KR102265025B1 - Curable composition, manufacturing method of cured product, and cured product thereof - Google Patents

Abstract

Disclosed are a curable composition excellent in viscosity and adhesion, a method for producing a cured product, and a cured product thereof. 20 to 90 parts by mass of a cationically polymerizable component (A), 1 to 10 parts by mass of a cationic polymerization initiator (B), 1 to 30 parts by mass of a radically polymerizable component (C), and 0 to 10 parts by mass of a radical polymerization initiator (D) It contains a mass part so that (A) component and (C)component may become 100 mass parts, (A) component is an aromatic epoxy compound (A1) and the glycidyl product of a polyhydric alcohol 200 or more molecular weight, or polyhydric alcohol alkylene oxide The glycidyl product (A2) of the adduct and the oxetane compound (A3) are essential components, and the (A1) component is 35 to 50 mass parts per 100 parts by mass in total of the (A) component and the (C) component. It is negative, and (C) component makes the compound (C1) which has an epoxy group and an ethylenically unsaturated group, or an acrylic acid ester of C2-C20 alcohol etc. (C2) an essential component.

Description

Curable composition, manufacturing method of cured product, and cured product thereof

The present invention relates to a curable composition, a method for producing a cured product, and a cured product thereof, and more particularly, to a curable composition excellent in viscosity and adhesiveness, a method for producing a cured product, and a cured product thereof.

Curable compositions are used in fields, such as an ink, a paint, various coating agents, an adhesive agent, and an optical member. Various reports are made regarding improvement of such a curable composition.

For example, the energy-beam curable composition containing a cationically polymerizable component and a radically polymerizable component, and its hardened|cured material are proposed by the following patent documents 1-3. Specifically, in Patent Document 1, an adhesive composition for a polarizing plate excellent in initial curability and adhesiveness is proposed. In addition, in patent document 2, when manufacturing a polarizing plate using a resin film with a low moisture permeability as a protective film, even if the humidity of the application environment is high, curability is excellent, and the adhesive force after a certain time is good with respect to various forces, even after a durability test A low-viscosity photocurable adhesive which does not cause a problem and has good adhesive strength after completion of the moist and heat resistance test has been proposed. Moreover, in patent document 3, the high heat resistance containing an unsaturated alicyclic epoxy ester compound, high refractive index-ization, and the active energy ray polymeric resin composition which can make transparency compatible are proposed.

Japanese Laid-Open Patent Publication No. 2014-105218 Japanese Laid-Open Patent Publication No. 2015-143352 Japanese Laid-Open Patent Publication No. 2015-168757

However, even in the curable compositions proposed in Patent Documents 1 to 3, curability and adhesiveness may not always be satisfied, and a new curable composition capable of achieving high compatibility with viscosity and adhesiveness is currently in demand. the situation of

Accordingly, an object of the present invention is to provide a curable composition excellent in viscosity and adhesiveness, a method for producing a cured product, and a cured product thereof.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject could be eliminated if it was a curable composition which has a specific composition, as a result of earnestly examining in order to solve the said subject, and came to complete this invention.

That is, the curable composition of the present invention contains 20 to 90 parts by mass of a cationically polymerizable component (A), 1 to 10 parts by mass of a cation polymerization initiator (B), and 1 to 30 parts by mass of a radically polymerizable component (C); 0-10 mass parts of radical polymerization initiator (D) contains so that the sum total of the said cationically polymerizable component (A) and the said radically polymerizable component (C) may become 100 mass parts,

The cationically polymerizable component (A) is an aromatic epoxy compound (A1), a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more, or a glycidylated product (A2) of a polyhydric alcohol alkylene oxide adduct, and an oxetane compound ( A3) as an essential component, and the aromatic epoxy compound (A1) is 35 to 50 parts by mass relative to 100 parts by mass in total of the cationically polymerizable component (A) and the radically polymerizable component (C),

The radically polymerizable component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylic acid ester of an alcohol having 2 to 20 carbon atoms or a methacrylic acid ester of an alcohol having 2 to 20 carbon atoms (C2) ) as an essential component.

