に、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環含有基、又はハロゲン原子を表し、上記アルキル基及びアリールアルキル基中のアルキレン部分は、不飽和結合、−Ｏ−又は−Ｓ−で置換されている場合もあり、Ｒ¹⁰⁹、Ｒ¹¹⁰、Ｒ¹¹¹、Ｒ¹¹²、Ｒ¹¹⁷、Ｒ¹¹⁸、Ｒ¹¹⁹、Ｒ¹²⁰、Ｒ¹²⁵、Ｒ¹²⁶、Ｒ¹²⁷、Ｒ¹²⁸、Ｒ¹²⁹、Ｒ¹³⁰、Ｒ¹³¹及びＲ¹³²は、隣接するＲ¹⁰⁹、Ｒ¹¹⁰、Ｒ¹¹¹、Ｒ¹¹²、Ｒ¹¹⁷、Ｒ¹¹⁸、Ｒ¹¹⁹、Ｒ¹²⁰、Ｒ¹²⁵、Ｒ¹²⁶、Ｒ¹²⁷、Ｒ¹²⁸、Ｒ¹²⁹、Ｒ¹³⁰、Ｒ¹³¹及びＲ¹³²同士で環を形成している場合もある。）

(R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹² , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ , R ¹¹⁸ , R ¹¹⁹ , R ¹²⁰ , R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ and R ¹³² are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms, respectively. Represents an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or a halogen atom, and is an alkylene in the above alkyl group and arylalkyl group. Substituents may be substituted with unsaturated bonds, -O- or -S-, R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹² , R ¹¹⁷ , R ¹¹⁸ , R ¹¹⁹ , R ¹²⁰ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ and R ¹³² are adjacent R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹² , R ¹¹⁷ , R ¹¹⁸ , R ¹¹⁹ , R ¹²⁰ , R ^125. , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ and R ¹³² may form a ring.)

In the compounds in the above group, the ^{alkyl groups having 1 to 20 carbon atoms represented by R 1 to} R ¹⁹⁰ include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl and iso-. Butyl, amyl, iso-amyl, tert-amyl, hexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, Isotridecyl, myristyl, palmityl, stearyl, trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluoroethyl, difluoroethyl, heptafluoropropyl, hexafluoropropyl, pentafluoropropyl, tetrafluoropropyl, Examples thereof include trifluoropropyl, perfluorobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like.
Examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^{1 to} R ¹⁹⁰ include methyloxy, ethyloxy, iso-propyloxy, propyloxy, butyloxy, pentyloxy, iso-pentyloxy, hexyloxy, and heptyloxy. Examples include octyloxy and 2-ethylhexyloxy.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ^{1 to} R ¹⁹⁰ include phenyl, naphthyl, anthracene-1-yl, phenanthrene-1-yl, o-tolyl, m-tolyl, p-tolyl, and 4 -Vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-t-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2) -Ethylhexyl) phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4 -Di-t-butylphenyl, 2,5-di-t-butylphenyl, 2,6-di-t-butylphenyl, 2,4-di-t-pentylphenyl, 2,5-di-t-amyl Phenyl, cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-trichlorophenyl, 4-trifluorophenyl, perfluorophenyl and the like can be mentioned.
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ^{1 to} R ¹⁹⁰ include benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, 4-chlorophenylmethyl and the like. ,
Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R ^{1 to} R ¹⁹⁰ include pyrrolyl, pyridyl, pyrimidyl, pyridadyl, piperazyl, piperidin, pyranyl, pyrazolyl, triazil, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, and benzoimidazolyl. , Triazolyl, frills, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolidine, benzoxazolyl, isothiazolidine, isooxazolidine, indolyl, urolysyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinone-1 -Il, 2-piperidin-1-yl, 2,4-dioxyimidazolidine-3-yl, 2,4-dioxyoxazolidine-3-yl and the like can be mentioned.
Examples of the halogen atom represented by R ^{1 to} R ¹⁹⁰ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Among the compounds in the above group, the substituents selected from the groups represented by the formulas (V-1), (V-2) and (V-3) represented by ^{M 1 to} M ^{4 are R 109 to} R ^132. Alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, and 2 to 2 carbon atoms. Examples of the heterocycle-containing group and halogen atom of 20 include those exemplified by ^{R 1 to} R ^{190 above.}
Adjacent R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹² , R ¹¹⁷ , R ¹¹⁸ , R ¹¹⁹ , R ¹²⁰ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ and R ¹³² Examples of the ring that may be formed in the above include heterocycles such as piperidine ring, piperazine ring, morpholine ring, lactam ring, pyridine ring, pyrimidine ring, quinoline ring, imidazole ring, oxazole ring, imidazolidine ring, and pyrazolidine ring. Alternatively, cyclic alkanes such as cyclopentane ring and cyclohexane ring, aromatic rings such as benzene ring, naphthalene ring and phenanthrene ring can be mentioned, and these rings may be fused or substituted with other rings. Good.

Among the compounds in the above group, a phenol compound substituted with a halogen atom or an alkyl halide group is preferable because it has a high reaction rate at the time of energy irradiation described later, and among them, a polyfunctional phenol compound is preferable.

