TWI727026B - Hardenable composition, method of manufacturing hardened material and hardened material - Google Patents

Abstract

The present invention provides a curable composition with a high glass transition temperature and excellent adhesion of a cured product, a method for manufacturing a cured product, and a cured product.

The curable composition of the present invention contains: cationic polymerizable component (A), cationic polymerization initiator (B), radical polymerizable component (C), radical polymerization initiator (D) and selected from The following formula (I)

(式中，X為碳原子數1~7之烷基等)表示之單體所得之聚合物、由下述式(II)

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

(式中，R¹表示氫原子等，X’為碳原子數1~7之烷基等)表示之單體所得之聚合物等所成群組之重量平均分子量1,000~30,000的聚合物(E)，且(A)成分係以分子量200以上之多元醇的環氧丙基化物等與氧雜環丁烷化合物作為必須成分，(C)成分係以具有環氧基及乙烯性不飽和基之化合物、或碳原子數2~20之醇的丙烯酸酯等作為必須成分。

(In the formula, R ¹ represents a hydrogen atom, etc., and X'is an alkyl group with 1 to 7 carbon atoms, etc.) represents a group of polymers with a weight average molecular weight of 1,000 to 30,000 (E ), and component (A) is composed of epoxy propyl compounds of polyols with a molecular weight of 200 or more and oxetane compounds as essential components, and component (C) is composed of epoxy groups and ethylenically unsaturated groups Compounds or acrylates of alcohols with 2 to 20 carbon atoms are essential components.

Description

Hardenable composition, method of manufacturing hardened material and hardened material

The present invention relates to a curable composition, a method for manufacturing a cured product, and a cured product, and in detail, a curable composition with a high glass transition temperature and excellent adhesion, a method for manufacturing a cured product, and a cured product.

The curable composition is used in fields such as inks, paints, various coating agents, adhesives, and optical components. There are various reports on the improvement of this kind of curable composition.

For example, the following Patent Documents 1 to 4 propose energy ray curable compositions containing cationically polymerizable components and radically polymerizable components and their cured products. Specifically, Patent Document 1 proposes an adhesive composition for polarizing plates that is excellent in initial curability and adhesiveness. In addition, in Patent Documents 2 and 3, it is proposed that even when a resin film with low moisture permeability is used as a protective film, the adhesive force can be quickly exhibited after light irradiation, and after a certain period of time, the adhesive force is good for various forces. Endurance test There is no problem afterwards, and the adhesive force after the end of the damp heat resistance test is also a low-viscosity light-curing adhesive. 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 or high refractive index and transparency. 性resin composition.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: JP 2014-105218 A

Patent Document 2: Japanese Patent Application Publication No. 2015-040283

Patent Document 3: Japanese Patent Application Publication No. 2015-143352

Patent Document 4: Japanese Patent Application Publication No. 2015-168757

However, even for the curable compositions proposed in Patent Documents 1 to 4, the curability and adhesiveness may not always be satisfied. The current situation is that it is desired to have a high degree of curability and adhesiveness. Hardening composition.

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

The inventors of the present invention have intensively studied in order to solve the above-mentioned problems, and found that if it is a curable composition having a specific composition, the above-mentioned problems can be overcome and the present invention has been completed.

(式中，X為碳原子數1~7之烷基、碳原子數1~7之烷氧基、碳原子數6~12之芳基、碳原子數6~12之芳氧基或碳原子數6~10之脂環式烴基、或此等之基中的氫原子經選自由環氧基、氧雜環丁烷基、羥基及羧基所成群組之1種以上之基取代者)表示之單體所得之聚合物、由下述式(II)、

(式中，R¹表示氫原子、甲基或鹵素原子，X’為碳原子數1~7之烷基、碳原子數6~12之芳基或碳原子數6~10之脂環式烴基、或此等之基中的氫原子經選自由環氧基、氧雜環丁烷基、羥基及羧基所成群組之1種以上之基取代者)表示之單體所得之聚合物、選自前述式(I)表示之單體之二種以上之單體所得之聚合物、選自由前述式(II)表示之單體之二種以上之單體所得之聚合物、及選自由前述式(I)表示之單體及前述式(II)表示之單體所得之聚合物所成群組之重量平均分子量1,000~30,000的聚合物 (E)，且前述陽離子聚合性成分(A)係以分子量200以上之多元醇的環氧丙基化物、或多元醇環氧烷加成物之環氧丙基化物(A1)及氧雜環丁烷化合物(A2)作為必須成分，前述自由基聚合性成分(C)係以具有環氧基及乙烯性不飽和基之化合物(C1)、或碳原子數2~20之醇的丙烯酸酯或碳原子數2~20之醇的甲基丙烯酸酯(C2)作為必須成分。在此，重量平均分子量係指在四氫呋喃(THF)溶劑中，藉由GPC測量，以苯乙烯換算求得的重量平均分子量。 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 choose from the following formula (I)

