JP6993766B2 - 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. Regarding the cured product.

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

For example, Patent Documents 1 to 4 below propose an energy ray-curable composition containing a cationically polymerizable component and a radically polymerizable component, or a cured product thereof. Specifically, Patent Document 1 proposes an adhesive composition for a polarizing plate having excellent initial curability and adhesiveness. Further, in Patent Document 2, even when a resin film having low moisture permeability is used as a protective film, the adhesive force is immediately developed after irradiation with light, and the adhesive force after a certain period of time is good against various forces. Therefore, a low-viscosity photocurable adhesive that does not cause a problem even after the durability test and has good adhesive strength after the completion of the moisture resistance test has been proposed. Further, Patent Document 3 proposes an active energy ray-polymerizable resin composition containing an unsaturated alicyclic epoxy ester compound, which can achieve both high heat resistance, high refractive index and transparency.

Japanese Unexamined Patent Publication No. 2014-105218 Japanese Unexamined Patent Publication No. 2015-040283 Japanese Unexamined Patent Publication No. 2015-168757

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 may be highly compatible. At present, there is a demand for a new curable composition that can be used.

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

As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that a curable composition having a specific composition can solve the above-mentioned 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、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）１～２０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、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、オキセタン化合物（Ａ２）と、を必須成分とし、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質量部に対して、前記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３５～６５質量部、前記オキセタン化合物（Ａ２）が１５～２１質量部、脂環式エポキシ化合物（Ａ３）が０～３０質量部、芳香族エポキシ化合物（Ａ４）が０～５０質量部、ビニルエーテル化合物が０～２０質量部であり、
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である多価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である多価アルコールのメタクリル酸エステル（Ｃ２）を必須成分とし、
前記式（Ｉ）中のＸおよび前記式（ＩＩ）中のＸ’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種以上の基で部分的に置換された炭素原子数１～４のアルキル基であ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 30 to 89 parts by mass of the cationically polymerizable component (A), 1 to 10 parts by mass of the cationic polymerization initiator (B), and 10 to 50 parts by mass of the radically polymerizable component (C). Parts, 1 to 10 parts by mass of the 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. An alicyclic hydrocarbon group of number 6 to 10, or a hydrogen atom in these groups 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 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. It is represented by an alicyclic hydrocarbon group, 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). From the polymer obtained from the above-mentioned monomer, the 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, and polymers obtained from the monomers represented by the formula (I) and the monomers represented by the formula (II). 1 to 20 parts by mass of the polymer (E) having a weight average molecular weight of 1,000 to 30,000, the cationically polymerizable component (A), the radically polymerizable component (C), and the polymer (E). ) And so that the total is 100 parts by mass.
The cationically polymerizable component (A) contains the glycidylated product of a polyhydric alcohol or the glycidylated product (A1) as an adduct of a polyhydric alcohol alkylene oxide as an essential component and the oxetane compound (A2) as essential components, and the cationically polymerizable component (A). A glycidyl compound of the polyhydric alcohol or a glycidyl compound of the polyhydric alcohol alkylene oxide adduct with respect to a total of 100 parts by mass of the radically polymerizable component (C) and the polymer (E). A1) is 35 to 65 parts by mass, the oxetane compound (A2) is 15 to 21 parts by mass, the alicyclic epoxy compound (A3) is 0 to 30 parts by mass, and the aromatic epoxy compound (A4) is 0 to 50 parts by mass. , Vinyl ether compound is 0 to 20 parts by mass,
The radically polymerizable component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, an acrylic acid ester of a polyhydric alcohol having 2 to 20 carbon atoms, or 2 to 20 carbon atoms. The essential component is the methacrylic acid ester (C2) of the polyhydric alcohol.
A carbon in which X in the formula (I) and X'in the formula (II) are 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. It is characterized by being an alkyl group having 1 to 4 atoms. 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 aromatic epoxy compound (A3) is preferably a polyfunctional aromatic epoxy compound. 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). Is preferable.

