TW201809020A - Curable composition, cured product production method, and cured product therefrom - Google Patents

Abstract

Provided are a curable composition that provides a cured product with a high glass transition temperature and excellent adhesion, a cured product production method, and a cured product therefrom. The curable composition includes: a cationically polymerizable component (A); a cationic polymerization initiator (B); a radically polymerizable component (C); a radical polymerization initiator (D); and a polymer (E) having a weight-average molecular weight of 1,000-30,000 and selected from the group consisting of a polymer obtained from the monomer represented by formula (I) (in the formula, X is a C1-7 alkyl group, or the like) and a polymer obtained from the monomer represented by formula (II) (in the formula, R1 represents a hydrogen atom, or the like, and X' is a C1-7 alkyl group, or the like). Component (A) includes, as essential components, a glycidylated product of a polyhydric alcohol having a molecular weight of at least 200, and an oxetane compound. Component (C) includes, as an essential component, a compound which has an epoxy group and an ethylenically unsaturated group, or a C2-20 acrylic acid ester of an alcohol.

Description

Hardenable composition, method for producing hardened material, and hardened material

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

The curable composition is used in the fields of inks, coatings, various coating agents, adhesives, and optical members. There have been various reports on the improvement of such hardenable compositions.

For example, in the following Patent Documents 1 to 4, an energy ray-curable composition containing a cation polymerizable component and a radical polymerizable component and a cured product thereof are proposed. Specifically, Patent Document 1 proposes an adhesive composition for a polarizing plate having excellent initial hardenability and adhesion. Further, in Patent Documents 2 and 3, even when a resin film with low moisture permeability is used as a protective film, the adhesion force can be quickly exhibited after light irradiation, and after a certain period of time, various adhesion forces are good, and the durability test is good. No problem occurred afterwards, and the light-curing adhesive with low viscosity was also good in adhesion after the end of the moist-heat resistance test. In addition, Patent Document 4 proposes an active energy ray polymerization containing an unsaturated alicyclic epoxy ester compound that can have both high heat resistance, high refractive index, and transparency. Sexual resin composition.

[Prior technical literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Laid-Open No. 2014-105218

Patent Document 2: Japanese Patent Application Laid-Open No. 2015-040283

Patent Document 3: Japanese Patent Laid-Open No. 2015-143352

Patent Document 4: Japanese Patent Application Laid-Open No. 2015-168757

However, even with the curable composition proposed in Patent Documents 1 to 4, there is a case where the curability and adhesion may not be satisfied. The current situation is to expect a novel, highly curable composition. Hardening composition.

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

As a result of careful study by the present inventors in order to solve the above-mentioned problems, it has been found that if the curable composition has a specific composition, the above-mentioned problems can be overcome and the present invention has been completed.

That is, the curable composition of the present invention contains a cationic polymerizable component (A), a cationic polymerization initiator (B), a radical polymerizable component (C), and a radical polymerization initiator (D). And selected from the following formula (I) (Where X is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a carbon atom A hydrogen atom in an alicyclic hydrocarbon group of 6 to 10 or these groups is substituted by one or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group, and a carboxyl group) A polymer obtained from a monomer of 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 group having 6 to 10 carbon atoms Or a polymer in which a hydrogen atom in these groups is substituted with one or more types of monomers selected from the group consisting of epoxy, oxetanyl, hydroxyl, and carboxyl groups; A polymer obtained from two or more monomers of the monomer represented by the aforementioned formula (I), a polymer selected from two or more monomers of the monomer represented by the aforementioned formula (II), and a polymer selected from the aforementioned formula The polymer (E) having a weight average molecular weight of 1,000 to 30,000 in a group of the monomer represented by (I) and the polymer obtained from the monomer represented by the aforementioned formula (II), and the aforementioned cationically polymerizable component (A) is based on The glycidyl epoxide of a polyhydric alcohol having a molecular weight of 200 or more, or the glycidyl epoxide (A1) and oxetane compound (A2) of a polyhydric alcohol alkylene oxide adduct are essential components, and the above radical polymerizability The component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylate of an alcohol having 2 to 20 carbon atoms or an alcohol having 2 to 20 carbon atoms. Methacrylate (C2) as an essential component. Here, the weight average molecular weight refers to a weight average molecular weight determined by GPC measurement in a tetrahydrofuran (THF) solvent by styrene conversion.

In the curable composition of the present invention, the cationically polymerizable component (A) preferably further contains an alicyclic epoxy compound (A3). In the curable composition of the present invention, the polyhydric alcohol in the glycidyl alcohol of the polyhydric alcohol having a molecular weight of 200 or more or the glycidyl oxide (A1) of the polyalkylene oxide adduct has a condensation A cyclic polyol is preferred. In the curable composition of the present invention, the polymer (E) is a polymer obtained from a monomer represented by the formula (I) and a monomer represented by the formula (II), and X is an aryl group having 6 to 12 carbon atoms, X 'in the formula (II) is an alkyl group having 1 to 7 carbon atoms, and the alkyl group is preferably substituted with an epoxy group. The cationically polymerizable component (A) is 30 to 70 parts by mass, the cationically polymerizable initiator (B) is 0.001 to 10 parts by mass, and the radically polymerizable component (C) is 30 to 60 parts by mass. The radical polymerization initiator (D) is 1 to 10 parts by mass, and the aforementioned polymer (E) It is preferably 1 to 20 parts by mass, and the total of the cationically polymerizable component (A), the radically polymerizable component (C), and the polymer (E) is preferably 100 parts by mass.

The method for producing a cured product of the present invention is one in which active energy rays are irradiated or heated to the curable composition of the present invention.