(In the formula, X is an alkyl group with 1 to 7 carbon atoms, an alkoxy group with 1 to 7 carbon atoms, an aryl group with 6 to 12 carbon atoms, an aryloxy group with 6 to 12 carbon atoms or a carbon atom The alicyclic hydrocarbon group of number 6 to 10, or the hydrogen atom in these groups is substituted by one or more groups selected from the group consisting of epoxy group, oxetanyl group, hydroxyl group and carboxyl group). The polymer obtained from the monomer of the following formula (II),

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a halogen atom, and X'is an alkyl group with 1 to 7 carbon atoms, an aryl group with 6 to 12 carbon atoms or an alicyclic hydrocarbon group with 6 to 10 carbon atoms , Or the hydrogen atom in these groups is substituted by one or more groups selected from the group consisting of epoxy group, oxetanyl group, hydroxyl group and carboxyl group) represented by the polymer, selected Polymers derived from two or more monomers of the monomers represented by the aforementioned formula (I), polymers selected from two or more monomers of the monomers represented by the aforementioned formula (II), and polymers selected from the aforementioned formulas (I) The monomer represented by the formula (II) and the polymer obtained from the monomer represented by the formula (II) form a polymer (E) with a weight average molecular weight of 1,000 to 30,000, and the aforementioned cationically polymerizable component (A) is The glycidyl compound of polyols with a molecular weight of 200 or more, or the glycidyl compound (A1) and oxetane compound (A2) of polyol alkylene oxide adducts as essential components, the aforementioned radical polymerizability 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 a methacrylate of an alcohol having 2 to 20 carbon atoms (C2 ) As an essential ingredient. Here, the weight average molecular weight refers to the weight average molecular weight obtained by GPC measurement in tetrahydrofuran (THF) solvent and calculated in terms of styrene.

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

The method for producing a hardened product of the present invention involves irradiating or heating the hardenable composition of the present invention with active energy rays.

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

According to the present invention, it is possible to provide a curable composition with a high glass transition temperature of the cured product and excellent adhesion, a method for producing a cured product, and a cured product thereof. The curable composition of the present invention is particularly useful for adhesives.

Form of invention

The curable composition of the present invention will be described in detail below.

The curable composition of the present invention contains: cationic polymerizable component (A), cationic polymerization initiator (B), radical polymerizable component (C), radical polymerization initiator (D) and selected from A polymer derived from a monomer represented by the following formula (I), a polymer derived from a monomer represented by the following formula (II), a monomer selected from two or more monomers represented by the following formula (I) The obtained polymer, the polymer obtained from two or more monomers selected from the monomer represented by the following formula (II), and the polymer selected from the monomer represented by the following formula (I) and the following formula (II) The weight of the group of the polymer obtained from the monomer 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 a glycidyl compound of a polyol having a molecular weight of 200 or more, or a glycidyl compound (A1) of a polyol alkylene oxide adduct, and The oxetane compound (A2) is an essential component, and the radically polymerizable component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, or acrylic acid of an alcohol with 2 to 20 carbon atoms Ester or methacrylate (C2) of alcohol with 2 to 20 carbon atoms is an essential component.

Here, in formula (I), X is an alkyl group with 1 to 7 carbon atoms, an alkoxy group with 1 to 7 carbon atoms, an aryl group with 6 to 12 carbon atoms, and an aromatic group with 6 to 12 carbon atoms. An oxy group or an alicyclic hydrocarbon group with 6 to 10 carbon atoms, or the hydrogen atom in these groups is one or more selected from the group consisting of epoxy group, oxetanyl group, hydroxyl group and 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 with 1 to 7 carbon atoms, an aryl group with 6 to 12 carbon atoms, or 6 to 10 carbon atoms. The alicyclic hydrocarbon group or the hydrogen atom in these groups is substituted by one or more groups selected from the group consisting of epoxy group, oxetanyl group, hydroxyl group and carboxyl group.

The cationically polymerizable component (A) of the curable composition of the present invention is a compound that is polymerized or crosslinked by a cationic polymerization initiator activated by energy ray irradiation or heating. Examples include epoxy compounds, oxetane compounds, and vinyl ether compounds.

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

The glycidyl compound of the polyol with a molecular weight of 200 or more or the glycidyl compound (A1) of the polyol alkylene oxide adduct can be exemplified by the epoxy resin of the polyol or polyol alkylene oxide adduct. It is propylated, and the molecular weight of the glycidate is 200 or more.

The glycidyl product (A1) of the polyol having a molecular weight of 200 or more or the glycidyl product (A1) of the polyol alkylene oxide adduct includes 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 Propyl ether, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, dicyclopentadiene dimethanol diglycidyl ether, etc. Propylene oxide, and combining one or more types of alkylene oxide with propylene glycol, trimethylol propylene Polyglycidyl etherate of polyether polyol and diglycidyl ester of aliphatic long-chain dibasic acid obtained by addition of aliphatic polyols such as alkane and glycerol.

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

The glycidyl product of a polyol with a molecular weight of 200 or more, or the glycidyl product of a polyol alkylene oxide adduct (A1) contains saturated condensed rings, which can improve the hardenability and adhesion of the cured product. So better.

