JP2017179161A - Curable composition, manufacturing method of cured article and the cured article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition high in glass transition temperature of a cured article and excellent in adhesiveness, a manufacturing method of a cured article and the cured article.SOLUTION: There is provided a curable composition containing a cationic polymerizable component (A) of 30 to 80 pts.mass, a cationic polymerization initiator (B) of 1 to 10 pts.mass, a radical polymerizable component (C) of 0 to 50 pts.mass, a radical polymerization initiator (D) of 0 to 10 pts.mass, and a polymer selected from a polymer obtained from a monomer represented by the formula (I), a polymer obtained from a (meth)acrylate monomer and the like and having weight average molecular weight of 1,000 to 30,000 (E) of 1 to 30 pts.mass, the (A) component is a glycidyl compound or the like of polyalcohol having molecular weight of 200 or more and an aliphatic epoxy compound and the (C) component is a compound or the like having an epoxy group or the like. (I), where X is a C1 to 7 alkyl group, a C1 to 7 alkoxy group, a C6 to 12 aryl group or the like.SELECTED DRAWING: None

Description

  The present invention relates to a curable composition, a method for producing a cured product, and a cured product thereof, and more specifically, a curable composition having a high glass transition temperature and excellent adhesion, a method for producing the cured product, and the method thereof. It relates to a cured product.

  Curable compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members and the like. Various reports have been made regarding the improvement of such a curable composition.

  For example, Patent Documents 1 to 3 below propose an energy ray curable composition containing a cationic polymerizable component and a radical polymerizable component or a cured product thereof. Specifically, in Patent Document 1, a polarizing plate adhesive composition excellent in initial curability and adhesiveness is disclosed in Patent Document 2, and in Patent Document 2, high heat resistance and high refractive index containing an unsaturated alicyclic epoxy ester compound. Patent Document 3 discloses an active energy ray-polymerizable resin composition that can achieve both transparency and transparency, and has low viscosity, excellent curability, and adhesion to various plastic films including (meth) acrylic resins and cycloolefin polymers. Active energy ray-curable adhesive compositions for plastic films and the like that are excellent in strength and colorless and transparent have been proposed.

JP 2014-105218 A JP2015-168757A Japanese Patent Laying-Open No. 2015-229744

  However, even with the curable compositions proposed in Patent Documents 1 to 3, the curability and adhesion may not always be satisfactory, and both curability and adhesion are highly compatible. Under the present circumstances, a new curable composition that can be prepared is desired.

  Therefore, an object of the present invention is to provide a curable composition having a high glass transition temperature of the cured product and excellent adhesion, a method for producing the cured product, and a cured product thereof.

  As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by a curable composition having a specific composition, and has completed the present invention.

（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、またはこれらの基中の水素原子が、エポキシ基、オキセタン基、水酸基およ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）で表される単量体から得られるポリマー、下記式（ＩＩ）、

（式中、Ｒ^１は、水素原子、メチル基また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、またはこれらの基中の水素原子が、エポキシ基、オキセタン基、水酸基およ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）で表される単量体から得られるポリマー、前記式（Ｉ）で表される単量体から選択される二種以上の単量体から得られるポリマー、前記式（ＩＩ）で表される単量体から選択される二種以上の単量体からな得られるポリマー、並びに前記式（Ｉ）で表される単量体および前記式（ＩＩ）で表される単量体から得られるポリマーからなる群より選択される重量平均分子量１，０００〜３０，０００であるポリマー（Ｅ）を含有し、
前記カチオン重合性成分（Ａ）が、分子量２００以上の多価アルコールのグリシジル化物、または多価アルコールアルキレンオキサイド付加物のグリシジル化物（Ａ１）を必須成分とし、
前記ラジカル重合性成分（Ｃ）が、エポキシ基およびエチレン性不飽和基を有する化合物（Ｃ１）、または炭素原子数２〜２０であるアルコールのアクリル酸エステルあるいは炭素原子数２〜２０であるアルコールのメタクリル酸エステル（Ｃ２）を必須成分とすることを特徴とするものである。ここで、重量平均分子量とは、テトラヒドロフラン（ＴＨＦ）溶媒中、ＧＰＣにより測定し、スチレン換算で求めた重量平均分子量をいう。 That is, the curable composition of the present invention comprises a cationic polymerizable component (A), a cationic polymerization initiator (B), a radical polymerizable component (C), a radical polymerization initiator (D), and the following formula ( I),

(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. The alicyclic hydrocarbon group of several 6 to 10 or a hydrogen atom in these groups is substituted with one or more groups selected from the group consisting of epoxy group, oxetane group, hydroxyl group and carboxyl group A polymer obtained from a monomer represented by the formula (II):

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a halogen atom, and X ′ represents an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 6 to 10 carbon atoms. An alicyclic hydrocarbon group, or a hydrogen atom in these groups is substituted with one or more groups selected from the group consisting of epoxy groups, oxetane groups, hydroxyl groups and carboxyl groups). A polymer obtained from two or more kinds of monomers selected from the monomers represented by the formula (I), a monomer represented by the formula (II) From the group consisting of a polymer obtained from two or more selected monomers, a monomer represented by the formula (I) and a polymer obtained from the monomer represented by the formula (II) Selected weight average molecular weight 1,000-30, Containing 00 at which the polymer (E),
The cation polymerizable component (A) is a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more or a glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct,
The radical polymerizable component (C) is an epoxy group and an ethylenically unsaturated group compound (C1), an acrylate ester of an alcohol having 2 to 20 carbon atoms, or an alcohol having 2 to 20 carbon atoms. Methacrylic acid ester (C2) is an essential component. Here, the weight average molecular weight is a weight average molecular weight measured by GPC in a tetrahydrofuran (THF) solvent and obtained in terms of styrene.

