TWI788285B - Curable composition, method for producing cured product, and cured product - Google Patents

Abstract

The present invention provides a curable composition having a high glass transition temperature and excellent adhesion, a method for producing the cured product, and the cured product.

表示之單體所得之聚合物、由下述式(II)

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)1~20質量份，使(A)與(C)與(E)之合計成為100質量份，(A)係以多元醇之環氧丙基化物等(A1)及氧雜環丁烷化合物(A2)為必須成分，(A1)為35~65質量份，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)等為必須成分。 The curable composition of the present invention contains: 15 to 90 parts by mass of a cationic polymerizable component (A), 1 to 10 parts by mass of a cationic polymerization initiator (B), and 10 to 50 parts by mass of a radically polymerizable component (C). Parts by mass, 1 to 10 parts by mass of radical polymerization initiator (D) and selected from the following formula (I)

The polymer obtained from the monomer represented by the following formula (II)

1 to 20 parts by mass of polymer (E) with a weight average molecular weight of 1,000 to 30,000, which is a group of polymers obtained from the indicated monomers, so that the total of (A), (C) and (E) becomes 100 parts by mass , (A) is based on polyhydric alcohol glycidyl compound (A1) and oxetane compound (A2) as essential components, (A1) is 35~65 parts by mass, free radical polymerizable component (C) The compound (C1) having an epoxy group and an ethylenically unsaturated group is an essential component.

Description

Curable composition, method for producing cured product, and cured product

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

Curable compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members, etc. Various reports have been made on the improvement of such curable compositions.

For example, the following Patent Documents 1 to 3 propose energy ray-curable compositions containing cationically polymerizable components and radically polymerizable components, and cured products thereof. Specifically, Patent Document 1 proposes an adhesive composition for polarizing plates excellent in initial curability and adhesiveness. In addition, in Patent Document 2, it is proposed that even when a resin film with low moisture permeability is used as a protective film, after light irradiation, the adhesive force can be quickly exhibited, and for various forces, the adhesive force after a certain period of time is good. After the durability test It is also a low-viscosity light-curing adhesive that does not cause problems and has good adhesion after the heat-and-humidity test. In addition, Patent Document 3 proposes an active energy ray polymerizable compound containing an unsaturated alicyclic epoxy ester compound that can achieve both high heat resistance or high refractive index and transparency. Resin composition.

[Prior Art Literature] [Patent Document]

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

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

Patent Document 3: Japanese Patent Laid-Open No. 2015-168757

However, even the curable compositions proposed in Patent Documents 1 to 3 may not always be able to satisfy the curability and adhesiveness, and the present situation is that a novel composition capable of highly curable and adhesive properties is desired. hardening composition.

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

As a result of earnest research to solve the above-mentioned problems, the inventors of the present invention found that the above-mentioned problems can be overcome if the curable composition has a specific composition, and completed the present invention.

(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、或此等之基中之氫原子經選自由環氧基、氧雜環丁烷基、羥基及羧基所成群之1種以上之基所取代者)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、或此等之基中之氫原子經選自由環氧基、氧雜環丁烷基、羥基及羧基所成群之1種以上之基所取代者)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、選自前述式(II)表示之單體之二種以上之單體所得之聚合物及由前述式(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)1~20質 量份，使前述陽離子聚合性成分(A)與前述自由基聚合性成分(C)與前述聚合物(E)之合計成為100質量份，前述陽離子聚合性成分(A)係以多元醇之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)為必須成分，相對於前述陽離子聚合性成分(A)與前述自由基聚合性成分(C)與前述聚合物(E)之合計100質量份時，前述多元醇之環氧丙基化物或多元醇環氧烷加成物之環氧丙基化物(A1)為35~65質量份，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的多元醇之丙烯酸酯或碳原子數2~20的多元醇之甲基丙烯酸酯(C2)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: 15 to 90 parts by mass of cationic polymerizable component (A), 1 to 10 parts by mass of cationic polymerization initiator (B), radical polymerizable component (C) 10 to 50 parts by mass, 1 to 10 parts by mass of a 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 An alicyclic hydrocarbon group with a number of 6 to 10, or a hydrogen atom in these groups is substituted by one or more groups selected from epoxy groups, oxetanyl groups, hydroxyl groups, and carboxyl groups) The polymer obtained from the monomer of the following formula (II)