Commercially available products can be used for the glycidyl product of a polyol having a molecular weight of 200 or more or the glycidyl product (A1) of a polyol alkylene oxide adduct. Examples include DenacolEX-121, DenacolEX-171, 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 -920, DenacolEX-931 (manufactured by nagasechemtex (stock) company); Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite70P, Epolite200P, Epolite400P, Epolite1500NP, Epolite1600, Epolite80MF, Epolite100MF (manufactured by Kyoeisha Chemical Co., Ltd.), ADEKA GLYCIROL ED-503, ADEKA GLYCIROL ED-503G, ADEKA GLYCIROL ED-506, ADEKA GLYCIRED-523T, ADEKA GLYCIROL ADEKA GLYCIROL RESIN EP-4088S, ADEKA RESIN EP-4080E (made by ADEKA Corporation), etc.

The above-mentioned oxetane compound (A2) includes 3,7-bis(3-oxocyclobutyl)-5-oxa-nonane, 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 Cyclobutyl methoxy) methyl) propane, ethylene glycol bis (3-ethyl-3-oxocyclobutyl methyl) ether, triethylene glycol bis (3-ethyl-3-oxocyclobutyl methyl) ether, four Ethylene glycol bis(3-ethyl-3-oxocyclobutylmethyl)ether, 1,4-bis(3-ethyl-3-oxobutylmethoxy)butane, 1,6-bis(3-ethyl Difunctional aliphatic oxetane compounds such as oxy-3-oxocyclobutylmethoxy) hexane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl 3-(hexyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxyl Monofunctional oxetane compounds such as methyl)oxetane and 3-ethyl-3-(chloromethyl)oxetane. These can be used individually by 1 type or in combination of 2 or more types. Among the above-mentioned oxetane compounds (A2), the polyfunctional oxetane compound is preferable because the glass transition temperature of the cured product is high.

Commercial products can be used for the oxetane compound (A2), and examples include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-Hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.); ARON OXETANE OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (Tohya Synthetic Co., Ltd.) ) Company system), ETERNACOLL OXBP, OXTP (Ube Industries Co., Ltd. system), etc.

The above-mentioned alicyclic epoxy compound (A3) means that the ethylene oxide ring is directly bonded to a saturated ring without a bonding group. Specific examples of the alicyclic epoxy compound (A3) can be exemplified by using a polyglycidide etherate of a polyol having at least one alicyclic ring or a compound containing a cyclohexene or cyclopentene ring with an oxidizing agent Cyclohexene oxide or cyclopentene oxide-containing compound obtained by epoxidation. Examples include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy -1-methylhexane carboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexane carboxylate, 3, 4-Epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexane carboxylate, 3,4-epoxy-5-methylcyclohexylmethyl -3,4-Epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methyl Cyclohexane carboxylate, methylene bis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2, 2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexane carboxylate), epoxy six Dioctyl hydrogen phthalate, di-2-ethylhexyl epoxy hexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2- Epoxy-2-epoxyethylcyclohexane, α-pinene oxide, limonene dioxide, etc. Alicyclic epoxy compound (A3) from the From the viewpoint of high adhesion, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate or 3,4-epoxy-1-methylcyclohexyl- 3,4-Epoxy-1-methylhexane carboxylate.

Commercial products can be used for the alicyclic epoxy compound (A3), and examples thereof include CELLOXID2021P, CELLOXID2081, CELLOXID2000, and CELLOXID3000 (manufactured by DAICEL Corporation).

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 those having at least one aromatic ring such as phenol, cresol, and butylphenol. Polyhydric phenol or its alkylene oxide adduct mono/polypropylene etherate, for example, bisphenol A, bisphenol F, or the glycidyl etherate of these compounds added with alkylene oxide or Epoxy novolac resin; mono/polyglycidyl etherate of aromatic compounds with two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, catechol, etc.; phenyl dimethanol or phenyl dimethanol Glycidyl etherate of aromatic compounds with two or more alcoholic hydroxyl groups such as ethanol and phenyl dibutanol; carboxylic acids with two or more phthalic acid, terephthalic acid, trimellitic acid, etc. The glycidyl ester of the polybasic acid aromatic compound, the glycidyl ester of benzoic acid, the styrene oxide or the epoxide of divinylbenzene, etc.

Commercial products can be used for the above-mentioned aromatic epoxy compound (A4), 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 (manufactured by Nagase Chemtex Co., Ltd.); OGSOL PG-100, OGSOL EG-200, OGSOLEG-210, OGSOL EG-250 (Osaka Gas Chemical Co., Ltd.) (Shares) company); HP4032, HP4032D, HP4700 (manufactured by DIC Corporation); ESN-475V (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); Epikote YX8800 (manufactured by Mitsubishi Chemical Corporation); Marproof G- 0105SA, Marproof G-0130SP (manufactured by NOF 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 (manufactured by Nippon Kayaku Co., Ltd.); ADEKA RESIN EP-4000, ADEKA RESINEP-4005, ADEKA RESIN EP-4100, ADEKA RESIN EP-4901 (made by ADEKA Corporation); TECHMORE VG-3101L (made by Printec Corporation), etc. Among the above-mentioned aromatic epoxy compounds (A4), polyfunctional ones are preferred because they are excellent in curability.

The vinyl ether compound includes, for example, 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, etc.