As the phenol compound substituted with a halogen atom or an alkyl halide group, any one or two or more of the hydrogen atoms bonded to the benzene ring or the naphthalene ring in the compound shown in the above group are used. A compound substituted with a halogen atom or an alkyl halide group is preferable, and a compound in which either a benzene ring with a hydroxyl group or a hydrogen atom bonded to a naphthalene ring is substituted with a halogen atom or an alkyl halide group is more preferable. In the benzene ring bonded to the hydroxyl group, the halogen atom or the alkyl halide group may be bonded to the hydroxyl group at any of the ortho, para, and meta positions. Further, in the naphthalene ring bonded to the hydroxyl group, the relationship between the hydroxyl group and the halogen atom or the alkyl halide group is as follows: 1,2-position substitution, 1,3-position substitution, 1,4-position substitution, 1,5-position substitution, 1 , 6-position substitution, 1,7-position substitution, 1,8-position substitution, 2,3-position substitution, 2,6-position substitution, 2,7-position substitution. The number of substituents, which are halogen atoms or alkyl halide groups, is preferably 1 to 5 and more preferably 4 to 5 in the phenol compound.

It is more preferable that the halogen atom in the halogen atom and the halogen atom in the alkyl halide group is a fluorine atom from the viewpoint of further enhancing the reactivity of the polymerization initiator of the present invention and increasing the hardness of the cured product.

When the phenol compound is a polyfunctional phenol compound, the polyfunctional phenol compound may be a compound having two or more hydroxyl groups in one benzene ring or naphthalene ring, or a benzene ring or naphthalene having one hydroxyl group. In some cases, the ring is a compound in which two or more ^{rings are bonded via the groups represented by M 1 to} M ^{4 described above.}

The phenol compound preferably has a molecular weight of 100 or more and 800 or less, and more preferably 100 or more and 500 or less, from the viewpoint of enhancing reactivity.

Conventionally known polymerization initiators may corrode metals, but in the present invention, by using a phenol compound as a polymerization initiator, hydrogen ions generated in the process of producing a cured product are returned to the phenol compound, so that the metal is used. The effect of not corroding can be obtained.

The polymerization initiator of the present invention functions as a cationic polymerization initiator or an anionic polymerization initiator.

The curable composition of the present invention contains the above-mentioned polymerization initiator (A) and polymerizable organic substance (B).

The ratio of the above-mentioned polymerization initiator (A) to the polymerizable organic substance (B) described later is not particularly limited, and it may be used in a generally normal ratio within a range that does not impair the object of the present invention. The polymerization initiator (A) can be preferably 0.1 to 20 mol%, more preferably 1 to 15 mol% with respect to 100 mol% of the polymerizable organic substance (B). 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 polymerizable organic substance (B) used in the present invention is a compound that undergoes a polymerization or cross-linking reaction with a polymerization initiator activated by irradiation with active energy rays or heating. Examples thereof include an alicyclic epoxy compound (B1), an aliphatic epoxy compound (B2), an aromatic epoxy compound (B3), an oxetane compound (B4), and a vinyl ether compound (B5). Examples of the anionic polymerizable organic substance include acrylic acid, acrylic acid ester, butadiene, benzene, toluene, xylene and the like.

Specific examples of the alicyclic epoxy compound (B1) include cyclohexene oxide and cyclopentene oxide-containing compounds obtained by epoxidizing a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. For example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4 -Epoxycyclohexylmethyl-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, 7-oxa Bicyclo [4.1.0] heptane, poly [oxy- (1-oxo-1,6-hexanediyl)]] derivative, bis hexanediate [(7-oxabicyclo [4.1.0] heptane-3) -Il) methyl], α-pinene oxide, limonendioxide and the like can be mentioned, and these can be used alone or in admixture of two or more.
Examples of the alicyclic epoxy compound (B1) include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate. The rate is preferable from the viewpoint of improving adhesion.

As the alicyclic epoxy compound (B1), a commercially available product can be used, for example, celoxide 2021P, celoxide 2081, celoxide 2000, celoxide 3000, cyclomer M100 (manufactured by Daicel); CYRACURE UVR-6128 ( Dow Chemical Co., Ltd.) and the like.

When the curable composition of the present invention is cationically polymerizable, the alicyclic epoxy compound (B1) is 0 to 70% by mass, particularly 20 to 65%, based on 100% by mass of the polymerizable organic substance (B). The mass% is preferable because the viscosity, coatability and reactivity are improved. The amount of the alicyclic epoxy compound (B1) referred to here does not include the amount of the polymer having a weight average molecular weight of 1000 to 500,000, which will be described later (the amount of the aliphatic epoxy compound (B2) below, the aroma). The same applies to the amount of the group epoxy compound (B3) and the amount of the polyfunctional epoxy compound).

