JP6883021B2 - Curable composition, method for producing cured product, and cured product thereof - Google Patents

Description

The present invention relates to a curable composition, a method for producing a cured product, and a cured product thereof. Specifically, the present invention relates to a curable composition having a high glass transition temperature of the cured product and excellent adhesion, a method for producing the cured product, and the like. Regarding cured products.

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

For example, Patent Documents 1 to 3 below propose an energy ray-curable composition containing a cationically polymerizable component and a radically polymerizable component, or a cured product thereof. For example, Patent Document 1 proposes an adhesive composition for a polarizing plate having excellent initial curability and adhesiveness. Further, in Patent Document 2, the activity for plastic films, etc., which has low viscosity, is excellent in curability, is excellent in adhesive strength to various plastic films, etc. even if the atmospheric humidity at the time of coating and curing is high, and is also excellent in colorless transparency. Energy ray-curable adhesive compositions have been proposed. Further, in Patent Document 3, for plastic films and the like having low viscosity, excellent curability, excellent adhesive strength to various plastic films including (meth) acrylic resin and cycloolefin polymer, and excellent colorless transparency. Active energy ray-curable adhesive compositions have been proposed.

Japanese Unexamined Patent Publication No. 2014-105218 Japanese Unexamined Patent Publication No. 2015-057467 Japanese Unexamined Patent Publication No. 2015-229744

However, even the curable compositions proposed in Patent Documents 1 to 3 may not always be satisfactory in terms of curability and adhesion, and the curability and adhesion should be highly compatible with each other. At present, there is a demand for a new curable composition capable of producing the same.

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

As a result of diligent studies to solve the above problems, the present inventors have found that a curable composition having a specific composition can solve the above problems, and have 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得られるポリマー、または前記式（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であって、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種以上の基を有するポリマー（Ｅ）１〜３０質量部とを、前記カチオン重合性成分（Ａ）と前記ラジカル重合性成分（Ｃ）と前記ポリマー（Ｅ）との合計が１００質量部となるように含有し、
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）と、脂環式エポキシ化合物（Ａ２）と、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）を含み、かつ、
前記分子量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）が、飽和縮合環を有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 contains 30 to 99 parts by mass of the cationically polymerizable component (A), 0.1 to 10 parts by mass of the cationic polymerization initiator (B), and 0 to 0 to 10 parts by mass of the radically polymerizable component (C). 55 parts by mass, radical polymerization initiator (D) 0 to 10 parts by mass, 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. 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. A polymer obtained from a monomer represented by (is), the following formula (II),

(In the formula, R ¹ 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). From a polymer obtained from the above-mentioned monomer, a polymer obtained from two or more kinds of monomers selected from the above-mentioned monomer represented by the formula (I), and the above-mentioned monomer represented by the formula (II). Select from the group consisting of polymers obtained from two or more selected monomers, or polymers obtained from the monomer represented by the formula (I) and the monomer represented by the formula (II). A polymer (E) having a weight average molecular weight of 1,000 to 30,000 and having one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group and 1 to 30 parts by mass of the polymer (E). Is contained so that the total of the cationically polymerizable component (A), the radically polymerizable component (C), and the polymer (E) is 100 parts by mass.
The cationically polymerizable component (A) is an essential component of a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more, a glycidylated product of a polyhydric alcohol alkylene oxide adduct (A1), and an alicyclic epoxy compound (A2). age,
The radically polymerizable component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, an acrylic acid ester of an alcohol having 2 to 20 carbon atoms, or an alcohol having 2 to 20 carbon atoms. Contains methacrylic acid ester (C2) and
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, is characterized by having a saturated condensed ring. Here, the weight average molecular weight means 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 polyhydric alcohol in 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 fused ring. It is preferable to have. Further, in the curable composition of the present invention, the alicyclic epoxy compound (A2) is 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 7-oxabicyclo [4.1]. .0] heptane, bishexanoate bis [(7-oxabicyclo [4.1.0] heptane-3-yl) methyl], 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethylmetha It is preferably one or more selected from the group consisting of acrylate and limonendioxide. Further, 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.

