KR102278179B1 - Curable composition, manufacturing method of cured product, and cured product thereof - Google Patents

Abstract

(식 중, X는, 탄소 원자수 1∼7의 알킬기 등)으로 표시되는 단량체로부터 얻어지는 폴리머, 식(II)

(식 중, R¹은 수소 원자 등을 나타내고, X'는 탄소 원자수 1∼7의 알킬기 등)으로 표시되는 단량체로부터 얻어지는 폴리머 등으로부터 선택되는 중량 평균 분자량 1,000∼30,000인 폴리머(E) 1∼30 질량부을 함유하고, (A) 성분이 분자량 200 이상의 다가 알코올의 글리시딜화물 등과 지환식 에폭시 화합물\이며, (C) 성분이 에폭시기 등을 가지는 화합물 등이다.Disclosed are a curable composition having a high glass transition temperature and excellent adhesion, a method for producing a cured product, and a cured product thereof.
30-99 mass parts of a cationically polymerizable component (A), 0.1-10 mass parts of a cation polymerization initiator (B), 0-55 mass parts of a radically polymerizable component (C), and 0-10 mass parts of a radical polymerization initiator (D) parts by mass and formula (I)

A polymer obtained from a monomer represented by (wherein, X is an alkyl group having 1 to 7 carbon atoms, etc.), formula (II)

Polymers (E) having a weight average molecular weight of 1,000 to 30,000 selected from polymers obtained from monomers represented by (wherein, R ¹ represents a hydrogen atom, etc., and X' is an alkyl group having 1 to 7 carbon atoms, etc.) It contains 30 parts by mass, the component (A) is a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more, and an alicyclic epoxy compound, and the component (C) is a compound having an epoxy group or the like.

Description

Curable composition, manufacturing method of cured product, and cured product thereof

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

Curable compositions are used in fields, such as an ink, a paint, various coating agents, an adhesive agent, and an optical member. Various reports have been made about such improvement of the curable composition.

For example, the energy-beam curable composition containing a cationically polymerizable component and a radically polymerizable component, or its hardened|cured material is proposed by the following patent documents 1-3. For example, in patent document 1, the adhesive composition for polarizing plates excellent in initial stage sclerosis|hardenability and adhesiveness is proposed. Further, in Patent Document 2, an active energy ray-curable type used for plastic films having low viscosity, excellent curability, excellent adhesion to various plastic films, etc. even at high atmospheric humidity during application and curing, and excellent colorless transparency Adhesive compositions have been proposed. Further, in Patent Document 3, active energy used for plastic films having low viscosity, excellent curability, excellent adhesion to various plastic films including (meth)acrylic resins and cycloolefin polymers, etc., and excellent colorless transparency A line-curable adhesive composition has been proposed.

Japanese Laid-Open Patent Publication No. 2014-105218 Japanese Laid-Open Patent Publication No. 2015-057467 Japanese Laid-Open Patent Publication No. 2015-229744

However, even in the curable compositions proposed in Patent Documents 1 to 3, curability and adhesiveness may not always be satisfactory, and a new curable composition capable of making both curability and adhesiveness highly compatible is currently demanded. the situation of

Then, the objective of this invention is high glass transition temperature of hardened|cured material, and it is providing the curable composition excellent in adhesiveness, the manufacturing method of hardened|cured material, and its hardened|cured material.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject could be eliminated if it was a curable composition which has a specific composition, as a result of earnestly examining in order to solve the said subject, and came to complete this invention.

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 cation polymerization initiator (B), 0 to 55 parts by mass of the radically polymerizable component (C), 0-10 parts by mass of a radical polymerization initiator (D);

Formula (I)

(wherein 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 6 carbon atoms -10 alicyclic hydrocarbon groups, or hydrogen atoms in these groups are substituted with one or more groups selected from the group consisting of 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)

(Wherein, 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 an alicyclic carbonation having 6 to 10 carbon atoms. A polymer obtained from a monomer represented by a hydrogen 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; a monomer represented by the formula (I) A polymer obtained from two or more monomers selected from, a polymer obtained from two or more monomers selected from the monomers represented by the formula (II), or a monomer represented by the formula (I) and a monomer represented by the formula (II) 1 to 30 parts by mass of a polymer (E) having a weight average molecular weight of 1,000 to 30,000 selected from the group consisting of polymers obtained from monomers, the cationically polymerizable component (A), the radically polymerizable component (C), and the polymer (E) It contains so that the total of 100 parts by mass,

The cationically polymerizable component (A) contains, as essential components, 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) and an alicyclic epoxy compound (A2), ,

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 or a methacrylic acid ester of an alcohol having 2 to 20 carbon atoms (C2) ) as an essential component. Here, the weight average molecular weight means the weight average molecular weight measured by GPC in a tetrahydrofuran (THF) solvent and calculated|required in styrene conversion.