In the curable composition of this invention, it is preferable that the said cationically polymerizable component (A1) is a polyfunctional aromatic epoxy compound. Moreover, in the curable composition of this invention, it is preferable that the said oxetane compound (A3) is a polyfunctional oxetane compound. Further, in the curable composition of the present invention, the acrylic acid ester of an alcohol having 2 to 20 carbon atoms or methacrylic acid ester (C2) of an alcohol having 2 to 20 carbon atoms (C2) is an acrylic acid ester or methacrylic having a cyclic structure. It is preferably an acid ester. Moreover, in the curable composition of this invention, the said cyclic structure is the following group,

It is preferable that at least one selected from

The manufacturing method of the hardened|cured material of this invention is characterized by irradiating an active energy ray to the curable composition of this invention, or heating.

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

ADVANTAGE OF THE INVENTION According to this invention, the curable composition excellent in viscosity and adhesiveness, the hardened|cured material manufacturing method, and its hardened|cured material can be provided. The curable composition of the present invention is particularly useful for adhesives.

Hereinafter, the curable composition of this invention is demonstrated in detail.

The curable composition of this invention contains 20-90 mass parts of cationically polymerizable components (A), 1-10 mass parts of cation polymerization initiators (B), 1-30 mass parts of radically polymerizable components (C), and radical polymerization 0-10 mass parts of initiators (D) are contained so that the sum total of a cationically polymerizable component (A) and a radically polymerizable component (C) may become 100 mass parts. In the curable composition of the present invention, the cationically polymerizable component (A) is a glycidylated product of an aromatic epoxy compound (A1) and a polyhydric alcohol having a molecular weight of 200 or more, or a glycidylated product of a polyhydric alcohol alkylene oxide adduct (A2) ) and an oxetane compound (A3) as essential components, and the aromatic epoxy compound (A1) is 35 to 100 parts by mass in total of the cationically polymerizable component (A) and the radically polymerizable component (C). 50 parts by mass. Further, the radically polymerizable component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylic acid ester of an alcohol having 2 to 20 carbon atoms or a methacrylic acid ester of an alcohol having 2 to 20 carbon atoms ( C2) is an essential ingredient.

The cationically polymerizable component (A) which concerns on the curable composition of this invention is a compound which raise|generates polymerization or a crosslinking reaction with the cationic polymerization initiator activated by energy-beam irradiation or heating. An epoxy compound, an oxetane compound, a vinyl ether compound, etc. are mentioned.

The cationically polymerizable component (A) according to the curable composition of the present invention is a glycidylated product of an aromatic epoxy compound (A1) and a polyhydric alcohol having a molecular weight of 200 or more, or a glycidylated product of a polyhydric alcohol alkylene oxide adduct (A2) And although the oxetane compound (A3) is made into essential components, As another epoxy compound, an alicyclic epoxy compound, a vinyl ether compound, etc. can also be used.

The said aromatic epoxy compound (A1) represents the epoxy compound containing an aromatic ring, As a specific example of an aromatic epoxy compound, polyhydric phenol which has at least 1 aromatic ring, such as phenol, cresol, butylphenol, or its alkylene oxide addition mono/polyglycidyl ether products of water, such as bisphenol A, bisphenol F, or glycidyl ether products of a compound obtained by adding an alkylene oxide thereto, and epoxy novolac resins; mono/polyglycidyl ether products of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol; glycidyl ether products of aromatic compounds having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol and phenyldibutalol; and glycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid, glycidyl esters of benzoic acid, and epoxides of styrene oxide or divinylbenzene.