In the above-mentioned cationically polymerizable component (A), the above-mentioned molecular weight Epoxy propyl compound of polyhydric alcohol of 200 or more, or glycidyl compound of polyhydric alcohol alkylene oxide adduct (A1), oxetane compound (A2), alicyclic epoxy compound (A3) , The use ratio of aromatic epoxy compound (A4) and vinyl ether compound is based on 100 parts by mass of the cationically polymerizable component (A), the epoxy propyl compound of the polyol with a molecular weight of 200 or more, or the polyol alkylene oxide The epoxy propyl compound (A1) of the adduct (A1) 40~70 mass parts, the oxetane compound (A2) 30~60 mass parts, the alicyclic epoxy compound (A3) 0~50 mass parts, aromatic The epoxy compound (A4) 0-30 parts by mass and the vinyl ether compound 0-20 parts by mass are preferred because they can improve viscosity, coatability, reactivity, and curability.

The cationic polymerization initiator (B) of the curable composition of the present invention refers to a compound that can release a substance that initiates cationic polymerization by energy ray irradiation or heating. It can be used, and it is preferably released by energy ray irradiation. The double salt of the onium salt of Lewis acid or its derivative. Representatives of this compound include salts of cations and anions represented by the following general formula, [A] ^r+ [B] ^r-.

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

In addition, 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. R ^{2 of a} can be the same or different independently. In addition, at least one of them is preferably an organic group as described above having an aromatic ring. Q is an atom or group of atoms selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N=N. Moreover, when the valence of Q in the cation [A] ^r+ is q, the relationship of r=aq (but N=N is regarded as the valence 0) must be established.

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

In addition, here, L is the metal or semimetal (Metalloid) of the central atom of the 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 of 3-7. In addition, when the valence of L in the anion [B] ^r- is regarded as p, the relationship r=bp must be established.

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

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

In the curable composition of the present invention, among such onium salts, it is particularly effective to use the following aromatic onium salts (A) to (C). Among these, 1 type can be used individually or in mixture of 2 or more types.

(A) Phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate and other aryl diazonium salts

(B) Diphenyl hexafluoroantimonate, bis(4-methylphenyl) hexafluorophosphate, bis(4-tert-butylphenyl) hexafluorophosphate, tolylcumene Diaryl iodonium salts such as pentafluorophenyl borate

(C) The following alumium cations represented by group I or group II and hexafluoroantimony ions, hexafluorophosphate ions, tetrakis (pentafluorophenyl) borate ions, etc.

<Group I>

<Group II>

Moreover, other preferable ones include (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) Benzene]-iron-hexafluorophosphate and other iron-arene complexes, or ginseng (acetone) aluminum, ginseng (acetate ethyl) aluminum, ginseng (salicylic aldehyde) aluminum and other aluminum complexes Mixtures with silanols such as triphenylsilanol; thiophenium salt, thiolanium, benzylammonium, pyridinium salt, hydrazinium salt, etc.; diethylenetriamine, tris Polyalkyl polyamines such as ethylene triamine and tetraethylene pentamine; 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophor Alicyclic polyamines such as ketonediamines; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylmethane, etc.; the above-mentioned polyamines are made by general methods Glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, etc. or glycidyl of carboxylic acid Polyepoxy adduct modified products produced by the reaction of various epoxy resins such as esters; the above-mentioned organic polyamines are reacted with carboxylic acids such as phthalic acid, isophthalic acid, and dimer acid by a general method The manufactured amide modified product; the above-mentioned polyamines, formaldehyde and other aldehydes, phenols, cresols, xylenol, tertiary butylphenol, resorcinol, etc. have at least Mannich modified product produced by phenolic reaction in a reactive site of aldehyde; polycarboxylic acid (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid) Acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylglutaric acid, 2-methyl Aliphatic dicarboxylic acids such as suberic acid, 3,8-dimethyl sebacic acid, 3,7-dimethyl sebacic acid, hydrogenated dimer acid, dimer acid; phthalic acid, terephthalic acid Aromatic dicarboxylic acids such as dicarboxylic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid, trimesic acid, castor Tricarboxylic acids such as trimers of sesame oil fatty acids; tetracarboxylic acids such as pyromellitic acid, etc.) anhydrides; dicyandiamide, imidazoles, carboxylic acid esters, sulfonate esters, amine imides, etc.

Among these, from the viewpoint of practicality and improvement of photosensitivity, it is preferable to use aromatic iodonium salt, aromatic sulphur salt, iron-arene complex; relative to 100% by mass of cationic polymerization initiator (B), and More preferably, it contains at least 0.1% by mass or more of an aromatic sulfonium salt having the following structure.

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 the number of carbon atoms from 1 to 10 alkyl group, C 1-10 alkoxy group or C 2-10 ester group, R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, a halogen atom or the number of carbon atoms An alkyl group of 1 to 10, R ²⁵ represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 10 carbon atoms, or any substituent selected from the following chemical formulas (A) to (C), An ^q- represents q For a valence anion, p represents a coefficient that 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 with 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 with 1 to 10 carbon atoms.