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 preferably a polyhydric alcohol having a condensed ring. Do. Further, in the curable composition of the present invention, the alicyclic epoxy compound (A2) is 3',4'-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, 7-oxabicyclo[4.1. 0]heptane, poly[oxy-(1-oxo-1,6-hexanediyl)] derivative, hexanedioic acid bis[(7-oxabicyclo[4.1.0]heptan-3-yl)methyl], 1,2 - At least one selected from the group consisting of -epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate and limonene dioxide is preferable. 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), wherein X in the formula (I) is, It is a C6-C12 aryl group, X' in the said Formula (II) is a C1-C7 alkyl group, It is preferable that the said alkyl group is substituted by the epoxy group.

The manufacturing method of the hardened|cured material of this invention is characterized by irradiating an active energy ray to the curable composition of this invention, or heating.

The hardened|cured material of this invention is a hardened|cured material of the curable composition of this invention, It is characterized by the above-mentioned.

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

Hereinafter, the curable composition of this invention is demonstrated in detail.

The curable composition of this invention contains 30-99 mass parts of cationically polymerizable components (A), 0.1-10 mass parts of cation polymerization initiators (B), 0-55 mass parts of radically polymerizable components (C), and radical polymerization 2 selected from 0 to 10 parts by mass of initiator (D), a polymer obtained from a monomer represented by the following formula (I), a polymer obtained from a monomer represented by the following formula (II), and a monomer represented by the following formula (I) A polymer obtained from at least two kinds of monomers, a polymer obtained from two or more kinds of monomers selected from monomers represented by the following formula (II), 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 a polymer (E) having a weight average molecular weight of 1,000 to 30,000 selected from the group consisting of In the curable composition of the present invention, 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), and an alicyclic epoxy compound ( A2) as 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, or having 2 to 20 carbon atoms The methacrylic acid ester of alcohol (C2) is an essential component.

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, or an aryloxy group having 6 to 12 carbon atoms. Alternatively, an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a hydrogen atom in these groups is substituted with one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group.

Here, in 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, an aryl group having 6 to 12 carbon atoms, or an aryl group having 6 to carbon atoms. The alicyclic hydrocarbon group represented by 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.

The cationically polymerizable component (A) concerning the curable composition of this invention is a compound which raise|generates polymerization or a crosslinking reaction with the cationic polymerization initiator activated by energy-beam irradiation or heating. An epoxy compound, an oxetane compound, a vinyl ether compound, etc. are 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 of a polyhydric alcohol alkylene oxide adduct (A1), and an alicyclic epoxy compound (A2) ) as an essential component, but an aromatic epoxy compound (A3) or the like can also be used as other epoxy compounds. As for the ratio of the said (A1) component and (A2) component in a cationically polymerizable component (A), 90 mass % or more is preferable.

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

As the glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more or the glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct, 1,4-butanediol diglycidyl ether, 1,6-hexanediol glycidyl Ether, 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 Glycidyl ether of polyhydric alcohols such as glycidyl ether, diglycidyl ether of polypropylene glycol, and dicyclopentadiene dimethanol diglycidyl ether, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerin The polyglycidyl ether product of the polyether polyol obtained by adding 1 type, or 2 or more types of alkylene oxide, and the diglycidyl ester of an aliphatic long-chain dibasic acid are mentioned.

Examples of the glycidyl product of polyhydric alcohol or the glycidyl product (A1) of the polyhydric alcohol alkylene oxide adduct include monoglycidyl ethers of aliphatic higher alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, and epoxystear. octyl acid, butyl epoxystearate, epoxidized soybean oil, epoxidized polybutadiene, and the like.

As 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, one having a saturated condensed ring is preferable from the viewpoint of improving the curability and adhesion of the cured product.

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 (A1), a commercially available product 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, Dena Call 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 Co., Ltd.); Eporite M-1230, Eporite 40E, Eporite 100E, Eporite 200E, Eporite 400E, Eporite 70P, Eporite 200P, Eporite 400P, Eporite 1500NP, Eporite 1600, Eporite 80MF, Eporite 100MF ( Kyoeisha Chemical (manufactured by Kyoeisha Chemical Co., Ltd.), adecaglycerol ED-503, adecaglycerol ED-503G, adecaglycerol ED-506, adecaglycerol ED -523T, Adeka Resin EP-4088S, Adeka Resin EP-4080E (manufactured by ADEKA Corporation), and the like.