(In the formula, ^R1 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 a polymer in which the hydrogen atoms in these groups are replaced by a monomer represented by one or more groups selected from epoxy groups, oxetanyl groups, hydroxyl groups, and carboxyl groups), The polymer obtained from two or more monomers of monomers represented by the aforementioned formula (I), the polymer obtained from two or more monomers selected from the monomers represented by the aforementioned formula (II), and the polymer obtained by the aforementioned formula (I) ) represented by the monomer represented by the above-mentioned formula (II) and the polymer obtained by the monomer represented by the aforementioned formula (II) have a weight average molecular weight of 1,000 to 30,000 polymer (E) 1 to 20 parts by mass, so that the aforementioned cationic polymerizable component (A ) and the total of the above-mentioned radical polymerizable component (C) and the above-mentioned polymer (E) become 100 parts by mass, and the above-mentioned cationic polymerizable component (A) is made of polyhydric alcohol glycidyl compound or polyhydric alcohol alkylene oxide The glycidyl compound (A1) and the oxetane compound (A2) of the finished product are essential components, and the aforementioned cation polymerizable component (A), the aforementioned radical polymerizable component (C) and the aforementioned polymer ( When the total of E) is 100 parts by mass, the glycidyl compound of the aforementioned polyol or the glycidyl compound (A1) of the alkylene oxide adduct of the polyol is 35 to 65 parts by mass, and the radical polymerizable component ( C) It is based on a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylate ester of a polyol with 2 to 20 carbon atoms or a methacrylate ester (C2) of a polyol with a carbon number of 2 to 20 is an essential ingredient. Here, the weight average molecular weight refers to the weight average molecular weight obtained in terms of styrene by GPC measurement in a tetrahydrofuran (THF) solvent.

In the curable composition of the present invention, it is preferable that the cationically polymerizable component (A) further contains an aromatic epoxy compound (A3). Moreover, in the curable composition of this invention, it is preferable that the said aromatic epoxy compound (A3) is a polyfunctional aromatic epoxy compound. In addition, in the curable composition of the present invention, the aforementioned polymer (E) is a polymer obtained from a monomer represented by the aforementioned formula (I) and a monomer represented by the aforementioned formula (II), and in the aforementioned formula (I), 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 by an epoxy group.

The method for producing the curable composition of the present invention is to irradiate the curable composition of the present invention with active energy rays, or to hot.

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 having a high glass transition temperature and excellent adhesion, a method for producing a cured product, and a cured product thereof. The curable composition of the present invention can be used especially as an adhesive.

The form of implementing the invention

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

The curable composition of the present invention contains: 15 to 90 parts by mass of a cationic polymerizable component (A), 1 to 10 parts by mass of a cationic polymerization initiator (B), and 10 to 50 parts by mass of a radically polymerizable component (C). Parts by mass, 1 to 10 parts by mass of a radical polymerization initiator (D), and a polymer obtained from a monomer represented by the following formula (I), a polymer obtained from a monomer represented by the following formula (II) , a polymer obtained from two or more monomers selected from the monomers represented by the aforementioned formula (I), a polymer obtained from two or more monomers selected from the monomers represented by the aforementioned formula (II), and a polymer obtained by the aforementioned formula (II) 1 to 20 parts by mass of the polymer (E) having a weight average molecular weight of 1,000 to 30,000 and a polymer obtained from the monomer represented by (I) and the monomer represented by the aforementioned formula (II).

In the curable composition of the present invention, the aforementioned cationic polymerizable component (A) is a glycidyl compound of a polyol or a glycidyl compound of a polyalcohol alkylene oxide adduct (A1) and oxetane Alkanes (A2) is an essential component, and when the total of cationically polymerizable component (A), radically polymerizable component (C) and polymer (E) is 100 parts by mass, glycidyl compound of polyol or polyol The glycidyl compound (A1) of the alkylene oxide adduct is 35 to 65 parts by mass. In addition, the radically polymerizable component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylate ester of a polyol with 2 to 20 carbon atoms or a polyol with 2 to 20 carbon atoms The methacrylate (C2) 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, or an aromatic group with 6 to 12 carbon atoms. Oxygen group or alicyclic hydrocarbon group with 6 to 10 carbon atoms, or a group in which the hydrogen atom in these groups is selected from the group consisting of epoxy group, oxetanyl group, hydroxyl group and carboxyl group replaced by.

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 an aryl group with 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 cationic polymerizable component (A) of the curable composition of the present invention is a cationic polymerization initiator activated by energy ray irradiation or heating, and undergoes macromolecularization or crosslinking reaction. Examples thereof include epoxy compounds, oxetane compounds, vinyl ether compounds, and the like.

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

Glycidylated products of the above-mentioned polyols or glycidated products (A1) of polyol alkylene oxide adducts include those obtained by glycidylating polyhydric alcohols or polyol alkylene oxide adducts , and the molecular weight of the glycidyl compound is preferably 250 or more.

Glycidylated products of the above-mentioned polyols or glycidated products (A1) of polyol alkylene oxide adducts include 1,4-butanediol diglycidyl ether, 1,6-hexanediol Diglycidyl Ether, Neopentyl Glycol Diglycidyl Ether, Triglycidyl Ether of Glycerol, Triglycidyl Ether of Trimethylolpropane, Tetraglycidyl Ether of Sorbitol, Dipentaerythritol Hexaglycidyl ether, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, glycidyl ether of polyols such as dicyclopentadiene dimethanol diglycidyl ether, and Polyglycidyl ether compounds of polyether polyols, aliphatic long Diglycidyl ester of chain dibasic acid.