As said aromatic epoxy compound (A1), a commercial item can be used, For example, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX- 711, Denacol EX-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 Corporation); ESN-475V (manufactured by Nittetsu Sumikin Chemical Co., Ltd.); Epikote YX8800 (manufactured by Mitsubishi Chemical Co., Ltd.); Mapproof G-0105SA, Mapproof G-0130SP (manufactured by Nichiyu Co., Ltd.); Epiclone N-665, Epiclone HP-7200 (manufactured by DIC Corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (Nippon Kayaku Co., Ltd.) ) manufactured by ); Adecare resin EP-4000, Adecare resin EP-4005, Adecare resin EP-4100, Adecare resin EP-4901 (manufactured by ADEKA Corporation); TECHMORE VG-3101L (manufactured by Printec Co., Ltd.) and the like. As said aromatic epoxy compound (A1), since it is excellent in sclerosis|hardenability, a polyfunctional thing is preferable.

Examples of the glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more or the glycidylated product (A2) of a polyhydric alcohol alkylene oxide adduct include those obtained by glycidylating a polyhydric alcohol or polyhydric alcohol alkylene oxide adduct, The molecular weight of the glycidylated product is 200 or more.

As the glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more or the glycidylated product (A2) of the polyhydric alcohol alkylene oxide adduct, 1,4-butanediol diglycidyl ether, 1,6-hexanediol glycidyl 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 Glycidyl ether of polyhydric alcohols such as glycidyl ether, diglycidyl ether of polypropylene glycol, and dicyclopentadiene dimethanol diglycidyl ether, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerin The polyglycidyl ether product of the polyether polyol obtained by adding 1 type, or 2 or more types of alkylene oxide, and the diglycidyl ester of an aliphatic long-chain dibasic acid are mentioned.

Examples of the glycidyl product of polyhydric alcohol or the glycidyl product (A1) of the polyhydric alcohol alkylene oxide adduct include monoglycidyl ether of an aliphatic higher alcohol, glycidyl ester of a higher fatty acid, epoxidized soybean oil, and epoxystearic acid. octyl, butyl epoxystearate, epoxidized soybean oil, epoxidized polybutadiene, and the like.

As the glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more, or the glycidylated product (A2) of a polyhydric alcohol alkylene oxide adduct, one having a saturated condensed ring is preferable from the viewpoint of improving the curability and adhesiveness of the cured product.

As the glycidylated product of the polyhydric alcohol having a molecular weight of 200 or more, or the glycidylated product (A2) of the polyhydric alcohol alkylene oxide adduct (A2), a commercially available product can be used, for example, denacol EX-121 and 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, Dena Call EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX -850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941 , denacol EX-920, denacol EX-931 (manufactured by Nagase Chemtex Co., Ltd.); Eporite M-1230, Eporite 40E, Eporite 100E, Eporite 200E, Eporite 400E, Eporite 70P, Eporite 200P, Eporite 400P, Eporite 1500NP, Eporite 1600, Eporite 80MF, Eporite 100MF ( Kyoeisha Chemical (manufactured by Kyoeisha Chemical Co., Ltd.), adecaglycerol ED-503, adecaglycerol ED-503G, adecaglycerol ED-506, adecaglycerol ED -523T, Adeka Resin EP-4088S, Adeka Resin EP-4080E (manufactured by ADEKA Corporation), and the like.

Examples of the oxetane compound (A3) include 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene; 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycolbis(3- Ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, 1,4 Bifunctional aliphatic oxetane compounds such as -bis(3-ethyl-3-oxetanylmethoxy)butane and 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, 3-ethyl-3-[ (phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl) ) and monofunctional oxetane compounds such as 3-ethyl-3-(chloromethyl)oxetane and the like. These can be used individually by 1 type or in combination of 2 or more type, and since a polyfunctional oxetane compound improves sclerosis|hardenability and adhesiveness of hardened|cured material, it is preferable.

As said oxetane compound (A3), a commercial item can be used, For example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (Maruzen Petrochemical ) (manufactured by Co., Ltd.); Aronoxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toah Synthetic Co., Ltd.), etanacol OXBP, OXTP (Ube Heungsan) Co., Ltd.) and the like.

