KR102272147B1 - 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, 하기 식(II)

(식 중, R¹은 수소 원자 등을 나타내고, X'는 탄소 원자수 1∼7의 알킬기 등)으로 표시되는 단량체로부터 얻어지는 폴리머 등(E) 1∼20 질량부를, (A) 성분과 (C) 성분의 합계가 100질량부가 되도록 함유하고, (A) 성분이, 다가 알코올의 글리시딜화물 등(A1)과, 옥세탄 화합물(A2)을 필수 성분으로 하고, (C) 성분이, 에폭시기 및 에틸렌성 불포화기를 가지는 화합물(C1) 등을 필수 성분으로 한다.Provided 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. 45 to 90 parts by mass of a cationically polymerizable component (A), 0.001 to 15 parts by mass of a cationic polymerization initiator (B), 1 to 15 parts by mass of a radically polymerizable component (C), 1 to 10 parts by mass of a radical polymerization initiator (D); and the formula (I)

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

(wherein, R ¹ represents a hydrogen atom, etc., X' represents an alkyl group having 1 to 7 carbon atoms, etc.) 1 to 20 parts by mass of a polymer obtained from a monomer, etc. (E), (A) component and (C ) contained so that the total of the component may be 100 parts by mass, (A) component is a polyhydric alcohol glycidylated product (A1) and an oxetane compound (A2) as essential components, (C) component is an epoxy group and a compound (C1) having an ethylenically unsaturated group as essential components.

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 are made regarding improvement of such a 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. Specifically, in Patent Document 1, an adhesive composition for a polarizing plate excellent in initial curability and adhesiveness is proposed. In addition, in Patent Document 2, even when a resin film having a low moisture permeability is used as a protective film, the adhesive force is rapidly expressed after light irradiation, and the adhesive force after a certain period of time is good with respect to various forces, and does not cause a problem even after the durability test, A low-viscosity photocurable adhesive with good adhesive strength after completion of the heat-and-moisture test has been proposed. Moreover, in patent document 3, the high heat resistance containing an unsaturated alicyclic epoxy ester compound, high refractive index-ization, and the active energy ray polymeric resin composition which can make transparency compatible are proposed.

Japanese Laid-Open Patent Publication No. 2014-105218 Japanese Laid-Open Patent Publication No. 2015-040283 Japanese Laid-Open Patent Publication No. 2015-168757

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

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 this invention contains 45-90 mass parts of cationically polymerizable components (A), 0.001-15 mass parts of cation polymerization initiators (B), 1-15 mass parts of radically polymerizable components (C), 1 to 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 A polymer obtained from a monomer represented by -10 alicyclic hydrocarbon groups, 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 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 hydrocarbon having 6 to 10 carbon atoms. A polymer obtained from a monomer represented by a 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 a monomer represented by the above formula (I) A polymer obtained from two or more kinds of monomers selected, a polymer obtained from two or more kinds of monomers selected from monomers represented by the formula (II), and a monomer represented by the formula (I) and a monomer represented by the formula (II) 1 to 20 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 a polymer obtained from the cationically polymerizable component (A), the radically polymerizable component (C) and the polymer (E) It contains so that the total may be 100 parts by mass,

The cationically polymerizable component (A) contains, as essential components, a glycidylated product of a polyhydric alcohol or a glycidylated product of a polyhydric alcohol alkylene oxide adduct (A1) and an oxetane 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 a polyhydric alcohol having 2 to 20 carbon atoms or a methacrylic acid ester of a polyhydric alcohol having 2 to 20 carbon atoms. It is characterized by having (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, it is preferable to further contain an aromatic epoxy compound (A3) as the cationically polymerizable component (A). Moreover, in the curable composition of this invention, it is preferable that the said aromatic epoxy compound (A3) is 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), wherein X in the formula (I) is, It is a C6-C12 aryl group, X' in 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 45-90 mass parts of cationically polymerizable components (A), 0.001-15 mass parts of cation polymerization initiators (B), 1-15 mass parts of radically polymerizable components (C), and radical polymerization 1 to 10 parts by mass of an 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), 2 selected from 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), and a polymer obtained from a monomer represented by the following formula (I) and a monomer represented by the following formula (II) 1 to 20 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) contains a glycidylated product of a polyhydric alcohol or a glycidylated product of a polyhydric alcohol alkylene oxide adduct (A1) and an oxetane compound (A2) as essential components. 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 a polyhydric alcohol having 2 to 20 carbon atoms or methacrylic acid of a polyhydric alcohol having 2 to 20 carbon atoms. Acid ester (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 contains a glycidylated product of a polyhydric alcohol or a glycidylated product of a polyhydric alcohol alkylene oxide adduct (A1) and an oxetane compound (A2) as essential components. However, as another epoxy compound, an aromatic epoxy compound (A3), an alicyclic epoxy compound (A4), etc. can also be used.