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 characterized by being a cured product of the curable composition of the present invention.

According to the present invention, it is possible to provide a curable composition having a high glass transition temperature of a cured product and excellent adhesion, a method for producing a cured product, and a cured product thereof. 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 30 to 99 parts by mass of the cationically polymerizable component (A), 0.1 to 10 parts by mass of the cationic polymerization initiator (B), and 0 to 55 parts by mass of the radically polymerizable component (C). Parts, 0 to 10 parts by mass of the radical polymerization initiator (D), a polymer obtained from a monomer represented by the following formula (I), and a polymer obtained from a monomer represented by the following formula (II). , A polymer obtained from two or more types of monomers selected from the monomers represented by the following formula (I), and two or more types of singles selected from the monomers represented by the following formula (II). A weight average molecular weight of 1,000 selected from the group consisting of a polymer obtained from a polymer, or a polymer obtained from a monomer represented by the following formula (I) and a monomer represented by the following formula (II). 1 to 30 parts by mass of the polymer (E), which is ~ 30,000, is contained so that the total of the component (A), the component (C) and the component (E) is 100 parts by mass. In the curable composition of the present invention, the cationically polymerizable component (A) is a glycidyl compound of a polyhydric alcohol having a molecular weight of 200 or more, or a glycidyl compound (A1) of a polyhydric alcohol alkylene oxide adduct, and an alicyclic epoxy. The compound (A2) is an essential component, and the radically polymerizable component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylic acid ester of an alcohol having 2 to 20 carbon atoms. Alternatively, an alcohol methacrylic acid ester (C2) having 2 to 20 carbon atoms is an essential component.

ここで、式（Ｉ）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 (I), 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, and an aryl group having 6 to 12 carbon atoms. An oxy group or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or one or more groups in which the hydrogen atom in these groups is selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group. It has been replaced.

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

The cationically polymerizable component (A) according to the curable composition of the present invention is a compound that undergoes a polymerization or cross-linking reaction by a cationic polymerization initiator activated by energy ray irradiation or heating. Epoxy compounds, oxetane compounds, vinyl ether compounds and the like can be mentioned.

The cationically polymerizable component (A) according to the curable composition of the present invention 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, and an alicyclic epoxy compound. Although (A2) is an essential component, an aromatic epoxy compound (A3) or the like can also be used as the other epoxy compound. The ratio of the (A1) component and the (A2) component in the cationically polymerizable component (A) is preferably 90% by mass or more.

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

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

As glycidylated products of polyhydric alcohols or glycidylated products (A1) of polyhydric alcohol alkylene oxide adducts, monoglycidyl ethers of aliphatic higher alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, and octyl epoxide stearate are further used. , Butyl epoxide stearate, epoxidized soybean oil, epoxidized polybutadiene and the like.

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

As 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, commercially available products can be used, for example, Denacol EX-121 and 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-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 Glycyllol ED-503 , Adeka Glycyrrol ED-503G, Adeka Glycyrrol ED-506, Adeka Glycyrrol ED-523T, Adeka Resin EP-4088S, Adeka Resin EP-4080E (manufactured by ADEKA Corporation) and the like.

The alicyclic epoxy compound (A2) refers to a compound in which an oxylane ring is directly formed on a saturated ring without a bonding group. As a specific example of the alicyclic epoxy compound (A2), it is obtained by epoxidizing a polyglycidyl etherified compound of a polyhydric alcohol having at least one alicyclic ring or a compound containing cyclohexene or cyclopentene ring with an oxidizing agent. Cyclohexene oxide and cyclopentene oxide-containing compounds can be mentioned. For example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4 -Epoxy Cyclohexylmethyl-6-Methyl-3,4-Epoxycyclohexanecarboxylate, 3,4-Epoxy-3-methylcyclohexanemethyl-3,4-Epoxy-3-methylcyclohexanecarboxylate, 3,4-Epoxy-5 -Methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxy) Cyclohexane), Propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadiene diepoxyside, ethylenebis (3,4-epoxy) Cyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene Examples thereof include oxidase and limonendioxide. Examples of the alicyclic epoxy compound (A2) 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 (A2), a commercially available product can be used, and examples thereof include celoxide 2021P, celoxide 2081, celoxide 2000, and celoxide 3000 (manufactured by Daicel Corporation).