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

According to the present invention, a hardened composition having a high glass transition temperature and excellent adhesion, a method for producing a hardened product, and a hardened product thereof can be provided. The curable composition of the present invention is particularly useful as an adhesive.

Embodiment of the invention

Hereinafter, the curable composition of the present invention will be described in detail.

The curable composition of the present invention contains a cationically polymerizable component (A), a cation polymerization initiator (B), a radical polymerizable component (C), a radical polymerization initiator (D), and a component selected from the group consisting of A polymer obtained from a monomer represented by the following formula (I), a polymer obtained from a monomer represented by the following formula (II), two or more monomers selected from the monomers represented by the following formula (I) The polymer obtained, a polymer obtained from two or more monomers selected from the monomers represented by the following formula (II), and a polymer selected from the monomers represented by the following formula (I) and represented by the following formula (II) The weight of the group of polymers obtained from the monomers Polymer (E) with an average molecular weight of 1,000 to 30,000. In the curable composition of the present invention, the cationically polymerizable component (A) is an epoxypropylated product of a polyhydric alcohol having a molecular weight of 200 or more, or an epoxypropylated product (A1) of a polyhydric alcohol alkylene oxide adduct, and An oxetane compound (A2) is an essential component, and the radical polymerizable component (C) is acrylic acid having a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an alcohol having 2 to 20 carbon atoms An ester or a methacrylate (C2) of an alcohol having 2 to 20 carbon atoms 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, and an aromatic group having 6 to 12 carbon atoms. An oxygen group or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a hydrogen atom in these groups is one or more selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group, and a carboxyl group. Replaced by the base.

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

The cationically polymerizable component (A) of the curable composition of the present invention is a compound that generates a polymerization or cross-linking reaction by activating or activating a cationic polymerization initiator with energy rays. Examples thereof include epoxy compounds, oxetane compounds, and vinyl ether compounds.

The cationically polymerizable component (A) of the curable composition of the present invention is an epoxypropylate (A1) and an oxalate of a polyhydric alcohol or a polyhydric alcohol alkylene oxide adduct of a molecular weight of 200 or more. The cyclobutane compound (A2) is an essential component, but other epoxy compounds such as an alicyclic epoxy compound (A3) and an aromatic epoxy compound (A4) can also be used.

Examples of the epoxy-propylated product of a polyhydric alcohol having a molecular weight of 200 or more or the epoxy-propylated product (A1) of a polyhydric alcohol alkylene oxide adduct include epoxy resins obtained by polyhydric alcohols or polyalkylene oxide adducts. Propylated, and the molecular weight of the epoxy propylate is 200 or more.

Examples of the glycidyl alcohol of the polyol having a molecular weight of 200 or more, or the glycidyl oxide (A1) of the polyol alkylene oxide adduct include 1,4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, triglycidyl ether of glycerol, triglycidyl ether of trimethylolpropane, tetraepoxy of sorbitol Propylene ether, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, dicyclopentadiene dimethanol diglycidyl ether, etc. Oxypropyl ether, and one or two or more alkylene oxides, propylene glycol, and trimethylolpropane A polyglycidyl etherate of a polyether polyol obtained by addition of an aliphatic polyhydric alcohol such as alkane and glycerol, and a dipropylene glycol of an aliphatic long-chain dibasic acid.

The glycidyl alcohol of a polyhydric alcohol or the glycidyl alcohol (A1) of an alkylene oxide adduct of a polyhydric alcohol may further include a monoglycidyl ether of an aliphatic higher alcohol or a glycidyl ester of a higher fatty acid. , Epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized soybean oil, epoxidized polybutadiene, etc.

Glycidyl compounds of polyhydric alcohols having a molecular weight of 200 or more, or glycidyl epoxides (A1) of polyhydric alcohol alkylene oxide adducts contain saturated condensed rings, which can improve the hardenability and adhesion of the cured product. It is better.

Commercially available products can be used as the glycidyl epoxides of the above-mentioned polyhydric alcohols having a molecular weight of 200 or more, or the glycidyl epoxide adducts of polyols (A1), and examples include DenacolEX-121, DenacolEX-171, and DenacolEX. -192, DenacolEX-211, DenacolEX-212, DenacolEX-313, DenacolEX-314, DenacolEX-321, DenacolEX-411, DenacolEX-421, DenacolEX-512, DenacolEX-521, DenacolEX-611, DenacolEX-612, DenacolEX-614 , DenacolEX-622, DenacolEX-810, DenacolEX-811, DenacolEX-850, DenacolEX-851, DenacolEX-821, DenacolEX-830, DenacolEX-832, DenacolEX-841, DenacolEX-861, DenacolEX-911, DenacolEX-941, DenacolEX-911 -920, DenacolEX-931 (produced by nagasechemtex); Epolite M-1230, Epolite 40E, Epolite100E, Epolite 200E, Epolite400E, Epolite70P, Epolite200P, Epolite400P, Epolite1500NP, Epolite1600, Epolite80MF, Epolite100MF (Kyoeisha Chemical Co., Ltd.), ADEKA GLYCIROL ED-503, ADEKA GLYCIROL ED-503G, ADEKA GLYCIROL ED-506, ADEKA GLYCIROL RESIN EP-4088S, ADEKA RESIN EP-4080E ((share) made by ADEKA Corporation), etc.