Glycidyl compounds of polyols or glycidyl compounds (A1) of alkylene oxide adducts of polyols, further examples include monoglycidyl ethers of aliphatic higher alcohols or glycidyl esters of higher fatty acids, Epoxidized soybean oil, epoxy octyl stearate, epoxy butyl stearate, epoxidized soybean oil, epoxidized polybutadiene, etc.

The glycidyl compound of polyol or the glycidyl compound of polyol alkylene oxide adduct (A1) contains a saturated condensed ring, which can improve the curability and adhesiveness of the cured product, so it is preferable.

As the glycidyl compound of the above-mentioned polyhydric alcohol or the glycidyl compound (A1) of the polyol alkylene oxide adduct, a commercially available product can be used, for example, Denacol EX-121, Denacol EX-171, Denacol EX-192 , Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Dcnacol EX-512, Denacol EX-521, Denacol EX-611 , Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832 , Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase Chemtex Co., Ltd.); EpoliteM-1230, Epolite40E, Epolite100E, Epolite200E, Epolite400E, Epolite70P, Epolite200P, Epolite400P, Epolite1500NP, Epolite1600, Epolite80MF, Epolite100MF (Kyoeisha Chemical Co., Ltd. manufactured), ADEKA GLYCIROLED-503, ADEKA GLYCIROLED-503G, ADEKA GLYCIROLED-506, ADEKA GLYCIROLED-523T, ADEKA Resin-4088S, ADEKA Resin-4080E (manufactured by ADEKA Corporation), etc.

The aforementioned oxetane compound (A2) includes 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,4-bis[(3-ethyl-3-oxocyclo Butylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxocyclobutylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxo 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 -3-oxetanylmethoxy)hexane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethane Base-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxy A functional oxetane compound, etc., which is one of 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. In particular, polyfunctional oxetane compounds are preferred because they improve the curability and adhesion of cured products.

The above-mentioned oxetane compound (A2) can be a commercially available product, for example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (Maruzen Petrochemical Co., Ltd. system); ARON OXETANEOXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (Dong Yasei (stock) Company system), ETERNACOLL OXBP, OXTP (Ube Industries Co., Ltd. system), etc.

The above-mentioned aromatic epoxy compound (A3) refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound (A3) include those having at least one aromatic ring such as phenol, cresol, and butylphenol. Mono/polyglycidyl ether compounds of polyphenols or their alkylene oxide adducts, such as bisphenol A, bisphenol F, or glycidyl ether compounds of these compounds added with alkylene oxide or Epoxy novolak resins; mono/polyglycidyl ether compounds of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol or hydroquinone or catechol; phenyldimethanol or phenyldimethanol Glycidyl ether compounds of aromatic compounds having two or more alcoholic hydroxyl groups, such as ethanol and phenyldibutanol; phthalic acid, terephthalic acid, trimellitic acid, etc., having two or more carboxyl groups Glycidyl ester of polybasic acid aromatic compound of acid, glycidyl ester of benzoic acid, styrene oxide or epoxide of divinylbenzene, etc.

Commercially available products can be used for the above-mentioned aromatic epoxy compound (A3), for example, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Oncoat EX -1020, Oncoat EX-1030, Oncoat EX-1040, Oncoat EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat1012 (manufactured by Nagase Chemtex Co., Ltd.); OGSOLPG-100, OGSOLEG- 200, OGSOLEG-210, OGSOLEG-250 (manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC Co., Ltd.); Division system); EpikoteYX8800 (Mitsubishi Chemical Corporation); Marproof G-0105SA, Marproof G-0130SP (NOF Corporation); EPICLONN-665, EPICLONNHP-7200 (DIC Corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (Nippon Kayaku Co., Ltd.); ADEKA ResinEP-4000, ADEKA ResinEP-4005, ADEKA ResinEP-4100, ADEKA ResinEP-4901 (manufactured by ADEKA Corporation); TECHMORE VG-3101L (manufactured by Printec Corporation) and the like. Among the above-mentioned aromatic epoxy compounds (A3), polyfunctional ones are preferred because they are excellent in curability.

The above-mentioned alicyclic epoxy compound (A4) means that an oxirane ring is directly bonded to a saturated ring without a bonding group. Specific examples of the alicyclic epoxy compound (A4) include polyglycidyl ether compounds of polyhydric alcohols having at least one alicyclic ring or compounds containing cyclohexene or cyclopentene rings as oxidizing agents. A compound containing cyclohexene oxide or cyclopentene oxide obtained by epoxidation. Examples include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy Base-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexylcarboxylate, 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-methyl Cyclohexane carboxylate, methylenebis(3,4-epoxycyclohexane), propane- 2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, Ethylbis(3,4-epoxycyclohexanecarboxylate), Dioctyl epoxyhexahydrophthalate, Di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxyethylcyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene oxide, limonene dioxide, etc. . The alicyclic epoxy compound (A4) is preferably 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 3,4- Epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate.

A commercial item can be used for the said alicyclic epoxy compound (A4), For example, CELLOXID 2021P, CELLOXID 2081, CELLOXID 2000, CELLOXID 3000 (made by (stock) DAICEL company) etc. are mentioned.