The aliphatic epoxy compound (B2) refers to an epoxy compound that is not classified into the alicyclic epoxy compound (B1) or the aromatic epoxy compound (B3) described later, and specific examples of the aliphatic epoxy compound include fat. Monofunctional epoxy compounds such as glycidyl etherified compounds of group alcohols and glycidyl esters of alkylcarboxylic acids, polyglycidyl etherified compounds of aliphatic polyvalent alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, etc. Examples include polyfunctional epoxy compounds. Typical compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and glycerin. Triglycidyl ether, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, hydrogenated bisphenol diglycidyl ether, dicyclopentadiene dimethanol diglycidyl ether, polypropylene Polyether polyol obtained by adding one or more alkylene oxides to glycidyl ethers of polyhydric alcohols such as diglycidyl ethers of glycols and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin. Polyglycidyl etherified products and diglycidyl esters of aliphatic long-chain dibasic acids can be mentioned. Further, monoglycidyl ether of an aliphatic higher alcohol, glycidyl ester of a higher fatty acid, epoxidized soybean oil, octyl epoxide stearate, butyl epoxidized stearate, epoxidized soybean oil, epoxidized polybutadiene and the like can be mentioned. Seeds and above can be mixed and used.
As the aliphatic epoxy compound (B2), a glycidyl etherified product of an aliphatic alcohol or a polyglycidyl etherified product of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof is preferable because the viscosity, coatability and reactivity are improved. Further, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether or 1,6-hexanediol diglycidyl ether are preferable.

As the aliphatic epoxy compound (B2), commercially available products can be used, for example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-221, Denacol EX-212, Denacol EX. -313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX -622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX -911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase ChemteX Corporation); Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P , Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Adeka Resin EP-4088S, Adeka Glycyllol ED-503, Adeka Glycyllol ED-503G, Adeka Glycyllol ED-506 523T (manufactured by ADEKA Corporation) and the like can be mentioned.

When the curable composition of the present invention is cationically polymerizable, the content of the aliphatic epoxy compound (B2) is 0 to 70% by mass, particularly 20 to 65% by mass, based on 100% by mass of the polymerizable organic substance (B). % Is preferable because the viscosity, coatability and reactivity are improved.

The aromatic epoxy compound (B3) refers to an epoxy compound having a plurality of epoxy groups and containing an aromatic ring, and specific examples of the polyfunctional aromatic epoxy compound include at least one such as phenol, cresol, and butylphenol. A mono / polyglycidyl etherified product of a monovalent phenol having an aromatic ring or an alkylene oxide adduct thereof, for example, bisphenol A, bisphenol F, or a glycidyl etherified product or a phenol novolac type epoxy compound obtained by further adding an alkylene oxide to these products. Glysidyl ether of an aromatic compound having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol; polyglycidyl of an aromatic compound having two or more alcoholic hydroxyl groups such as benzenedimethanol, benzenediethanol, and benzenedibutanol. Ethereate; polyglycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, and polyglycidyl esters of benzoic acids such as benzoic acid, toluic acid, and naphthoic acid. Examples thereof include glycidyl ester of benzoic acid, styrene oxide, epoxidized product of divinylbenzene and the like, and these can be used alone or in admixture of two or more.
Among them, polyglycidyl ethers of phenols, polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups, polyglycidyl ethers of polyhydric phenols, polyglycidyl esters of benzoic acids, and polyglycidyl esters of polybasic acids. It is preferable to contain at least one selected from the above group from the viewpoint of reducing the viscosity of the curable composition.
As the aromatic epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol E type epoxy compound, and a phenol novolac type epoxy compound are preferable because they have excellent curability.

As the aromatic epoxy compound (B3), commercially available products can be used, for example, Denacol EX-121, Denacol EX-145, 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); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (DIC) ESN-475V (manufactured by Nippon Steel & Sumitomo Metal Corporation); Epicoat YX8800 (manufactured 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 (Nippon Kayaku) Adeka Resin EP-3300E, Adeka Resin EP-3950S, Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (manufactured by ADEKA); TECHMORE VG-3101L (manufactured by DIC), etc. Can be mentioned.

When the curable composition of the present invention is cationically polymerizable, the aromatic epoxy compound (B3) is 0 to 70% by mass, particularly 20 to 65% by mass, based on 100% by mass of the polymerizable organic substance (B). Is preferable from the viewpoint of improving curability.

In the curable composition of the present invention, it is preferable that the polymerizable organic substance (B) contains a polyfunctional epoxy compound from the viewpoint of improving curability and hardness of the cured product. Examples of the polyfunctional epoxy compound include the alicyclic epoxy compound (B1), the aliphatic epoxy compound (B2), and the aromatic epoxy compound (B3), which are polyfunctional. From the viewpoint of improving the curability and the hardness of the cured product, when the curable composition of the present invention is cationically polymerizable, the polyfunctional epoxy compound is 0 to 0 to 100% by mass of the polymerizable organic substance (B). It is preferably 90% by mass, particularly 20 to 80% by mass.

Examples of the oxetane compound (B4) include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 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 glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, Bifunctional oxetane compounds such as 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, 3-ethyl-3- (3-ethyl-3-oxetanylmethyloxymethyl) oxetane, and xylylenebis oxetane, 3- Ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) ) Oxetane, a monofunctional oxetane compound such as 3-ethyl-3- (chloromethyl) oxetane and the like can be mentioned, and a monofunctional aliphatic oxetane compound is preferable from the viewpoint of viscosity and reactivity. These can be used individually by 1 type or in combination of 2 or more types.

As the oxetane compound (B4), a commercially available product containing a cationically polymerizable monomer as a main component can be used. For example, Aron oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, Examples thereof include OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.), Ethanacole OXBP, and OXTP (manufactured by Ube Industries, Ltd.).