Examples of the oxetane compound (A2) include 3,7-bis (3-oxocyclobutyl) -5-oxa-nonane and 1,4-bis [(3-ethyl-3-oxo Butylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxocyclobutylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxy Cyclobutylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxocyclobutylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxocyclobutylmethyl) ether, tetra Ethylene glycol bis (3-ethyl-3-oxocyclobutylmethyl) ether, 1,4-bis (3-ethyl-3-oxocyclobutylmethoxy) butane, 1,6-bis (3-ethyl Difunctional aliphatic oxetane compounds such as phenyl-3-oxocyclobutylmethoxy) hexane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl 3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxyl A functional oxetane compound such as methyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane, and the like. These can be used individually by 1 type or in combination of 2 or more types. Among the oxetane compounds (A2), the polyfunctional oxetane compound is preferred because the glass transition temperature of the cured product is high.

As the oxetane compound (A2), a commercially available product can be used, and examples thereof include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-Hydroxybutyl vinyl ether (manufactured by Maruzan Petrochemical Co., Ltd.); ARON OXETANE OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (East Asia Synthetic (shares ), Etc.), ETERNACOLL OXBP, OXTP (made by Ube Kosan Co., Ltd.).

The above-mentioned alicyclic epoxy compound (A3) refers to one in which an ethylene oxide ring is directly bonded to a saturated ring without a bonding group. Specific examples of the alicyclic epoxy compound (A3) include a polyoxypropylene etherate of a polyol having at least one alicyclic ring or a compound containing a cyclohexene or cyclopentene ring as an oxidizing agent. A compound containing cyclohexene oxide or cyclopentene oxide obtained by epoxidation. Examples thereof include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy Methyl-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3, 4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl -3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-formyl Methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2, 2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadiene diepoxide, ethylidene bis (3,4-epoxycyclohexanecarboxylate), epoxy hexa Dioctyl hydrophthalate, di-2-ethylhexyl hexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2- Epoxy-2-epoxyethylcyclohexane, α-pinene oxide, limonene dioxide, and the like. The alicyclic epoxy compound (A3) is extracted from From the viewpoint of high adhesion, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 3,4-epoxy-1-methylcyclohexyl- 3,4-epoxy-1-methylhexanecarboxylic acid ester.

A commercial item can be used for the said alicyclic epoxy compound (A3), For example, CELLOXID2021P, CELLOXID2081, CELLOXID2000, CELLOXID3000 (made by DAICEL), etc. are mentioned.

The above-mentioned aromatic epoxy compound (A4) refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound (A4) include phenol, cresol, and butylphenol having at least one aromatic ring. Examples of the polyhydric phenol or the mono / polypropylene oxide etherate of an alkylene oxide adduct include bisphenol A, bisphenol F, or a propylene oxide etherified compound of these compounds and an alkylene oxide adduct. Epoxy novolac resins; mono / polyglycidyl etherate of aromatic compounds with more than two phenolic hydroxyl groups, such as resorcinol or hydroquinone, catechol, etc .; phenyldimethanol or phenyldihydride Glycidyl etherate of aromatic compounds having two or more alcoholic hydroxyl groups, such as ethanol and phenyl dibutanol; carboxylic acids having two or more such as phthalic acid, terephthalic acid, trimellitic acid, etc. The polypropyl acid aromatic compounds of epoxy propyl esters, benzoic acid propylene oxide esters, styrene oxide or divinylbenzene epoxy oxide.

As the aromatic epoxy compound (A4), a commercially available product can be used, and examples thereof include DenacolEX-146, DenacolEX-147, DenacolEX-201, DenacolEX-203, DenacolEX-711, DenacolEX-721, On Court EX-1020, On Court EX-1030, On Court EX-1040, On Court EX-1050, On Court EX- 1051, On Court EX-1010, On Court EX-1011, On Court 1012 (produced by nagase chemtex); OGSOL PG-100, OGSOL EG-200, OGSOLEG-210, OGSOL EG-250 (Osaka Gas Chemical ( Shares) company system); HP4032, HP4032D, HP4700 (manufactured by DIC (stock) company); ESN-475V (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); EpikoteYX8800 (manufactured by Mitsubishi Chemical (stock) company); Marproof G- 0105SA, Marproof G-0130SP (manufactured by Japan Petroleum Corporation); EPICLONN-665, EPICLONHP-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 (made by Nippon Kayaku Co., Ltd.); ADEKA RESIN EP-4000, ADEKA RESINEP-4005, ADEKA RESIN EP-4100, ADEKA RESIN EP-4901 (made by ADEKA); TECHMORE VG-3101L (made by Printec). Among the above-mentioned aromatic epoxy compounds (A4), polyfunctional ones are preferred because they are excellent in hardenability.

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, and 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-cyclohexane dimethanol divinyl ether, and the like.

In the cationically polymerizable component (A), the molecular weight Epoxypropyl compounds of polyhydric alcohols of 200 or more, epoxypropyl compounds (A1), oxetane compounds (A2), and alicyclic epoxy compounds (A3) of polyol alkylene oxide adducts The use ratio of the aromatic epoxy compound (A4) and vinyl ether compound is based on 100 parts by mass of the cationically polymerizable component (A), a glycidyl alcohol of a polyhydric alcohol having a molecular weight of 200 or more, or a polyhydric alcohol alkylene oxide. 40 to 70 parts by mass of the epoxy propyl compound (A1) of the adduct, 30 to 60 parts by mass of the oxetane compound (A2), 0 to 50 parts by mass of the alicyclic epoxy compound (A3), aromatic 0-30 parts by mass of the epoxy compound (A4) and 0-20 parts by mass of the vinyl ether compound are preferable because they can improve viscosity, coatability, reactivity, and hardenability.

The cationic polymerization initiator (B) of the curable composition of the present invention refers to a compound that releases a substance that initiates cationic polymerization by irradiation with energy rays or heating, and is preferably released by irradiation with energy rays. A double salt of an onium salt of a Lewis acid or a derivative thereof. Representative examples of this compound include salts of cations and anions represented by the following general formula and [A] ^{r +} [B] ^r- .