The aromatic epoxy compound (A3) refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound include polyhydric phenol having at least one aromatic ring such as phenol, cresol, and butylphenol. , A mono / polyglycidyl etherified product of the alkylene oxide adduct, for example, bisphenol A, bisphenol F, or a glycidyl etherified product or an epoxynovolac resin of a compound obtained by further adding an alkylene oxide to these; two such as resorcinol, hydroquinone, and catechol. Mono / polyglycidyl etherified product of the above aromatic compound having a phenolic hydroxyl group; glycidyl etherified product of an aromatic compound having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol, and phenyldibutanol; phthalic acid, terephthalate Examples thereof include glycidyl ester of a polybasic acid aromatic compound having two or more carboxylic acids such as acid and trimellitic acid, glycidyl ester of benzoic acid, and an epoxidized product of styrene oxide or divinylbenzene.

As the aromatic epoxy compound (A3), 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 Co., Ltd.) (Manufactured by); ESN-475V (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.); Epicoat YX8800 (manufactured by Mitsubishi Chemical Co., Ltd.); Marproof G-0105SA, Marproof G-0130SP (manufactured by Nichiyu Co., Ltd.); Epicron N-665, Epicron HP-7200 (manufactured by DIC Co., Ltd.); 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.); Adecaledin EP-4000, Adecaledin EP-4005, Adecaledin EP-4100, Adecaledin EP-4901 (manufactured by ADEKA Co., Ltd.); (Manufactured by Printec Co., Ltd.) and the like. As the aromatic epoxy compound, a polyfunctional one is preferable because it has excellent curability.

Examples of the oxetane compound include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, and 1,2-bis [(. 3-Ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, triethylene Glycolbis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycolbis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6 Bifunctional aliphatic oxetane compounds such as −bis (3-ethyl-3-oxetanylmethoxy) hexane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3 Examples thereof include monofunctional oxetane compounds such as −ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, and 3-ethyl-3- (chloromethyl) oxetane. These can be used individually by 1 type or in combination of 2 or more types.

As the oxetane compound, a commercially available product containing 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.) (Manufactured by); Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-111, OXT-212 (manufactured by Toa Synthetic Co., Ltd.), Etanacol OXBP, OXTP (Ube Industries, Ltd.) (Manufactured by the company) and the like.

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

In the cationically polymerizable component (A), a glycidylated product of a polyvalent alcohol having a molecular weight of 200 or more or a glycidylated product of a polyhydric alcohol alkylene oxide adduct (A1), an alicyclic epoxy compound (A2), an aromatic epoxy compound ( The ratio of A3), the oxetane compound and the vinyl ether compound to 100 parts by mass of the cationically polymerizable component (A) is 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). ) 10 to 99 parts by mass, alicyclic epoxy compound (A2) 1 to 50 parts by mass, aromatic epoxy compound (A3) 0 to 80 parts by mass, oxetane compound 0 to 50 parts by mass, vinyl ether compound 0 to 20 parts by mass, Is preferable because it improves viscosity, coatability, reactivity and curability.

The cationic polymerization initiator (B) according to the curable composition of the present invention may be any compound capable of releasing a substance that initiates cationic polymerization by irradiation with energy rays or heating. , Preferably a double salt, which is an onium salt that releases Lewis acid upon irradiation with 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, 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.
[LY _b ] ^r-
Can be represented by.

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 tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF ₄ ) ^- , Hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , hexafluoroarsenate (AsF ₆ ) ⁻ , hexachloroantimonate (SbCl ₆ ) ^{− and the} like can be mentioned.

The anion [B] ^r- is expressed by the following general formula.
[LY _b-1 (OH)] ^r-
The structure represented by is also preferably used. L, Y, b are the same as above. Other anions that can be used include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonic acid ion (FSO ₃ ) ⁻ , and toluene sulfonic acid anion. , Trinitrobenzene sulfonic acid anion, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctanesulfonate, 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. From these, one of them can be used alone, or two or more of them can be mixed and used.