When the curable composition of the present invention is cationically polymerizable, the oxetane compound (B4) is 0 to 80% by mass, particularly 20 to 75% by mass, based on 100% by mass of the polymerizable organic substance (B). This is preferable because the viscosity, coatability and reactivity are improved.

Examples of the vinyl ether compound (B5) 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, and triethylene glycol vinyl ether. Examples thereof include 2-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.

Further, a polymer having a weight average molecular weight of 1000 to 500,000 and selected from the following (i) to (v) (hereinafter, also simply referred to as a polymer) can be added to the curable composition of the present invention. ..
(I) A monomer polymer represented by the following formula (I).
(Ii) A monomer polymer represented by the following formula (II).
(Iii) A copolymer of two or more kinds of monomers selected from the monomers represented by the following formula (I).
(Iv) A copolymer of two or more types of monomers selected from the monomers represented by the following formula (II).
(V) A copolymer of a monomer represented by the following formula (I) and a monomer represented by the following formula (II).

As the polymer, it is preferable that the monomer constituting the polymer contains the following (I)'or the following (II)'.
(I)': One or more compounds represented by the following formula (I) in which X in the formula (I) is selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group. An alkyl group having 1 to 7 carbon atoms substituted with a group, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or 6 carbon atoms. A compound that is an alicyclic hydrocarbon group of 10.
(II)': One or more compounds represented by the following (II) in which X'in the following formula (II) is selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group. A compound which is an alkyl group having 1 to 7 carbon atoms substituted with a group, an aryl group having 6 to 12 carbon atoms, or an alicyclic hydrocarbon group having 6 to 10 carbon atoms.

（式中、Ｘは、炭素原子数１〜７のアルキル基、炭素原子数１〜７のアルコキシ基、炭素原子数６〜１２のアリール基、炭素原子数６〜１２のアリールオキシ基もしくは炭素原子数６〜１０の脂環式炭化水素基、又はこれらの基中の水素原子が、エポキシ基、オキセタン基、水酸基及びカルボキシル基からなる群より選択される１種以上の基で置換されたものである）

(In the formula, X is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a carbon atom. An alicyclic hydrocarbon group of number 6 to 10 or a hydrogen atom in these groups is substituted with one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group. is there)

（式中、Ｒ¹⁹⁴は、水素原子、メチル基又はハロゲン原子を表し、Ｘ’は、炭素原子数１〜７のアルキル基、炭素原子数６〜１２のアリール基もしくは炭素原子数６〜１０の脂環式炭化水素基、又はこれらの基中の水素原子が、エポキシ基、オキセタン基、水酸基及びカルボキシル基からなる群より選択される１種以上の基で置換されたものである。)

(In the formula, R ¹⁹⁴ represents a hydrogen atom, a methyl group or a halogen atom, and X'is an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms or 6 to 10 carbon atoms. The alicyclic hydrocarbon group, or the hydrogen atom in these groups, is substituted with one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group.)

Examples of the alkyl group having 1 to 7 carbon atoms represented by X in the above formula (I) include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, and amyl. Examples thereof include iso-amyl, tert-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl and the like. Among these, an alkyl group having 1 to 4 carbon atoms or a group having 1 to 1 or more carbon atoms partially substituted with one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group. The alkyl group of 4 is preferable from the viewpoint of curability.

Examples of the alkoxy group having 1 to 7 carbon atoms represented by X in the above formula (I) include methoxy, ethoxy, propyloxy, iso-propyloxy, butyloxy, sec-butyloxy, tert-butyloxy and iso-butyloxy. Amiloxy, iso-amyloxy, tert-amyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, tert-Heptyloxy and the like can be mentioned. Among these, an alkyl group having 1 to 4 carbon atoms or a group having 1 to 1 or more carbon atoms partially substituted with one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group. The alkoxy group of 4 is preferable from the viewpoint of curability.

Examples of the aryl group having 6 to 12 carbon atoms represented by X in the above formula (I) include phenyl, methylphenyl, naphthyl and the like.

Examples of the aryloxy group having 6 to 12 carbon atoms represented by X in the above formula (I) include phenyloxy, methylphenyloxy, and naphthyloxy.

Examples of the alicyclic hydrocarbon group having 6 to 10 carbon atoms represented by X in the above formula (I) include cyclohexyl, methylcyclohexyl, norbornyl, bicyclopentyl, bicyclooctyl, trimethylbicycloheptyl, and tricyclooctyl. , Tricyclodecanyl, spirooctyl, spirobicyclopentyl, adamantyl, isobornyl and the like.

In the above formula (I), when a part of X is substituted with an epoxy group or an oxetane group, the monomer represented by the formula (I) is, for example, the following formulas (1) to (3). Examples thereof include monomers represented by.

（式中、Ｒ¹⁹⁵は、水素原子又は炭素原子数１〜６のアルキル基を表し、ｍは、１〜６の整数である。）

(In the formula, R ¹⁹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m is an integer of 1 to 6).

（式中、Ｒ¹⁹⁶は、水素原子又は炭素原子数１〜６のアルキル基を表し、ｎは、１〜６の整数である。）

(In the formula, R ¹⁹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).

（式中、Ｒ¹⁹⁷は、水素原子又は炭素原子数１〜６のアルキル基を表し、ｓは、１〜６の整数である。）。

(In the formula, R ¹⁹⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and s is an integer of 1 to 6).

