TWI732844B - Curable composition, method of manufacturing hardened product, and hardened product - Google Patents

Abstract

Provides a curable composition with excellent adhesion and adhesion, a method for manufacturing a cured product, and a cured product.

Containing 20 to 90 parts by mass of cationic polymerizable component (A), 1 to 10 parts by mass of cationic polymerization initiator (B), 1 to 30 parts by mass of radical polymerizable component (C), and radical polymerization initiator ( D) 0-10 parts by mass, so that component (A) and component (C) become 100 parts by mass, and component (A) is an aromatic epoxy compound (A1); a glycidyl compound of a polyhydric alcohol with a molecular weight of 200 or more , Or the glycidyl compound (A2) of the polyol alkylene oxide adduct; and the oxetane compound (A3) as an essential component, relative to 100 parts by mass of the total of (A) component and (C) component In other words, the component (A1) is 35-50 parts by mass, and the component (C) is a compound having an epoxy group and an ethylenically unsaturated group (C1), or an acrylate of an alcohol with 2-20 carbon atoms, etc. (C2 ) As an essential ingredient.

Description

Curable composition, method of manufacturing hardened material, and hardened material

The present invention relates to a curable composition, a method of manufacturing a cured product, and a cured product thereof, and in detail, relates to a curable composition having excellent adhesion and adhesion, a method of manufacturing a cured product, and a cured product thereof.

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

For example, in the following Patent Documents 1 to 3, an energy ray curable composition containing a cation polymerizable component and a radical polymerizable component and a cured product thereof are proposed. Specifically, Patent Document 1 proposes an adhesive composition for polarizing plates that is excellent in initial curing properties and adhesiveness. In addition, Patent Document 2 proposes that when manufacturing a polarizing plate using a resin film with low moisture permeability as a protective film, even if the humidity of the coating environment is high, the curability is excellent, and after a certain period of time, the adhesion to various forces is Good, there is no problem after the endurance test, and the adhesive force after the end of the damp heat resistance test is also good. A low-viscosity light-curing adhesive. Furthermore, in Patent Document 3, it is proposed that an unsaturated alicyclic epoxy ester compound containing an unsaturated alicyclic epoxy ester compound can have both high heat resistance or high refractive index and transparency. Active energy ray polymerizable resin composition.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2014-105218 A

[Patent Document 2] JP 2015-143352 A

[Patent Document 3] JP 2015-168757 A

However, even for the curable compositions proposed in Patent Documents 1 to 3, there may be situations in which curability and adhesion cannot be satisfied. The current situation is that it is desired to have both high adhesion and adhesion. Novel curable composition.

Therefore, the object of the present invention is to provide a curable composition with excellent adhesiveness and adhesion, a method for producing a cured product, and a cured product thereof.

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

That is, the curable composition of the present invention is characterized by containing 20 to 90 parts by mass of cationic polymerizable component (A), 1 to 10 parts by mass of cationic polymerization initiator (B), and radical polymerizable component (C) 1~30 quality Parts, 0-10 parts by mass with the radical polymerization initiator (D), so that the total of the aforementioned cationically polymerizable component (A) and the aforementioned radically polymerizable component (C) becomes 100 parts by mass, and the aforementioned cationically polymerizable component (A), aromatic epoxy compound (A1); glycidyl compound of polyol with a molecular weight of 200 or more, or glycidyl compound of polyol alkylene oxide adduct (A2); and oxetane The compound (A3) is an essential component, and the aromatic epoxy compound (A1) is 35-50 mass parts relative to the total 100 parts by mass of the cationic polymerizable component (A) and the radical polymerizable component (C) Parts, the aforementioned radically polymerizable component (C), a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylate of an alcohol having 2 to 20 carbon atoms or an alcohol having 2 to 20 carbon atoms The methacrylate (C2) is an essential ingredient.

的一種以上。 In the curable composition of the present invention, the cationically polymerizable component (A1) is preferably a polyfunctional aromatic epoxy compound. Furthermore, in the curable composition of the present invention, the aforementioned oxetane compound (A3) is preferably a polyfunctional oxetane compound. Furthermore, in the curable composition of the present invention, the aforementioned C 2-20 alcohol acrylate or C 2-20 alcohol methacrylate (C2) preferably has a cyclic structure Acrylate or methacrylate. Furthermore, in the curable composition of the present invention, the aforementioned ring structure is preferably selected from the following group

More than one kind.