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

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

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

<Group I>

<Group II>

Also, those other preferred, (eta ^{5-2,4-cyclopentadiene-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 (salitylaldehidato) aluminum, and silanols such as triphenylsilanol. Mixtures of; salts such as thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, hydrazinium salt; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine; 1,2-diaminocyclohexane, 1,4-diamino Alicyclic polyamines such as -3,6-diethylcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylene diamine, diaminodiphenylmethane and diaminodiphenylsulfone; Polyepoxy addition-modified product produced by reacting with various epoxy resins such as glycidyl ethers such as bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether or glycidyl esters of carboxylic acid by a conventional method; the above organic Amidation modified products produced by reacting polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimeric acid by a conventional method; the above polyamines and aldehydes such as formaldehyde and phenols, cresols, xylenols, etc. Mannig-modified products produced by reacting tributylphenol, resorcin and other phenols having at least one aldehyde reaction-reactive site with a nucleus by a conventional method; polyvalent carboxylic acids (succinic acid, malonic acid, succinic acid). , Glutalic acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladiponic acid, 3-methyladiponic acid, 3-methylpentanedioic acid, 2-methyl Aliphatic dicarboxylic acids such as octanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid; phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc. Aromatic dicarboxylic acids; cyclohexanedicarbo Alicyclic dicarboxylic acids such as acids; tricarboxylic acids such as trimellitic acid, trimesic acid, trimer of castor oil fatty acid; tetracarboxylic acids such as pyromellitic acid) acid anhydrides; dicyandiamides, imidazoles, carboxylic acid esters , Sulphonic acid ester, amineimide and the like.

Among these, from the viewpoint of practical use and improvement of photosensitivity, it is preferable to use an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-alene complex, and an aromatic sulfonium salt having the following structure is used as 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 independently hydrogen atoms, halogen atoms, and carbon atoms, respectively. It represents an alkyl group of 1 to 10, 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 are independently hydrogen atoms and halogens, respectively. represents an atom or an alkyl group having 1 to 10 carbon ^{atoms, R 25} is a hydrogen atom, a halogen atom, an alkyl group, or the following chemical formula 1 to 10 carbon atoms (a) ~ one selected from (C) It 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 independently hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms and 1 carbon atom. Represents an alkoxy group of 10 or an ester group of 2 to 10 carbon atoms, and R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ independently represent hydrogen atoms, halogen atoms or 1 to 10 carbon atoms, respectively. Represents the alkyl group of.

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 , 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 represented halogen atom include fluorine, chlorine, bromine, iodine 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 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 as alkyl groups with 1 to 10 carbon atoms. Methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3- Methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl , Bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tridecafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl , Methoxymethyl, 1,2-epoxyethyl, methoxyethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, t-butylthiomethyl, 4-pentenyloxymethyl, trichloroethoxymethyl, bis (2-chloroethoxy) Methyl, methoxycyclohexyl, 1- (2-chloroethoxy) ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl, trimethylsilylethyl, t-butyldimethylsilyloxymethyl, 2- (trimethylsilyl) ethoxymethyl, t-butoxy Carbonylmethyl, ethyloxycarbonylmethyl, ethylcarbonylmethyl, t-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl, acetylethyl, 2-methoxy-1-propenyl, hydroxymethyl , 2-Hydroxyethyl, 1-Hydroxyethyl, 2-Hydroxypropyl, 3-Hydroxypropyl, 3-Hydroxybutyl, 4-Hi Examples thereof include droxybutyl and 1,2-dihydroxyethyl.

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 , as alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, s-butyloxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethyloxy, 3-methoxypropyloxy, 4- Examples thereof include methoxybutyloxy, 2-butoxyethyloxy, methoxyethoxyethyloxy, methoxyethoxyethoxyethyloxy, 3-methoxybutyloxy, 2-methylthioethyloxy, 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 as ester groups with 2 to 10 carbon atoms include methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy and propionyl. Examples thereof include oxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, t-butylcarbonyloxy, methoxyacetyloxy, benzoyloxy and the like.