The said alicyclic epoxy compound (A2) refers to the thing in which the oxirane ring is couple|bonded with the saturated ring directly without a bonding group. Specific examples of the alicyclic epoxy compound (A2) include cyclohexene oxide and cyclopentene oxide obtained by epoxidizing a polyglycidyl ether product of a polyhydric alcohol having at least one alicyclic ring or a compound containing cyclohexene or cyclopentene ring with an oxidizing agent. containing compounds. For example, 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-Methyl-3,4-epoxycyclohexylethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methyl Cyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylethyl) adipate, 3, 4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis ( 3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate , 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pineneoxide, limonene dioxide and the like. As the alicyclic epoxy compound (A2), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methyl Hexane carboxylate is preferable from a viewpoint of an adhesive improvement.

As said alicyclic epoxy compound (A2), a commercial item can be used, For example, Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000 (made by Daicel Corporation) etc. exist.

The said aromatic epoxy compound (A3) represents the epoxy compound containing an aromatic ring, As a specific example of an aromatic epoxy compound, polyhydric phenol which has at least 1 aromatic ring, such as phenol, cresol, butylphenol, or its alkylene oxide adduct Mono/polyglycidyl ether products, for example, bisphenol A, bisphenol F, or glycidyl ether products or epoxy novolac resins of compounds obtained by adding an alkylene oxide to these; mono/polyglycidyl ether products of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol; glycidyl ether products of aromatic compounds having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol and phenyldibutanol; and 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 epoxides of styrene oxide or divinylbenzene.

As said aromatic epoxy compound (A3), a commercial item can be used, For example, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX- 711, Denacol EX-721, Oncoat EX-1020, Oncoat EX-1030, Oncoat EX-1040, Oncoat EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat 1012 (manufactured by 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 (manufactured by DIC Corporation); ESN-475V (manufactured by Nittetsu Sumikin Chemical Co., Ltd.); Epikote YX8800 (manufactured by Mitsubishi Chemical Co., Ltd.); Mapproof G-0105SA, Mapproof G-0130SP (manufactured by Nichiyu Co., Ltd.); Epiclone N-665, Epiclone HP-7200 (manufactured by DIC Corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (Nippon Chemical Co., Ltd.) manufactured by the company); Adecare resin EP-4000, Adecare resin EP-4005, Adecare resin EP-4100, Adecare resin EP-4901 (manufactured by ADEKA Corporation); TECHMORE VG-3101L (manufactured by Printec Co., Ltd.) and the like. As said aromatic epoxy compound, since it is excellent in sclerosis|hardenability that it is polyfunctional, it is preferable.

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

As said oxetane compound, the commercial item which has a cationically polymerizable monomer as a main component can be used, For example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (Maruzen Petrochemical) Chemicals (manufactured by 丸善石油chemical); Aronoxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toah Synthetic Co., Ltd.), etanacol OXBP, OXTP (Ube Heungsan) Co., Ltd.) 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, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1 ,4-butanediol divinyl ether, 1,6-cyclohexanedimethanol divinyl ether, and the like.

In the cationically polymerizable component (A), a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more or a glycidylated product of a polyhydric alcohol alkylene oxide adduct (A1), an alicyclic epoxy compound (A2), an aromatic epoxy compound ( A3), the usage ratio of an oxetane compound and a vinyl ether compound is the glycidyl product of the polyhydric alcohol 200 or more molecular weight 200 or more, or the glycidyl product of the polyhydric alcohol alkylene oxide adduct with respect to 100 mass parts of cationically polymerizable components (A). (A1) 10-99 mass parts, alicyclic epoxy compound (A2) 1-50 mass parts, aromatic epoxy compound (A3) 0-80 mass parts, oxetane compound 0-50 mass parts, vinyl ether compound 0-20 mass It is preferable at the point that a viscosity, coatability, reactivity, and sclerosis|hardenability improve.

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, but is preferably used for irradiation with energy rays. It is an onium salt that releases a Lewis acid by a double salt, or a derivative thereof. As a representative example of such a compound, the following general formula,

[A] ^r+ [B] ^r-

A salt of a cation and an anion 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 displayed as

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 from 1 to 5; a R ² may be each independent and may be the same or different. Moreover, it is preferable that at least 1 is the above organic group which has an aromatic ring. Q is an atom or 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 set to q, it is necessary to establish a relationship such that r=aq (however, N=N is treated as valence 0)

In addition, it is preferable that anion [B] ^r- is a halide complex, and the structure is, for example, the following general formula,

[LY _b ] ^r-

can be displayed as

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 used as 3-7. In addition, when the valence of L in the anion [B] ^r- is set to p, it is necessary to establish a relationship such that r = bp.