^{Examples of the halogen atom represented by R 194} in the above formula (II) include fluorine, chlorine, bromine, iodine and the like. The alkyl group having 1 to 7 carbon atoms represented by X', the aryl group having 6 to 12 carbon atoms, and the alicyclic hydrocarbon group having 6 to 10 carbon atoms have the number of carbon atoms represented by X. Examples thereof include alkyl groups 1 to 7, aryl groups having 6 to 12 carbon atoms, and alicyclic hydrocarbon groups having 6 to 10 carbon atoms, which are exemplified above.

In the above formula (II), when a part of X'is substituted with an epoxy group or an oxetane group, the monomer represented by the formula (II) is represented by the following formulas (4) to (6). The ones that are represented are listed.

（式中、Ｒ¹⁹⁴は、上記式（ＩＩ）と同じであり、Ｒ¹⁹⁸は、水素原子又は炭素原子数１〜６のアルキル基を表し、ｔは、１〜６の整数である。）

(In the formula, R ¹⁹⁴ is the same as the above formula (II), R ¹⁹⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and t is an integer of 1 to 6).

（式中、Ｒ¹⁹⁴は、上記式（ＩＩ）と同じであり、Ｒ¹⁹⁹は、水素原子又は炭素原子数１〜６のアルキル基を表し、ｑは、１〜６の整数である。）

(In the formula, R ¹⁹⁴ is the same as the above formula (II), R ¹⁹⁹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and q is an integer of 1 to 6).

（式中、Ｒ¹⁹⁴は、上記式（ＩＩ）と同じであり、Ｒ²⁰⁰は、水素原子又は炭素原子数１〜６のアルキル基を表し、ｙは、１〜６の整数である。）。

(In the formula, R ¹⁹⁴ is the same as the above formula (II), R ²⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and y is an integer of 1 to 6).

In the above polymer, the adhesiveness is such that the proportion of the monomers constituting the polymer is 10 to 100% by mass of the monomer corresponding to the above (I)'or the above (II)'. Is preferable because it improves.

The ratio of the polymer used to the organic substance (B) is 10 to 30 parts by mass, preferably 15 to 20 parts by mass with respect to 100 parts by mass of the organic substance (B).

A known polymerization initiator can be further added to the curable composition of the present invention. Known cationic polymerization initiators include, for example, a double salt which is an onium salt that releases Lewis acid when irradiated with active energy rays, or a derivative thereof. Typical examples of such compounds 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 and 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 perchlorate ion (ClO ₄ ) ⁻ , tetrafluoroborate ion (BF ₄ ) ⁻ , hexafluorophosphate ion (PF ₆ ) ^{− and the} like. Inorganic ion; fluorosulfonic acid ion (FSO ₃ ) ^- , toluene sulfonic acid anion, trinitrobenzene sulfonic acid ion, camphor sulfonic acid ion, nonafluorobutane sulfonic acid ion, hexadecafluorooctane sulfonic acid ion and other sulfonic acid ions; Tetraaryl sulphonate ion, tetrax (pentafluorophenyl) sulphonic acid ion and other sulphonic acid ions; methane carboxylic acid ion, ethane carboxylic acid ion, propane carboxylic acid ion, butane carboxylic acid ion, octane carboxylic acid ion, trifluoromethane carboxylic acid ion, benzene carboxylate ion, a carboxylate ion such as p- toluenesulfonic acid ^{_{ion; (CF 3 CF 2) 3}} PF 3 -, (CF 3 CF 2 CF 2) 3 PF 3 -, ((CF 3) 2 CFCF 2) 3 ^{_{PF 3 -, ((CF 3}} ) 2 CFCF 2) 2 PF 4 - fluorinated alkyl fluorophosphoric acid ion and the like; trifluoromethyl sulfite ion (CF ₃ SO ₃₎ ^-, methyl sulfate ion _(CH 3 _OSO 3) ^- , Bis (trifluoromethanesulfonyl) imide ion, tris (trifluoromethanesulfonyl) methide ion and the like.

The anion [B] ^r- is the following general formula,
[LY _b-1 (OH)] ^r-
The structure represented by is also preferably used.

Above [(R ² ) _a Q] ^{r +}
Examples of the cation having the structure represented by (1) include those described in Group I or Group II below.

As the preferred polymerization initiator other than other phenolic compounds, (eta ^{5-2,4-cyclopentadiene-1-yl)} [(1,2,3,4,5,6-η) - (1 -Methylethyl) benzene] -iron-arene complexes such as iron-hexafluorophosphate, and aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, and tris (salityl aldehyde) aluminum. A mixture with silanols such as triphenylsilanol can also be mentioned.

Among these, from the viewpoint of practical use and photosensitivity, it is preferable to use an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-alene complex, and the aromatic sulfonium salt represented by the following general formula (IV) has sensitivity. It is more preferable from the viewpoint of.