Here, the cation [A] ^{r + is} preferably an onium, and its structure can be represented, for example, by the following general formula [(R ² ) _a Q] ^{r +} .

Here, R ² is an organic group having 1 to 60 carbon atoms and may contain atoms other than several carbon atoms. a is an integer from 1 to 5. Each of R ^{2 of a} may be independently the same or different. Moreover, it is preferable that at least one is an organic group as mentioned above which has an aromatic ring. Q is an atom or a group of atoms selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N = N. When the atomic valence of Q in the cation [A] ^{r +} is q, the relationship of r = aq (however, N = N is regarded as atomic valence 0) must be established.

The anion [B] ^{r- is} preferably a halide complex, and its structure can be represented by the following general formula [LY _b ] ^r- .

In addition, here, L is a metal or semimetal (Metalloid) which is the central atom of a halide complex, which is B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. Y is a halogen atom. b is an integer from 3 to 7. When the atomic valence of L in the anion [B] ^r- is taken as p, the relationship of r = bp must be established.

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

The anion [B] ^r- may also be a structure represented by the following general formula [LY _b-1 (OH)] ^r- . L, Y, and b are the same as described above. In addition, other usable anions include perchlorate ion (ClO ₄ ) ^- , trifluoromethylsulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonic acid ion (FSO ₃ ) ^- , toluenesulfonic acid anion, Trinitrobenzene sulfonate anion, camphor sulfonate, nonafluorobutane sulfonate, hexafluorooctane sulfonate, tetraarylborate, and (pentafluorophenyl) borate.

Among the onium salts of the curable composition of the present invention, it is particularly effective to use the following onium salts of (a) to (c). Among these, one kind may be used alone or two or more kinds may be used in combination.

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

(B) Diphenylfluorene hexafluoroantimonate, bis (4-methylphenyl) fluorene hexafluorophosphate, bis (4-tert-butylphenyl) fluorene hexafluorophosphate, tolylcumene Diarylsulfonium salt

(C) A sulfonium salt of a sulfonium cation and a hexafluoroantimony ion, a hexafluorophosphate ion, a (pentafluorophenyl) borate ion, etc. represented by the following group I or group II

<Group I>

<Group II>

Other preferred examples include (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) Benzene] -iron-aromatic hydrocarbon complexes such as iron-hexafluorophosphate, or aluminum complexes of ginseng (ethylacetone) aluminum, ginseng (ethylacetate) aluminum, ginseng (salicylaldehyde) aluminum, etc. Mixtures with silanols such as triphenylsilanol; salts of thienylium, thiolanium, benzylammonium, pyridinium, hydrazinium, etc .; diethylenetriamine, triamine Polyalkyl polyamines such as ethylenetriamine, tetraethylenepentamine, etc .; 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophor Alicyclic polyamines such as ketodiamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylphosphonium, etc .; the above polyamines are made by a general method Glycidyl ethers such as phenylglycidyl ether, butylglycidyl ether, bisphenol A-glycidyl ether, bisphenol F-glycidyl ether or carboxylic acid Polyepoxy addition modification produced by reaction of various epoxy resins such as esters; the above-mentioned organic polyamines are combined with phthalic acid and m-benzene by a general method Modified amidines produced by the reaction of carboxylic acids such as formic acid and dimer acid; the above-mentioned polyamines and aldehydes such as formaldehyde and phenol, cresol, xylenol, third butylphenol, Resorcinol is a Mannich modification produced by a phenol reaction with at least one aldolization site in the core; polycarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyl adipic acid, 3-methyl adipic acid, 3 -Methyl glutaric acid, 2-methyl suberic acid, 3,8-dimethylsebacic acid, 3,7-dimethylsebacic acid, hydrogenated dimer acid, dimer acid, etc. Carboxylic acids; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc .; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid, Tricarboxylic acids such as trimesic acid and castor oil fatty acid terpolymers; tricarboxylic acids such as pyromellitic acid; tetracarboxylic acids such as pyromellitic acid; dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters Amine .

Among these, it is preferable to use an aromatic sulfonium salt, an aromatic sulfonium salt, and an iron-aromatic hydrocarbon complex from the viewpoint of practicality and improvement of light sensitivity; and 100% by mass of the cationic polymerization initiator (B), and It is more preferable that the aromatic sulfonium salt has the following structure and contains at least 0.1% by mass or more.

Here, in the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ^19, and R ²⁰ each independently represent a hydrogen atom, a halogen atom, and a carbon number of 1 to Alkyl group of 10, alkoxy group of 1 to 10 carbon atoms, or ester group of 2 to 10 carbon atoms, and R ²¹ , R ²² , R ^23, and R ²⁴ each independently represent a hydrogen atom, a halogen atom, or a carbon atom 1 to 10 alkyl groups, 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 chemical formulae (A) to (C), and An ^q- represents q Valence anion, p represents a coefficient which makes the charge neutral.

Here, in the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ^38, and R ³⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms R ³⁰ , R ³¹ , R ³² , R ^33, and R ³⁴ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms.