The said alicyclic epoxy compound refers to the thing in which the oxirane ring is directly couple|bonded with the saturated ring without a bonding group. Specific examples of the alicyclic epoxy compound include cyclohexene oxide or cyclopentene oxide-containing compound obtained by epoxidizing a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring or a compound containing cyclohexene or cyclopentene ring with an oxidizing agent. can be heard For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4- Epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl -3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4- Epoxycyclohexylethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxy) Cyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, and di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pineneoxide, and limonene dioxide. have. Examples of the alicyclic epoxy compound include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, or 3,4-epoxy-1-methylcyclohexyl-3; 4-epoxy-1-methylhexanecarboxylate is preferable from a viewpoint of an adhesive improvement.

As said alicyclic epoxy compound, a commercial item can be used, For example, Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000 (made by Daicel Corporation) etc. exist.

Examples of the vinyl ether compound include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, Ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1 ,4-butanediol divinyl ether, 1,6-cyclohexanedimethanol divinyl ether, and the like.

In the cationically polymerizable component (A), an aromatic epoxy compound (A1), a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more, or a glycidylated product of a polyhydric alcohol alkylene oxide adduct (A2) and an oxetane compound (A3) ), the use ratio of the alicyclic epoxy compound and the vinyl ether compound is 30 to 80 parts by mass of the aromatic epoxy compound (A1) with respect to 100 parts by mass in total of the cationically polymerizable component (A) and the radically polymerizable component (C); 10 to 30 parts by mass of a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more or a glycidylated product (A2) of a polyhydric alcohol alkylene oxide adduct, 10 to 30 parts by mass of an oxetane compound (A3), 0 to an alicyclic epoxy compound It is preferable that it is 20 mass parts and 0-20 mass parts of vinyl ether compounds from a viscosity, applicability|paintability, reactivity, and sclerosis|hardenability improving.

The cationic polymerization initiator (B) according to the curable composition of the present invention may be any compound capable of releasing a substance that initiates cationic polymerization by irradiation with energy rays or heating, but is preferably used for irradiation with energy rays. It is an onium salt that releases a Lewis acid by a double salt, or a derivative thereof. As a representative example of such a compound, the following general formula

[A] ^r+ [B] ^r-

A salt of a cation and an anion represented by .

Here, the cation [A] ^r+ is preferably onium, and its structure is, for example, the following general formula

[(R ¹ ) _a Q] ^r+

can be displayed as

Here, R ¹ is an organic group having 1 to 60 carbon atoms and may contain several atoms other than carbon atoms. a is an integer from 1 to 5; a R ¹ may be each independent and may be the same or different. Moreover, it is preferable that at least 1 is the above organic group which has an aromatic ring. Q is an atom or group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N=N. Further, when the valence of Q in the cation [A] ^r+ is set to q, it is necessary to establish a relationship such that r=aq (however, N=N is treated as valence 0)

In addition, the anion [B] ^r- is preferably a halide complex, and the structure thereof is, for example, the following general formula

[LY _b ] ^r-

can be displayed as

Here, L is a metal or metalloid that is the central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr , Mn, Co, and the like. Y is a halogen atom. b is an integer used as 3-7. In addition, when the valence of L in the anion [B] ^r- is set to p, it is necessary to establish a relationship such that r = bp.

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

In addition, the anion [B] ^r- is represented by the following general formula

[LY _{b - 1} (OH)] ^{r -}

A structure represented by can also be preferably used. L, Y and b are the same as above. In addition, as anions that can be used in addition, perchlorate ion (ClO ₄ ) ^- , trifluoromethylsulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonic acid ion (FSO ₃ ) ^- , toluenesulfonic acid anion, trinitrobenzenesulfonic acid anion , camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraarylborate, tetrakis(pentafluorophenyl)borate, and the like.