（式中、Ｒ²⁰¹、Ｒ²⁰²、Ｒ²⁰³、Ｒ²⁰⁴、Ｒ²⁰⁵、Ｒ²⁰⁶、Ｒ²⁰⁷、Ｒ²⁰⁸、Ｒ²⁰⁹及びＲ²¹⁰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、Ｒ²¹¹、Ｒ²¹²、Ｒ²¹³及びＲ²¹⁴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、Ｒ²¹⁵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 ²⁰¹ , R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ , R ²⁰⁹ and R ²¹⁰ 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 ²¹¹ , R ²¹² , R ²¹³ and R ²¹⁴ are independently hydrogen atoms, halogen atoms or Represents an alkyl group having 1 to 10 carbon atoms, R ²¹⁵ 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、Ｒ²²¹、Ｒ²²²、Ｒ²²³、Ｒ²²⁴、Ｒ²²⁵、Ｒ²²⁶、Ｒ²²⁷、Ｒ²²⁸、Ｒ²²⁹、Ｒ²³⁰、Ｒ²³¹、Ｒ²³²、Ｒ²³³及びＲ²³⁴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、Ｒ²³⁵、Ｒ²³⁶、Ｒ²³⁷、Ｒ²³⁸、Ｒ²³⁹、Ｒ²³⁰、Ｒ²⁴¹、Ｒ²⁴²、Ｒ²⁴³、Ｒ²⁴⁴、Ｒ²⁴⁵、Ｒ²⁴⁶、Ｒ²⁴⁷及びＲ²⁴⁸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 ²²¹ , R ²²² , R ²²³ , R ²²⁴ , R ²²⁵ , R ²²⁶ , R ²²⁷ , R ²²⁸ , R ²²⁹ , R ²³⁰ , R ²³¹ , R ²³² , R ²³³ and R ²³⁴ are independent of each other. , Hydrogen atom, halogen atom, alkyl group with 1 to 10 carbon atoms, alkoxy group with 1 to 10 carbon atoms or ester group with 2 to 10 carbon atoms, R ²³⁵ , R ²³⁶ , R ²³⁷ , R ²³⁸ , R ²³⁹ , R ²³⁰ , R ²⁴¹ , R ²⁴² , R ²⁴³ , R ²⁴⁴ , R ²⁴⁵ , R ²⁴⁶ , R ²⁴⁷ and R ²⁴⁸ are independently alkyl hydrogen atoms, halogen atoms or 1 to 10 carbon atoms. Represents an atom.)

Commercially available products can also be used as the cationic polymerization initiator. For example, Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6976, Cyracure UVI-6990, Cyracure UVI-6992, Cyracure UVI-950 (US Union Carbide). Irgacure 250, Irgacure 261, Irgacure 270, Irgacure PAG103, Irgacure PAG121, Irgacure PAG203, Irgacure PAG290, Irgacure CGI725, Irgacure CGI1380, Irgacure CGI1907, Irgacure GSID26 151, SP-170, SP-171, SP-172 (manufactured by ADEKA), DAICATII (manufactured by Daicel), UVAC1591 (manufactured by Daicel Ornex), CI-2481, CI-2734, CI-2823, CI-2758 (Manufactured by Nippon Soda), FFC509 (3M), Sun Aid SI-45L, Sun Aid SI-60L, Sun Aid SI-80L, Sun Aid SI-100L, Sun Aid SI-110L, Sun Aid SI-150L and Sun Aid SI-180L (Sanshin) BBI-102, BBI-103, BBI-105, BBI-106, BBI-109, BBI-110, BBI-201, BBI, 301, BI-105, DPI-105, DPI-106, DPI -109, DPI-201, DTS-102, DTS-103, DTS-105, NDS-103, NDS-105, NDS-155, NDS-159, NDS-165, TPS-102, TPS-103, TPS-105 , TPS-106, TPS-109, TPS-1000, MDS-103, MDS-105, MDS-109, MDS-205, MPI-103, MPI-105, MPI-106, MPI-109, DS-100, DS -101, MBZ-101, MBZ-201, MBZ-301, NAI-100, NAI-101, NAI-105, NAI-106, NAI-109, NAI-1002, NAI-1003, NAI-1004, NB-101 , NB-201, NDI-101, NDI-105, NDI-106, NDI-109, PAI01, PAI-101, PAI-106, PAI-1001, PI-105, PI-106, PI-109, PYR-100, SI-101, SI-105, SI-106 and SI-109 (manufactured by Midori Kagaku Co., Ltd.), KayaCure PCI-204, KayaCure PCI-205, KayaCure PCI-615, KayaCure PCI-625, Kayarad 220 and Kayarad 620, PCI-061T, PCI-062T, PCI-020T, PCI-022T (manufactured by Nippon Kayaku Co., Ltd.), SP-150, SP-170, SP-171 (manufactured by ADEKA) and the like can be mentioned.

Known anionic polymerization initiator, an alkali _{metal, n-C 4 H 9 Li} , NaNH 2, Na- naphthalene, Grignard reagents, ROLi, _{K-benzophenone, NaOH, NR 3, H 2} O, ROH , and the like ..

The ratio of the polymerization initiator other than the phenol compound to the polymerization initiator (A) of the present invention is 0 to 10 parts by mass of the known polymerization initiator with respect to 100 parts by mass of the polymerization initiator (A). preferable.

Further, a silane coupling agent can be used in the present invention. As the silane coupling agent, for example, epoxy functional alkoxysilane can be used, for example, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyl. Examples thereof include oxypropylmethyldiethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

Commercially available products can also be used as the silane coupling agent having a glycidyl epoxy group. For example, D2632, G0261, G0210, T2675 (manufactured by Tokyo Kasei Co., Ltd.); KBM-303, KBM-402, KBM-403, KBE- 402, KBE-403 (manufactured by Shin-Etsu Silicone Co., Ltd.) and the like can be mentioned.