Among the compounds 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 atom 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 each} represent an alkyl group having 1 to 10 carbon atoms, and examples thereof Methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, pentyl, isopentyl, t-pentyl, hexyl, cyclohexyl, heptyl, Octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl Methyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloro Methyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nine Fluorobutyl, decafluoropentyl, tridecylhexyl, pentafluoroheptyl, heptafluorooctyl, methoxymethyl, 1,2-epoxyethyl, methoxyethyl, methoxy Ethoxy Methyl, methylthiomethyl, ethoxyethyl, butoxymethyl, t-butylthiomethyl, 4-pentenyloxymethyl, trichloroethoxymethyl, bis (2- (Chloroethoxy) methyl, methoxycyclohexyl, 1- (2-chloroethoxy) ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl, trimethyl Silylethyl, t-butyldimethylsilyloxymethyl, 2- (trimethylsilyl) ethoxymethyl, t-butoxycarbonylmethyl, ethoxycarbonylmethyl Methyl, ethylcarbonylmethyl, t-butoxycarbonylmethyl, propenyloxyethyl, methacryloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl, acetamidine Ethyl, 2-methoxy-1-propenyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4 -Hydroxybutyl, 1,2-dihydroxyethyl, and the like.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ^{39 having} an alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, Butoxy, s-butoxy, t-butoxy, isobutoxy, pentyloxy, isopentyloxy, t-pentoxy, hexyloxy, cyclohexyloxy, cyclohexylmethoxy , Tetrahydrofuranoxy, tetrahydropyranyloxy, 2-methoxyethoxy, 3-methoxypropoxy, 4-methoxybutoxy, 2-butoxyethoxy, methoxy Ethoxyethoxy, methoxyethoxyethoxyethoxy, 3-methoxybutoxy, 2-methylthioethoxy, trifluoromethoxy 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 , An ester group having 2 to 10 carbon atoms represented by R ²⁹ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ^38, and R ³⁹ includes methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, and phenoxy Carbonyl, ethoxy, propionyl, butyloxy, chloroethoxy, dichloroethoxy, trichloroethoxy, trifluoroethoxy, t-butylcarbonyl Oxygen, methoxyethoxy, benzyloxy and the like.

The ratio of the cationic polymerization initiator (B) to the cationic polymerizable component (A), the radical polymerizable component (C), and the polymer (E) is 100 mass parts, and the cationic polymerization initiator (B ) 0.001 to 10 parts by mass, preferably 0.1 to 10 parts by mass. When it is too small, it may easily become insufficiently hardened, and when it is too large, it may adversely affect various physical properties such as the water absorption of the hardened material and the strength of the hardened material.

The radically polymerizable component (C) of the curable composition of the present invention is an acrylate or an alcohol having 2 to 20 carbon atoms or a compound having an epoxy group and an ethylenically unsaturated group (C1) or an alcohol having 2 to 20 carbon atoms. ~ 20 alcohol methacrylate (C2) is an essential component.

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

Examples of the acrylate of the alcohol having 2 to 20 carbon atoms or the methacrylate (C2) of the alcohol having 2 to 20 carbon atoms include aromatic or aliphatic alcohols having at least one hydroxyl group in the molecule and their rings An acrylate or methacrylate obtained by reacting an oxane adduct with acrylic acid or methacrylic acid. Specific examples include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isoamyl acrylate, and lauryl propyl Enoate, octadecyl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, isofluorenyl 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-caprolactone modified dipentaerythritol hexaacrylate, 2-ethylhexyl methacrylate, 2 -Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, isoamyl methacrylate, lauryl methacrylate, octadecyl methacrylate, isooctyl methacrylate , Tetrahydrofurfuryl methacrylate, isofluorenyl methacrylate, benzyl methacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate , 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethyl Alcohol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethyl Acrylate, dipentaerythritol hexamethacrylate, ε-caprolactone modified dipentaerythritol hexamethacrylate and the like. Among these acrylates or methacrylates, polyacrylates of polyhydric alcohols or polymethacrylates of polyhydric alcohols are particularly preferred.

Examples of the radical polymerizable component (C) include compounds other than (C1) or (C2), which can be polymerized or cross-linked by a radical polymerization initiator activated by irradiation with energy rays or heating, and examples thereof include For example, allyl carbamate compounds, unsaturated polyester compounds, styrene Compounds etc. The ratio of the (C1) component and the (C2) component in the radical polymerizable component (C) is preferably 50% by mass or more.

The radical initiator (D) of the curable composition of the present invention is not particularly limited, and a known one can be used. For example, acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, thioxanthone-based compounds, ketone-based compounds, oxime-based compounds, and the like can be used.

The polymer (E) of the curable composition of the present invention is selected from a polymer obtained from a monomer represented by the above formula (I), a polymer obtained from a monomer represented by the above formula (II), and selected from the above formula (II) I) A polymer obtained from two or more monomers represented by the monomer, a polymer selected from the group consisting of two or more monomers represented by the above formula (II), and a monomer represented by the above formula (I) And the polymer obtained from the monomer represented by the formula (II), and the weight average molecular weight is 1,000 to 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, and iso -Butyl, pentyl, iso-pentyl, tert-pentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl and the like. Among these, from the viewpoint of hardenability, an alkyl group having 1 to 4 carbon atoms or a part thereof is selected from one or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group, and a carboxyl group. Substituted alkyl groups having 1 to 4 carbon atoms are preferred.

Examples of the alkoxy group having 1 to 7 carbon atoms represented by X in the formula (I) include methoxy, ethoxy, propoxy, iso-propoxy, and butoxy Group, sec-butoxy, tert-butoxy, iso-butoxy, pentyloxy, iso-pentoxy, tert-pentoxy, hexyloxy, 2-hexyloxy, 3-hexyloxy Group, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, tert-heptyloxy and the like. Among these, from the viewpoint of hardenability, an alkoxy group having 1 to 4 carbon atoms or one or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group, and a carboxyl group is performed. Partially substituted alkoxy groups having 1 to 4 carbon atoms are preferred.

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 a phenoxy group, a methylphenoxy group, and a naphthyloxy group.