The method for producing a cured product of the present invention is characterized by irradiating the curable composition of the present invention with active energy rays or heating.

The cured product of the present invention is characterized by the cured product of the curable composition of the present invention.

According to the present invention, it is possible to provide a curable composition with excellent adhesiveness and 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.

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

The curable composition of the present invention, when the total of the cationically polymerizable component (A) and the radically polymerizable component (C) is 100 parts by mass, it contains 20 to 90 parts by mass of the cationically polymerizable component (A), and cationically polymerized Starter (B) 1 to 10 parts by mass, 1 to 30 parts by mass of the radical polymerizable component (C), and 0 to 10 parts by mass of the radical polymerization initiator (D). In the curable composition of the present invention, the cationically polymerizable component (A) is an aromatic epoxy compound (A1); a glycidyl compound of a polyhydric alcohol with a molecular weight of 200 or more, or a polyhydric alcohol alkylene oxide adduct Glycidyl compound (A2); and oxetane compound (A3) are essential components, and are aromatic relative to the total 100 parts by mass of the cationic polymerizable component (A) and the radical polymerizable component (C) The group epoxy compound (A1) is 35 to 50 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 of an alcohol having 2 to 20 carbon atoms, or an alcohol having 2 to 20 carbon atoms The methacrylate (C2) is an essential ingredient.

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

The cationically polymerizable component (A) and the cationically polymerizable component (A) of the curable composition of the present invention are aromatic epoxy compounds (A1); glycidyl compounds of polyhydric alcohols with a molecular weight of 200 or more, or polyhydric alcohol rings The glycidyl compound (A2) of the oxane adduct; and the oxetane compound (A3) are essential components, but as other epoxy compounds, alicyclic epoxy compounds and vinyl ether compounds can also be used .

The above-mentioned aromatic epoxy compound (A1) refers to an epoxy compound containing an aromatic ring. Specific examples of the aromatic epoxy compound include polyphenols having at least one aromatic ring such as phenol, cresol, and butylphenol. Or Mono/polyglycidyl etherate of alkylene oxide adducts, such as bisphenol A, bisphenol F, or the glycidyl etherate or epoxy novolak resin of these compounds further added with alkylene oxide; m-phenylene Mono/polyglycidyl etherate of aromatic compounds with two or more phenolic hydroxyl groups, such as diphenol, hydroquinone, catechol, etc.; phenyl dimethanol, phenyl diethanol, phenyl dibutanol, etc. Glycidyl etherate of aromatic compounds with two or more alcoholic hydroxyl groups; glycidyl esters of polybasic aromatic compounds with two or more carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, etc. , Glycidyl ester of benzoic acid, epoxide of styrene oxide or divinylbenzene, etc.

The above-mentioned aromatic epoxy compound (A1), commercially available products can be used, for example, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Oncoat EX-1020, Oncoat EX-1030, Oncoat EX-1040, Oncoat EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat 1012 (manufactured by Nagase ChemteX Co., Ltd.); Ogsol PG-100 , Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC Co., Ltd.); ESN-475V (Nippon Steel & Sumikin Chemical Co., Ltd.) Co., Ltd.); Epicoat YX8800 (manufactured by Mitsubishi Chemical Corporation); Marproof G-0105SA, Marproof G-0130SP (manufactured by NOF Corporation); Epiclon N-665, Epiclon HP-7200 (DIC (shares) ) Company system); 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 Resin EP-4005, ADEKA Resin EP-4100, ADEKA Resin EP-4901 ((share) ADEKA Company system); TECHMORE VG-3101L ((share) Printec company system), etc. With regard to the aromatic epoxy compound (A1), a polyfunctional one is preferred because of its excellent curability.

The glycidyl compound (A2) of the polyhydric alcohol with a molecular weight of 200 or more or the glycidyl compound (A2) of the polyhydric alcohol alkylene oxide adduct includes the glycidylization of the polyhydric alcohol or the polyhydric alcohol alkylene oxide adduct Furthermore, the molecular weight of the glycidyl compound is 200 or more.