In the compound represented by the above general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , Halogen represented by 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 represent alkyl groups with 1 to 10 carbon atoms, including 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 Group, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloro Methyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nine Fluorobutyl, decafluoropentyl, tridecafluorohexyl, pentafluoroheptyl, heptafluorooctyl, methoxymethyl, 1,2-epoxyethyl, methoxyethyl, methoxy Ethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, t-butylthiomethyl, 4-pentenoxymethyl, trichloroethoxymethyl, Bis(2-chloroethoxy)methyl, methoxycyclohexyl, 1-(2-chloroethoxy)ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl , Trimethylsilylethyl, t-butyldimethylsilyloxymethyl, 2-(trimethylsilyl)ethoxymethyl, t-butoxycarbonylmethyl, ethyl Oxycarbonylmethyl, ethylcarbonylmethyl, t-butoxycarbonylmethyl, acryloxyethyl, methacryloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl Group, acetoxyethyl, 2-methoxy-1-propenyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxy Butyl, 4-hydroxybutyl, 1,2-dihydroxyethyl, etc.

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 represent alkoxy groups having 1 to 10 carbon atoms, including methoxy, ethoxy, propoxy, isopropoxy, Butoxy, s-butoxy, t-butoxy, isobutoxy, pentoxy, isopentoxy, t-pentoxy, hexyloxy, cyclohexyloxy, cyclohexylmethoxy , Tetrahydrofuranoxy, tetrahydropyranoxy, 2-methoxyethoxy, 3-methoxypropoxy, 4-methoxybutoxy, 2-butoxyethoxy, methoxy Group 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 , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ represent ester groups with 2 to 10 carbon atoms, including methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, and phenoxy Carbonyl, acetoxy, propoxy, butoxy, chloroacetoxy, dichloroacetoxy, trichloroacetoxy, trifluoroacetoxy, t-butylcarbonyl Oxy, methoxyacetoxy, benzyloxy and the like.

With respect to 100 parts by mass of the cationic polymerizable component (A), radical polymerizable component (C), and polymer (E) in total, the usage ratio of the cationic polymerization initiator (B) is the cationic polymerization initiator (B) ) 0.001-10 parts by mass, preferably 0.1-10 parts by mass. When it is too small, it is easy to become insufficiently hardened, and when it is too much, it may adversely affect various physical properties such as the water absorption rate and the strength of the hardened product.

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

The compound (C1) having an epoxy group and an ethylenically unsaturated group includes, for example, epoxy acrylate or epoxy methacrylate, specifically, conventionally known aromatic epoxy resins and alicyclics Formula epoxy resin, aliphatic epoxy resin, etc., and acrylic acid or methacrylic acid reaction obtained acrylate. Among these epoxy acrylates or epoxy methacrylates, acrylate or methacrylate of glycidyl ether of alcohols is particularly preferred.

The above-mentioned acrylates of alcohols with 2 to 20 carbon atoms or methacrylates (C2) of alcohols with 2 to 20 carbon atoms include aromatic or aliphatic alcohols having at least one hydroxyl group in the molecule and their rings Acrylate or methacrylate obtained by reacting an oxane adduct with acrylic acid or methacrylic acid. Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isoamyl acrylate, lauryl acrylate can be cited. Acrylate, octadecyl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, benzyl acrylate, 1,3-butanediol diacrylate, 1,4- Butylene glycol 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, 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 dimethyl methacrylate Base acrylate, polypropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, ε-caprolactone modified dipentaerythritol hexamethyl Acrylic etc. Moreover, among these acrylates or methacrylates, polyacrylates of polyols or polymethacrylates of polyols are particularly preferred.

The above-mentioned radical polymerizable component (C) can be a compound other than (C1) or (C2), which is activated by energy ray irradiation or heating, and undergoes polymerization or crosslinking reaction. Examples include Such as allyl carbamate compounds, unsaturated polyester compounds, styrene series Compound etc. The ratio of the above-mentioned (C1) component and (C2) component in the radically 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 conventional ones can be used. For example, ketone-based compounds such as acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, and thioxanthone-based compounds, and oxime-based compounds can be used.

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

The alkyl group having 1 to 7 carbon atoms represented by X in the above formula (I) includes methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso -Butyl, pentyl, iso-pentyl, tert-pentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, etc. Among these, from the viewpoint of curability, an alkyl group having 1 to 4 carbon atoms or one or more groups selected from the group consisting of epoxy group, oxetanyl group, hydroxy group and carboxyl group are partly used. The substituted alkyl group having 1 to 4 carbon atoms is preferred.

The alkoxy group having 1 to 7 carbon atoms represented by X in the above formula (I) includes methoxy, ethoxy, propoxy, iso-propoxy, butoxy Group, sec-butoxy, tert-butoxy, iso-butoxy, pentoxy, iso-pentoxy, tert-pentoxy, hexyloxy, 2-hexoxy, 3-hexoxy Group, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, tert-heptyloxy, etc. Among these, from the standpoint of curability, 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 are used. Partially substituted alkoxy groups having 1 to 4 carbon atoms are preferred.