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

In addition, the anion [B] ^r- is represented by the following general formula,

[LY _b-1 (OH)] ^r-

A structure represented by can also be preferably used. L, Y and b are the same as above. In addition, as anions that can be used in addition, perchlorate ion (ClO ₄ ) ^- , trifluoromethylsulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonic acid ion (FSO ₃ ) ^- , toluenesulfonic acid anion, trinitrobenzenesulfonic acid anion , camphorsulfonate, nonafluorobutanesulfonate, 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. Among these, the 1 type can be used individually or 2 or more types can be mixed and used.

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

(B) Diphenyliodonium hexafluoroantimonate, di(4-methylphenyl)iodonium hexafluorophosphate, di(4-tert-butylphenyl)iodonium hexafluorophosphate, tricumyliodonium tetrakis ( Diaryliodonium salts such as pentafluorophenyl) borate

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

<Group I>

<Group II>

Moreover, as another preferable thing, (η ⁵ -2,4-cyclopentadien-1-yl)[(1,2,3,4,5,6-η)-(1-methylethyl)benzene]- Iron-arene complexes such as iron-hexafluorophosphate, aluminum complexes such as tris(acetylacetonate)aluminum, tris(ethylacetonate acetate)aluminum, tris(salicylaldehyde)aluminum, and triphenyl mixtures with silanols such as silanol; salts such as thiophenium salt, thioranium salt, benzylammonium, pyridinium salt, and hydrazinium salt; polyalkyl polyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; The above polyamines, glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, or glycidyl esters of carboxylic acid, etc. polyepoxy addition-modified products prepared by reacting various epoxy resins of amidation-modified products produced by reacting the organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimer acid by a conventional method; Manufactured by reacting the polyamines with aldehydes such as formaldehyde and phenols having at least one aldehyde reactive site in the nucleus, such as phenol, cresol, xylenol, tert-butylphenol, resorcin, by a conventional method Mannichation modified product; Polyhydric carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanoic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyl aliphatic dicarboxylic acids such as adipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanoic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid and dimer acid; , terephthalic acid, isophthalic acid, aromatic dicarboxylic acids such as naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; Tricarboxylic acids such as trimellitic acid, trimesic acid, and a trimer of castor oil fatty acid; pyromelli acid anhydrides of tetracarboxylic acids such as toric acid; and dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, and amineimides.

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

wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, and 1 carbon atom. represents an alkyl group of -10, an alkoxy group of 1 to 10 carbon atoms, or an ester group of 2-10 carbon atoms, R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, a halogen atom or carbon represents an alkyl group having 1 to 10 atoms, R ²⁵ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or any substituent selected from the following formulas (A) to (C), An ^{q −} represents an anion having a q valence, and p represents a coefficient for neutralizing the charge.

wherein 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; represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an ester group having 2 to 10 carbon atoms, R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ are each Independently, a hydrogen atom, a halogen atom, or a C1-C10 alkyl group is represented.

In the compound represented by the 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 halogen atom represented include fluorine, chlorine, bromine, and iodine.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , 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 include, as an alkyl group having 1 to 10 carbon atoms, methyl , ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoro Romethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoro Ethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tridecafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl, methoxymethyl, 1,2-epoxyethyl, methoxyethyl, Methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, tert-butylthiomethyl, 4-pentenyloxymethyl, trichloroethoxymethyl, bis(2-chloroethoxy)methyl, methoxycyclo Hexyl, 1-(2-chloroethoxy)ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl, trimethylsilylethyl, tert-butyldimethylsilyloxymethyl, 2-(trimethylsilyl)ethoxymethyl, tert-butoxycarbonylmethyl, ethyloxycarbonylmethyl, ethylcarbonylmethyl, tert-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxyethyl, 2-methyl-2-adamantyloxy Carbonylmethyl, acetylethyl, 2-methoxy-1-propenyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl , 4-hydroxybutyl, 1,2-dihydroxyethyl, etc. for example.

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 the alkoxy group having 1 to 10 carbon atoms are methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, sec- Butyloxy, tert-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-Methoxyethyloxy, 3-methoxypropyloxy, 4-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 the ester group having 2 to 10 carbon atoms include methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, and phenoxycarbonyl. carbonyl, acetoxy, propionyloxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, tert-butylcarbonyloxy, methoxyacetyloxy, benzoyloxy, etc. can be heard

(A) The use ratio of the cationic polymerization initiator (B) with respect to a total of 100 mass parts of (A) component, (C)component, and (E) component is 0.1-10 mass parts of cationic polymerization initiators (B) Preferably 1-6 is the mass part. When too small, hardening tends to become inadequate easily, and when too large, it may exert a bad influence on various physical properties, such as water absorption of hardened|cured material and hardened|cured material intensity|strength.