A sensitizer and / or a sensitizer aid can be 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 polymerization initiator (A) and promotes the polymerization initiation reaction by the polymerization initiator (A). 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、Ｒ²⁵¹及びＲ²⁵²は、各々独立に炭素原子数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、Ｒ²⁵³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 ²⁵¹ and R ²⁵² independently represent an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 12 carbon atoms, and R ²⁵³ has a hydrogen atom or 1 to 6 carbon atoms. Represents an alkyl group.)

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-Ethyl-9,10-dipentyloxyanthracene,
2-Methyl- or 2-ethyl-9,10-dihexyloxyanthracene and the like.

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

（式中、Ｒ²⁵⁴及びＲ²⁵⁵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 ²⁵⁴ and R ²⁵⁵ 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-ethoxy-4-methoxynaphthalene,
1,4-Diethoxynaphthalene,
1,4-Dipropoxynaphthalene,
1,4-Dibutoxynaphthalene, etc.

The ratio of the sensitizer and the sensitizer to the polymerizable organic substance (B) 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 mass of the polymerizable organic substance (B).

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, polymethylmethacrylate, methylmethacrylate-ethylacrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, and (meth) acrylic acid-. Examples thereof include methyl methacrylate copolymer, glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester and the like.

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

The curable composition of the present invention is applied onto a support substrate by a 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 , Acrylic resin such as polyacrylic acid ester; polycarbonate; polysulfone; polyether sulfone; polyether ketone; polyetherimide; polyoxyethylene, norbornene 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.

Further, as long as the effects of the present invention are not impaired, other monomers, other energy ray-sensitive polymerization initiators, inorganic fillers, organic fillers, pigments, colorants such as dyes, antifoaming agents, thickeners, etc. Surfactants, leveling agents, flame retardants, tinctures, diluents, plasticizers, stabilizers, polymerization inhibitors, UV absorbers, antioxidants, antioxidants, flow modifiers, adhesion promoters, etc. Various resin additives and the like can be added.

When the curable composition of the present invention is cured 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 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 for 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.

Oligomers are formed by irradiation with active energy rays, but the reaction is stopped by the entry of phenoside anions into the ends of the oligomers. Therefore, by heating to 80 ° C. or higher, the phenoxide anion at the end of the oligomer dissociates and polymerization starts again to form a polymer, and the oligomer also functions as a latent oligomer.

Specific applications of the curable composition of the present invention include optical films, polarizing plates, adhesives, glasses, optical materials typified by imaging lenses, paints, coating agents, automobile interior / exterior materials, lining agents, and inks. , Resist, liquid resist, printing plate, insulating varnish, insulating sheet, laminated board, printed board, for semiconductor devices, for LED packages, for liquid crystal inlets, for organic EL, for optical elements, for electrical insulation, for electronic parts, Used for encapsulants for separation films, molding materials, putties, glass fiber impregnants, sealants, passivation films for semiconductors and solar cells, interlayer insulating films, protective films, and backlights for liquid crystal display devices. Prism lens sheet, Frenel lens sheet used for screens of projection TVs, lens part of lens sheet such as lenticular lens sheet, or backlight using such sheet, optical lens such as micro lens, optical element , Optical connectors, optical waveguides, casting agents for optical modeling, and the like.

For example, in the case of application as an optical film, a metal, wood, rubber, plastic, glass, ceramic product or the like is used as a base material, and the curable composition of the present invention is applied to the base material by the above-mentioned means. It is cured by irradiating light or heating by means. As a typical configuration of the optical film, a transparent support provided with various layers such as an undercoat layer, an antireflection layer, a hard coat layer, a gas barrier layer, a lubricating layer, and an adhesive layer, as needed. ..

Further, as the support substrate, an inorganic material is used as the substrate, and a film coated by the above method, or a vacuum vapor deposition method, an ion plating method, a plasma CVD method, an ion assist method, a reactive sputtering method, and a chemical vapor phase. It is also possible to use a laminated film prepared by various vapor deposition methods such as a growth method.
When laminating the film by the vapor deposition method, it is preferable to use glass as the base material, and the film thickness varies depending on the type of the inorganic material used and the like, but is, for example, 5 to 300 nm. The vapor-deposited film may be formed on only one side of the substrate, or may be formed on both sides of the substrate.
Examples of the inorganic material include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), indium (In), sodium (Na), and boron (. Oxides such as B), titanium (Ti), lead (Pb), zirconium (Zr), ittrium (Y), antimony (Sb), indium tin oxide composite oxide (abbreviated as ITO), antimony tin composite Composite oxides such as oxides (abbreviated as ATO) can be used.

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.

[Examples 1-28, Comparative Examples 1-3]
Each component was sufficiently mixed with the formulations shown in the following [Table 1] to [Table 5] to obtain Actual Compositions 1-28 and Comparative Compositions 1-3, respectively. The numerical values related to the blending of [Table 1] to [Table 5] represent the molar% of the polymerization initiator (A) when the polymerizable organic substance (B) is 100% by mass, and the other components. Represents a mass part.