The glycidyl compound (A2) of the polyhydric alcohol with a molecular weight of 200 or more or the glycidyl compound (A2) of the polyhydric alcohol alkylene oxide adduct includes 1,4-butanediol diglycidyl ether, 1,6-hexane Glycol diglycidyl ether, neopentyl glycol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, Diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, glycidyl ether of polyhydric alcohols such as dicyclopentadiene dimethanol diglycidyl ether, and glycidyl ether of polyhydric alcohols such as propylene glycol, trimethylolpropane, A polyglycidyl etherate of a polyether polyol obtained by adding aliphatic polyols such as glycerin to one or more alkylene oxides, and diglycidyl esters of aliphatic long-chain dibasic acids.

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

For glycidyl compounds of polyols with a molecular weight of 200 or more, or glycidyl compounds (A2) of polyol alkylene oxide adducts, those with saturated condensed rings will improve the curability and adhesion of the cured product Sex, so better.

The glycidyl compound of a polyhydric alcohol with a molecular weight of 200 or more, or the glycidyl compound (A2) of a polyhydric alcohol alkylene oxide adduct can be used commercially, such as 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, Denacol EX-512, Denacol EX-521 , Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830 , Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase ChemteX Co., Ltd.); Epolight M-1230, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 1500NP, Epolight 1600, Epolight 80MF, Epolight 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), ADEKA Glycirol ED-503, ADEKA Glycirol ED-503G, ADEKA Glycirol ED-506, ADEKA Glycirol ED-523T, ADEKA Resin EP-4088S, ADEKA Resin EP-4080E (made by ADEKA Corporation), etc.

The above-mentioned oxetane compound (A3) includes 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,4-bis[(3-ethyl-3 -Oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3- Bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, triethyl Glycol bis(3-ethyl-3-oxetanyl methyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanyl methyl) ether, 1,4- Two of bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, etc. Functional aliphatic oxetane compound; 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane Alkyl, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane, 3-ethyl-3 -Monofunctional oxetane compounds such as (chloromethyl)oxetane, etc. These can be used singly or in combination of two or more. The polyfunctional oxetane compound is preferred because the hardenability and adhesion of the cured product are increased.

For the oxetane compound (A3), commercially available products can be used, and examples include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, and 4-hydroxybutyl vinyl ether (Maruzen Petroleum Chemical Co., Ltd.); Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.), Eternacoll OXBP, OXTP ( Ube Industries (stock) company system) and so on.

The aforementioned alicyclic epoxy compound refers to a saturated ring that is directly bonded to an oxirane ring without passing through a bonding group. Specific examples of alicyclic epoxy compounds include those obtained by epoxidizing a polyglycidyl etherate of a polyol having at least one alicyclic ring or a compound containing a cyclohexene or cyclopentene ring with an oxidizing agent. Compounds containing cyclohexene oxide or cyclopentene oxide. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-1-methyl Cyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxy Cyclohexane carboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexane carboxylate, 3,4-epoxy 5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexane carboxylate, bis(3,4-epoxycyclohexylmethyl) adipate, 3 ,4-Epoxy-6-methylcyclohexane 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-epoxycyclohexyl) Alkyl carboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-ring Oxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene oxide, limonene dioxide, etc. For alicyclic epoxy compounds, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate or 3,4-cyclic Oxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate is preferable from the viewpoint of improving adhesion.

The above-mentioned alicyclic epoxy compound can be a commercially available one, for example, Celloxide 2021P, Celloxide 2081, Celloxide 2000, Celloxide 3000 (made by Daicel Corporation), etc.

The above-mentioned vinyl ether compounds include, for example, diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, and 2-ethylhexyl vinyl ether. 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.