The aryl group having 6 to 12 carbon atoms represented by X in the above formula (I) includes a phenyl group, a methylphenyl group, and a naphthyl group.

The aryloxy group having 6 to 12 carbon atoms represented by X in the above formula (I) includes a phenoxy group, a methylphenoxy group, a naphthoxy group, and the like.

The alicyclic hydrocarbon group with 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, isobornyl, etc.

These alkyl groups, alkoxy groups, aryl groups, aryloxy groups and alicyclic hydrocarbon groups can be selected from the group consisting of epoxy, oxetanyl, hydroxy and carboxyl groups. It is substituted by more than one group of groups.

In the above formula (I), a part of X is a monomer represented by the formula (I) when it is substituted with an epoxy group or an oxetanyl group. Examples include the 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 the formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and s is an integer of 1 to 6.

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

In the above formula (II), the alkyl group with 1 to 7 carbon atoms, the aryl group with 6 to 12 carbon atoms or the alicyclic hydrocarbon group with 6 to 10 carbon atoms of X'can be exemplified by the above formula (I) Same thing.

In the above formula (II), when a part of X'is substituted with an epoxy group or an oxetanyl group, the monomer represented by the formula (II) may be represented by the following formulas (4) to (6) By.

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

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

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

In the above-mentioned polymer (E), the usage ratio of the monomers constituting the polymer is that the above-mentioned X is a carbon substituted with one or more groups selected from the group consisting of epoxy, cyclobutanyl, hydroxyl, and carboxyl groups In the case of an alkyl group with 1 to 7 atoms, an aryl group with 6 to 12 carbon atoms, or an alicyclic hydrocarbon group with 6 to 10 carbon atoms, make the monomer represented by (I) or (II) above 10-100 mass % Is used, because the adhesion is improved, so it is better.

In the curable composition of the present invention, relative to cationic poly The total of the synthetic component (A), the radical polymerizable component (C), and the polymer (E) is 100 parts by mass, the cationic polymerizable component (A) is 30 to 70 parts by mass, and the cationic polymerization initiator ( B) is 0.001-10 parts by mass, the above-mentioned radical polymerizable component (C) is 30-60 parts by mass, the above-mentioned radical polymerization initiator (D) is 1-10 parts by mass, and the above-mentioned polymer (E) is 1 ~20 parts by mass is better. If the blending ratio is other than the above, the curability and adhesion of the cured product may be deteriorated.

In the curable composition of the present invention, a sensitizer and/or a sensitizer auxiliary may be further used as needed. 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). In addition, the sensitization aid is a compound that further promotes the action of the sensitizer.

Examples of sensitizers and sensitization aids include anthracene-based compounds and naphthalene-based compounds.

Examples of the anthracene 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 with 1 to 6 carbon atoms.

When specific examples of the anthracene compound represented by the above formula (7) are given, there are the following compounds.

Examples include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-dibutyl Oxyanthracene, 9,10-dipentyloxyanthracene, 9,10-dihexoxyanthracene, 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-dipentyloxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene, etc.

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.

When specific examples of the naphthalene-based compound represented by the above formula (8) are given, there are 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, etc.

Compared with the above-mentioned cationically polymerizable component (A), it increases The use ratio of the sensitizer and the sensitization aid is not particularly limited, as long as it is within a range that does not hinder the purpose of the present invention, it may be used in a general use ratio, for example, relative to 100 parts by mass of the above-mentioned cationically polymerizable component (A), From the viewpoint of improving the curability, it is preferable that the sensitizer and the sensitization aid are each 0.1 to 3 parts by mass.

In the curable composition of the present invention, a silane coupling agent can be used as needed. As the silane coupling agent, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, and methyltrimethoxysilane can be used. , Methyl triethoxy silane, ethyl trimethoxy silane, ethyl trimethoxy silane and other alkyl functional alkoxy silanes, vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethyl Alkenyl functional alkoxysilanes such as oxysilane, allyltrimethoxysilane, etc., 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane Methoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethyl Oxyoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyl diethoxysilane, β-(3,4-epoxycyclohexyl)ethyl Epoxy functional alkoxysilane such as trimethoxysilane, N-β(aminoethyl)-γ-aminopropyl trimethoxysilane, γ-aminopropyltriethoxysilane, N -Phenyl-γ-aminopropyltrimethoxysilane such as amino functional alkoxysilane, γ-mercaptopropyltrimethoxysilane such as mercapto functional alkoxysilane, tetraisopropane titanium oxide, Titanium alkoxides such as tetra-n-butane titanium oxide, titanium dioctyloxy bis (octyl glycolate), titanium diisopropoxy bis (ethyl acetyl acetate), etc. Zirconium compounds such as titanium clamp compounds, zirconium tetraacetone acetone, zirconium tributoxy monoacetone zirconium acetonate, zirconium compounds such as zirconium tributoxy stearate, methyl triisocyanate silane And other isocyanate silanes, etc.

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

In the curable composition of the present invention, by using a thermoplastic organic polymer as needed, the properties of the cured product can also be improved. Thermoplastic organic polymers, for example, polystyrene, polymethyl methacrylate, methyl methacrylate ethyl acrylate copolymer, methyl methacrylate glycidyl methacrylate copolymer, poly(methyl) Acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, glycidyl (meth)acrylate-polymethyl(meth)acrylate copolymer, polyethylene Butyral, cellulose ester, polyacrylamide, saturated polyester, etc.