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 meta of an alcohol having 2 to 20 carbon atoms. Acrylic acid ester (C2) is an essential component.

The compound (C1) having an epoxy group and an ethylenically unsaturated group includes, for example, an epoxy acrylate or an epoxy methacrylate, and specifically, a conventionally known aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, etc.; It is an acrylate obtained by making acrylic acid or methacrylic acid react. Among these epoxy acrylates or epoxy methacrylates, acrylates or methacrylates of glycidyl ethers of alcohols are particularly preferable.

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 oxide adduct thereof and acrylates or methacrylates obtained by reacting with acrylic acid or methacrylic acid. Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, isooctyl acrylate, tetrahydrofur Furyl acrylate, isobornyl acrylate, benzyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene Glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ε-capro Lactone-modified dipentaerythritol hexaacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, isoamyl methacrylate, lauryl methacrylate, stearyl Methacrylate, isooctyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, benzyl methacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1 ,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethyl Allpropane trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, ε-caprolactone-modified dipentaerythritol hexamethacrylate, and the like are exemplified. And among these acrylates or methacrylates, polyacrylates of polyhydric alcohols or polymethacrylates of polyhydric alcohols are particularly preferable.

As said radically polymerizable component (C), the compound which polymerizes or crosslinks with the radical polymerization initiator activated by energy ray irradiation or heating other than (C1) or (C2) can also be used, For example, allyl urethane compounds, unsaturated polyester compounds, styrene compounds, and the like. As for the ratio of the said (C1) component and (C2) component in a radically polymerizable component (C), 50 mass % or more is preferable.

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

The polymer (E) related to the curable composition of the present invention is selected from a polymer obtained from the monomer represented by the formula (I), a polymer obtained from the monomer represented by the formula (II), and a monomer represented by the formula (I). A polymer obtained from two or more monomers, a polymer obtained from two or more monomers selected from the monomers represented by the formula (II), and a monomer represented by the formula (I) and a monomer represented by the formula (II). It is selected from the group which consists of the polymer obtained, and a weight average molecular weight is 1,000-30,000 in terms of polystyrene.

Examples of the alkyl group having 1 to 7 carbon atoms represented by X in the formula (I) include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, 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 an alkyl group having 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 is a point of curability preferred in

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

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

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

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

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

In the formula (I), in the case where a part of X is substituted with an epoxy group or an oxetane group, the monomer represented by the formula (I) is, for example, represented by the following formulas (1) to (3) There are monomers that become

Here, in Formula (1), R<^3> represents a hydrogen atom or a C1-C6 alkyl group, and m is an integer of 1-6.

Here, in Formula (2), R<^4> represents a hydrogen atom or a C1-C6 alkyl group, and n is an integer of 1-6.

Here, in Formula (3), R<^5> represents a hydrogen atom or a C1-C6 alkyl group, and s is an integer of 1-6.

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

In the formula (II), as an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, X' is represented by the formula (I) and The same can be exemplified.

In the formula (II), when a part of X' is substituted with an epoxy group or an oxetane group, examples of the monomer represented by the formula (II) include those represented by the following formulas (4) to (6). can be heard

Here, in Formula (4), R<^1> is the same as that of said Formula (II), R<^6> represents a hydrogen atom or a C1-C6 alkyl group, and t is an integer of 1-6.

Here, in Formula (5), R<^1> is the same as that of said Formula (II), R<^7> represents a hydrogen atom or a C1-C6 alkyl group, and q is an integer of 1-6.

Here, in Formula (6), R<^1> is the same as that of said Formula (II), R<^8> represents a hydrogen atom or a C1-C6 alkyl group, and y is an integer of 1-6.

In the above-mentioned polymer (E), the ratio of the monomer constituting the polymer to be used is, wherein X is an epoxy group, an oxetane group, a hydroxyl group, and a carboxyl group having 1 to 7 carbon atoms substituted with one or more groups selected from the group consisting of In the case of an alkyl group, an aryl group having 6 to 12 carbon atoms, or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, the monomer represented by (I) or (II) is 10 to 100% by mass. It is preferable at the point that adhesiveness improves.