The alicyclic hydrocarbon group having 6 to 10 carbon atoms represented by X in the above formula (I) includes cyclohexyl, methylcyclohexyl, norbornyl, dicyclopentyl, bicyclooctyl, and trimethylbicycloheptyl , Tricyclooctyl, tricyclodecyl, spirooctyl, spirobicyclopentyl, adamantyl, isofluorenyl and the like.

These alkyl, alkoxy, aryl, aryloxy, and alicyclic hydrocarbon groups may be selected from the group consisting of hydrogen atoms of epoxy, oxetanyl, hydroxy, and carboxyl groups. Replaced by a group of more than one type.

In the above formula (I), a part of X is a monomer represented by the formula (I) when substituted with an epoxy group or an oxetanyl group, and examples thereof include monomers represented by the following formulas (1) to (3). body.

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

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

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

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

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

When a part of X 'in the above formula (II) is substituted with an epoxy group or an oxetanyl group, examples of the monomer represented by the formula (II) include the following formulae (4) to (6) By.

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

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

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

In the polymer (E), the proportion of the monomers constituting the polymer is such that X is a carbon substituted with one or more groups selected from the group consisting of an epoxy group, a cyclocyclobutane group, a hydroxyl group, and a carboxyl group. When an alkyl group having 1 to 7 atoms, an aryl group having 6 to 12 carbon atoms, or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, the monomer represented by the above (I) or (II) is 10 to 100 mass % Is used, and it is preferable because the adhesion is improved.

The curable composition of the present invention is The total of the synthesizable component (A), the radical polymerizable component (C) and the polymer (E) is 100 parts by mass, the cationically polymerizable component (A) is 30 to 70 parts by mass, and the cation polymerization initiator ( B) is 0.001 to 10 parts by mass, the radical polymerizable component (C) is 30 to 60 parts by mass, the radical polymerization initiator (D) is 1 to 10 parts by mass, and the polymer (E) is 1 ~ 20 parts by mass is preferred. When the blending ratio is outside the above range, there is a concern that the hardenability and adhesiveness of the hardened material are deteriorated.

In the curable composition of the present invention, a sensitizer and / or a sensitizer can be further used as required. The sensitizer is a compound that exhibits maximum absorption at a wavelength longer than the maximum absorption wavelength shown by the cationic polymerization initiator (B), and promotes the polymerization initiation reaction by the cationic polymerization initiator (B). The sensitizer is a compound that further promotes the action of the sensitizer.

Examples of the sensitizer and the sensitizer include anthracene-based compounds and naphthalene-based compounds.

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

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

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

Examples include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-dibutyl Anthracene, 9,10-dipentoxyanthracene, 9,10-dihexyloxyanthracene, 9,10-bis (2-methoxyethoxy) anthracene, 9,10-bis (2-ethyl (Oxyethoxy) 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-di Propoxyanthracene, 2-methyl- or 2-ethyl-9,10-diisopropoxyanthracene, 2-methyl- or 2-ethyl-9,10-dibutoxyanthracene, 2- Methyl- or 2-ethyl-9,10-dipentoxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene, and the like.

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

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.

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

Compared with the above-mentioned cationically polymerizable component (A), The use ratio of the sensitizer and the sensitizing aid is not particularly limited, and it may be used in a generally used ratio within a range that does not hinder the object of the present invention, for example, with respect to 100 parts by mass of the cation polymerizable component (A), From the viewpoint of improving the hardenability, the sensitizer and the sensitizing aid are each preferably 0.1 to 3 parts by mass.

In the curable composition of the present invention, a silane coupling agent can be used as necessary. As the silane coupling agent, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane -Functional alkoxysilanes such as methyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethyl Alkenyl-functional alkoxysilanes such as oxysilane, allyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethyl Oxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Epoxy-functional alkoxysilanes such as trimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N -Phenyl -amino-functional alkoxysilanes such as -γ-aminopropyltrimethoxysilane, mercapto-functional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, tetraisopropane titanium oxide, tetra-n-butane Titanium alkoxides such as titanium alkoxides, titanium dioctyloxybis (ethylene octyl glycolate), titanium diisopropoxybis (ethylacetamidine acetate), etc. Titanium clamp compounds, zirconium tetraacetammonium acetone zirconium, zirconium triacetoxyzirconium acetonate, zirconium triacetoxide, zirconium tributoxide, etc., methyl triisocyanate silane Isocyanate silanes, etc.

The amount of the silane coupling agent used is not particularly limited, and it is generally in the range of 0.01 to 20 parts by mass based on 100 parts by mass of the total amount of solids in the curable composition.

In the curable composition of the present invention, the properties of the cured product can also be improved by using a thermoplastic organic polymer as required. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate copolymer, methyl methacrylate glycidyl methacrylate copolymer, and poly (meth) Acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate copolymer, glycidyl (meth) acrylate-polymeth (meth) acrylate copolymer, polyethylene Butyral, cellulose ester, polypropylene amidamine, saturated polyester, etc.

In the hardenable composition of the present invention, an ultraviolet absorber may be further used as required, or it may be inactive at normal temperature, and the protective group may be activated by detachment by heating to a specific temperature / light irradiation / acid, etc., and exhibit ultraviolet absorption. Ability compound.

In addition, as long as the effect of the present invention is not impaired, colorants, defoamers, tackifiers, surfactants, leveling agents, flame retardants, polyhydric alcohols, inorganic fillers, organic fillers, pigments, and dyes can be added as needed Agents, thixotropic agents, diluents, plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow regulators, adhesion promoters, etc. Various resin additives, etc.