Examples of the glycidylated product of the polyhydric alcohol or the glycidylated product (A1) of the polyhydric alcohol alkylene oxide adduct include those obtained by glycidylating a polyhydric alcohol or polyhydric alcohol alkylene oxide adduct, glycidylated product It is preferable that the molecular weight of is 250 or more.

As the glycidylated product of the polyhydric alcohol or the glycidylated product (A1) of the polyhydric alcohol alkylene oxide adduct, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neo Pentyl glycol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl of polyethylene glycol ether, glycidyl ether of polyhydric alcohols such as diglycidyl ether of polypropylene glycol, dicyclopentadiene dimethanol diglycidyl ether, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerin, or The polyglycidyl ether product of the polyether polyol obtained by adding 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 a 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 octyl epoxystearate. , butyl epoxystearate, epoxidized soybean oil, epoxidized polybutadiene, and the like.

As the glycidylated product of a polyhydric alcohol or the glycidylated product (A1) of a polyhydric alcohol alkylene oxide adduct, it is preferable to have a saturated condensed ring, since sclerosis and adhesiveness of the cured product are improved.

Commercially available products can be used as the glycidylated product of the polyhydric alcohol or the glycidylated product (A1) of the polyhydric alcohol alkylene oxide adduct, for example, denacol EX-121, denacol EX-171, and denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX- 512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase Chemtex 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.

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 glycolbis(3- Ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, 1,4 Bifunctional aliphatic oxetane compounds such as -bis(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) ) and monofunctional oxetane compounds such as 3-ethyl-3-(chloromethyl)oxetane and the like. Especially, since adhesiveness improves a bifunctional aliphatic oxetane compound, it is preferable. These can be used individually by 1 type or in combination of 2 or more type.

As said oxetane compound (A2), a commercial item can be used, For example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (Maruzen Petrochemical ) (manufactured by Co., Ltd.); 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.

The aromatic epoxy compound (A3) represents an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound (A3) include polyhydric phenols having at least one aromatic ring, such as phenol, cresol, and butylphenol, or its alkyl Mono/polyglycidyl ether products of renoxide adducts, for example, bisphenol A, bisphenol F, or glycidyl ether products or epoxy novolac resins of compounds obtained by adding 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; glycytyl esters of polybasic aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, etc., glycytyl esters of benzoic acid, epoxides of styrene oxide or divinylbenzene, and the like.

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-711. Cole EX-721, On-coat EX-1020, On-coat EX-1030, On-coat EX-1040, On-coat EX-1050, On-coat EX-1051, On-coat EX-1010, On-coat EX-1011, On-coat 1012 (manufactured by Nagase Chemtex 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 Nippon Chemical Co., Ltd.); Epicoat 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 Kayaku Co., Ltd.) ) manufactured by ); 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.) etc. are mentioned. As said aromatic epoxy compound (A3), since it is excellent in sclerosis|hardenability, a polyfunctional thing is preferable.

The said alicyclic epoxy compound (A4) 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 (A4) 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-pinene oxide, limonene dioxide, and the like. As the alicyclic epoxy compound (A4), 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 (A4), a commercial item can be used, For example, Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000 (made by Daicel Corporation) etc. exist.

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 or a glycidylated product of a polyhydric alcohol alkylene oxide adduct (A1), an oxetane compound (A2), an aromatic epoxy compound (A3), an alicyclic The usage ratio of a formula epoxy compound (A4) and a vinyl ether compound is the glycidyl product (A1) of the glycidyl product of polyhydric alcohol or polyhydric alcohol alkylene oxide adduct with respect to 100 mass parts of cationically polymerizable components (A). 50 to 80 parts by mass, 20 to 50 parts by mass of an oxetane compound (A2), 0 to 50 parts by mass of an aromatic epoxy compound (A3), 0 to 30 parts by mass of an alicyclic epoxy compound (A4), 0 to 20 parts by mass of a vinyl ether compound A negative thing is preferable since a viscosity, applicability|paintability, reactivity, and hardenability improve.