The aforementioned vinyl ether compounds include, 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, 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.

Among the above-mentioned cationically polymerizable components (A), the above-mentioned glycidyl compound of the polyol or the glycidyl compound of the polyalcohol alkylene oxide adduct (A1), the oxetane compound (A2), the aromatic Epoxy compound (A3), alicyclic epoxy compound (A4) and vinyl ether compound When the ratio is 100 parts by mass of the total of cationically polymerizable component (A), radically polymerizable component (C) and polymer (E), glycidyl compound of polyol or polyol alkylene oxide 50-90 parts by mass of glycidyl compound (A1), 10-50 parts by mass of oxetane compound (A2), 0-50 parts by mass of aromatic epoxy compound (A3), alicyclic ring When the oxygen compound (A4) is 0 to 30 parts by mass and the vinyl ether compound is 0 to 20 parts by mass, it is preferable because the viscosity, coatability, reactivity, and curability can be improved.

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, and can be used when it is released by energy ray irradiation. Double salts of onium salts of Lewis acids or their derivatives. Representative examples 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 onium, and its structure can be represented by the following general formula [(R ² ) _a Q] ^r+ , for example.

Furthermore, 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. a R ² can be independently the same or different. Moreover, it is preferable that at least one is the above-mentioned organic group which has an aromatic ring. Q is an atom or an atom group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N=N. Also, when the atomic valence of Q in the cation [A] ^r+ is q, the relationship of r=aq (but N=N is regarded as atomic valence 0) must be established.

Also, 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 from 3 to 7. Also, 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, tetrakis (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroboric acid (BF ₄ ) ^- , hexafluorophosphate (PF ₆ ) ^- , hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarsenate (AsF ₆ ) ^- , hexachloroantimonate (SbCl ₆ ) ^- and so on.

Also, as the anion [B] ^r-, a structure represented by the following general formula [LY _b-1 (OH)] ^r- can also be used. The L, Y, and b systems are the same as above. In addition, other usable anions include perchlorate ion (ClO ₄ ) ^- , trifluoromethylsulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonate ion (FSO ₃ ) ^- , toluenesulfonate anion, Trinitrobenzenesulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraarylborate, tetrakis(pentafluorophenyl)borate, etc.

In the curable composition of the present invention, among such onium salts, It is especially effective to use the following aromatic onium salts (A)~(C). Among these, 1 type can be used individually or 2 or more types can be mixed and used.

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

(B) Diphenyliodonium hexafluoroantimonate, bis(4-methylphenyl)iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, tolyl cumene Diaryliodonium salts such as yliodonium(pentafluorophenyl)borate

(C) Percilium salts of the following group I or II borate cations and hexafluoroantimony ions, hexafluorophosphate ions, tetrakis(pentafluorophenyl)borate ions, etc.

Also, other preferred ones include (η ⁵ -2,4-cyclopentadien-1-yl)[(1,2,3,4,5,6-η)-(1-methylethyl) Iron-arene complexes of benzene]-iron-hexafluorophosphate, etc., or aluminum complexes of ginseng (acetylacetone) aluminum, ginseng (ethyl acetate) aluminum, ginseng (salicylaldehyde) aluminum, etc. Mixtures with silanols such as triphenylsilanol; salts of thiophenium salt, tetrahydrothiophene iron salt (thiolanium), benzyl ammonium, pyridinium salt, hydrazinium salt (hydrazinium) and other salts; diethylenetriamine, three Polyalkylpolyamines such as ethylenetriamine and tetraethylenepentamine; 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophor Alicyclic polyamines such as ketone diamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylmethane, etc.; making the above polyamines by general methods Glycidyl ethers such as phenylglycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, etc., or glycidyl esters of carboxylic acids The polyepoxy addition modification produced by reacting various epoxy resins such as phthalates; the reaction of the above-mentioned organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid, and dimer acid by a general method The manufactured amidation modified substance; the above-mentioned polyamines and aldehydes such as formaldehyde and phenols, cresols, xylenols, tertiary butylphenols, resorcinols, etc. have at least one core Mannich-modified substances produced by phenolic reactions in the reactive sites of hydroformylation; 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-methyladipic acid, 3-methyladipic acid, 3-methylglutaric acid, 2-methyl Suberic acid, 3,8-dimethylsebacic acid, 3,7-dimethylsebacic acid, hydrogenated dimer acid, aliphatic dicarboxylic acids such as dimer acid; phthalic acid, terephthalic acid Aromatic dicarboxylic acids such as formic acid, isophthalic acid, and naphthalene dicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid, trimesic acid, castor oil Tricarboxylic acids such as trimers of fatty acids; anhydrides of tetracarboxylic acids such as pyromellitic acid); dicyandiamide, imidazoles, carboxylates, sulfonates, amidoimides, etc.