Among the above-mentioned cationically polymerizable components (A), aromatic epoxy compounds (A1), glycidyl compounds of polyhydric alcohols with a molecular weight of 200 or more, or glycidyl compounds of polyhydric alcohol alkylene oxide adducts (A2), and oxygen The use ratio of ethidium compound (A3), alicyclic epoxy compound and vinyl ether compound increases viscosity, coatability, reactivity and curability, so it is relative to cationic polymerizable component (A) and The total 100 parts by mass of the radical polymerizable component (C) is based on 30~80 parts by mass of the aromatic epoxy compound (A1); the glycidyl compound of the polyol with a molecular weight of 200 or more, or the polyol alkylene oxide 10-30 parts by mass of glycidyl compound (A2); 10-30 parts by mass of oxetane compound (A3); 0-20 parts by mass of alicyclic epoxy compound; 0-20 parts by mass of vinyl ether compound The mass part is better.

The cationic polymerization initiator (B) of the curable composition of the present invention can be used as long as it is a compound that can release a substance that initiates cationic polymerization by energy ray irradiation or heating. The double salt of the onium salt of Lewis acid or its derivative is released by the irradiation of energy rays. 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 an onium, and its structure can be represented by the following general formula [(R ¹ ) _a Q] ^{r+, for} example.

In addition, R ¹ here is an organic group having 1 to 60 carbon atoms and no matter how many atoms other than carbon atoms are contained. a is an integer from 1 to 5. R ^{1 of a} may be the same or different independently. Furthermore, it is preferable that at least one of them is 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, and N=N. In addition, when the valence of Q in the cation [A] ^r+ is q, the relationship r=aq must be established (however, N=N is regarded as the valence 0).

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.

Furthermore, here, L is the metal or 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 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, tetrafluoroboric acid root (BF ₄₎ ^-, hexafluorophosphate (PF ₆₎ ^-, hexafluoroantimonate (SbF ₆₎ ^-, hexafluoroarsenate (AsF ₆₎ ^-, hexachloro antimonate (SbCl ₆₎ ^- and the like.

In addition, the anion [B] ^r- may preferably also use a structure represented by the _{following general formula [LY b-1} (OH)] ^r-. 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 (1) to (3). Among these, one kind can be used alone, or two or more kinds can be mixed and used.

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

(2) Diphenyl hexafluoroantimonate, bis(4-methylphenyl) hexafluorophosphate, bis(4-tert-butylphenyl) hexafluorophosphate, tolyl cumene Diaryl iodonium salts such as pentafluorophenyl borate

(3) The sulfonium cation represented by the following group I or group II and the hexafluoroantimony ion, hexafluorophosphate ion, tetrakis (pentafluorophenyl) borate ion, etc.

<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 of silanol and triphenylsilanol; thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, (jinjing) salt, etc.; diethylenetriamine, triethylenetriamine, tetrazinc Polyalkyl polyamines such as ethylenepentamine; esters of 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine, etc. Cyclic polyamines; aromatic polyamines such as m-xylene diamine, diaminodiphenylmethane, diaminodiphenyl sulfonate, etc.; the above-mentioned polyamines and phenylglycidol are combined by ordinary methods Polyether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether and other glycidyl ethers, or glycidyl esters of carboxylic acids, etc., are produced by the reaction of various epoxy resins. Epoxy group addition modifiers; the above-mentioned organic polyamines and carboxylic acids such as phthalic acid, isophthalic acid, and dimer acids are reacted to produce an aminated modifiers by general methods; by general methods It is produced by reacting the above-mentioned polyamines with aldehydes such as formaldehyde and phenols, cresols, xylenol, tertiary butylphenol, resorcinol, etc. in the nucleus with at least one aldehyde-reactive site Mannich chemical modification; polycarboxylic acid (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane Acid, 2-methyl succinic acid, 2-methyl adipic acid, 3-methyl adipic acid, 3-methyl glutaric acid, 2-methyl suberic acid, 3,8-dimethyl sebacic acid Aliphatic dicarboxylic acids such as acid, 3,7-dimethyl sebacic acid, hydrogenated dimer acid, dimer acid, etc.; of phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, etc. Aromatic dicarboxylic acids; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; tricarboxylic acids such as trimellitic acid, trimellitic acid, and trimer of castor oil fatty acid; pyromellitic acid, etc. Tetracarboxylic acids, etc.) anhydrides; dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imines, etc.