  In the curable composition of the present invention, the glycidylated product of the polyhydric alcohol having a molecular weight of 200 or more or the glycidylated product (A1) of the polyhydric alcohol alkylene oxide adduct is a polyhydric alcohol having a condensed ring. Preferably there is. In the curable composition of the present invention, the polymer (E) is a polymer obtained from the monomer represented by the formula (I) and the monomer represented by the formula (II). X in the formula (I) is an aryl group having 6 to 12 carbon atoms, and X ′ in the formula (II) is an alkyl group having 1 to 7 carbon atoms, It is preferred that the group is substituted with an epoxy group. Furthermore, in the curable composition of the present invention, the cationic polymerizable component (A) is 1 to 50 parts by mass, the cationic polymerization initiator (B) is 1 to 10 parts by mass, and the radical polymerizable component (C). Is 40 to 90 parts by mass, the radical polymerization initiator (D) is 1 to 10 parts by mass, and the polymer (E) is preferably 1 to 20 parts by mass. The total of the cationic polymerizable component (A), the radical polymerizable component (C), and the polymer (E) is 100 parts by mass.

  The method for producing a cured product of the present invention is characterized in that the curable composition of the present invention is irradiated with active energy rays or heated.

  The cured product of the present invention is a cured product of the curable composition of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the glass transition temperature of hardened | cured material is high and can provide the curable composition which is excellent in adhesiveness, the manufacturing method of hardened | cured material, and its hardened | cured material. The curable composition of the present invention is particularly useful for adhesives.

Hereinafter, the curable composition of the present invention will be described in detail.
The curable composition of the present invention comprises a cationic polymerizable component (A), a cationic polymerization initiator (B), a radical polymerizable component (C), a radical polymerization initiator (D), and the following formula (I): A polymer obtained from a monomer represented by the following formula (II), a polymer obtained from a monomer represented by the following formula (II), or two or more types selected from monomers represented by the following formula (I): A polymer obtained from a monomer, a polymer obtained from two or more monomers selected from monomers represented by the following formula (II), a monomer represented by the following formula (I), and It contains a polymer (E) having a weight average molecular weight of 1,000 to 30,000 selected from the group consisting of polymers obtained from monomers represented by the following formula (II). In the curable composition of the present invention, the cationic polymerizable component (A) contains a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more or a glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct as a radical component. The polymerizable component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, an acrylate ester of an alcohol having 2 to 20 carbon atoms, or a methacrylic compound of an alcohol having 2 to 20 carbon atoms. Acid ester (C2).

ここで、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、またはこれらの基中の水素原子が、エポキシ基、オキセタン基、水酸基およ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。

Here, 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 An alicyclic hydrocarbon group having 6 to 10 carbon atoms, 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.

ここで、式中、Ｒ^１は、水素原子、メチル基また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、またはこれらの基中の水素原子が、エポキシ基、オキセタン基、水酸基およ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。

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

  The cationically polymerizable component (A) according to the curable composition of the present invention is a compound that undergoes a polymerization or a crosslinking reaction by a cationic polymerization initiator activated by energy ray irradiation or heating, and includes an epoxy compound and an oxetane compound. And vinyl ether compounds.

  As the epoxy compound, a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more or a glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct is an essential component. In addition, an aromatic epoxy compound (A2) or an alicyclic epoxy is used. A compound (A3) etc. can be used.

  Examples of the glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more or the glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct include those obtained by glycidylating a polyhydric alcohol or a polyhydric alcohol alkylene oxide adduct. The molecular weight of the compound is 200 or more.

  Examples of the glycidylated product of polyhydric alcohol having a molecular weight of 200 or more or the glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neo Pentyl glycol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, dicyclo Polyglycol glycidyl ether such as pentadiene dimethanol diglycidyl ether, propylene glycol, trimethylo Propane, polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as glycerin, and diglycidyl esters of aliphatic long-chain dibasic acids.

  As glycidylated polyhydric alcohol or glycidylated polyhydric alcohol alkylene oxide adduct (A1), monoglycidyl ether of higher aliphatic alcohol, glycidyl ester of higher fatty acid, epoxidized soybean oil, octyl epoxy stearate , Epoxy butyl stearate, epoxidized soybean oil, epoxidized polybutadiene and the like.

  As the glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more or the glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct, those having a saturated condensed ring are preferred because the curability and adhesion of the cured product are improved.