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 hardened 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 15 to 90 parts by mass of the cationically polymerizable component (A), 1 to 10 parts by mass of the cationic polymerization initiator (B), and 10 to 50 parts by mass of the radically polymerizable component (C). , 1 to 10 parts by mass of the radical polymerization initiator (D), a polymer obtained from the monomer represented by the following formula (I), a polymer obtained from the monomer represented by the following formula (II), the following. A polymer obtained from two or more kinds of monomers selected from the monomers represented by the formula (I), and two or more kinds of monomers selected from the monomers represented by the following formula (II). A weight average molecular weight of 1,000 to selected from the group consisting of a polymer obtained from the above, a polymer represented by the following formula (I) and a polymer represented by the following formula (II). It contains 1 to 20 parts by mass of the polymer (E) which is 30,000.

In the curable composition of the present invention, the cationically polymerizable component (A) is indispensable to be a glycidylated product of a polyhydric alcohol or a glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct, and an oxetane compound (A2). A glycidyl compound of a polyhydric alcohol or a polyhydric alcohol alkylene with respect to a total of 100 parts by mass of the cationically polymerizable component (A), the radically polymerizable component (C), and the polymer (E). The glycidyl compound (A1) of the oxide adduct is 35 to 65 parts by mass. The radically polymerizable component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, an acrylic acid ester of a polyhydric alcohol having 2 to 20 carbon atoms, or 2 to 20 carbon atoms. An essential component is a methacrylic acid ester (C2) of a certain polyhydric alcohol.

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, 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. Number 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. be.

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. Examples thereof include epoxy compounds, oxetane compounds, vinyl ether compounds and the like.

The cationically polymerizable component (A) according to the curable composition of the present invention contains a glycidylated product of a polyhydric alcohol or a glycidylated product (A1) as an adduct of a polyhydric alcohol alkylene oxide, and an oxetane compound (A2) as essential components. However, as other epoxy compounds, an alicyclic epoxy compound (A 4 ), an aromatic epoxy compound (A 3 ) and the like can also be used.

Examples of the glycidylated product (A1) of the polyhydric alcohol or the polyhydric alcohol alkylene oxide adduct include those obtained by glycidylating the polyhydric alcohol or the polyhydric alcohol alkylene oxide adduct, and the molecular weight of the glycidylated product is 250. The above is preferable.

Examples of the glycidylated product of the polyvalent alcohol or the glycidylated product (A1) of the polyhydric alcohol alkylene oxide adduct include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl 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, dicyclopentadiene dimethanol diglycidyl Polyglycidyl ether of a polyether polyol obtained by adding one or more alkylene oxides to a glycidyl ether of a polyhydric alcohol such as an ether, or an aliphatic polyvalent alcohol such as propylene glycol, trimethylolpropane, or glycerin. Examples thereof include diglycidyl esters of compounds and aliphatic long-chain dibasic acids.

Further, as the glycidylated product of a polyhydric alcohol or the glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct, monoglycidyl ether of an aliphatic higher alcohol, glycidyl ester of a higher fatty acid, epoxidized soybean oil, octyl epoxide stearate, etc. Examples include butyl epoxide stearate, epoxidized soybean oil, epoxidized polybutadiene and the like.

As the glycidylated product of the polyhydric alcohol or the glycidylated product (A1) of the 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 or the glycidylated product (A1) of the polyhydric alcohol alkylene oxide adduct, commercially available products can be used, for example, Denacol EX-121, Denacol EX-171, and Denacol EX-192. , Denacol EX-221, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611. , Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832. , Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase ChemteX Corporation); Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Adeka Glycyllol ED-503, Adeka Glycyllol ED- 503G, ADEKA Glycyllol ED-506, ADEKA Glycyrrol ED-523T, ADEKA REGIN EP-4088S, ADEKA REGIN EP-4080E (manufactured by ADEKA Corporation) and the like can be mentioned.