Among these, from the viewpoint of practicality and improvement of photosensitivity, it is preferable to use aromatic iodonium salts, aromatic permeic acid salts, and iron-aromatic complexes; More preferably, it contains at least 0.1% by mass of an aromatic percited 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, a carbon number of 1~ An alkyl group of 10, an alkoxy group with 1 to 10 carbon atoms, or an ester group with 2 to 10 carbon atoms, R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, a halogen atom or a carbon atom number An alkyl group of 1~10, ^R25 represents a hydrogen atom, a halogen atom, an alkyl group with 1~10 carbon atoms or any substituent selected from the following chemical formulas (A)~(C), An ^q- represents q Valence of anion, p represents the coefficient to make 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, or an alkyl group having 1 to 10 carbon atoms An alkoxy group or an ester group with 2 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.

Among the compounds represented by the above general 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 ,} The halogen atoms represented by 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 may be Examples thereof include fluorine, chlorine, bromine, iodine and the like.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ^{35 , R 36 ,} R ³⁷ , R ³⁸ and R ³⁹ 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 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, heptadecafluorooctyl, methoxymethyl, 1,2-epoxyethyl, methoxyethyl, methoxy ethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, t-butylthiomethyl, 4-pentenyloxymethyl, trichloroethoxymethyl, Bis(2-chloroethoxy)methyl, methoxycyclohexyl, 1-(2-chloroethoxy)ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl , trimethylsilylethyl, t-butyldimethylsilyloxymethyl, 2-(trimethylsilyl)ethoxymethyl, t-butoxycarbonylmethyl, ethyl Oxycarbonylmethyl, ethylcarbonylmethyl, t-butoxycarbonylmethyl, acryloxyethyl, methacryloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl radical, acetylethyl, 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 with 1 to 10 carbon atoms, including methoxy, ethoxy, propoxy, isopropoxy, Butoxy, s-butoxy, t-butoxy, isobutoxy, pentyloxy, isopentyloxy, t-pentyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethoxy , tetrahydrofuranoxy, tetrahydropyranyloxy, 2-methoxyethoxy, 3-methoxypropoxy, 4-methoxybutoxy, 2-butoxyethoxy, methoxy ethoxyethoxy, methoxyethoxyethoxyethoxy, 3-methoxybutoxy, 2-methylthioethoxy, trifluoromethoxy, 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 ester groups with 2 to 10 carbon atoms, including methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, phenoxy ylcarbonyl, acetyloxy, propionyloxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, t-butylcarbonyl Oxygen, methoxyacetyloxy, benzoyloxy, etc.

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

The above-mentioned 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, alicyclic Acrylic acid esters obtained by reacting formula epoxy resin, aliphatic epoxy resin, etc. with acrylic acid or methacrylic acid. Among these epoxy acrylates or epoxy methacrylates, acrylates or methacrylates of glycidyl ethers of alcohols are 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 and their rings having at least one hydroxyl group in the molecule. Acrylate or methacrylate obtained by reacting oxane adduct with acrylic acid or methacrylic acid. Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isoamyl acrylate, lauryl acrylate, octadecyl acrylate, isooctyl acrylate, acrylate, tetrahydrofurfuryl acrylate, isocamphoryl acrylate, benzyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol Alcohol Diacrylate, Diethylene Glycol Diacrylate, Triethylene Glycol Diacrylate, Neopentyl Glycol Diacrylate, Polyethylene Glycol Diacrylate, Polypropylene Glycol Dipropylene ester, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ε-caprolactone modified dipentaerythritol hexaacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, isopentyl methacrylate, lauryl methacrylate, octadecyl methacrylate, isooctyl methacrylate, tetrahydro Furfuryl methacrylate, isocamphoryl methacrylate, benzyl methacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate , polypropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, ε-caprolactone modified dipentaerythritol hexamethacrylate, etc. . Moreover, among these acrylates or methacrylates, polyol polyacrylates or polyol polymethacrylates are particularly preferred.

The above-mentioned radical polymerizable component (C) can use a compound other than (C1) or (C2), which undergoes a polymerization or crosslinking reaction by a radical polymerization initiator activated by energy ray irradiation or heating. For example, an allyl urethane compound, an unsaturated polyester compound, a styrene-type compound, etc. are mentioned. It is preferable that the ratio of the said (C1) component and (C2) component in a radically polymerizable component (C) is 50 mass % or more.

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

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

The alkyl group with 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 them, from the viewpoint of hardenability, an alkyl group having 1 to 4 carbon atoms may be partially substituted with one or more groups selected from epoxy groups, oxetanyl groups, hydroxyl groups, and carboxyl groups. An alkyl group with 1 to 4 carbon atoms is preferred.

An alkoxy group having 1 to 7 carbon atoms represented by X in the above formula (I) includes methoxy, ethoxy, propoxy, iso-propoxy, butoxy, sec-butoxy , tert-butoxy, iso-butoxy, pentyloxy, iso-pentyloxy, tert-pentyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, tert-heptyloxy, etc. 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 epoxy, oxetanyl, hydroxyl and carboxyl groups carry out the moiety replace An alkoxy group with 1 to 4 carbon atoms is preferred.