  As the glycidylated product of polyhydric alcohol having a molecular weight of 200 or more or the glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct, commercially available products can be used, for example, Denacol EX-121, Denacol EX-171. , Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-512, 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 E -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 (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.) Adekaglycilol ED-503, Adekaglycilol ED-503G, Adekaglycilol ED-506, Adekaglycilol ED-523T, Adekaresin EP-4088S Adecaresin EP-4080E ((Ltd.) ADEKA Co., Ltd.), and the like.

  The aromatic epoxy compound (A2) 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, butylphenol, or the like. , Mono / polyglycidyl etherified products of the alkylene oxide adducts, for example, bisphenol A, bisphenol F, or glycidyl etherified compounds of compounds obtained by further adding alkylene oxide to these and epoxy novolac resins; two such as resorcinol, hydroquinone and catechol Mono / polyglycidyl etherified products of aromatic compounds having the above phenolic hydroxyl groups; aromatic compounds having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol, and phenyldibutanol Glycidyl etherified product: glycidyl ester of polybasic aromatic compound having two or more carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, glycidyl ester of benzoic acid, epoxide of styrene oxide or divinylbenzene It is done.

  As the aromatic epoxy compound (A2), commercially available products can be used. 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 (Nagase Chemtex Co., Ltd.); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (DIC Corporation) ESN-475V Epicote YX8800 (manufactured by Mitsubishi Chemical Corporation); Marproof G-0105SA, Marproof G-0130SP (manufactured by NOF Corporation); Epicron N-665, Epicron HP -7200 (made 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.); Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (manufactured by ADEKA Corporation); TECHMORE VG-3101L (Co., Ltd.) Manufactured) and the like. As the aromatic epoxy compound, a polyfunctional one is preferable because of excellent curability.

  The alicyclic epoxy compound (A3) refers to a saturated ring in which an oxirane ring is directly formed without a bonding group. Specific examples of the alicyclic epoxy compound (A2) can be obtained by epoxidizing a polyglycidyl etherified product of a polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. Examples include cyclohexene oxide and cyclopentene oxide-containing compounds. 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-methylcyclohexylmethyl-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 diepoxide, 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 oxide and limonene dioxide. As the alicyclic epoxy compound (A2), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxyl The rate is preferable from the viewpoint of improving adhesion.

  As said alicyclic epoxy compound (A3), a commercially available thing can be used, for example, Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000 (made by Daicel Corporation) etc. are mentioned.

  Examples of the oxetane compound 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, 1,6 -Bifunctional aliphatic oxetaneation such as bis (3-ethyl-3-oxetanylmethoxy) hexane , 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3 And monofunctional oxetane compounds such as-(hydroxymethyl) oxetane and 3-ethyl-3- (chloromethyl) oxetane. These can be used alone or in combination of two or more.

  As said oxetane compound, the commercially available thing which has a cationically polymerizable monomer as a main component can be used, for example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (Maruzen Petrochemical Co., Ltd.) Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.), Etanacol OXBP, OXTP (Ube Industries, Ltd.) Etc.).

  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, 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, 1,6-cyclohexanedimethanol divinyl ether.

  In the cationic polymerizable component (A), a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more, or a glycidylated product of a polyhydric alcohol alkylene oxide adduct (A1), an aromatic epoxy compound (A2), an alicyclic epoxy compound The proportion of (A3), oxetane compound and vinyl ether compound used is glycidylated product of polyhydric alcohol or polyhydric alcohol alkylene oxide adduct having a molecular weight of 200 or more with respect to 100 parts by mass of the cationic polymerizable component (A) ( A1) 10-100 parts by mass, aromatic epoxy compound (A2) 0-50 parts by mass, alicyclic epoxy compound (A3) 0-80 parts by mass, oxetane compound 0-50 parts by mass, vinyl ether compound 0-20 parts by mass Is better in viscosity, coatability, reactivity and curability. Preferable to.

The cationic polymerization initiator (B) according to the curable composition of the present invention may be any compound as long as it can release a substance that initiates cationic polymerization by energy ray irradiation or heating. Preferably, it is a double salt that is an onium salt that releases a Lewis acid upon irradiation with energy rays, or a derivative thereof. Representative examples of such compounds include the following general formula:
[A] ^{r +} [B] ^r-
And cation and anion salts represented by the formula:

Here, the cation [A] ^{r +} is preferably onium, and the structure thereof is, for example, the following general formula:
[(R ² ) _a Q] ^{r +}
Can be expressed as

Further, R ² is an organic group having 1 to 60 carbon atoms and any number of atoms other than carbon atoms. a is an integer of 1 to 5. The a R ^{2 s} 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 a valence of zero.

The anion [B] ^r- is preferably a halide complex, and the structure thereof is, for example, the following general formula:
[LY _b ] ^r- .

Further, here, L is a metal or metalloid which is a central atom of a 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 3-7. Further, when the valence of L in the anion [B] ^r− is p, it is necessary that the relationship r = b−p holds.

Specific examples of the anion [LY _b ] ^r- of the above general formula include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF ₄ ) ⁻ , Examples include hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , hexafluoroarsenate (AsF ₆ ) ⁻ , hexachloroantimonate (SbCl ₆ ) ^{− and the} like.