The following compounds (A-1) to (A-6) were used as the polymerization initiator (A).
A-1: 2,3-difluorophenol A-2: pentafluorophenol A-3: 3-fluorocatechol A-4: tetrafluorohydroquinone A-5: octafluorobiphenol A-6: 4-fluorophenol

Examples of the polymerizable organic substance (B) include the following compounds (B1-1) to (B1-2), (B2-1), (B3-1), (B2-2) and (B4-1) to (B4). -2) was used.
Compound B1-1: Celoxide 2021P (Alicyclic epoxy: manufactured by Daicel)
Compound B1-2: Celoxide 3000 (alicyclic epoxy: manufactured by Daicel)
Compound B2-1: Neopentyl glycol diglycidyl ether Compound B3-1: Adecaledin EP-4100L (bisphenol A type polyfunctional epoxy: manufactured by ADEKA)
Compound B2-2: Adecaledin EP-4088S (dicyclopentadiene type polyfunctional epoxy: manufactured by ADEKA Corporation)
Compound B4-1: Aron Oxetane OXT-221 (Oxetane: manufactured by Toagosei Co., Ltd.)
Compound B4-2: Aron Oxetane OXT-101 (Oxetane: manufactured by Toagosei Co., Ltd.)

The following compounds (C-1) and (C-2) were used as the polymer.
Compound C-1: Copolymer of 70 parts by mass of methyl methacrylate and 30 parts by mass of glycidyl methacrylate (weight average molecular weight 8000)
Compound C-2: Copolymer of 70 parts by mass of methyl methacrylate and 30 parts by mass of glycidyl methacrylate (weight average molecular weight 15000)

The following compound A'-1 was used as another polymerization initiator.
Compound A'-1: A 50% by mass propylene carbonate solution of a mixture of the compound represented by the following formula (S-1) and the compound represented by the following formula (S-2).

[Evaluation Examples 1-28, Comparative Evaluation Examples 1-3]
The following (hardness) or (adhesion) evaluation was performed on the Example compositions obtained in Examples 1 to 28 and the Comparative Compositions obtained in Comparative Examples 1 to 3. The results are shown in [Table 1] to [Table 5] above.
(hardness)
The implementation composition and the comparative composition were placed in a quartz tube, sealed, and exposed with a UV irradiation device (high-pressure mercury lamp manufactured by Eye Graphics). The exposed composition was placed in a screw tube, sealed, and heated in an oven at 80 ° C. for 3 hours to obtain a cured product. The shore hardness A of this cured product was measured.
(Adhesion)
The implementation composition and the comparative composition were placed in a quartz tube, sealed, and exposed with a UV irradiation device (high-pressure mercury lamp manufactured by Eye Graphics). The exposed composition was coated on various substrates using a wire bar coater to a thickness of about 30 μm, heated in an oven at 60 ° C. for 2 hours, and then heated at 80 ° C. for 2 hours and 100 ° C. for 2 hours. A cured film was obtained on various substrates.
The various base materials are as follows.
・ Glass ・ PMMA: Technoroy 125S001 (manufactured by Sumitomo Chemical Co., Ltd.)
・ TAC: FT TD 80 ULM (Fuji Film Co., Ltd.)
The adhesion of the film surface of the obtained cured film was evaluated according to the method described in JIS K5600 (adhesiveness; cross-cut method). A cellophane adhesive tape (manufactured by Nichiban Co., Ltd., CT-18) was used for the test. The evaluation was performed according to the following criteria.
⊚: There were no squares of the film peeled off from the base material, and the number of squares of the coating remaining on the base material was 100. ○: The number of squares of the coating remaining on the base material was 90 to 99. The number of squares of the coating film remaining on the base material was 70 to 89, and the adhesion was poor. ×: The number of squares of the coating film remaining on the base material was 69 or less. Adhesion is extremely poor. The number of squares of the coating film remaining on the untreated PET substrate after the test was calculated. In the table, "100/100" means that all 100 squares remained on the base material, and "96/100" means 96 out of 100 squares. Remains on the base material, and the four squares are peeled off from the base material by the adhesive tape.

From [Table 1] to [Table 5], it is clear that the curable composition of the present invention has excellent hardness or adhesion to a substrate and has high curability.

Claims (5)

Either a polymerization initiator (A) containing at least one phenol compound and a hydrogen atom containing a polymerizable organic substance (B) and the phenol compound is bonded to a benzene ring or a naphthalene ring to which a hydroxyl group is bonded. It is a compound substituted with a fluorine atom or an alkyl fluoride group, and contains 20 to 65% by mass of an alicyclic epoxy compound in the polymerizable organic substance (B), or the polymerizable organic substance (B). A curable composition containing 20 to 75% by mass of an oxetane compound in 100% by mass. The curability according to claim 1, wherein the total amount of the alicyclic epoxy compound and the oxetane compound in the polymerizable organic substance (B) is 100% by mass, or the aliphatic epoxy compound or the aromatic epoxy compound is contained. Composition. The curable composition according to claim 1 or 2 , wherein the polymerizable organic substance (B) contains a polyfunctional epoxy compound. A method for producing a cured product, wherein the curable composition according to any one of claims 1 to 3 is cured by irradiating it with active energy rays or by heating. A cured product of the curable composition according to any one of claims 1 to 3.