Among these, in terms of practicality and improvement in light sensitivity, it is particularly preferable to use aromatic iodonium salts, aromatic sulphur salts, and iron-arene complexes; more preferably, it is more preferable than cationic polymerization initiators ( B) For 100% by mass, it contains at least 0.1% by mass or more of the 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 1~10 alkyl, 1~10 alkoxy or 2~10 ester group, R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom and a halogen atom Or an alkyl group with 1 to 10 carbon atoms, R ²⁵ represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or any substituent selected from the following chemical formulas (A) to (C), An ^q- represents an anion of q valence, and 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 a carbon atom number of 1 ~10 alkoxy group or ester group with 2~10 carbon atoms, R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent a hydrogen atom, a halogen atom or a carbon atom number of 1-10 alkyl.

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 can be} Examples 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, ethoxycarbonyl Methyl, ethylcarbonylmethyl, t-butoxycarbonylmethyl, acryloxyethyl, methacryloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl, ethyl Acetylethyl, 2-methoxy-1-propenyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 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.

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 or carbon number of an alcohol having 2 to 20 carbon atoms 2-20 alcohol methacrylate (C2) as an essential ingredient. Among (C2), acrylate or methacrylate having a cyclic structure is particularly preferred; more preferably, the cyclic structure is one or more selected from the following group.

The compound (C1) having an epoxy group and an ethylenically unsaturated group includes, for example, epoxy acrylate or epoxy methacrylate. Specifically, it is a conventionally known aromatic epoxy resin and alicyclic epoxy resin. Epoxy resins, aliphatic epoxy resins, etc., are acrylates obtained by reacting with acrylic acid or methacrylic acid. Among these epoxy acrylates or epoxy methacrylates, particularly preferred ones are acrylates or methacrylates of glycidyl ethers of alcohols.

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 Acrylate or methacrylate obtained by reacting alkylene oxide adduct with acrylic acid or methacrylic acid. Specifically, examples include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, acrylic acid Isooctyl ester, methyl tetrahydrofuran acrylate, isobornyl acrylate, benzyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate , Diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol four Acrylate, dipentaerythritol hexaacrylate, ε-caprolactone modified dipentaerythritol hexaacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, Isoamyl methacrylate, lauryl methacrylate, stearyl methacrylate, isooctyl methacrylate, methyl tetrahydrofuran methacrylate, isocamyl 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 Ester, dipentaerythritol hexamethacrylate, ε-caprolactone modified dipentaerythritol hexamethacrylate, ethoxylated tripropylene isocyanurate Acid ester, ethoxylated isocyanuric acid trimethacrylate, ε-caprolactone modified ginseng-(2-acryloyloxyethyl) isocyanurate, ε-caprolactone modified Quality parameters-(2-methacryloyloxyethyl) isocyanurate and the like. Furthermore, among these acrylates or methacrylates, polyacrylates of polyols or polymethacrylates of polyols are particularly preferred.

The above-mentioned radically polymerizable component (C) may also be a compound other than (C1) or (C2) that undergoes polymerization or cross-linking reaction by a radical polymerization initiator activated by energy ray irradiation or heating. For example, an allyl carbamate compound, an unsaturated polyester compound, a styrene compound, etc. are mentioned. In the radically polymerizable component (C), the ratio of the above-mentioned (C1) component and (C2) component is preferably 50% by 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, ketone-based compounds such as acetophenone-based compounds, diphenylethylenedione-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and oxime-based compounds can be used.

In the curable composition of the present invention, the cationic polymerizable component (A) is 20 to 90 parts by mass; the cationic polymerization initiator (B) is 1 to 10 parts by mass, preferably 1 to 6 parts by mass; The radical polymerizable component (C) is 1-30 parts by mass; the above-mentioned radical polymerization initiator (D) is 0-10 parts by mass. If it is other than the above-mentioned blending ratio, the curability and adhesion of the cured product may deteriorate. In addition, the total of the cation polymerizable component (A) and the radical polymerizable component (C) is 100 parts by mass. Moreover, (A1) component is 35-50 mass parts with respect to the total of 100 mass parts of cationic polymerizable component (A) and radical polymerizable component (C).