Further, the anion [B] ^r- is represented by the following general formula:
[LY _b-1 (OH)] ^r-
The thing of the structure represented by can also be used preferably. L, Y, and b are the same as described above. Other anions that can be used include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , and toluenesulfonate anion. , Trinitrobenzenesulfonate anion, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.

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

  (I) Aryl diazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate

  (B) Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, and tricumyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt

  (C) sulfonium salts such as sulfonium cations and hexafluoroantimony ions, hexafluorophosphate ions, tetrakis (pentafluorophenyl) borate ions represented by the following group I or group II

<Group I>

<Group II>

Other preferable examples include (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron. -Iron-arene complexes such as hexafluorophosphate, aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum and silanols such as triphenylsilanol A mixture of thiophenium, thioranium, benzylammonium, pyridinium, hydrazinium, and the like; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine; 1,2-diaminocyclohexane, 1,4-diamino -3,6-di Cycloaliphatic polyamines such as tilcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone; the above polyamines, phenylglycidyl ether, butylglycidyl ether, bisphenol A-diglycidyl Polyepoxy addition-modified products produced by reacting various epoxy resins such as ethers, glycidyl ethers such as bisphenol F-diglycidyl ether or glycidyl esters of carboxylic acids; the above organic polyamines and phthalates An amidation-modified product produced by reacting a carboxylic acid such as acid, isophthalic acid or dimer acid by a conventional method; Mannich-modified products produced by reacting phenols having at least one aldehyde-reactive site with nuclei such as diol, cresol, xylenol, tert-butylphenol, and resorcin; Acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methyl Aliphatic dicarboxylic acids such as pentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid; phthalic acid, terephthalic acid, isophthalic acid Aromatic dicarboxylic acids such as acid and naphthalenedicarboxylic acid; cyclohexanedicarboxylic acid Alicyclic dicarboxylic acids such as: trimellitic acid, trimesic acid, trimeric acid such as trimer of castor oil fatty acid; tetracarboxylic acids such as pyromellitic acid] acid anhydrides; dicyandiamide, imidazoles, carboxylic acid ester, sulfone Examples include acid esters and amine imides.

  Among these, it is preferable to use an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-arene complex from the viewpoint of practical use and improvement of photosensitivity, and an aromatic sulfonium salt having the following structure is converted into a cationic polymerization initiator (B ) It is more preferable to contain at least 0.1% by mass with respect to 100% by mass.

ここで、式中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９およびＲ^２０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のアルコキシ基または炭素原子数２〜１０のエステル基を表し、Ｒ^２１、Ｒ^２２、Ｒ^２３およびＲ^２４は、それぞれ独立に、水素原子、ハロゲン原子または炭素原子数１〜１０のアルキル基を表し、Ｒ^２５は、水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基または下記化学式（Ａ）〜（Ｃ）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。

Here, in the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a halogen atom, or a carbon atom number. Represents 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 R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, a halogen atom, Represents an atom or an alkyl group having 1 to 10 carbon atoms, and R ²⁵ is any one selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or the following chemical formulas (A) to (C). Represents a substituent, An ^q- represents a q-valent anion, and p represents a coefficient for neutralizing the charge.

ここで、式中、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^２６、Ｒ^２７、Ｒ^２８、Ｒ^２９、Ｒ^３５、Ｒ^３６、Ｒ^３７、Ｒ^３８およびＲ^３９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のアルコキシ基または炭素原子数２〜１０のエステル基を表し、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３およびＲ^３４は、それぞれ独立に、水素原子、ハロゲン原子または炭素原子数１〜１０のアルキル基を表す。

Here, in the formula, 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 ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 carbon atom. Represents an alkoxy group having 1 to 10 carbon atoms or an ester group having 2 to 10 carbon atoms, and R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent a hydrogen atom, a halogen atom or 1 to 10 carbon atoms. Represents an alkyl group.

In the compound represented by the above general formula (1), 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, in ^{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 and ^{R 39} Examples of the halogen atom represented include fluorine, chlorine, bromine and iodine.

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 An alkyl group having 1 to 10 carbon atoms represented by R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ Is 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, -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-butoxycarbonylmethyl, ethyloxy Carbonylmethyl, 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-hydroxybutyl, 1,2-dihydroxyethyl and the like.

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 ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ , the alkoxy group having 1 to 10 carbon atoms includes methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, s-butyloxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethyloxy, 3-methoxypropyloxy, 4- Methoxybutyloxy, 2-butoxyethylo Shi, methoxyethoxyethyl oxy, methoxyethoxyethoxyethyl oxy, 3-methoxy-butyloxy, 2-methylthioethyl oxy, trifluoromethyloxy and the like.

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 ²⁶ , R ²⁷ , R ²⁸ R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ are ester groups having 2 to 10 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy, propionyl Examples include oxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, t-butylcarbonyloxy, methoxyacetyloxy, and benzoyloxy.

  The proportion of the cationic polymerization initiator (B) used relative to 100 parts by mass of the cationic polymerizable component (A), the radical polymerizable component (C), and the polymer (E) is the cationic polymerization initiator (B ) 0.001-15 parts by mass, preferably 0.1-10 parts by mass, more preferably 2-10 parts by mass. If the amount is too small, curing tends to be insufficient, and if the amount is too large, various physical properties such as the water absorption rate and the strength of the cured product may be adversely affected.