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

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

(B) Diphenyliodonium hexafluoroantimonate, di(4-methylphenyl)iodonium hexafluorophosphate, di(4-tert-butylphenyl)iodonium hexafluorophosphate, tricumyliodonium tetrakis ( Diaryliodonium salts such as pentafluorophenyl) borate

(C) Sulfonium salts such as sulfonium cations and hexafluoroantimony ions, hexafluorophosphate ions and tetrakis(pentafluorophenyl)borate ions represented by the following group I or group II

<Group I>

<Group II>

Moreover, as another preferable thing, (η ⁵ -2,4-cyclopentadien-1-yl)[(1,2,3,4,5,6-η)-(1-methylethyl)benzene]- Iron-arene complexes such as iron-hexafluorophosphate, aluminum complexes such as tris(acetylacetonate)aluminum, tris(ethylacetonate acetate)aluminum, tris(salicylaldehyde)aluminum, and triphenyl mixtures with silanols such as silanol; salts such as thiophenium salt, thioranium salt, benzylammonium salt, pyridinium salt, and hydrazinium salt; polyalkyl polyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; The above polyamines, glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, or glycidyl esters of carboxylic acid, etc. polyepoxy addition-modified products prepared by reacting various epoxy resins of amidation-modified products produced by reacting the organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimer acid by a conventional method; Manufactured by reacting the polyamines with aldehydes such as formaldehyde and phenols having at least one aldehyde reactive site in the nucleus, such as phenol, cresol, xylenol, tert-butylphenol, resorcin, by a conventional method Mannichation modified product; Polyhydric carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanoic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyl aliphatic dicarboxylic acids such as adipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanoic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid and dimer acid; , terephthalic acid, isophthalic acid, aromatic dicarboxylic acids such as naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; Tricarboxylic acids such as trimellitic acid, trimesic acid, and a trimer of castor oil fatty acid; pyromelli acid anhydrides of tetracarboxylic acids such as toric acid; and dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, and amineimides.

Among these, it is preferable to use an aromatic aluminum iodide salt, an aromatic sulfonium salt, and an iron- arene complex from the viewpoint of practical use and photosensitivity improvement, and an aromatic sulfonium salt having the following structure is used as a cationic polymerization initiator (B) 100% by mass It is more preferable to contain at least 0.1% by mass or more.

wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, and 1 carbon atom. represents an alkyl group of -10, an alkoxy group of 1 to 10 carbon atoms, or an ester group of 2-10 carbon atoms, R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, a halogen atom or carbon represents an alkyl group having 1 to 10 atoms, R ²⁵ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or any substituent selected from the following formulas (A) to (C), An ^{q −} represents an anion having a q valence, and p represents a coefficient for neutralizing the charge.

wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ ,

R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ are each independently a hydrogen atom; represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an ester group having 2 to 10 carbon atoms, R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ are each Independently, a hydrogen atom, a halogen atom, or a C1-C10 alkyl group is represented.

In the compound 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 Halogen represented by ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ Examples of the atom include fluorine, chlorine, bromine, and iodine.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ include, as an alkyl group having 1 to 10 carbon atoms, methyl , ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoro Romethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoro Ethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tridecafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl, methoxymethyl, 1,2-epoxyethyl, methoxyethyl, Methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, tert-butylthiomethyl, 4-pentenyloxymethyl, trichloroethoxymethyl, bis(2-chloroethoxy)methyl, methoxycyclo Hexyl, 1-(2-chloroethoxy)ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl, trimethylsilylethyl, tert-butyldimethylsilyloxymethyl, 2-(trimethylsilyl)ethoxymethyl, tert-butoxycarbonylmethyl, ethyloxycarbonylmethyl, ethylcarbonylmethyl, tert-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxyethyl, 2-methyl-2-adamantyloxy Carbonylmethyl, acetylethyl, 2-methoxy-1-propenyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl , 4-hydroxybutyl, 1,2-dihydroxyethyl, etc. for example.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ as the alkoxy group having 1 to 10 carbon atoms are methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, sec- Butyloxy, tert-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-Methoxyethyloxy, 3-methoxypropyloxy, 4-methoxybutyloxy, 2-butoxyethyloxy, methoxyethoxyethyloxy, methoxyethoxyethoxyethyloxy, 3-methoxybutyloxy , 2-methylthioethyloxy, trifluoromethyloxy, and the like.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ as the ester group having 2 to 10 carbon atoms include methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, and phenoxycarbonyl. carbonyl, acetoxy, propionyloxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, tert-butylcarbonyloxy, methoxyacetyloxy, benzoyloxy, etc. can be heard