Examples of the oxetane compound (A2) include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-. Bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether , Triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, Bifunctional aliphatic oxetane compounds such as 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) Examples include monofunctional oxetane compounds such as oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, and 3-ethyl-3- (chloromethyl) oxetane. Will be. These can be used alone or in combination of two or more. In particular, a polyfunctional oxetane compound is preferable because it increases the curability and adhesion of the cured product.

As the oxetane compound (A2), a commercially available product can be used, for example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.); Aron oxetane OXT. -121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-221, OXT-212 (manufactured by Toa Synthetic Co., Ltd.), Ethanacole OXBP, OXTP (manufactured by Ube Industries, Ltd.), etc. Will be.

The alicyclic epoxy compound (A 4 ) refers to a compound in which an oxylan ring is directly formed on a saturated ring without a bonding group. Specific examples of the alicyclic epoxy compound (A 4 ) are obtained by epoxidizing a polyglycidyl etherified compound of a polyhydric alcohol having at least one alicyclic ring or a compound containing cyclohexene or a 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. -Epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexanemethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5 -Methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxy) Cyclohexane), Propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadienediepoxiside, 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 limonendioxide. Examples of the alicyclic epoxy compound (A 4 ) include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexane. Carboxylate is preferable from the viewpoint of improving adhesion.

As the alicyclic epoxy compound (A 4 ), 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 (A 3 ) refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound (A 3 ) include at least one aromatic ring such as phenol, cresol, and butylphenol. A mono / polyglycidyl etherified product of a polyhydric phenol or an alkylene oxide adduct thereof, for example, a glycidyl etherified product or an epoxynovolak resin of bisphenol A, bisphenol F, or a compound obtained by further adding an alkylene oxide to these; resorcinol or hydroquinone, Mono / polyglycidyl etherified product of aromatic compound having two or more phenolic hydroxyl groups such as catechol; glycidyl etherified product of aromatic compound having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol and phenyldibutanol. Examples thereof include glycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid, glycidyl esters of benzoic acid, and epoxidates of styrene oxide or divinylbenzene.

As the aromatic epoxy compound (A 3 ), 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 (manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (DIC Co., Ltd.) ESN-475V (manufactured by Nippon Steel & Sumitomo Metal Corporation); Epicoat YX8800 (manufactured by Mitsubishi Chemical Co., Ltd.); Marproof G-0105SA, Marproof G-0130SP (manufactured by 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.); TECHMORE VG- 3101L (manufactured by Printec Co., Ltd.) and the like can be mentioned. As the aromatic epoxy compound (A3), a polyfunctional compound is preferable because it has excellent curability.

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

In the cationically polymerizable component (A), the glycidylated product of the polyhydric alcohol or the glycidylated product of the polyhydric alcohol alkylene oxide adduct (A1), the oxetane compound (A2), the alicyclic epoxy compound ( A4), and the aromatic. The proportion of the epoxy compound (A 3 ) and the vinyl ether compound used is polyvalent with respect to 100 parts by mass of the total of the cationically polymerizable component (A), the radically polymerizable component (C), and the polymer (E). 35 to 65 parts by mass of glycidylated product of alcohol or glycidylated product of polyhydric alcohol alkylene oxide adduct (A1), 15 to 40 parts by mass of oxetane compound (A2), 0 to 30 parts by mass of alicyclic epoxy compound (A4), It is preferable that the aromatic epoxy compound (A 3 ) is 0 to 50 parts by mass and the vinyl ether compound is 0 to 20 parts by mass because the viscosity, coatability, reactivity and curability are improved.

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 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-
Can be mentioned as cation and anion salts 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 to 5. The a R ^2s are independent of each other 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 is established (however, N = N is treated as having a valence of 0).