  The radical polymerizable component (C) according to the curable composition of the present invention is a compound (C1) having an epoxy group and an ethylenically unsaturated group, an acrylate ester of an alcohol having 2 to 20 carbon atoms, or the number of carbon atoms. The methacrylic acid ester (C2) of alcohol which is 2 to 20 is an essential component.

  Examples of the compound (C1) having an epoxy group and an ethylenically unsaturated group include epoxy acrylate or epoxy methacrylate. Specifically, conventionally known aromatic epoxy resins, alicyclic epoxy resins, An acrylate obtained by reacting an aliphatic epoxy resin or the like with acrylic acid or methacrylic acid. Among these epoxy acrylates or epoxy methacrylates, particularly preferred are acrylates or methacrylates of glycidyl ethers of alcohols.

  Examples of the acrylate of an alcohol having 2 to 20 carbon atoms or the methacrylate (C2) of an alcohol having 2 to 20 carbon atoms include aromatic or aliphatic alcohols having at least one hydroxyl group in the molecule, and alkylene thereof Examples thereof include acrylates or methacrylates obtained by reacting an oxide adduct with acrylic acid or methacrylic acid. Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, benzyl acrylate, 1,3 -Butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, Trimethylolpropane triacrylate, pentaerythritol tetraa Relate, dipentaerythritol hexaacrylate, ε-caprolactone modified dipentaerythritol hexaacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, isoamyl methacrylate, lauryl methacrylate, stearyl methacrylate, isooctyl methacrylate, tetrahydrofur Furyl methacrylate, isobornyl methacrylate, benzyl methacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol Dimethacrylate, polyethylene Glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, ε-caprolactone modified dipentaerythritol hexamethacrylate, and the like. Of these acrylates or methacrylates, polyhydric alcohol polyacrylates or polyhydric alcohol polymethacrylates are particularly preferred.

  As the radically polymerizable component (C), a compound that is polymerized or cross-linked by a radical polymerization initiator activated by energy ray irradiation or heating other than (C1) or (C2) can be used. Examples include urethane compounds, unsaturated polyester compounds, and styrene compounds. The proportion of the component (C1) and the component (C2) in the radical polymerizable component (C) is preferably 50% by mass or more.

  There is no restriction | limiting in particular as a radical initiator (D) which concerns on the curable composition of this invention, A well-known thing can be used. For example, ketone compounds such as acetophenone compounds, benzyl compounds, benzophenone compounds, and thioxanthone compounds, oxime compounds, and the like can be used.

  The polymer (E) according to the curable composition of the present invention is a polymer obtained from the monomer represented by the above formula (I), a polymer obtained from the monomer represented by the above formula (II), Polymer obtained from two or more monomers selected from monomers represented by formula (I), two or more monomers selected from monomers represented by formula (II) Selected from the group consisting of a polymer obtained from the above, a monomer represented by the above formula (I) and a polymer obtained from the monomer represented by the above formula (II), and the weight average molecular weight is in terms of polystyrene 1,000 to 30,000.

  Examples of the alkyl group having 1 to 7 carbon atoms represented by X in the formula (I) include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, Examples 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 1 to 1 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 4 alkyl groups are preferable from the viewpoint of curability.

  Examples of the alkoxy group having 1 to 7 carbon atoms represented by X in the formula (I) include methoxy, ethoxy, propyloxy, iso-propyloxy, butyloxy, sec-butyloxy, tert-butyloxy, iso-butyloxy, Amyloxy, iso-amyloxy, tert-amyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, and tert-heptyloxy. Among these, an alkoxy group having 1 to 4 carbon atoms, or 1 to 1 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 4 alkoxy groups are preferred 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, naphthyloxy and the like.

  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, tricyclooctyl. , Tricyclodecanyl, spirooctyl, spirobicyclopentyl, adamantyl, isobornyl and the like.

  These alkyl group, alkoxy group, aryl group, aryloxy group, and alicyclic hydrocarbon group are selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group, and a carboxyl group in which the hydrogen atom in these groups is 1 It may be substituted with more than one group.

  In the above formula (I), when a part of X is substituted with an epoxy group or an oxetane group, examples of the monomer represented by formula (I) include the following formulas (1) to (3): The monomer represented by these is mentioned.

ここで、式（１）中、Ｒ^３は、水素原子または炭素原子数１〜６のアルキル基を表し、ｍは、１〜６の整数である。

Here, in Formula (1), R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m is an integer of 1 to 6.

ここで、式（２）中、Ｒ^４は、水素原子または炭素原子数１〜６のアルキル基を表し、ｎは、１〜６の整数である。

Here, in formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.

ここで、式（３）中、Ｒ^５は、水素原子または炭素原子数１〜６のアルキル基を表し、ｓは、１〜６の整数である。

Here, in formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and s is an integer of 1 to 6.

In the above formula (II), examples of the halogen atom represented by R ¹ include fluorine, chlorine, bromine and iodine.