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 a maximum absorption at a wavelength longer than the maximum absorption wavelength shown by the cationic polymerization initiator (B), and promotes the polymerization initiation reaction caused 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 (1).

此處，式(1)中，R⁵⁰及R⁵¹係各自獨立地表示氫原子、碳原子數1~6之烷基或碳原子數2~12之烷氧基烷基，R⁵²表示氫原子或碳原子數1~6之烷基。

Here, in formula (1), 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 (1) are given, there are the following compounds.

For example, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-di Butoxyanthracene, 9,10-dipentyloxyanthracene, 9,10-dihexoxyanthracene, 9,10-bis(2-methoxyethoxy)anthracene, 9,10-bis(2- Ethoxyethoxy)anthracene, 9,10-bis(2-butoxyethoxy)anthracene, 9,10-bis(3-butoxypropoxy)anthracene, 2-methyl- or 2 -Ethyl-9,10-dimethoxyanthracene, 2-methyl- or 2-ethyl-9,10-di Ethoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipropoxyanthracene, 2-methyl- or 2-ethyl-9,10-diisopropoxyanthracene, 2- Methyl- or 2-ethyl-9,10-dibutoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipentoxyanthracene, 2-methyl- or 2-ethyl -9,10-Dihexyloxyanthracene and so on.

Examples of the naphthalene-based compound include those represented by the following formula (2).

此處，式(2)中，R⁵³及R⁵⁴係各自獨立地表示碳原子數1~6之烷基。

Here, in formula (2), R ⁵³ and R ⁵⁴ each independently represent an alkyl group having 1 to 6 carbon atoms.

When specific examples of the naphthalene compound represented by the above formula (2) are given, there are the following compounds.

For example, 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4- Hexyloxy-1-naphthol, 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene Naphthalene, 1,4-dibutoxynaphthalene, etc.

With respect to the above-mentioned cationically polymerizable component (A), the use ratio of the sensitizer and the sensitization aid is not particularly limited, as long as it is used in a general use ratio within a range that does not hinder the purpose of the present invention. For example, with respect to 100 parts by mass of the above-mentioned cationically polymerizable component (A), from the viewpoint of improving the curability, the sensitizer and the sensitization aid are preferably 0.1 to 3 parts by mass, respectively.

In the curable composition of the present invention, silicon can be used as needed Alkyl coupling agent. Silane coupling agent, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane can be used Alkyl functional alkoxysilanes such as silane, methyl triethoxy silane, ethyl trimethoxy silane, ethyl trimethoxy silane, vinyl trichlorosilane, vinyl trimethoxy silane, vinyl tris Alkenyl functional alkoxysilanes such as ethoxysilane and allyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethyl Oxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyl Trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropylmethyl diethoxysilane, β-(3,4-epoxycyclohexyl)ethyl Epoxy functional alkoxysilanes such as trimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyl trimethoxysilane, such as amino functional alkoxysilane, γ-mercaptopropyl trimethoxysilane, and other mercapto functional alkoxysilane, titanium tetraisopropoxide Titanium alkoxides such as tetra-n-butoxide titanium, titanium dioctyl bis (octyl glycolate), titanium diisopropoxy bis (ethyl acetyl acetate), etc. Zirconium compounds such as zirconium tetraacetone, zirconium tributoxy monoacetone, zirconium compounds such as zirconium tributoxy stearate, isocyanate silanes such as methyl triisocyanate silane, etc. Wait.

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, but by heating to a specific temperature/light irradiation/acid, etc., the protective group will be detached and activated to exhibit UV absorption. Ability compound.

Moreover, 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 promoters, etc.