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 cation polymerization initiator (B) is 0.1 to 10 parts by mass, preferably 1 -8 mass parts, 0-55 mass parts of said radically polymerizable component (C), 0-10 mass parts of said radical polymerization initiator (D), Preferably 0.1-8 mass parts, said polymer (E) is 1 -30 parts by mass. If it is other than the above-mentioned mixing ratio, there exists a possibility that sclerosis|hardenability and adhesiveness of hardened|cured material may become poor.

A sensitizer and/or a sensitizer adjuvant can further be used for the curable composition of this invention as needed. A sensitizer is a compound which shows maximum absorption in the wavelength longer than the maximum absorption wavelength which a cationic polymerization initiator (B) shows, and accelerates|stimulates the polymerization initiation reaction by a cationic polymerization initiator (B). Moreover, a sensitizer is a compound which accelerates|stimulates the action|action of a sensitizer further.

As a sensitizer and a sensitizer adjuvant, an anthracene type compound, a naphthalene type compound, etc. are mentioned.

As an anthracene-type compound, there exists a thing represented by following formula (7), for example.

Here, in formula (7), R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 12 carbon atoms, and R ⁵² is a hydrogen atom or a carbon atom. The number 1-6 alkyl group is shown.

Specific examples of the anthracene-based compound represented by the 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 2-ethyl-9,10-dipentyloxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene, etc. have.

As a naphthalene type compound, there exists a thing represented by following formula (8), for example.

Here, in 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 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, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, 1,4-dibutoxynaphthalene, and the like.

The ratio of use of the sensitizer and the sensitizer to the cationically polymerizable component (A) is not particularly limited, and it is preferably used in a generally normal ratio within the range that does not impair the object of the present invention, for example, It is preferable from a viewpoint of sclerosis|hardenability improvement that it is 0.1-3 mass parts, respectively, of a sensitizer and a sensitizer with respect to 100 mass parts of the said cationically polymerizable component (A).

A silane coupling agent can be used for the curable composition of this invention as needed. Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyl Alkenyl functional alkoxysilanes, such as alkyl functional alkoxysilanes, such as trimethoxysilane, vinyltrichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, and allyl trimethoxysilane, 3-methacryloxypropyl tri Ethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ- Epoxy functional alkoxysilanes, such as glycidoxypropyl trimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-β(aminoethyl )-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, amino-functional alkoxysilane such as N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. Titanium alkoxides such as mercapto functional alkoxysilane, titanium tetraisopropoxide, and titanium tetranormal butoxide, titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethylacetoacetate), etc. titanium chelates, zirconium chelates such as zirconium tetraacetylacetonate and zirconium tributoxy monoacetyl acetonate, zirconium acylates such as zirconium tributoxy monostearate, and isocyanate silanes such as methyl triisocyanate silane Can be used.

Although the usage-amount of the said silane coupling agent is not specifically limited, Usually, it is the range of 0.01-20 mass parts with respect to 100 mass parts of whole quantity of solids in a 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 as needed. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate ethyl acrylate copolymer, methyl methacrylate glycidyl methacrylate copolymer, poly(meth)acrylic acid, styrene-(meth). ) acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, glycidyl (meth)acrylate-polymethyl (meth)acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, saturated poly esters and the like.

In the curable composition of the present invention, if necessary, the UV absorber or UV absorber is inactive at room temperature, and the protecting group is detached by heating to a predetermined temperature, light irradiation, acid, etc. compounds may be used.

In addition, as long as the effects of the present invention are not impaired, colorants such as polyols, inorganic fillers, organic fillers, pigments, and dyes, defoamers, thickeners, surfactants, and leveling agents, if necessary and various resin additives such as flame retardants, thixotropic agents, diluents, plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow regulators, and adhesion promoters.

It does not restrict|limit especially for the curable composition of this invention, A solvent which can dissolve and disperse|distribute each component of said (A), (B), (C), (D), and (E) which is used normally can be used for it. 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; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; Ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, etc. of an ether ester solvent; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; Terpene hydrocarbon oils, such as turpentine oil, D-limonene, and pinene; Paraffinic solvents, such as petroleum alcohol, Swasol #310 (made by Cosmo Matsuyama Petroleum Co., Ltd.), and Sorvesso #100 (Exxon Chemical Corporation); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; Propylene carbonate, carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide , and water. These solvents can be used as 1 type or 2 or more types of mixed solvent.

Since sclerosis|hardenability, adhesiveness, and liquid storage stability improve, it is preferable that it is 5 mass parts or less, and, as for the curable composition of this invention, it is more preferable that it is 3 mass parts or less. When there is too much water|moisture content, since there exists a possibility that it may become cloudy or a component may precipitate, it is unpreferable.