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

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

The alicyclic hydrocarbon group with 6 to 10 carbon atoms represented by X in the above formula (I) may include cyclohexyl, methylcyclohexyl, norbornyl, dicyclopentyl, bicyclooctyl, trimethylbicycloheptyl , tricyclic octyl, tricyclodecanyl, spirooctyl, spirobicyclopentyl, adamantyl, isobornyl, etc.

These alkyl groups, alkoxy groups, aryl groups, aryloxy groups and alicyclic hydrocarbon groups can be hydrogen atoms in these groups selected from epoxy groups, oxetanyl groups, hydroxyl groups and carboxyl groups. Groups of one or more bases are substituted.

In the above-mentioned formula (I), a part of X is a monomer represented by the formula (I) when a part of X is substituted by 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.

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

In the above-mentioned 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 enumerated with the above-mentioned formula (I) the same.

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

Here, in the formula (4), ^R1 is the same as the above-mentioned formula (II), ^R6 represents a hydrogen atom or an alkyl group with 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-mentioned formula (II), R ⁷ represents a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, and q is an integer of 1 to 6.

Here, in the formula (6), ^R1 is the same as the above-mentioned formula (II), ^R8 represents a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, and y is an integer of 1 to 6.

In the above-mentioned polymer (E), the proportion of the monomers constituting the polymer is such that the above-mentioned X is a carbon substituted by one or more groups selected from the group consisting of epoxy group, cyclobutanyl group, hydroxyl group and carboxyl group 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, the monomer represented by the above (I) or (II) is 10 to 100 by mass % to use, because of improved adhesion, it is better.

In the curable composition of the present invention, the above-mentioned cationic polymerizable component (A) is 15-90 parts by mass, preferably 50-80 parts by mass, and the above-mentioned cationic polymerization initiator (B) is 1-10 parts by mass, preferably Preferably 1-6 parts by mass, the radical polymerizable component (C) is 10-50 parts by mass, preferably 10-20 parts by mass, the radical polymerization initiator (D) is 1-10 parts by mass, Preferably 1-5 parts by mass, the above-mentioned polymer (E) is 1-20 parts by mass, Preferably it is 5-15 mass parts. When the blending ratio is other than the above, the curability and adhesiveness of the cured product may be deteriorated. Moreover, the total of a cation polymerizable component (A), a radical polymerizable component (C), and a polymer (E) is 100 mass parts.

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

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

As an anthracene type compound, what is represented by following formula (7) is mentioned, for example.

Here, in formula (7), R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, or an alkoxyalkyl group with 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-based compound represented by the above formula (7) are given, the following compounds are given.

Examples include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-dibutyl oxygen Anthracene, 9,10-dipentyloxyanthracene, 9,10-dihexyloxyanthracene, 9,10-bis(2-methoxyethoxy)anthracene, 9,10-bis(2-ethoxy ethoxy)anthracene, 9,10-bis(2-butoxyethoxy)anthracene, 9,10-bis(3-butoxypropoxy)anthracene, 2-methyl- or 2-ethane -9,10-dimethoxyanthracene, 2-methyl- or 2-ethyl-9,10-diethoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipropane Oxyanthracene, 2-methyl- or 2-ethyl-9,10-diisopropoxyanthracene, 2-methyl- or 2-ethyl-9,10-dibutoxyanthracene, 2-methanthracene Base- or 2-ethyl-9,10-dipentyloxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene, etc.

Naphthalene-based compounds include, for example, 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, the following compounds are given.

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.

With respect to the above cationic polymerizable component (A), the ratio of the sensitizer and the sensitizer is not particularly limited, as long as it does not hinder the purpose of the present invention, it can be used in a generally used ratio, for example From the viewpoint of improving curability, the sensitizer and the sensitizing assistant are each preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the above-mentioned cationically polymerizable component (A).

In the curable composition of the present invention, a silane coupling agent may be used as needed. Silane coupling agents can be used such as dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane , methyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane and other alkyl-functional alkoxysilanes, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethyl Alkenyl functional alkoxysilane such as oxysilane, allyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane Dimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropylmethyldiethoxysilane Oxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyl Epoxy-functional alkoxysilane such as trimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N - Amino-functional alkoxysilanes such as phenyl-γ-aminopropyltrimethoxysilane, mercapto-functional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, titanium tetraisopropane oxide, Titanium alkoxides such as tetra-n-butane titanium oxide, titanium dioctyloxybis(octyl glycolate), titanium diisopropoxybis(ethyl acetylacetate) and other titanium chelates Zirconium chelates such as zirconium tetraacetylacetonate and zirconium tributoxymonoacetylacetonate, zirconium acyl compounds such as zirconium tributoxy monostearate Classes, isocyanate silanes such as methyl triisocyanate silane, etc.

The usage-amount of the said silane coupling agent is not specifically limited, Usually, it is the range of 0.01-20 mass parts with respect to 100 mass parts of total solids in a curable composition.

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

In the curable composition of the present invention, ultraviolet absorbers can be further used as needed, or they are inactive at room temperature, and the protective group will be detached and activated by heating to a specific temperature/light irradiation/acid, etc., and exhibit ultraviolet absorption. Ability compound.