The ratio of the cationic polymerization initiator (B) to 100 parts by mass in total of the component (A), the component (C) and the component (E) is 0.1 to 10 parts by mass, preferably 0.1 to 10 parts by mass of the cationic polymerization initiator (B). 1 to 6 parts by mass. If it is too small, curing tends to be insufficient, and if it is too large, it may adversely affect various physical properties such as the water absorption rate of the cured product and the strength of the cured product.

The radically polymerizable component (C) according to the curable composition of the present invention is a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylic acid ester of an alcohol having 2 to 20 carbon atoms or an alcohol having 2 to 20 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 and epoxy methacrylate. Specific examples thereof include conventionally known aromatic epoxy resins and alicyclic epoxy resins. It is an acrylate obtained by reacting an aliphatic epoxy resin or the like with acrylic acid or methacrylic acid. Of these epoxy acrylates or epoxy methacrylates, particularly preferred are acrylates or methacrylates of glycidyl ethers of alcohols.

As the acrylate of the alcohol having 2 to 20 carbon atoms or the methacrylate (C2) of the alcohol having 2 to 20 carbon atoms, an aromatic or aliphatic alcohol having at least one hydroxyl group in the molecule, and an 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, isobonyl 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, Trimethylol propantriacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ε-caprolactone-modified dipentaerythritol hexaacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, isoamyl methacrylate, lauryl methacrylate, Stearyl methacrylate, isooctyl methacrylate, tetrahydrofurfuryl methacrylate, isobonyl 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, trimethylpropantrimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, ε-caprolactone-modified dipentaerythritol hexamethacrylate, etc. Can be mentioned. Of these acrylates or methacrylates, polyacrylates of polyhydric alcohols or polymethacrylates of polyhydric alcohols are particularly preferable.

As the radically polymerizable component (C), a compound other than (C1) or (C2) that undergoes a polymerization or cross-linking reaction with a radical polymerization initiator activated by energy ray irradiation or heating can also be used, for example, allyl. Examples thereof include urethane compounds, unsaturated polyester compounds, and styrene compounds. The ratio of the component (C1) and the component (C2) in the radically polymerizable component (C) is preferably 50% by mass or more.

The radical initiator (D) according to the curable composition of the present invention is not particularly limited, and known radical initiators can be used. For example, a ketone compound such as an acetophenone compound, a benzyl compound, a benzophenone compound, a thioxanthone compound, an oxime compound, or the like can be used.

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

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 alkoxy group having 1 to 4 carbon atoms or one 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 has 1 to 1 carbon atoms. 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.

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

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.

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 the 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 the 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 the 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), the halogen atom represented by R ^1, fluorine, chlorine, bromine, and iodine.

In the above formula (II), the alkyl group having 1 to 7 carbon atoms of X', the aryl group having 6 to 12 carbon atoms, or the alicyclic hydrocarbon group having 6 to 10 carbon atoms is described in the above formula (I). ) Can be mentioned.

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.

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 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. 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 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. 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 above 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. Is.

In the polymer (E), the proportion of the monomer constituting the polymer is such that X 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. When it is 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, it is simply represented by (I) or (II) above. It is preferable to use it so that the weight is 10 to 100% by mass because the adhesiveness is improved.

In the curable composition of the present invention, the cationically polymerizable component (A) is 30 to 99 parts by mass, preferably 40 to 95 parts by mass, and the cationic polymerization initiator (B) is 0.1 to 10 parts by mass. Preferably, 1 to 8 parts by mass, the radically polymerizable component (C) is 0 to 55 parts by mass, and the radical polymerization initiator (D) is 0 to 10 parts by mass, preferably 0.1 to 8 parts by mass. The polymer (E) is 1 to 30 parts by mass. If the blending ratio is other than the above, the curability and adhesion of the cured product may deteriorate.

Further, a sensitizer and / or a sensitizing 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 cationic polymerization initiator (B) and promotes the polymerization initiation reaction by the cationic polymerization initiator (B). The sensitizer is a compound that further promotes the action of the sensitizer.

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

Examples of the anthracene-based compound include those represented by the following formula (7).