In the curable composition of the present invention, a UV absorber may be further used as needed, or it may be inactive at room temperature, and the protective group will be detached and activated by heating to a specific temperature/light irradiation/acid, etc., thereby exhibiting UV absorption Ability compound.

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

The curable composition of the present invention is not particularly limited, and commonly used solvents that can dissolve or disperse the above-mentioned (A), (B), (C), (D), and (E) components 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 diethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, etc.; 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); cellosolve 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; benzene, toluene, xylene, etc. BTX solvents; hexane, heptane Aliphatic hydrocarbon solvents such as, octane and cyclohexane; terpene hydrocarbon oils such as turpentine, D-limonene, and pinene; mineral spirits, Swasol#310 (manufactured by Cosmo Matsuyama Petroleum Co., Ltd.), Solvesso #100 (Exxon Chemical Company) and other paraffinic solvents; halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane, etc.; chlorobenzene, etc. Halogenated aromatic hydrocarbon solvents; propylene carbonate, carbitol-based solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethyl Acetamide, N-methylpyrrolidone, dimethyl sulfide, water, etc. These solvents can be used singly or as a mixture of two or more solvents.

The curable composition of the present invention improves curability, adhesiveness, and liquid storage stability, so the water 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 will cause white turbidity or doubts about the composition, so it is not good.

The curable composition of the present invention is applied to the supporting substrate by known means such as roll coater, curtain coater, various printing, dipping, and the like. In addition, once applied to a supporting substrate such as a film, it can be transferred to other supporting substrates, and the application method is not limited.

The material of the above-mentioned support matrix is not particularly limited, and ordinary users can be used, such as inorganic materials such as glass; diacetyl cellulose, triacetyl cellulose (TAC), acrylic cellulose, butyric cellulose Cellulose esters of cellulose, acetyl propyl cellulose, nitrocellulose, etc.; polyamide; polyimide; polyurethane; epoxy resin; polycarbonate; polyterephthalate Ethylene formate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene polyterephthalate, polyethylene-1,2- Polyesters such as diphenoxyethane-4,4'-dicarboxylate and polybutylene terephthalate; 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; polyether; polyether ketone; polyether ketone; poly Ether imine; polyoxyethylene, norbornene resin, cyclic olefin polymer (COP) and other polymer materials. In addition, it is also possible to perform corona discharge on the above supporting substrate Surface activation treatments such as treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, etc.

In the method of curing by irradiating the curable composition of the present invention with energy rays, the energy rays include ultraviolet rays, electron rays, X-rays, radiation rays, high frequency, etc., and ultraviolet rays are economically optimal. The light source of ultraviolet light can include ultraviolet laser, mercury lamp, xenon laser, metal halide lamp, etc.

The conditions of the method of curing the curable composition of the present invention by heating are 70 to 250° C. for 1 to 100 minutes. It can be pressurized after pre-bake (PAB; Pre applied bake) to perform post-bake (PEB; Post exposure bake); it can also be baked at different temperatures in several stages. Although the heating conditions vary depending on the types and blending ratios of the ingredients, for example, at 70~180℃, the oven is 5~15 minutes, and the heating plate is 1~5 minutes. Then, in order to harden the coating film, heat treatment is performed at 180 to 250°C, preferably 200 to 250°C, in an oven for 30 to 90 minutes, and a hot plate for 5 to 30 minutes to obtain a cured film.

Specific uses of the curable composition of the present invention or its cured product include adhesives, glasses, optical materials represented by photographic lenses, paints, coating agents, lining agents, inks, and resists. , Liquid resists, printing plates, color TVs, PC monitors, mobile information terminals, digital cameras, organic EL, touch panels and other display elements, insulating varnishes, insulating sheets, laminates, printed circuit boards, semiconductor devices/ LED encapsulation/liquid crystal injection port/organic EL/optical element/electrical insulation/electronic parts/separation film, etc. encapsulant, molding material, putty, glass fiber impregnant, wood powder filler, semiconductor use/ Passivation film for solar cells, etc. Interlayer insulating films, protective films, lenticular lens sheets used in the backlight of liquid crystal display devices, Fresnel lens sheets used in screens such as projection TVs, lens parts of lens sheets such as lenticular lens sheets, or use of such sheets The backlight, etc., microlens, etc., optical lenses, optical components, optical connectors, optical waveguides, optical molding agents, etc.

The display device can be enumerated on a transparent support provided with a primer layer, an anti-reflection layer, a polarizing element layer, a phase difference layer, a birefringence layer, a light scattering layer, a hard coating layer, a lubricating layer, a protective layer, etc., as required. Alternatively, a film made of the cured product of the present invention can be used for each layer.

[Example]

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

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

With the formulations shown in the following [Table 1] to [Table 3], each component was sufficiently mixed to obtain the curable composition of each of Examples 1 to 15 and the curable composition of Comparative Examples 1 to 3. In addition, the units of Examples and Comparative Examples are parts by mass.