The radically polymerizable component (C) according to the curable composition of the present invention is a compound (C1) having an epoxy group and an ethylenically unsaturated group, an acrylic acid ester of an alcohol having 2 to 20 carbon atoms, or meta of an alcohol having 2 to 20 carbon atoms. Acrylic acid ester (C2) is an essential component. Among (C2), acrylic acid ester or methacrylic acid ester having a cyclic structure is preferable, and more preferably, one or more types having a cyclic structure selected from the following group are used. desirable.

The compound (C1) having an epoxy group and an ethylenically unsaturated group includes, for example, an epoxy acrylate or an epoxy methacrylate, and specifically, a conventionally known aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, etc.; It is an acrylate obtained by making acrylic acid or methacrylic acid react. Among these epoxy acrylates or epoxy methacrylates, acrylates or methacrylates of glycidyl ethers of alcohols are particularly preferable.

As the acrylate of the alcohol having 2 to 20 carbon atoms or the methacrylate (C2) of the alcohol having 2 to 20 carbon atoms, an aromatic or aliphatic alcohol having at least one hydroxyl group in the molecule, and an alkylene oxide adduct thereof and acrylates or methacrylates obtained by reacting with acrylic acid or methacrylic acid. Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, Isooctyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, benzyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, di Ethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaeryth Ritol hexaacrylate, ε-caprolactone-modified dipentaerythritol hexaacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, isoamyl methacrylate, Lauryl methacrylate, stearyl methacrylate, isooctyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, benzyl methacrylate, 1,3-butanediol dimethacrylate, 1,4 -Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, poly Propylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, ε-caprolactone-modified dipentaerythritol hexamethacrylate, ethoxylated isocyanate nuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, ε-caprolactone-modified tris-(2-acryloxyethyl)isocyanurate, ε-caprolactone-modified tris-(2-methacryloxyethyl) ) isocyanurate and the like. And among these acrylates or methacrylates, polyacrylates of polyhydric alcohols or polymethacrylates of polyhydric alcohols are particularly preferable.

As said radically polymerizable component (C), the compound which polymerizes or crosslinks with the radical polymerization initiator activated by energy ray irradiation or heating other than (C1) or (C2) can also be used, For example, allyl urethane compounds, unsaturated polyester compounds, styrene compounds, and the like. As for the ratio of the said (C1) component and (C2) component in a radically polymerizable component (C), 50 mass % or more is preferable.

There is no restriction|limiting in particular as a radical initiator (D) which concerns on the curable composition of this invention, A well-known thing can be used. For example, ketone-based compounds such as acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, and dioxanthone-based compounds, and oxime-based compounds can be used.

In the curable composition of the present invention, the cationically polymerizable component (A) is 20 to 90 parts by mass, the cation polymerization initiator (B) is 1 to 10 parts by mass, preferably 1 to 6 parts by mass, the radical polymerizable A component (C) is 1-30 mass parts, and the said radical polymerization initiator (D) is 0-10 mass parts. If it is other than the above-mentioned mixing ratio, there exists a possibility that sclerosis|hardenability and adhesiveness of hardened|cured material may become poor. And the sum total of a cationically polymerizable component (A) and a radically polymerizable component (C) is 100 mass parts. In addition, (A1) component is 35-50 mass parts with respect to a total of 100 mass parts of a cationically polymerizable component (A) and a radically polymerizable component (C).