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 the formula (7), R ⁵⁰ and R ⁵¹ independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy alkyl group having 2 to 12 carbon atoms, and R ⁵² is a hydrogen atom. Alternatively, it represents an alkyl group having 1 to 6 carbon atoms.

Specific examples of the anthracene-based 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-dipropoxyanthracene, 2-methyl- or 2-ethyl-9,10-diisopropoxyanthracene, 2-methyl- or 2-ethyl-9,10-dibutoxyanthracene, 2-methyl-or Examples thereof include 2-ethyl-9,10-dipentyloxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene.

Examples of the naphthalene compound include those represented by the following formula (8).

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 the formula (8), R ⁵³ and R ⁵⁴ each independently represent an alkyl group having 1 to 6 carbon atoms.

Specific examples of the naphthalene-based 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 thereof include 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene and 1,4-dibutoxynaphthalene.

The ratio of the sensitizer and the sensitizer to the cationically polymerizable component (A) is not particularly limited, and the sensitizer and the sensitizer may be used at a generally normal ratio within a range that does not impair the object of the present invention. 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 with respect to 100 parts by weight of the cationically polymerizable component (A).

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

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

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

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

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

The curable composition of the present invention uses a solvent capable of dissolving or dispersing each of the above-mentioned components (A), (B), (C), (D) and (E), which are not particularly limited and are usually used. Can be done. 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 , 2-Diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether and other ether solvents; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, succinic acid Ester-based solvents such as dimethyl and texanol; Cellosolve-based solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol-based solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol. Aether ester type such as ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, etc. Solvents; BTX-based solvents such as benzene, toluene, xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane; terpene hydrocarbon oils such as terepine oil, D-lymonen, pinen; mineral spirit, swazole # Paraffinic solvents such as 310 (manufactured by Cosmo Matsuyama Oil Co., Ltd.) and Solbesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane, etc. Solvents: Halogenized 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, dimethylsulfoxide, water and the like. These solvents can be used as one kind or a mixed solvent of two or more kinds.

Since the curable composition of the present invention improves curability, adhesiveness, and liquid storage stability, the water content is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. If there is too much water, it may become cloudy or the components may precipitate, which is not preferable.

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

The material of the support substrate is not particularly limited, and a commonly used material can be used. For example, an inorganic material such as glass; diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl, etc. can be used. Cellulose esters such as cellulose and nitrocellulose; polyamide; polyimide; polyurethane; epoxy resin; polycarbonate; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxy Polyesters such as ethane-4,4'-dicarboxylate, polybutylene terephthalate; polystyrene; polyolefins such as polyethylene, polypropylene, polymethylpentene; vinyl compounds such as polyvinyl acetate, polyvinyl chloride, polyvinyl fluoride; polymethylmethacrylate , Polyacrylate and other acrylic resins; polycarbonate; polysulfone; polyethersulfone; polyetherketone; 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.

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

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

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

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

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

[Examples 1 to 10, Reference Example 1 and Comparative Example 1]
Each component was sufficiently mixed with the formulations shown in [Table 1] and [Table 2] below to obtain curable compositions of Examples 1 to 10, Reference Example 1 and Comparative Example 1, respectively. The unit of Examples and Comparative Examples is parts by mass.

The following compounds (A1-1) to (A1-2) and (A2-1) to (A2-2) were used as the cationically polymerizable component (A).
Compound (A1-1): Adeka Resin EP-4088L (manufactured by ADEKA Corporation)
Compound (A1-2): 1,6-Hexanediol diglycidyl ether Compound (A2-1): Celoxide 2021P (Alicyclic epoxy: manufactured by Daicel Corporation)
Compound (A2-2): Limonene dioxide Compound (A4-1): Aron Oxetane OXT-221 (manufactured by Toagosei Corporation)

The following compound (B-1) was used as the cationic polymerization initiator (B).
Compound B-1: A 50% propylene carbonate solution of 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 radically polymerizable component (C).
Compound (C2-1): 1,6-Hexanediol diacrylate Compound (C2-2): Ethoxylated isocyanuric acid triacrylate Compound (C2-3): Tetrahydrofurfuryl acrylate

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.
Polymer (E-1): 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)

The glass transition temperature (Tg), elastic modulus and adhesion of each of the obtained curable compositions of Examples 1 to 10, Reference Example 1 and Comparative Example 1 were evaluated according to the following procedure. The results are shown together in [Table 1] and [Table 2].