The cationic polymerization initiator (B) according to the curable composition of the present invention is not limited by 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, it is preferable that the cation [A]r+ is 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 several atoms other than carbon atoms. a is an integer from 1 to 5; a pieces of R ² are 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. In addition, 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).

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

[LY _b ] with ^r-

can be displayed

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. Moreover, 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 other anions that can be used, perchlorate ion (ClO ₄ ) ^- , trifluoromethylsulfite ion (CF ₃ SO ₃ ) - , fluorosulfonic acid ion (FSO ₃ ) ^- , toluenesulfonic acid anion, trinitrobenzenesulfonic acid anion , camphor sulfonate, 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, tolylcumyliodoniumtetrakis ( 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, triphenylsilanol, etc. mixtures with silanols; salts such as thiophenium salt, thioranium salt, benzylammonium salt, 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-dimethyldecanedioic 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 to 10, an alkoxy group having 1 to 10 carbon atoms, or an ester group having 2 to 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, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms represents an alkoxy group or an ester group having 2 to 10 carbon atoms, and R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms. indicates.

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, ethyl octyl, 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. can be exemplified.

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 usage ratio of the cationic polymerization initiator (B) with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component is 0.001-15 mass parts of cationic polymerization initiators (B), Preferably 0.1-10 mass parts 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 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.

Examples of the compound (C1) having an epoxy group and an ethylenically unsaturated group include epoxy acrylate or epoxy methacrylate, and specifically, conventionally known aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, etc. , an acrylate obtained by reacting acrylic acid or methacrylic acid. 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 A urethane compound, an unsaturated polyester compound, a styrenic compound, etc. are mentioned. 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, and tricyclooctyl. , tricyclodecanyl, spirooctyl, spirobicyclopentyl, adamantyl, isobornyl and the like.

In these alkyl groups, alkoxy groups, aryl groups, aryloxy groups and alicyclic hydrocarbon groups, hydrogen atoms in these groups may be 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.

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), X' is 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, which is the same as in the formula (I). 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 amount of the monomer represented by (I) or (II) is 10 to 100% by mass. , which is preferable because the adhesiveness is improved.

In the curable composition of this invention, the said cationically polymerizable component (A) is 45-90 mass parts with respect to a total of 100 mass parts of a cationically polymerizable component (A), a radically polymerizable component (C), and a polymer (E). , 0.001 to 15 parts by mass of the cationic polymerization initiator (B), 1 to 15 parts by mass of the radically polymerizable component (C), 1 to 10 parts by mass of the radical polymerization initiator (D), and the polymer (E) It is 1-20 mass parts. 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 a C1-C6 alkyl group.

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 preferable to use it 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., and activated, and the UV absorbing ability is expressed Further 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 , various resin additives such as flame retardant, thixotropic agent, diluent, plasticizer, stabilizer, polymerization inhibitor, ultraviolet absorber, antioxidant, antistatic agent, flow regulator, adhesion promoter and the like can be added.

It does not restrict|limit especially for the curable composition of this invention, The solvent which can melt|dissolve or disperse|distribute each component of said (A), (B), (C), (D), and (E) which is normally used can be used. 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 terpine oil, D-limonene, and pinene; Paraffinic solvents, such as mineral spirit, 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 the curable composition of this invention improves sclerosis|hardenability, adhesiveness, and liquid storage stability, it is preferable that it is 5 mass parts or less, and 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 bases, such as a film, it can also transfer on another support base, and there is no restriction|limiting in the application method.

The material of the support base is not particularly limited, and those commonly used can be used, and examples thereof include those made of an inorganic material 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-cyclohexanedimethylene 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, a surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment may be applied to the support substrate.

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: Post exposure bake) may be carried out, and you may bake at the temperature of several different steps. Although heating conditions differ depending on the kind and mixing ratio of each component, for example, it is 70-180 degreeC, 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, Display elements such as PC monitors, portable information terminals, digital cameras, organic EL and touch panels, insulating varnish, insulating sheets, laminates, printed circuit boards, semiconductor devices, LED packages, liquid crystal inlet, organic EL, optical devices, etc. Encapsulant for electrical insulation, electronic component, separator, etc., molding material, putty, glass fiber impregnating agent, sealing agent, passivation film for semiconductor, solar cell, etc., interlayer insulating film, protective film, used for backlight of liquid crystal display device A lens part of a lens sheet such as a prism lens sheet, a Fresnel lens sheet used for a screen such as a projection TV, a lenticular lens sheet, or a backlight using such a sheet, an optical lens such as a micro lens, an optical element, an optical connector , optical waveguides, casting agents for optical molding, and the like.