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

Further, here, L is a metal or metalloid that is the central atom of the halide complex, and is 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, and tetrafluoroborate (BF ₄ ) ^- ,. Hexafluoroborate (PF ₆ ) ^- , hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarsenate (AsF ₆ ) ^- , hexachloroantimonate (SbCl ₆ ) ^-and the like can be mentioned.

Further, 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 sulphonate, nonafluorobutane sulphonate, 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) iodinenium hexafluorophosphate, di (4-tert-butylphenyl) iodinenium hexafluorophosphate, trilucmiliodonium tetrakis (pentafluorophenyl) borate, etc. Iodium 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>

In addition, other preferable ones are (η ^5-2,4 -cyclopentadiene-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron. -Iron-allene complex such as hexafluorophosphate, aluminum complex such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salitylaldehidat) 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; the above polyamines and phenylglycidyl ether, butylglycidyl ether, 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 dimer acid by a conventional method; Mannich's modified product produced by reacting a nucleus such as tributylphenol and resorcin with at least one phenol having an aldehyde oxidation-reactive site by a conventional method; polyvalent carboxylic acid (succinic acid, malonic acid, succinic acid). , Glutalic acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-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 and the like. Aromatic dicarboxylic acids; cyclohexanedicarbo Acid anhydrides of 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; 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-arene 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 atom, halogen atom and carbon atom number, respectively. 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, and ^R25 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or any of the following chemical formulas (A) to (C). Represents a substituent, An ^q- represents a q-valent anion, and p represents a coefficient that neutralizes 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, and 1 carbon atom. Represents an alkoxy group of up to 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 a hydrogen atom, a halogen atom or an ester group having 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 22 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-H Examples thereof include droxybutyl, 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 , 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 having 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 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, an acrylic acid ester of an alcohol having 2 to 20 carbon atoms, or an acrylic acid ester having 2 to 20 carbon atoms. The essential component is a methacrylic acid ester (C2) of an alcohol of 2 to 20.

Examples of the compound (C1) having an epoxy group and an ethylenically unsaturated group include epoxy acrylate and epoxy methacrylate, and 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 alcoholic glycidyl ethers.

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 propanetriacrylate, 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, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, ε-caprolactone-modified dipentaerythritol hexamethacrylate, etc. Can be mentioned. Of these acrylates or methacrylates, polyhydric alcohol polyacrylates or polyhydric alcohol polymethacrylates 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 irradiation with energy rays 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) to 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 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), and the above. A polymer obtained from two or more kinds of monomers selected from the monomers represented by the formula (I), and two or more kinds of monomers selected from the monomers represented by the above formula (II). Selected from the group consisting of the polymer obtained from the above, and the polymer represented by the above formula (I) and the above-mentioned monomer represented by the formula (II), the weight average molecular weight is converted into 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 to 4 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. Amyloxy, 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 a group having 1 to 1 to 4 carbon atoms partially substituted with one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group. The alkoxy group of 4 is preferable from the viewpoint of curability.

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

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

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

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 a monomer 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), examples of the halogen atom represented by R ¹ include fluorine, chlorine, bromine, iodine and the like.

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 of X'is the above formula (I). ) And the same 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 15 to 90 parts by mass, preferably 50 to 80 parts by mass, and the cationic polymerization initiator (B) is 1 to 10 parts by mass, preferably 1. ~ 6 parts by mass, the radical polymerizable component (C) is 10 to 50 parts by mass, preferably 10 to 20 parts by mass, and the radical polymerization initiator (D) is 1 to 10 parts by mass, preferably 1 to 5 parts by mass. The polymer (E) is 1 to 20 parts by mass, preferably 5 to 15 parts by mass. If the mixing ratio is other than the above, the curability and adhesion of the cured product may deteriorate. The total of the cationically polymerizable component (A), the radically polymerizable component (C), and the polymer (E) is 100 parts by mass.