(Glass transition temperature and elastic modulus)
Each of the obtained curable compositions of Examples 1 to 10, Reference Example 1 and Comparative Example 1 was applied on a polyethylene terephthalate (PET) film to a thickness of 30 μm with a bar coater, and a metal halide lamp was used. The energy of 3000 mJ / cm ^{2 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)
The viscosity of each of the obtained curable compositions of Examples 1 to 10, Reference Example 1 and Comparative Example 1 at 25 ° C. was measured with an E-type viscometer. The results are shown together in [Table 1] and [Table 2].

(Adhesion)
After applying the curable compositions of Examples 1 to 10, Reference Example 1 and Comparative Example 1 obtained above to one corona-treated PMMA film (Sumitomo Chemical Co., Ltd .: Technoroy 125S001), respectively. Another COP (cycloolefin polymer, manufactured by Nippon Zeon Co., Ltd .: product number Zeonoa film 14-060) film that has undergone corona discharge treatment is bonded using a laminator, and 1000 mJ / using an electrodeless ultraviolet lamp A test piece was obtained by irradiating light corresponding to ^{cm 2 through the COP film and adhering.} 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] to [Table 2], it is clear that the curable composition of the present invention has a high glass transition temperature of the cured product and is excellent in adhesion.

Claims (7)

30 to 99 parts by mass of the cationically polymerizable component (A), 0.1 to 10 parts by mass of the cationic polymerization initiator (B), 0 to 55 parts by mass of the radically polymerizable component (C), and the radical polymerization initiator (D). ) 0 to 10 parts by mass 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. 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. A polymer obtained from a monomer represented by (is), the following formula (II),

(In the formula, R ¹ 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). From a polymer obtained from the above-mentioned monomer, a polymer obtained from two or more kinds of monomers selected from the above-mentioned monomer represented by the formula (I), and the above-mentioned monomer represented by the formula (II). Select from the group consisting of polymers obtained from two or more selected monomers, or polymers obtained from the monomer represented by the formula (I) and the monomer represented by the formula (II). A polymer (E) having a weight average molecular weight of 1,000 to 30,000 and having one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group and 1 to 30 parts by mass of the polymer (E). Is contained so that the total of the cationically polymerizable component (A), the radically polymerizable component (C), and the polymer (E) is 100 parts by mass.
The cationically polymerizable component (A) is an essential component of a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more, a glycidylated product of a polyhydric alcohol alkylene oxide adduct (A1), and an alicyclic epoxy compound (A2). age,
The radically polymerizable component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, an acrylic acid ester of an alcohol having 2 to 20 carbon atoms, or an alcohol having 2 to 20 carbon atoms. Contains methacrylic acid ester (C2) and
A curable composition, wherein 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, has a saturated condensed ring. The curable composition according to claim 1, wherein the polyhydric alcohol in the glycidylate of a polyhydric alcohol having a molecular weight of 200 or more or the glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct is a polyhydric alcohol having a fused ring. .. The alicyclic epoxy compound (A2) is 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 7-oxabicyclo [4.1.0] heptane, hexane diacid bis [( Selected from the group consisting of 7-oxabicyclo [4.1.0] heptane-3-yl) methyl], 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethylmethacrylate and limonendioxide. The curable composition according to claim 1, which is one or more of the curable compositions. The polymer (E) is a polymer obtained from the monomer represented by the formula (I) and the monomer represented by the formula (II), and X in the formula (I) is Claim 1 which is an aryl group having 6 to 12 carbon atoms, in which 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. The curable composition according to description. A method for curing a curable composition, which comprises irradiating the curable composition according to any one of claims 1 to 4 with active energy rays. A method for curing a curable composition, which comprises heating the curable composition according to any one of claims 1 to 4. A cured product according to any one of claims 1 to 4, wherein the cured product is a cured product of the curable composition.