Also, as long as the effect of the present invention is not impaired, coloring agents such as polyols, inorganic fillers, organic fillers, pigments, dyes, defoamers, tackifiers, surfactants, leveling agents, flame retardants, etc. can be added as needed. Various resin additives such as additives, thixotropic agents, diluents, plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow regulators, adhesion accelerators, etc.

The curable composition of the present invention is not particularly limited, and may be A commonly used solvent capable of dissolving or dispersing the respective components of (A), (B), (C), (D) and (E) above is used. Examples of solvents 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 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-based solvents such as pentanediol isobutyric acid (Texanol); cellosolve-based 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, etc. ether ester solvents; benzene, toluene, xylene, etc. BTX solvents; hexane Aliphatic hydrocarbon solvents such as , heptane, octane, and cyclohexane; terpene-based hydrocarbon oils such as turpentine, D-limonene, and pinene; mineral spirits, Swasol#310 (manufactured by Cosmo Matsuyama Oil Co., Ltd. ), Solvesso#100 (Exxon Chemical Co.) Halogenated aromatic hydrocarbon solvents such as benzene; propylene carbonate, carbitol-based solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N- Dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water, and the like. These solvents can be used alone or as a mixed solvent of two or more.

The curable composition of the present invention improves curability, adhesiveness, and liquid storage stability, so 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, there may be doubts about white turbidity or separation of components, 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, after being applied to a supporting substrate such as a film once, it may be transferred to another supporting substrate, and the application method is not limited.

The material of the above-mentioned support matrix is not particularly limited, and commonly used ones can be used, such as inorganic materials such as glass; diacetyl cellulose, triacetyl cellulose (TAC), acryl cellulose, butyryl cellulose Cellulose esters of cellulose, acetylpropionyl cellulose, nitrocellulose, etc.; polyamides; polyimides; polyurethanes; epoxy resins; polycarbonates; polyterephthalates Ethylene formate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, 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, polyvinyl fluoride, etc.; acrylic resins such as polymethyl methacrylate, polyacrylate, etc.; polycarbonate; Etherimide; polymer materials such as polyoxyethylene, norcamphene resin, cycloolefin polymer (COP), etc. In addition, surface activation treatments such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, etc. may be performed on the above-mentioned support base.

In the method of curing the curable composition of the present invention by irradiating energy rays, examples of the energy rays include ultraviolet rays, electron rays, X-rays, radiation rays, high frequency, etc., and ultraviolet rays are most economically optimal. The light source of ultraviolet rays includes ultraviolet lasers, mercury lamps, xenon lasers, metal halide lamps, and the like.

The conditions for 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 pre-baked (PAB; Pre applied bake) and then 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 70-180°C, it takes 5-15 minutes in an oven, and 1-5 minutes on a heating plate. Then, in order to harden the coating film, heat treatment is performed at 180-250°C, preferably 200-250°C, in an oven for 30-90 minutes, and on a heating plate for 5-30 minutes to obtain a cured film.

Specific applications of the curable composition of the present invention or its cured product include adhesives, eyeglasses, optical materials represented by photographic lenses, paints, coating agents, lining agents, inks, and resists. , liquid resist, printing plates, color TVs, PC monitors, mobile information terminals, digital cameras, organic EL, display elements such as touch panels, insulating varnishes, insulating sheets, laminates, printed substrates, semiconductor devices/ Encapsulant, molding material, putty, glass fiber impregnant, wood powder filler, semiconductor for LED encapsulation/liquid crystal injection port/organic EL/optical element/electrical insulation/electronic parts/separation film, etc. Passivation film for solar cells, interlayer insulating film, protective film, sapphire lens sheet used for backlight of liquid crystal display device, Fresnel lens sheet used for screen of projection TV, etc. Lens portion of lens sheet such as lenticular lens sheet, or backlight using such sheet, optical lens such as microlens, optical element, optical connector, optical waveguide, molding agent for optical molding, etc.

The display device of the present invention can be enumerated on the transparent support to be provided with a primer layer, an anti-reflection layer, a polarizer layer, a phase difference layer, a birefringence layer, a light scattering layer, a hard coat layer, a lubricating layer, and a protective layer. For each layer, a film made of the cured product of the present invention can be used for each layer.

[Example]

Examples and the like are given below to describe the present invention in more detail, but the present invention is not limited to these examples.

[Examples 1-19, Comparative Examples 1-8]

According to the preparation shown in the following [Table 1] to [Table 6], each component was fully mixed to obtain the curable compositions of Examples 1 to 19 and the curable compositions of Comparative Examples 1 to 8. In addition, the unit of an Example and a comparative example is a mass part.

As the cationically polymerizable component (A), the following compounds were used.

Compound (A1-1): Neopentyl glycol diglycidyl ether

Compound (A1-2): 1,4-Butanediol Diglycidyl Ether

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

Compound (A3-1): Bisphenol Diglycidyl Ether

Compound (A3-2): TECHMORE VG3101 (aromatic trifunctional Epoxy resin: (produced by Printec Co., Ltd.)