A sensitizer and/or a sensitizer adjuvant can further be used for the curable composition of this invention as needed. A sensitizer is a compound which shows maximum absorption in the wavelength longer than the maximum absorption wavelength which a cationic polymerization initiator (B) shows, and accelerates|stimulates the polymerization initiation reaction by a cationic polymerization initiator (B). Moreover, a sensitizer is a compound which accelerates|stimulates the action|action of a sensitizer further.

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

As an anthracene-type compound, there exists a thing represented by following formula (1), for example.

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 is a hydrogen atom or a carbon atom. The number 1-6 alkyl group is shown.

Specific examples of the anthracene-based compound represented by the formula (1) include the following compounds.

For example, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-dibutoxyanthracene, 9,10 -dipentyloxyanthracene, 9,10-dihexyloxyanthracene, 9,10-bis(2-methoxyethoxy)anthracene, 9,10-bis(2-ethoxyethoxy)anthracene, 9,10-bis (2-Butoxyethoxy)anthracene, 9,10-bis(3-butoxypropoxy)anthracene, 2-methyl- or 2-ethyl-9,10-dimethoxyanthracene, 2-methyl- or 2-ethyl -9,10-diethoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipropoxyanthracene, 2-methyl- or 2-ethyl-9,10-diisopropoxyanthracene, 2-methyl- or 2-ethyl-9,10-dibutoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipentyloxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene, etc. have.

As a naphthalene type compound, there exists a thing represented by following formula (2), for example.

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

Specific examples of the naphthalene-based compound represented by the formula (2) include the following compounds.

For example, 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyloxy-1-naphthol, 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, 1,4-dibutoxynaphthalene, and the like.

The ratio of use of the sensitizer and the sensitizer to the cationically polymerizable component (A) is not particularly limited, and it is preferably used in a generally normal ratio within the range that does not impair the object of the present invention, for example, It is preferable from a viewpoint of sclerosis|hardenability improvement that it is 0.1-3 mass parts, respectively, of a sensitizer and a sensitizer with respect to 100 mass parts of the said cationically polymerizable component (A).

A silane coupling agent can be used for the curable composition of this invention as needed. Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyl Alkenyl functional alkoxysilanes, such as alkyl functional alkoxysilanes, such as trimethoxysilane, vinyltrichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, and allyl trimethoxysilane, 3-methacryloxypropyl tri Ethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ- Epoxy functional alkoxysilanes, such as glycidoxypropyl trimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-β(aminoethyl )-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, amino-functional alkoxysilane such as N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. Titanium alkoxides such as mercapto functional alkoxysilane, titanium tetraisopropoxide, and titanium tetranormal butoxide, titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethylacetoacetate), etc. titanium chelates, zirconium chelates such as zirconium tetraacetylacetonate and zirconium tributoxy monoacetyl acetonate, zirconium acylates such as zirconium tributoxy monostearate, and isocyanate silanes such as methyl triisocyanate silane Can be used.

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

The properties of the cured product can also be improved by using a thermoplastic organic polymer in the curable composition of the present invention as needed. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate ethyl acrylate copolymer, methyl methacrylate glycidyl methacrylate copolymer, poly(meth)acrylic acid, styrene-(meth). ) acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, glycidyl (meth)acrylate-polymethyl (meth)acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, saturated poly esters and the like.

In the curable composition of the present invention, if necessary, the UV absorber or UV absorber is inactive at room temperature, and the protecting group is detached by heating to a predetermined temperature, light irradiation, acid, etc. compounds may be used.

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

It does not restrict|limit especially for the curable composition of this invention, A solvent which can dissolve and disperse|distribute each component of said (A), (B), (C), and (D) which is normally used can be used. Examples of the solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; Ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, etc. of an ether ester solvent; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; Terpene hydrocarbon oils, such as turpentine oil, D-limonene, and pinene; Paraffinic solvents, such as petroleum alcohol, Swasol #310 (made by Cosmo Matsuyama Petroleum Co., Ltd.), and Sorvesso #100 (Exxon Chemical Corporation); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; Propylene carbonate, carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide , and water. These solvents can be used as 1 type or 2 or more types of mixed solvent.