The curable composition of this invention is applied on a support base material by well-known means, such as a roll coater, a curtain coater, various printing, and immersion. Moreover, after carrying out once on support substrates, such as a film, it can also be transcribe|transferred on another support substrate, and there is no restriction|limiting in the application method.

It does not restrict|limit especially as a material of the said support base, What is normally used can be used, For example, Inorganic materials, such as glass; cellulose esters such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, and nitrocellulose; polyamide; polyimide; Polyurethane; epoxy resin; polycarbonate; Polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanezymethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polybutyl polyesters such as lenterephthalate; polystyrene; polyolefins such as polyethylene, polypropylene, and polymethylpentene; vinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; polyetherimide; polymer materials such as polyoxyethylene, norbornene resin, and cycloolefin polymer (COP). In addition, you may perform surface activation processing, such as a corona discharge treatment, a flame treatment, an ultraviolet treatment, a high frequency treatment, a glow discharge treatment, an active plasma treatment, and a laser treatment, to the said support base body.

In the method of hardening the curable composition of this invention by irradiation of an energy ray, an ultraviolet-ray, an electron beam, X-ray, a radiation, a radio frequency etc. are mentioned as an energy-beam, and an ultraviolet-ray is economically most preferable. As a light source of an ultraviolet-ray, an ultraviolet laser, a mercury lamp, a xenon laser, a metal halide lamp, etc. are mentioned.

The conditions in the method of hardening the curable composition of this invention by heating are 1-100 minutes at 70-250 degreeC. After pre-baking (PAB; Pre applied bake), it may pressurize, post exposure bake (PEB) may be carried out, and you may bake at the temperature of several different steps. Although the heating conditions differ depending on the type and mixing ratio of each component, for example, at 70 to 180°C, for 5 to 15 minutes in an oven, and 1 to 5 minutes in the case of a hot plate. Then, in order to harden a coating film, a cured film can be obtained by heat-processing at 180-250 degreeC, Preferably it is 200-250 degreeC, 30-90 minutes in an oven, and 5-30 minutes in case of a hot plate.

Specific uses of the curable composition of the present invention or its cured product include adhesives, glasses, optical materials typified by imaging lenses, paints, coatings, linings, inks, resists, liquid resists, printing plates, color TVs, PC monitor, portable information terminal, digital camera, organic EL, display elements such as touch panel, insulating varnish, insulating sheet, laminated board, printed circuit board, for semiconductor device, for LED package, for liquid crystal inlet, for organic EL, for optical element, Encapsulant for electrical insulation/electronic component/separator, etc., casting material, putty, glass fiber impregnating agent, sealing agent, passivation film for semiconductor/solar cell, etc., interlayer insulating film, protective film, liquid crystal display A lens part of a lens sheet such as a prism lens sheet used for a backlight of a device, a Fresnel lens sheet used for a screen such as a projection TV, a lenticular lens sheet, or an optical lens such as a micro lens, such as a backlight using such a sheet; An optical element, an optical connector, an optical waveguide, a casting agent for optical shaping|molding, etc. are mentioned as an example.

In the display device of the present invention, each layer, such as 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 lubricant layer, and a protective layer, is provided on a transparent support body as needed One can be mentioned as an example, and the film which consists of the hardened|cured material of this invention can be used for each layer.

[Example]

Hereinafter, the present invention will be described in more detail by taking examples and the like, but the present invention is not limited to these examples.

[Examples 1 to 7, Reference Examples 1 to 4, Comparative Example 1]

Each component was sufficiently mixed by the formulation shown in [Table 1] and [Table 2] below to obtain the curable compositions of Examples 1 to 7 and Reference Examples 1 to 4 and the curable composition of Comparative Example 1, respectively. In addition, the unit of an Example and a comparative example is a mass part.

As the cationically polymerizable component (A), the following compounds (A1-1) to (A1-2) and (A2-1) to (A2-2) were used.

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 Co., Ltd.)

Compound (A2-2): limonene dioxide

Compound (A4-1): Aronoxetane OXT-221 (manufactured by Toa Synthesis Co., Ltd.)

The following compound (B-1) was used as a cationic polymerization initiator (B).

Compound (B-1): 50% solution of propylene carbonate of a mixture of a compound represented by the following formula (9) and a compound represented by the following formula (10)

As the radically polymerizable component (C), the following compound (C2-1) was used.

Compound (C2-1): 1,6-hexanediol diacrylate

Compound (C2-2): ethoxylated isocyanuric acid triacrylate

Compound (C2-3): tetrahydrofurfuryl acrylate

As the radical polymerization initiator (D), the following compound (D-1) was used.