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 sensitizing aid include anthracene-based compounds and naphthalene-based 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 alkoxyalkyl 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-based 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 sensitizing aid 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 sensitizing 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, allyltrimethoxysilanes, 3-methacryloxybropyrriethoxysilanes, 3-methacryloxybropyrtrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and other epoxy functional alkoxysilanes, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl Amino-functional alkoxysilanes such as -γ-aminopropyltrimethoxysilane, mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, titanium alkoxides such as titaniumtetraisopropoxide, titaniumtetranormalbutoxide, and titanium diocties. Titanium chelates such as loxybis (octylene glycolate) and titanium diisopropoxybis (ethylacetoacetate), zirconium tetraacetylacetonates, zirconium chelates such as zirconium tributoxymonoacetylacetonate, zirconium tributoxymono Zirconium 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 the solid matter in the curable composition.

If necessary, a thermoplastic organic polymer may be used in the curable composition of the present invention to improve the properties of the cured product. Examples of the thermoplastic organic polymer include polystyrene, polymethylmethacrylate, methylmethacrylateethylacrylate copolymer, methylmethacrylateglycidylmethacrylate 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.

If necessary, the curable composition of the present invention is further activated by desorbing the protecting group by an ultraviolet absorber, heating to a predetermined temperature, light irradiation, acid, etc., which are inactive at room temperature. It is also possible to use a compound that exhibits the ability to absorb ultraviolet rays.

Further, as long as the effect of the present invention is not impaired, if necessary, colorants such as polyols, inorganic fillers, organic fillers, pigments and dyes, defoaming agents, thickeners, surfactants, leveling agents, difficulties Various resin additives such as fueling agents, tincture agents, diluents, plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antioxidants, flow modifiers, adhesion promoters, etc. can be added. can.

For the curable composition of the present invention, a solvent capable of dissolving or dispersing each of the above-mentioned components (A), (B), (C), (D) and (E), which is not particularly limited and is usually used, is 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-based solvents such as hexane, heptane, octane, cyclohexane; terpene-based hydrocarbon oils such as terepine oil, D-limonen, pinen; mineral spirit, swazole # Paraffin-based 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 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 on a support substrate by a known means such as a roll coater, a curtain coater, various types of printing, and dipping. Further, it is also possible to apply it once on a support substrate such as a film and then transfer it onto another support substrate, and there is no limitation on the application method thereof.

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; diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionyl 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 and polymethylpentene; vinyl compounds such as polyvinyl acetate, polyvinyl chloride and 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 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 for curing the curable composition of the present invention by heating are 70 to 250 ° C. for 1 to 100 minutes. After pre-baking (PAB; Pre-exposure bake), it may be pressurized and post-baked (PEB; Post exposure bake), or it may be baked at several different temperature steps. The heating conditions vary depending on the type and mixing 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, for semiconductor devices, for LED packages, for liquid crystal inlets, organic Encapsulants for EL, optical elements, electrical insulation, electronic parts, separation films, molding materials, putties, 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 wrenchular 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. Examples thereof include those provided with each layer such as, and 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 7, Reference Examples 1 to 10 and Comparative Examples 1 and 2]
Each component was sufficiently mixed with the formulations shown in the following [Table 1] to [Table 4] to obtain curable compositions of Examples 1 to 7, Reference Examples 1 to 10 and Comparative Examples 1 and 2. The units of Examples, Reference Examples and Comparative Examples are parts by mass.

The following compounds were used as the cationically polymerizable component (A).
Compound (A1-1): Neopentyl glycol diglycidyl ether compound (A1-2): 1,4-butanediol diglycidyl ether compound (A2-1): Aronoxetane OXT-221 (manufactured by Toa Synthetic Co., Ltd.)
Compound (A3-1): Bisphenol type diglycidyl ether Compound (A3-2): TECHMORE VG3101 (Aromatic trifunctional epoxy: manufactured by Printec Co., Ltd.)