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

Compound (A1-1): ADEKA RESINEP-4088L (manufactured by ADEKA Corporation)

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

Compound (A1-3): neopentyl glycol diglycidyl ether

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

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

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

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

The following compounds (C2-1) to (C2-4) are used for the radically polymerizable component (C).

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

Compound (C2-2): Tricyclodecane dimethanol diacrylate

Compound (C2-3): Ethoxylated isocyanuric acid triacrylate

Compound (C2-4): Tetrahydrofurfuryl acrylate

The following compound (D-1) was used as the radical polymerization initiator (D).

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

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

Compound (E-1): a copolymer of 75 parts by mass of methacrylate 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 methacrylate, 35 parts by mass of styrene, and 30 parts by mass of glycidyl methacrylate (weight average molecular weight 8,000)

Regarding the obtained curable 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 recorded in [Table 1] ~ [Table 3].

(Glass transition temperature and elastic modulus at 80℃)

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

(Adhesion)

The above-obtained composition 1 to 15 of the example and the composition 1 to 3 of the comparative example were each coated on a corona treated PMMA film (manufactured by Sumitomo Chemical Co., Ltd.: Technolloy 125S001), and then a laminator was used Laminated with another COP (cycloolefin polymer, manufactured by Japan Zeon Co., Ltd.: model Zeonor Film 14-060) film treated by corona discharge, and irradiated with an electrodeless ultraviolet lamp through the COP film equivalent to 1000mJ/cm ^{The light of 2} is followed to obtain a test piece. A 90-degree peel test was performed on the obtained test piece.

From [Table 1] to [Table 3], it is known that the cured product of the curable composition system of the present invention has a high glass transition temperature and excellent adhesion.

Claims (6)

A curable composition containing: cationic polymerizable component (A), cationic polymerization initiator (B), radical polymerizable component (C), radical polymerization initiator (D) and selected from the following Formula (I)

(In the formula, X is an alkyl group with 1 to 7 carbon atoms, an alkoxy group with 1 to 7 carbon atoms, an aryl group with 6 to 12 carbon atoms, an aryloxy group with 6 to 12 carbon atoms or a carbon atom The alicyclic hydrocarbon group of number 6 to 10, or the hydrogen atom in these groups is substituted by one or more groups selected from the group consisting of epoxy group, oxetanyl group, hydroxyl group and carboxyl group) The polymer obtained from the monomer represented by the following formula (II)

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a halogen atom, and X'is an alkyl group with 1 to 7 carbon atoms, an aryl group with 6 to 12 carbon atoms or an alicyclic hydrocarbon group with 6 to 10 carbon atoms , Or the hydrogen atom in these groups is substituted by one or more groups selected from the group consisting of epoxy group, oxetanyl group, hydroxyl group and carboxyl group) represented by the polymer, A polymer selected from two or more monomers selected from the monomer represented by the aforementioned formula (I), a polymer selected from two or more monomers selected from the monomer represented by the aforementioned formula (II), and a polymer selected from the aforementioned A polymer (E) with a weight average molecular weight of 1,000 to 30,000 formed by the monomer represented by the formula (I) and the polymer obtained from the monomer represented by the aforementioned formula (II), the aforementioned cationically polymerizable component (A) is The glycidyl compound of polyols with a molecular weight of 200 or more, or the glycidyl compound (A1) and oxetane compound (A2) of polyol alkylene oxide adducts as essential components, the aforementioned radical polymerizability 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 a methacrylate of an alcohol having 2 to 20 carbon atoms (C2 ) As an essential component, the polyol in the glycidyl product of the polyol having a molecular weight of 200 or more or the glycidyl product of the polyol alkylene oxide adduct (A1) is a polyol having a condensed ring, Wherein the aforementioned cationic polymerizable component (A) is 30 to 70 parts by mass, the aforementioned cationic polymerization initiator (B) is 0.001 to 10 parts by mass, and the aforementioned radical polymerizable component (C) is 30 to 60 parts by mass, and the aforementioned free The base polymerization initiator (D) is 1-10 parts by mass, the aforementioned polymer (E) is 1-20 parts by mass, and the aforementioned cationically polymerizable component (A) and the aforementioned radically polymerizable component (C) are combined with the aforementioned polymer The total of the substance (E) is 100 parts by mass. The curable composition of claim 1, wherein the cationically polymerizable component (A) further contains an alicyclic epoxy compound (A3). The curable composition of claim 1, wherein the polymer (E) is obtained from the monomer represented by the aforementioned formula (I) and the monomer represented by the aforementioned formula (II) In the above formula (I), X is an aryl group with 6 to 12 carbon atoms, and X'in the above formula (II) is an alkyl group with 1 to 7 carbon atoms. The aforementioned alkyl group is an epoxy group Replaced. A hardening method of a hardening composition, which is to irradiate active energy rays to the hardening composition according to any one of claims 1 to 3. A hardening method of a hardening composition, which is to heat the hardening composition according to any one of claims 1 to 3. A hardened product, which is a hardened product of the hardenable composition according to any one of claims 1 to 3.