The curable composition of the present invention is not particularly limited, and a solvent generally used for dissolving or dispersing the components (A), (B), (C), (D), and (E) may 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 diethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; methyl acetate, Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, 2,2,4-trimethyl-1,3 -Ester solvents such as pentanediol isobutyric acid (Texanol); cellulosic solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso- or n-propanol, iso- Or alcohol solvents such as n-butanol and pentanol; 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 and other ether ester solvents; BTX solvents such as benzene, toluene, xylene; hexane, heptane , Aliphatic hydrocarbon solvents such as octane, cyclohexane; turpentine, D-limonene Terpene-based hydrocarbon oils such as terpinene and paraffin; paraffinic solvents such as mineral spirits, Swasol # 310 (manufactured by Cosmo Matsuyama Petroleum Co., Ltd.), Solvesso # 100 (Exxon Chemical Company), etc .; carbon tetrachloride, chloroform Halogenated aliphatic hydrocarbon solvents such as trichloroethylene, dichloromethane, 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; propylene carbonate, carbitol solvents, aniline, Ethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethyl Acetylamine, N-methylpyrrolidone, dimethylsulfinium, water, and the like. These solvents may be used singly or in a mixture of two or more kinds.

Since the hardenable composition of the present invention improves hardenability, adhesion, and liquid storage stability, the moisture content is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. When there is too much water, it may cause turbidity or analysis, so it is not good.

The hardenable composition of the present invention is applied to a support substrate by a well-known means such as a roll coater, a curtain coater, and various printing and dipping methods. In addition, once it is applied to a supporting substrate such as a film, it can be transferred to another supporting substrate, and there is no limitation on the applicable method.

The material of the above-mentioned support substrate is not particularly limited, and ordinary users can be used, and examples thereof include inorganic materials such as glass; diethyl cellulose, triethyl cellulose (TAC), propyl cellulose, and butyl cellulose. Cellulose esters of cellulose, ethoxypropyl cellulose, nitrocellulose, etc .; Polyamines; Polyimides; Polyurethanes; Epoxy Resins; Polycarbonates; Polyparaphenylene terephthalates Ethylene formate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene polyterephthalate, polyethylene-1,2- Diphenoxyethane-4,4'-dicarboxylate, polyesters such as polybutylene terephthalate; polystyrene; polyolefins such as polyethylene, polypropylene, polymethylpentene; Vinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; acrylic resins such as polymethylmethacrylate and polyacrylate; polycarbonate; polyfluorene; polyetherfluorene; polyetherketone; poly Etherimide; polymer materials such as polyoxyethylene, norbornene resin, and cycloolefin polymer (COP). In addition, a corona discharge can be performed on the support substrate. Surface activation treatment such as heat treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, activated plasma treatment, laser treatment, etc.

In the method for curing by irradiating the curable composition of the present invention with energy rays, examples of the energy rays include ultraviolet rays, electron rays, X-rays, radiation, and high frequencies. Ultraviolet rays are most economically optimal. Examples of the ultraviolet light source include ultraviolet lasers, mercury lamps, xenon lasers, and metal halide lamps.

The conditions for the method of hardening the curable composition of the present invention by heating are 70 to 250 ° C. and 1 to 100 minutes. After pre-baking (PAB; Pre applied bake), it can be pressurized for post-baking (PEB; Post exposure bake). It can also be baked at different stages of temperature. Although the heating conditions vary depending on the type and blending ratio of each component, for example, at 70 to 180 ° C, the oven is 5 to 15 minutes, and the heating plate is 1 to 5 minutes. Then, in order to harden the coating film, a hardened film can be obtained by heating at 180 to 250 ° C, preferably 200 to 250 ° C, in an oven for 30 to 90 minutes, and for a heating plate for 5 to 30 minutes.

Specific uses of the curable composition of the present invention or its cured product include adhesives, glasses, optical materials typified by photographic lenses, coatings, coating agents, lining agents, inks, and resists. , Liquid resists, printing plates, color TVs, PC monitors, mobile information terminals, digital cameras, organic ELs, touch panels and other display elements, insulating varnishes, insulating sheets, laminates, printed boards, semiconductor devices / Packaging materials for LED encapsulation / liquid crystal injection port / organic EL / optical element / electrical insulation / electronic parts / separation film, molding materials, putty, glass fiber impregnating agent, wood powder filler, semiconductor / Passive film for solar cells, etc. Interlayer insulation film, protective film, lenticular lens sheet used in backlight of liquid crystal display devices, Fresnel lens sheet used in screens of projection televisions, lens parts such as lenticular lens sheets, or the like Backlights, optical lenses such as micro lenses, optical elements, optical connectors, optical waveguides, molding agents for optical shaping, etc.

The display device can include various layers provided with a base coat, an anti-reflection layer, a polarizing element layer, a retardation layer, a birefringence layer, a light scattering layer, a hard coating layer, a lubricating layer, a protective layer, etc. on a transparent support as required. Alternatively, a thin film made of the cured product of the present invention can be used for each layer.

[Example]

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

[Examples 1 to 15, Comparative Examples 1 to 3]

The components shown in the following [Table 1] to [Table 3] were sufficiently mixed to obtain the curable composition of each of Examples 1 to 15 and the curable composition of Comparative Examples 1 to 3. Moreover, the unit of an Example and a comparative example is a mass part.

The cationically polymerizable component (A) uses the following compounds (A1-1) to (A1-3) and (A2-1) to (A3-1).

Compound (A1-1): ADEKA RESINEP-4088L ((shares) made by ADEKA)

Compound (A1-2): 1,6-hexanediol diglycidyl ether

Compound (A1-3): neopentyl glycol diglycidyl ether

Compound (A2-1): ARON OXETANE OXT-221 (manufactured by Toa Kosei Co., Ltd.)