In the curable composition of the present invention, commonly used solvents that can dissolve or disperse the above-mentioned (A), (B), (C) and (D) components can be used, and there is no particular limitation. 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; Ethyl ether, dioxane, tetrahydrofuran, Ether solvents such as 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, etc.; methyl acetate, ethyl acetate, acetic acid- Ester solvents such as n-propyl ester, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, Texanol, etc.; ethylene glycol monomethyl ether, ethylene glycol mono Cellulose series solvents such as ethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, pentanol, etc.; ethylene glycol monomethyl acetate, Ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl propionate Ether ester solvents such as oxyethyl; BTX solvents such as benzene, toluene, xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane, etc.; turpentine, D-limonene, pinium Terpene-based hydrocarbon oils such as olefins; mineral spirits, Swasol#310 (manufactured by Cosmo Songshan Petroleum Co., Ltd.), Solvesso#100 (Exxon Chemical Company) and other paraffin-based solvents; carbon tetrachloride, chloroform, trichloro Halogenated aliphatic hydrocarbon solvents such as ethylene, dichloromethane, 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; propylene carbonate, carbitol solvents, aniline, triethylamine , Pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, etc. These solvents can be used singly or as a mixed solvent of two or more kinds.

Since the curability, adhesiveness, and liquid storage stability are improved, the curable composition of the present invention preferably has a water content of 5 parts by mass or less, and more preferably 3 parts by mass or less. When the moisture is too much, it may become cloudy or may be out of the composition, so it is not good.

The curable composition of the present invention is a roll coater, shower The curtain coater, various printing, dipping and other well-known means are applied to the support substrate. In addition, it can also be applied to a supporting substrate such as a film at a time, and then transferred to other supporting substrates. The application method is not limited.

The material of the above-mentioned support matrix can be used by ordinary users without any special limitation. Examples include inorganic materials such as glass; diacetyl cellulose, triacetyl cellulose (TAC), acetyl 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. Furthermore, surface activation treatments such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment may also be performed on the above-mentioned support substrate.

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

The curable composition of the present invention is cured by heating The conditions in the method are 70~250℃, 1~100 minutes. Pressure can be applied after pre-bake (PAB; Pre applied bake), and 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, they are 70 to 180°C, 5 to 15 minutes in an oven, and 1 to 5 minutes on a hot plate. After that, in order to harden the coating film, a cured film can be obtained by heating at 180 to 250°C, preferably 200 to 250°C, in an oven for 30 to 90 minutes, and on a hot plate for 5 to 30 minutes.

Specific uses of the curable composition of the present invention or its cured product include adhesives, glasses, optical materials represented by photographic lenses, paints, coating agents, spacers, inks, photoresists, and liquids. Display components such as photoresist, printing plate, color TV, PC monitor, mobile information terminal, digital camera, organic EL, touch panel, etc., insulating paint, insulating sheet, laminate, printed circuit board, semiconductor device/LED packaging /For liquid crystal injection ports/for organic EL/for optical components/for electrical insulation/for electronic parts/for separation membranes, etc. Sealants, molding materials, putty, glass fiber impregnants, wood powder fillers, semiconductors/solar cells Passivation films, interlayer insulating films, protective films, lens parts of lens sheets used in backlights of liquid crystal display devices, Fresnel lens sheets used in screens such as projection TVs, and lentil lens sheets , Or use such thin sheets such as backlights, microlenses and other optical lenses, optical elements, optical connectors, optical waveguides, casting agents for optical molding, 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 retardation layer, and a birefringence layer as required. For each layer, light scattering layer, hard coat layer, lubricating layer, protective layer, etc., a thin film made of the hardened substance of the present invention can be used for each layer.

[Example]

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

[Examples 1 to 9, Comparative Examples 1 to 5]

The components were thoroughly mixed at the blending ratios shown in the following [Table 1] and [Table 2] to obtain the curable composition of Examples 1 to 9 and the curable composition of Comparative Examples 1 to 5, respectively. Furthermore, the unit of the blending amount of the examples and comparative examples is parts by mass.

The following compounds (A1-1), (A2-1) and (A3-1) are used as the cationically polymerizable component (A).

Compound (A1-1): Bisphenol type diglycidyl ether

Compound (A2-1): neopentyl glycol diglycidyl ether

Compound (A3-1): Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)

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 (3) and the compound represented by the following formula (4)

The radical polymerizable component (C) uses the following compound.

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 (C1-3): Epoxy Ester 200PA (manufactured by Kyoeisha Chemical Co., Ltd.)