  In the above formula (II), the alkyl group having 1 to 7 carbon atoms, the aryl group having 6 to 12 carbon atoms, or the alicyclic hydrocarbon group having 6 to 10 carbon atoms in X ′ is represented by the above formula (I ).

  In the above formula (II), when a part of X ′ is substituted with an epoxy group or an oxetane group, the monomer represented by formula (II) is represented by the following formulas (4) to (6). What is represented.

ここで、式（４）中、Ｒ^１は、上記式（ＩＩ）と同じであり、Ｒ^６は、水素原子または炭素原子数１〜６のアルキル基を表し、ｔは、１〜６の整数である。

Here, in the formula (4), R ¹ is the same as in the above formula (II), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and t is an integer of 1 to 6 It is.

ここで、式（５）中、Ｒ^１は、上記式（ＩＩ）と同じであり、Ｒ^７は、水素原子または炭素原子数１〜６のアルキル基を表し、ｑは、１〜６の整数である。

Here, in the formula (5), R ¹ is the same as in the above formula (II), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and q is an integer of 1 to 6. It is.

ここで、式（６）中、Ｒ^１は、上記式（ＩＩ）と同じであり、Ｒ^８は、水素原子または炭素原子数１〜６のアルキル基を表し、ｙは、１〜６の整数である。

Here, in the formula (6), R ¹ is the same as the formula (II), R ⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and y is an integer of 1 to 6. It is.

  In the polymer (E), the proportion of the monomer constituting the polymer is such that X is a carbon substituted with one or more groups selected from the group consisting of epoxy groups, oxetane groups, hydroxyl groups and carboxyl groups. In the case of an alkyl group having 1 to 7 atoms, an aryl group having 6 to 12 carbon atoms, or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, the unit represented by the above (I) or (II) It is preferable to use the polymer in an amount of 10 to 100% by mass because the adhesiveness is improved.

  In the curable composition of the present invention, the total amount of the cationic polymerizable component (A), the radical polymerizable component (C), and the polymer (E) is 100 parts by mass, and the cationic polymerizable component (A ) Is 1 to 50 parts by mass, the cationic polymerization initiator (B) is 1 to 10 parts by mass, the radical polymerizable component (C) is 40 to 90 parts by mass, and the radical polymerization initiator (D) is 1 to 10 parts. It is preferable that the mass and the polymer (E) are 1 to 20 parts by mass because the cured product has good curability and adhesion.

  If necessary, the curable composition of the present invention may further contain a sensitizer and / or a sensitization aid. 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 sensitization aid is a compound that further promotes the action of the sensitizer.

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

  As an anthracene type compound, what is represented by following formula (7) is mentioned, for example.

ここで、式（７）中、Ｒ^５０およびＲ^５１は、各々独立に水素原子、炭素原子数１〜６のアルキル基または炭素原子数２〜１２のアルコキシアルキル基を表し、Ｒ^５２は水素原子または炭素原子数１〜６のアルキル基を表す。

Here, in Formula (7), R ⁵⁰ and R ⁵¹ each 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 ⁵² represents a hydrogen atom. Alternatively, it represents an alkyl group having 1 to 6 carbon atoms.

  Specific examples of the anthracene compound represented by the above formula (7) include the following compounds.

  For example, 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-dipropoxyanthrace 2-methyl- or 2-ethyl-9,10-diisopropoxyanthracene, 2-methyl- or 2-ethyl-9,10-dibutoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipentyl Examples include oxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene.

  As a naphthalene-type compound, what is represented by following formula (8) is mentioned, for example.

ここで、式（８）中、Ｒ^５３およびＲ^５４は各々独立に炭素原子数１〜６のアルキル基を表す。

Here, in Formula (8), R ⁵³ and R ⁵⁴ each independently represents an alkyl group having 1 to 6 carbon atoms.

  Specific examples of the naphthalene compound represented by the above formula (8) include the following compounds.

  For example, 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyloxy-1-naphthol, 1,4-dimethoxynaphthalene, Examples include 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, 1,4-dibutoxynaphthalene, and the like.

  The use ratio of the sensitizer and the sensitization aid to the cationic polymerizable component (A) is not particularly limited, and may be used at a generally normal use ratio within a range not inhibiting the purpose of the present invention. It is preferable from a viewpoint of sclerosis | hardenability improvement that it is 0.1-3 mass parts of each of a sensitizer and a sensitization adjuvant with respect to 100 weight part of the said cation polymeric components (A).

  A silane coupling agent can be used for the curable composition of this invention as needed. Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkyl-functional alkoxysilanes, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and other alkenyl-functional alkoxysilanes, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ Epoxy functional alkoxysilanes such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl) -γ Aminofunctional alkoxysilanes such as aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, titanium Titanium alkoxides such as tetraisopropoxide and titanium tetranormal butoxide, titanium chelates such as titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethyl acetoacetate), zirconi Arm tetraacetyl acetonate, zirconium chelates such as zirconium tributoxy monoacetylacetonate, zirconium acylates such as zirconium tributoxy monostearate, an isocyanate silane such as methyl triisocyanate silane.