Examples of the display device include those in which 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. 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 20, Comparative Examples 1 to 7]

Each component was thoroughly mixed by the formulation shown in the following [Table 1] - [Table 5], and the curable composition of Examples 1-20 and the curable composition of Comparative Examples 1-7 were obtained, respectively. In addition, the unit of an Example and a comparative example is a mass part.

The following compound was used as a 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 Synthesis 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 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 a radically polymerizable component (C), the following compound was used.

Compound (C1-1): Epoxy ester M-600A (manufactured by Kyoeisha Chemical Co., Ltd.)

Compound (C1-2): Epoxy ester 70PA (manufactured by Kyoeisha Chemical Co., Ltd.)

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

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 of glycidyl methacrylate (weight average molecular weight 7,000)

As the polymer (E'), the following compound (E'-1) and the following (E'-2) were used.

Compound (E'-1): Copolymer of 75 mass parts of methyl methacrylate and glycidyl methacrylate 25 (weight average molecular weight 800)

Compound (E'-2): A copolymer of 75 parts by mass of methyl methacrylate and 25 of glycidyl methacrylate (weight average molecular weight 35,000)

Glass transition temperature (Tg), elastic modulus, viscosity, and adhesiveness were evaluated according to the following procedure about each curable composition of the obtained Examples 1-20 and Comparative Examples 1-7.

A result is written together in [Table 1] - [Table 5].

(Glass Transition Temperature and Modulus of Elasticity)

Each of the obtained curable compositions of Examples 1 to 20 and Comparative Examples 1 to 7 was applied on a polyethylene terephthalate (PET) film to a thickness of 30 µm with a bar coater, and 3000 mJ/cm using a metal halide lamp The energy of ^{2 was investigated.} 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.

About each of the obtained Examples 1-20 and each curable composition of Comparative Examples 1-7, the viscosity in 25 degreeC was measured with the E-type viscometer. A result is written together in [Table 1] - [Table 5].

(Adhesiveness)

After each of the compositions of Examples 1 to 20 and Comparative Examples 1 to 7 obtained above were coated with one corona-treated PMMA film (Sumitomo Chemical Co., Ltd.: Decnoroy 125S001), another corona discharge treatment was performed. COP (cycloolefin polymer, manufactured by Nippon Zeon: Part No. Zeonoa Film 14-060) film and laminator were used to bond, and using an electrodeless ultraviolet light lamp, light ^{equivalent to 1000 mJ/cm 2} was irradiated through the COP film. It adhered to obtain a test piece. The obtained test piece was subjected to a 90 degree peel test.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

From [Table 1] to [Table 5], it can be clearly seen that the curable composition of the present invention is excellent in the curability and adhesiveness of the cured product.

Claims (7)

45 to 90 parts by mass of a cationically polymerizable component (A), 0.001 to 15 parts by mass of a cationic polymerization initiator (B), 1 to 15 parts by mass of a radically polymerizable component (C), 1 to 10 parts by mass of a radical polymerization initiator (D); 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, 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' 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 10 carbon atoms. An alicyclic hydrocarbon group, or a hydrogen atom in these groups is substituted with at least one group selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group), at least two selected from the monomers represented by the formula (I) A polymer obtained from a monomer, a polymer obtained from two or more monomers selected from the monomers represented by the formula (II), and a polymer obtained from the monomer represented by the formula (I) and the monomer represented by the formula (II) 1 to 20 parts by mass of a polymer (E) having a weight average molecular weight of 1,000 to 30,000 selected from the group, 100 parts by mass of the total of the cationically polymerizable component (A), the radically polymerizable component (C) and the polymer (E) contain as much as possible,
The cationically polymerizable component (A) contains, as essential components, a glycidylated product of a polyhydric alcohol or a glycidylated product of a polyhydric alcohol alkylene oxide adduct (A1) and an oxetane 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 a polyhydric alcohol having 2 to 20 carbon atoms or a methacrylic acid ester of a polyhydric alcohol having 2 to 20 carbon atoms. A curable composition comprising (C2) as an essential component. According to claim 1,
The curable composition which further contains an aromatic epoxy compound (A3) as said cationically polymerizable component (A). 3. The method of claim 2,
The said aromatic epoxy compound (A3) is a polyfunctional aromatic epoxy compound, 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 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 1-4. The curing method of the curable composition which heats the curable composition in any one of Claims 1-4. The hardened|cured material which is a hardened|cured material of the curable composition in any one of Claims 1-4.