Compound (A3-1): CELLOXID2021P (alicyclic epoxy group: (manufactured by DAICEL))

As the cationic polymerization initiator (B), the following compound (B-1) was used.

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

As the radical polymerizable component (C), the following compounds (C2-1) to (C2-4) were used.

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

Compound (C2-2): Tricyclodecane dimethanol diacrylate

Compound (C2-3): ethoxylated isotricyanate triacrylate

Compound (C2-4): tetrahydrofurfuryl acrylate

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

Compound (D-1): IRGACURE184 (manufactured by BASF)

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

Compound (E-1): a copolymer of 75 parts by mass of methmethacrylate and 25 parts by mass of glycidyl methacrylate (weight average molecular weight 7,000)

Compound (E-2): a copolymer of 35 parts by mass of methmethacrylate, 35 parts by mass of styrene, and 30 parts by mass of epoxypropylmethacrylate (weight average molecular weight 8,000)

Regarding each of the obtained hardenable compositions of Examples 1 to 15 and Comparative Examples 1 to 3, the glass transition temperature (Tg), elastic modulus, and adhesion were evaluated according to the following procedures. The results are described in [Table 1] to [Table 3].

(Glass transition temperature and elastic modulus at 80 ° C)

Each of the obtained hardening compositions of Examples 1 to 15 and Comparative Examples 1 to 3 were coated on a polyethylene terephthalate (PET) film with a coating rod to form a thickness of 30 μm, and a metal halide lamp was used. Irradiated with energy of 3000mJ / cm ² . After 24 hours, the adhesive cured product was taken out from the film, and the viscoelasticity measuring device (DMA7100) manufactured by Hitachi High-Tech Science was used to measure Tg and the elastic modulus at 80 ° C.

(Adhesiveness)

The compositions 1 to 15 of the examples obtained above and the compositions 1 to 3 of the comparative examples were each coated on a corona-treated PMMA film (Technolloy 125S001 manufactured by Sumitomo Chemical Co., Ltd.), and then a laminator was used. Laminated with another piece of COP (cycloolefin polymer, Japan Zeon Corporation: Model Zeonor Film 14-060) film that has been treated with corona discharge. The electrodeless ultraviolet light is equivalent to 1000mJ / cm through the COP film. The light of ² was followed to obtain a test piece. The obtained test piece was subjected to a 90-degree peel test.

From [Table 1] to [Table 3], it is understood that the hardened composition-based hardened material of the present invention has a high glass transition temperature and excellent adhesion.

Claims (8)

A hardenable composition comprising: a cationic polymerizable component (A), a cationic polymerization initiator (B), a radical polymerizable component (C), a radical polymerization initiator (D), and a component selected from the group consisting of Formula (I) (Where X is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a carbon atom (The hydrogen atom in an alicyclic hydrocarbon group of 6 to 10 or these groups is substituted with one or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group, and a carboxyl group.) The polymer obtained from the 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 hydrocarbon group having 6 to 10 carbon atoms Or a polymer in which a hydrogen atom in these groups is substituted with a monomer selected from one or more groups selected from the group consisting of epoxy, oxetanyl, hydroxyl, and carboxyl groups, A polymer selected from two or more monomers of the monomer represented by the aforementioned formula (I), a polymer selected from two or more monomers selected from the monomers represented by the aforementioned formula (II), and a polymer selected from the foregoing The polymer (E) having a weight average molecular weight of 1,000 to 30,000 in a group formed by the monomer represented by the formula (I) and the polymer obtained from the monomer represented by the aforementioned formula (II), and the aforementioned cationic polymerizable component (A) is based on The glycidyl epoxide of a polyhydric alcohol having a molecular weight of 200 or more, or the glycidyl epoxide (A1) and oxetane compound (A2) of a polyhydric alcohol alkylene oxide adduct are essential components, and the above radical polymerizability The component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylate of an alcohol having 2 to 20 carbon atoms or an alcohol having 2 to 20 carbon atoms. Methacrylate (C2) as an essential component. The curable composition according to claim 1, wherein the cationically polymerizable component (A) further contains an alicyclic epoxy compound (A3). For example, the curable composition of claim 1, wherein the polyhydric alcohol in the glycidyl alcohol of the above-mentioned polyhydric alcohol having a molecular weight of 200 or more or the glycidyl oxide (A1) of the polyhydric alcohol alkylene oxide adduct has a condensation Polyols. For example, the curable composition of claim 1, wherein the polymer (E) is a polymer obtained from the monomer represented by the aforementioned formula (I) and the monomer represented by the aforementioned formula (II). X is an aryl group having 6 to 12 carbon atoms, X 'in the aforementioned formula (II) is an alkyl group having 1 to 7 carbon atoms, and the aforementioned alkyl group is substituted with an epoxy group. The curable composition according to claim 1, wherein the aforementioned cationically polymerizable The component (A) is 30 to 70 parts by mass, the cationic polymerization initiator (B) is 0.001 to 10 parts by mass, the radical polymerizable component (C) is 30 to 60 parts by mass, and the radical polymerization initiator (D) is 1 to 10 parts by mass, the polymer (E) is 1 to 20 parts by mass, and the cationically polymerizable component (A), the radically polymerizable component (C), and the polymer (E) The total is 100 parts by mass. A method for hardening a hardenable composition, which comprises irradiating an active energy ray to the hardenable composition of any one of claims 1 to 5. A method for hardening a hardenable composition, which comprises heating the hardenable composition according to any one of claims 1 to 5. A cured product, which is a cured product of the curable composition according to any one of claims 1 to 5.