  Although the usage-amount of the said silane coupling agent is not specifically limited, Usually, it is the range of 0.01-20 mass parts with respect to 100 mass parts of whole quantity of the solid substance in a curable composition.

  In the curable composition of the present invention, the properties of the cured product can be improved by using a thermoplastic organic polymer as 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, styrene- (meth) acrylic acid copolymer, Examples include (meth) acrylic acid-methyl methacrylate copolymer, glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.

  In the curable composition of the present invention, if necessary, the UV-absorbing agent is inactivated at room temperature, and the protective group is released by heating to a predetermined temperature, light irradiation, acid, etc. and activated. In addition, a compound exhibiting ultraviolet absorbing ability can also be used.

  In addition, as long as the effects of the present invention are not impaired, coloring agents such as polyols, inorganic fillers, organic fillers, pigments, dyes, antifoaming agents, thickeners, surfactants, leveling agents, difficulty Various resin additives such as flame retardants, thixotropic agents, diluents, plasticizers, stabilizers, polymerization inhibitors, UV absorbers, antioxidants, antistatic agents, flow regulators, adhesion promoters, etc. may be added. it can.

  The curable composition of the present invention is not particularly limited, and a solvent that can dissolve or disperse the components (A), (B), (C), (D) and (E) which are usually used is used. Can do. Examples of the solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1 Ether solvents such as 1,2-diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, succinic acid Ester solvents such as dimethyl and texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso Or alcohol solvents such as 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 ester solvents such as ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene hydrocarbon oils such as D-limonene and pinene; mineral spirit, Swazol # 310 (manufactured by Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.), etc. Paraffin solvents: Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Propylene carbonate, Carbitol solvents Aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water and the like. These solvents can be used as one or a mixture of two or more.

  In the curable composition of the present invention, the water content is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less, because the curability, adhesiveness, and liquid storage stability are improved. Too much moisture is not preferred because it may cause cloudiness or components may precipitate.

  The curable composition of the present invention is applied onto a supporting substrate by a known means such as a roll coater, a curtain coater, various types of printing, and immersion. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

  The material for the support substrate is not particularly limited and may be any commonly used material, such as inorganic materials such as glass; diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetylpropionyl. 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 and polybutylene terephthalate; polystyrene; polyethylene, polypropylene, polymethylpentene Polyolefins; Vinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; Acrylic resins such as polymethyl methacrylate and polyacrylate; Polycarbonate; Polysulfone; Polyethersulfone; Polyetherketone; Polyetherimide; , Polymer materials such as norbornene resin and cycloolefin polymer (COP). 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 energy rays, examples of energy rays include ultraviolet rays, electron beams, X-rays, radiation, high frequencies, and the like, and ultraviolet rays are most preferable economically. 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. and 1 to 100 minutes. After pre-baking (PAB), pressurization and post-baking (PEB) may be performed, or baking may be performed 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, in order to cure the coating film, a cured film can be obtained by heat treatment at 180 to 250 ° C., preferably 200 to 250 ° C., for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate.

  Specific applications of the curable composition of the present invention or a cured product thereof include adhesives, glasses, optical materials represented by imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, printing Plates, color TVs, PC monitors, personal digital assistants, digital cameras, organic EL, touch panels and other display elements, insulating varnishes, insulating sheets, laminates, printed boards, semiconductor devices, LED packages, liquid crystal inlets, organic Sealants for EL, optical elements, electrical insulation, electronic parts, separation membranes, molding materials, putty, glass fiber impregnating agents, sealants, passivation films for semiconductors and solar cells, interlayers Insulating film, protective film, prism lens sheet used for backlight of liquid crystal display device, Fresnellen used for screen of projection TV, etc. A lens, a lens part of a lens sheet such as a lenticular lens sheet, or a backlight using such a sheet, an optical lens such as a microlens, an optical element, an optical connector, an optical waveguide, an optical molding casting agent, etc. Can be mentioned.

  As a display device, 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 coating layer, a lubricating layer, a protective layer, etc., as necessary The film which consists of hardened | cured material of this invention can be used for each layer.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

[Examples 1-5, Comparative Examples 1-3]
The components shown in [Table 1] and [Table 2] below were mixed thoroughly to obtain curable compositions of Examples 1 to 5 and Comparative Examples 1 to 3, respectively. In addition, the unit of an Example and a comparative example is a mass part.

The following compounds (A1-1) to (A1-4) and (A3-1) were used as the cationic polymerizable component (A).
Compound A1-1: Adeka Resin EP-4088L (manufactured by ADEKA Corporation)
Compound A1-2: Hydrogenated bisphenol A diglycidyl ether Compound A1-3: 1,4-butanediol diglycidyl ether Compound A3-1: Celoxide 2021P (alicyclic epoxy: manufactured by Daicel Corporation)

The following compound (B-1) was used as the cationic polymerization initiator (B).
Compound B-1: A 50% solution of propylene carbonate in a mixture of a compound represented by the following formula (9) and a compound represented by the following formula (10)

The following compound (C2-1) was used as the radical polymerizable component (C).
Compound (C2-1): 1,6-hexanediol diacrylate

The following compound (D-1) was used as the radical polymerization initiator (D).
Compound (D-1): Irgacure 184 (manufactured by BASF)

As the polymer (E), the following compound (E-1) was used.
Compound (E-1): A copolymer of 75 parts by mass of methyl methacrylate and 25 parts by mass of glycidyl methacrylate (weight average molecular weight 7,000)
Polymer (E-2): copolymer of 35 parts by mass of methyl methacrylate, 35 parts by mass of styrene and 30 parts by mass of glycidyl methacrylate (weight average molecular weight 8,000)

  About each curable composition of obtained Examples 1-6 and Comparative Examples 1 and 2, according to the following procedure, evaluation of glass transition temperature (Tg), an elasticity modulus, adhesiveness (COP), and adhesiveness (TAC). Went. The results are shown in [Table 1] and [Table 2].