Compound (D-1): Irgacure 184 (manufactured by BASF)

As the polymer (E), the following compound (E-1) was used.

Polymer (E-1): A copolymer of 75 parts by mass of methyl methacrylate and 25 parts by mass of glycidyl methacrylate (weight average molecular weight 7,000)

Polymer (E-2): A 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 of 8,000)

About each curable composition of the obtained Examples 1-7, Reference Examples 1-4, and Comparative Example 1, the glass transition temperature (Tg), an elasticity modulus, and adhesiveness were evaluated according to the following procedure. A result is written together in [Table 1] and [Table 2].

(Glass Transition Temperature and Modulus of Elasticity)

Each of the obtained curable compositions of Examples 1 to 7, Reference Examples 1 to 4, 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. to irradiate an energy of 3000 mJ/cm ^{2 .} After 24 hours, the adhesive cured product 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 Sciences Co., Ltd.

(Viscosity)

About each curable composition of each of the obtained Examples 1-7, Reference Examples 1-4, and Comparative Example 1, the viscosity in 25 degreeC was measured with the E-type viscometer. A result is written together in [Table 1] and [Table 2].

(Adhesiveness)

The curable compositions of Examples 1 to 7, Reference Examples 1 to 4, and Comparative Example 1 obtained above were respectively coated on one corona-treated PMMA film (Sumitomo Chemical Co., Ltd.: Technoroy 125S001), and then 1 COP (cycloolefin polymer, manufactured by Nippon Zeon Co., Ltd.: Part No. Zeonoa Film 14-060) film subjected to corona discharge treatment of the intestine is bonded using a laminator, and 1000mJ/cm ^{2 using an electrodeless UV lamp} Corresponding light was irradiated over the COP film and adhere|attached, and the test piece was obtained. The obtained test piece was subjected to a 90 degree peel test. The results are shown in [Table 1] and [Table 2].

[Table 1]

[Table 2]

[Table 1] to [Table 2] show clearly that the curable composition of the present invention has a high glass transition temperature of the cured product and is excellent in adhesiveness.

Claims (7)

30-99 mass parts of a cationically polymerizable component (A), 0.1-10 mass parts of a cation polymerization initiator (B), 0-55 mass parts of a radically polymerizable component (C), and 0-10 mass parts of a radical polymerization initiator (D) mass and
A polymer obtained from a monomer represented by the following formula (I):

(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, or an aryloxy group having 6 to 12 carbon atoms. or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a hydrogen atom in these groups is substituted with one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group);
A polymer obtained from a monomer represented by the following formula (II):

(In the formula (II), R ¹ represents a hydrogen atom, a methyl group or a halogen atom, and X' represents an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl group having 6 to carbon atoms. The alicyclic hydrocarbon group of 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), selected from the monomers represented by the above formula (I) A polymer obtained from two or more monomers, a polymer obtained from two or more monomers selected from the monomers represented by the formula (II), or a monomer represented by the formula (I) and a monomer represented by the formula (II). 1 to 30 parts by mass of a polymer (E) having a weight average molecular weight of 1,000 to 30,000 selected from the group consisting of obtained polymers, the sum of the cationically polymerizable component (A), the radically polymerizable component (C), and the polymer (E) contains so that it becomes 100 parts by mass,
The cationically polymerizable component (A) contains, as essential components, 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) and an alicyclic epoxy compound (A2) and wherein 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 condensed ring,
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 or a methacrylic ester of an alcohol having 2 to 20 carbon atoms (C2 ) as an essential component, the curable composition. According to claim 1,
The alicyclic epoxy compound (A2) is 3',4'-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, 7-oxabicyclo[4.1.0]heptane, poly[oxy-(1) -oxo-1,6-hexanediyl)] derivative, hexanedioic acid bis[(7-oxabicyclo[4.1.0]heptan-3-yl)methyl], 1,2-epoxy-4-vinylcyclohexane, 3 , At least one selected from the group consisting of 4-epoxycyclohexylmethyl methacrylate and limonene dioxide, the curable composition. According to claim 1,
The polymer (E) is a polymer obtained from the monomer represented by the formula (I) and the monomer represented by the formula (II), wherein X in the formula (I) is an aryl group having 6 to 12 carbon atoms; The curable composition in which X' in the said formula (II) is a C1-C7 alkyl group, and the said alkyl group is substituted by the epoxy group. The hardening method of a curable composition which irradiates an active energy ray to the curable composition in any one of Claims 1-3. The curing method of a curable composition which heats the curable composition in any one of Claims 1-3. The hardened|cured material which is a hardened|cured material of the curable composition in any one of Claims 1-3. delete