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

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

As the radical polymerizable component (C), the following compounds were used.

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

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

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

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

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

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

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

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 methyl methacrylate and 25 parts by mass of glycidyl methacrylate (weight average molecular weight 800)

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

For each curable composition obtained in Examples 1 to 19 and Comparative Examples 1 to 8, glass transition temperature (Tg), elastic modulus, and adhesiveness were evaluated according to the following procedure. The results are recorded in [Table 1] ~ [Table 6].

(glass transition temperature and modulus of elasticity)

Each of the curable compositions obtained in Examples 1-19 and Comparative Examples 1-8 was 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 to The energy of 3000mJ/cm ² is irradiated. After 24 hours, the hardened adhesive was taken out from the film, and the elastic modulus at Tg and 80° C. was measured using a viscoelasticity measuring device (DMA7100) manufactured by Hitachi High-Tech Science.

(viscosity)

For the curable compositions obtained in Examples 1-19 and Comparative Examples 1-8 The viscosity at 25°C was measured with an E-type viscometer.

(adhesion: COP)

The curable compositions of Examples 1 to 19 and Comparative Examples 1 to 8 obtained above were each coated on a corona-treated PMMA film (manufactured by Sumitomo Chemical Co., Ltd.: Technolloy 125S001), and a laminator was used to Bond with another corona discharge treated COP (cycloolefin polymer, Japan Zeon Co., Ltd.: model Zeonor Film 14-060) film, and use an electrodeless ultraviolet lamp to irradiate through the COP film equivalent to 1000mJ/cm Step ² was followed to obtain a test piece. A 90-degree peel test was performed on the obtained test piece.

From [Table 1] to [Table 6], it can be seen that the curable composition of the present invention is a cured product with a high glass transition temperature and excellent adhesion.

Claims (7)

A curable composition comprising: 15 to 90 parts by mass of a cationic polymerizable component (A), 1 to 10 parts by mass of a cationic polymerization initiator (B), and 10 to 50 parts by mass of a radically polymerizable component (C) , free radical polymerization initiator (D) 1～10 mass parts and be selected from 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 An alicyclic hydrocarbon group with a number of 6 to 10, or a hydrogen atom in these groups is substituted by one or more groups selected from epoxy groups, oxetanyl groups, hydroxyl groups, and carboxyl groups) The polymer obtained from the monomer, the following formula (II)

(In the formula, ^R1 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 a polymer in which the hydrogen atoms in these groups are replaced by a monomer represented by one or more groups selected from epoxy groups, oxetanyl groups, hydroxyl groups, and carboxyl groups), The polymer obtained from two or more monomers of monomers represented by the aforementioned formula (I), the polymer obtained from two or more monomers selected from the monomers represented by the aforementioned formula (II), and the polymer obtained by the aforementioned formula (I) ) represented by the monomer represented by the above-mentioned formula (II) and the polymer obtained by the monomer represented by the aforementioned formula (II) have a weight average molecular weight of 1,000 to 30,000 polymer (E) 1 to 20 parts by mass, so that the aforementioned cationic polymerizable component (A ) and the total of the above-mentioned radical polymerizable component (C) and the above-mentioned polymer (E) become 100 parts by mass, and the above-mentioned cationic polymerizable component (A) is made of polyhydric alcohol glycidyl compound or polyhydric alcohol alkylene oxide The glycidyl compound (A1) and the oxetane compound (A2) of the finished product are essential components, and the aforementioned cation polymerizable component (A), the aforementioned radical polymerizable component (C) and the aforementioned polymer ( When the total of E) is 100 parts by mass, the glycidyl compound of the aforementioned polyol or the glycidyl compound (A1) of the alkylene oxide adduct of the polyol is 35 to 65 parts by mass, and the aforementioned oxetane compound (A2) 10 to 50 parts by mass, aromatic epoxy compound (A3) 0 to 50 parts by mass, alicyclic epoxy compound (A4) 0 to 30 parts by mass, vinyl ether compound 0 to 20 parts by mass, the radical The polymerizable component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylate ester of a polyol with 2 to 20 carbon atoms, or a methacrylic acid with a polyol with a carbon number of 2 to 20 Ester (C2) is an essential component. The curable composition according to claim 1, wherein the cationically polymerizable component (A) further contains an aromatic epoxy compound (A3). The curable composition according to claim 2, wherein the aforementioned aromatic epoxy compound (A3) is a polyfunctional aromatic epoxy compound. The curable composition according to claim 1, wherein the aforementioned polymer (E) is a polymer obtained from a monomer represented by the aforementioned formula (I) and a monomer represented by the aforementioned formula (II), and in the aforementioned formula (I) 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 substituted with an epoxy group. A method for curing a curable composition, comprising irradiating active energy rays on the curable composition according to any one of claims 1 to 4. A method for hardening a hardening composition, which comprises heating the hardening composition according to any one of claims 1-4. A cured product, which is a cured product of the curable composition according to any one of claims 1 to 4.