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 compounds were used as the radically 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 compounds (E-1) and (E-2) were used.
Compound (E-1): Copolymer of 75 parts by mass of methyl methacrylate and 25 parts of glycidyl methacrylate (weight average molecular weight 7,000)

The glass transition temperature (Tg), elastic modulus and adhesion of each of the obtained curable compositions of Examples 1 to 7, Reference Examples 1 to 10 and Comparative Examples 1 and 2 were evaluated according to the following procedure. .. The results are also shown in [Table 1] to [Table 4].

(Glass transition temperature and elastic modulus)
Each of the obtained curable compositions of Examples 1 to 7, Reference Examples 1 to 10 and Comparative Examples 1 and 2 was applied onto a polyethylene terephthalate (PET) film to a thickness of 30 μm with a bar coater. An energy of 3000 mJ / cm ² was irradiated using a metal halide lamp. 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 viscosities of the obtained curable compositions of Examples 1 to 7, Reference Examples 1 to 10 and Comparative Examples 1 and 2 at 25 ° C. were measured with an E-type viscometer.

(Adhesion: COP)
After applying the curable compositions of Examples 1 to 7, Reference Examples 1 to 10 and Comparative Examples 1 and 2 obtained above to one corona-treated PMMA film (Sumitomo Chemical Co., Ltd .: Technoroy 125S001), respectively. , Another COP (cycloolefin polymer, manufactured by Nippon Zeon: Part No. Zeonoa Film 14-060) film subjected to corona discharge treatment and bonded using a laminator, and to 1000 mJ / cm ² using a non-electrode ultraviolet light lamp. A test piece was obtained by irradiating the corresponding light through the COP film and adhering. The obtained test piece was subjected to a 90-degree peel test.

From [Table 1] to [Table 4], 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 (6)

30 to 89 parts by mass of the cationically polymerizable component (A), 1 to 10 parts by mass of the cationic polymerization initiator (B), 10 to 50 parts by mass of the radically polymerizable component (C), and 1 part of the radical polymerization initiator (D). ~ 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 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 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. It is represented by an alicyclic hydrocarbon group, 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). From the polymer obtained from the above-mentioned monomer, the 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, and polymers obtained from the monomers represented by the formula (I) and the monomers represented by the formula (II). 1 to 20 parts by mass of the polymer (E) having a weight average molecular weight of 1,000 to 30,000, the cationically polymerizable component (A), the radically polymerizable component (C), and the polymer (E). ) And so that the total is 100 parts by mass.
The cationically polymerizable component (A) contains the glycidylated product of a polyhydric alcohol or the glycidylated product (A1) as an adduct of a polyhydric alcohol alkylene oxide as an essential component and the oxetane compound (A2) as essential components, and the cationically polymerizable component (A). A glycidyl compound of the polyhydric alcohol or a glycidyl compound of the polyhydric alcohol alkylene oxide adduct with respect to a total of 100 parts by mass of the radically polymerizable component (C) and the polymer (E). A1) is 35 to 65 parts by mass, the oxetane compound (A2) is 15 to 21 parts by mass, the alicyclic epoxy compound (A4) is 0 to 30 parts by mass, and the aromatic epoxy compound (A3) is 0 to 50 parts by mass. , Vinyl ether compound is 0 to 20 parts by mass,
The radically polymerizable component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, an acrylic acid ester of a polyhydric alcohol having 2 to 20 carbon atoms, or 2 to 20 carbon atoms. The essential component is the methacrylic acid ester (C2) of the polyhydric alcohol.
A carbon in which X in the formula (I) and X'in the formula (II) are 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. A curable composition characterized by being an alkyl group having 1 to 4 atoms. The curable composition according to claim 1, wherein the aromatic epoxy compound (A3) is a polyfunctional aromatic epoxy compound. The curable composition according to claim 1 or 2, wherein the polymer (E) is a polymer obtained from the monomer represented by the formula (I) and the monomer represented by the formula (II). A method for curing a curable composition, which comprises irradiating the curable composition according to any one of claims 1 to 3 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 3. A cured product according to any one of claims 1 to 3, wherein the cured product is a cured product of the curable composition.