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

Compound (C2-2): 4-hydroxybutyl acrylate

Compound (C2-3): A-9300S (multifunctional acrylate; manufactured by Shinnakamura Chemical Industry Co., Ltd.)

Compound (C2-4): Viscoat#150 (methyl tetrahydrofuran acrylate; manufactured by Osaka Organic Chemical Industry Co., Ltd.)

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

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

For the obtained curable compositions of Examples 1 to 9 and Comparative Examples 1 to 5, the viscosity, adhesion, and curability were evaluated in accordance with the following procedures. The results are recorded in [Table 1] and [Table 2].

(Viscosity)

For the obtained curable compositions of Examples 1 to 9 and Comparative Examples 1 to 5, the viscosity at 25° C. was measured with an E-type viscometer. The results are recorded in [Table 1] and [Table 2].

(Adhesion)

The curable compositions of Examples 1 to 9 and Comparative Examples 1 to 5 obtained above were each coated on a corona treated PMMA film (Sumitomo Chemical Co., Ltd.: Technolloy 125S001), and then a laminator was used. ) Is bonded to another COP (cycloolefin polymer, Japan Zeon product: model ZeonorFilm 14-060) film treated by corona discharge, using an electrodeless ultraviolet lamp to irradiate the COP film with light equivalent to 1000mJ/cm ² Next, to obtain a test piece. A 90-degree peel test of the obtained test piece was performed.

(Hardening test)

Coat the curable compositions of Examples 1 to 9 and Comparative Examples 1 to 5 obtained above on a sheet of TAC film (Fuji Film: Model FT-TD60ULP), and then use a laminating machine and another sheet to undergo corona discharge treatment COP (Cycloolefin polymer, manufactured by Zeon, Japan: model ZeonorFilm 14-060) film was laminated, and then an electrodeless ultraviolet lamp was used to irradiate the COP film with light equivalent to 150mJ/cm ^{2 for} bonding to evaluate the curing speed. When the irradiation was less than 30 seconds, the resistance was evaluated as ○ when resistance was felt during peeling, and the evaluation was × when the peeling was easy even for 30 seconds or more. The shorter the hardening time, the better the hardening.

It can be seen from [Table 1] and [Table 2] that the curable composition of the present invention is excellent in viscosity and adhesion.

Claims (8)

A curable composition characterized by containing 70 to 90 parts by mass of cationic polymerizable component (A), 1 to 10 parts by mass of cationic polymerization initiator (B), and 10 to 30 parts by mass of radical polymerizable component (C) , 0-10 parts by mass of the radical polymerization initiator (D), so that the total of the aforementioned cationically polymerizable component (A) and the aforementioned radically polymerizable component (C) becomes 100 parts by mass, and the aforementioned cationically polymerizable component ( A), based on aromatic epoxy compound (A1); glycidyl compound of polyhydric alcohol with a molecular weight of 200 or more, or glycidyl compound of polyhydric alcohol alkylene oxide adduct (A2); and oxetane The compound (A3) is an essential component, and the aromatic epoxy compound (A1) is 35-50 mass parts relative to the total of 100 parts by mass of the cationic polymerizable component (A) and the radical polymerizable component (C) Parts, the aforementioned radically polymerizable component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylate of an alcohol with 2 to 20 carbon atoms, or an acrylate with 2 to 20 carbon atoms Alcohol methacrylate (C2) is an essential ingredient. The curable composition of claim 1, wherein the cationically polymerizable component (A1) is a polyfunctional aromatic epoxy compound. The curable composition of claim 1, wherein the aforementioned oxetane compound (A3) is a multifunctional oxetane compound. Such as the curable composition of claim 1, wherein the aforesaid C2-C20 alcohol acrylate or C2-C20 alcohol methacrylate (C2) is an acrylate having a cyclic structure or Methacrylate. The curable composition of claim 4, wherein the aforementioned ring structure is composed of the following group

More than one selected from among. A method for curing a curable composition, which is characterized by irradiating the curable composition according to any one of claims 1 to 5 with active energy rays. A hardening method for a hardening composition, characterized by heating the hardening composition according to any one of Claims 1 to 5. A hardened product characterized in that it is a hardened product of the hardenable composition according to any one of claims 1 to 5.