(Glass transition temperature and elastic modulus)
Each of the obtained curable compositions of Examples 1 to 5 and Comparative Examples 1 to 3 was applied on a polyethylene terephthalate (PET) film to a thickness of 30 μm with a bar coater, and 3000 mJ using a metal halide lamp. / Cm ² of energy was irradiated. After 24 hours, the cured adhesive was taken out from the film, and the elastic modulus at Tg and 80 ° C. was measured using a viscoelasticity measuring device (DMA7100) manufactured by Hitachi High-Tech Science Co., Ltd.

(viscosity)
About each of the obtained curable composition of Examples 1-5 and Comparative Examples 1-3, the viscosity in 25 degreeC was measured with the E-type viscosity meter. The results are shown in [Table 1] and [Table 2].

(Adhesion: COP)
The curable compositions of Examples 1 to 5 and Comparative Examples 1 to 3 obtained above were applied to one corona-treated PMMA film (Sumitomo Chemical Co., Ltd .: Technoloy 125S001), and then another corona. A COP (cycloolefin polymer, manufactured by Nippon Zeon: product number ZEONOR film 14-060) film and a laminator were bonded together using a discharge process, and light corresponding to 1000 mJ / cm ² was applied using an electrodeless ultraviolet lamp. The test piece was obtained by irradiating and bonding. The obtained test piece was subjected to a 90 degree peel test. The results are shown in [Table 1] and [Table 2].

  From [Table 1] and [Table 2], it is clear that the curable composition of the present invention has a high glass transition temperature and excellent adhesion.

Claims (7)

Cationic polymerizable component (A), cationic polymerization initiator (B), radical polymerizable component (C), radical polymerization initiator (D), the following formula (I),

(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. The alicyclic hydrocarbon group of several 6 to 10 or a hydrogen atom in these groups is substituted with one or more groups selected from the group consisting of epoxy group, oxetane group, hydroxyl group and carboxyl group A polymer obtained from a monomer represented by the formula (II):

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a halogen atom, and X ′ represents an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 6 to 10 carbon atoms. An alicyclic hydrocarbon group, or a hydrogen atom in these groups is substituted with one or more groups selected from the group consisting of epoxy groups, oxetane groups, hydroxyl groups and carboxyl groups). A polymer obtained from two or more kinds of monomers selected from the monomers represented by the formula (I), a monomer represented by the formula (II) From the group consisting of a polymer obtained from two or more selected monomers, a monomer represented by the formula (I) and a polymer obtained from the monomer represented by the formula (II) Selected weight average molecular weight 1,000-30, Containing 00 at which the polymer (E),
The cation polymerizable component (A) is a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more or a glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct,
The radical polymerizable component (C) is an epoxy group and an ethylenically unsaturated group compound (C1), an acrylate ester of an alcohol having 2 to 20 carbon atoms, or an alcohol having 2 to 20 carbon atoms. A curable composition comprising methacrylic acid ester (C2) as an essential component.   2. The curable composition according to claim 1, wherein the polyhydric alcohol in the glycidylation product of a polyhydric alcohol having a molecular weight of 200 or more or the glycidylation product (A1) of a polyhydric alcohol alkylene oxide adduct is a polyhydric alcohol having a condensed ring. .   The polymer (E) is a polymer obtained from the monomer represented by the formula (I) and the monomer represented by the formula (II), wherein X in the formula (I) is: 2. An aryl group having 6 to 12 carbon atoms, wherein X ′ in the formula (II) is an alkyl group having 1 to 7 carbon atoms, and the alkyl group is substituted with an epoxy group. Or the curable composition of 2.   1 to 50 parts by mass of the cationic polymerizable component (A), 1 to 10 parts by mass of the cationic polymerization initiator (B), 40 to 90 parts by mass of the radical polymerizable component (C), and the radical polymerization initiator. (D) is 1 to 10 parts by mass, the polymer (E) is 1 to 20 parts by mass, the cationic polymerizable component (A), the radical polymerizable component (C), and the polymer (E) The sum total of these is 100 mass parts, The curable composition as described in any one of Claims 1-3.   A curing method for a curable composition, wherein the curable composition according to any one of claims 1 to 4 is irradiated with an active energy ray.   A method for curing a curable composition, comprising heating the curable composition according to any one of claims 1 to 4. Hardened | cured material characterized by being the hardened | cured material of the curable composition as described in any one of Claims 1-4.