Since sclerosis|hardenability, adhesiveness, and liquid storage stability improve, it is preferable that the amount of water content is 5 mass parts or less, and, as for the curable composition of this invention, it is more preferable that it is 3 mass parts or less. When there is too much water|moisture content, since there exists a possibility that it may become cloudy or a component may precipitate, it is unpreferable.

The curable composition of this invention is applied on a support base material by well-known means, such as a roll coater, a curtain coater, various printing, and immersion. Moreover, after carrying out once on support substrates, such as a film, it can also be transcribe|transferred on another support substrate, and there is no restriction|limiting in the application method.

It does not restrict|limit especially as a material of the said support base, What is normally used can be used, For example, Inorganic materials, such as glass; cellulose esters such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, and nitrocellulose; polyamide; polyimide; Polyurethane; epoxy resin; polycarbonate; Polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanezymethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polybutyl polyesters such as lenterephthalate; polystyrene; polyolefins such as polyethylene, polypropylene, and polymethylpentene; vinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; polyetherimide; polymer materials such as polyoxyethylene, norbornene resin, and cycloolefin polymer (COP). In addition, you may perform surface activation processing, such as a corona discharge treatment, a flame treatment, an ultraviolet treatment, a high frequency treatment, a glow discharge treatment, an active plasma treatment, and a laser treatment, to the said support base body.

In the method of hardening the curable composition of this invention by irradiation of an energy ray, an ultraviolet-ray, an electron beam, X-ray, a radiation, a radio frequency etc. are mentioned as an energy-beam, and an ultraviolet-ray is economically most preferable. As a light source of an ultraviolet-ray, an ultraviolet laser, a mercury lamp, a xenon laser, a metal halide lamp, etc. are mentioned.

The conditions in the method of hardening the curable composition of this invention by heating are 1-100 minutes at 70-250 degreeC. After pre-baking (PAB; Pre applied bake), it may pressurize, post exposure bake (PEB) may be carried out, and you may bake at the temperature of several different steps. Although the heating conditions differ depending on the type and mixing ratio of each component, for example, at 70 to 180°C, for 5 to 15 minutes in an oven, and 1 to 5 minutes in the case of a hot plate. Then, in order to harden a coating film, a cured film can be obtained by heat-processing at 180-250 degreeC, Preferably it is 200-250 degreeC, 30-90 minutes in an oven, and 5-30 minutes in case of a hot plate.

Specific uses of the curable composition of the present invention or its cured product include adhesives, glasses, optical materials typified by imaging lenses, paints, coatings, linings, inks, resists, liquid resists, printing plates, color TVs, PC monitor, portable information terminal, digital camera, organic EL, display elements such as touch panel, insulating varnish, insulating sheet, laminated board, printed circuit board, for semiconductor device, for LED package, for liquid crystal inlet, for organic EL, for optical element, Encapsulant for electrical insulation/electronic component/separator, etc., casting material, putty, glass fiber impregnating agent, sealing agent, passivation film for semiconductor/solar cell, etc., interlayer insulating film, protective film, liquid crystal display A lens part of a lens sheet such as a prism lens sheet used for a backlight of a device, a Fresnel lens sheet used for a screen such as a projection TV, a lenticular lens sheet, or an optical lens such as a micro lens, such as a backlight using such a sheet; An optical element, an optical connector, an optical waveguide, a casting agent for optical shaping|molding, etc. are mentioned as an example.

As an example, a display device in which each layer such as an undercoat layer, an antireflection layer, a polarizing element layer, a retardation layer, a birefringence layer, a light scattering layer, a hard coat layer, a lubricating layer, and a protective layer is provided on a transparent support. The film which consists of the hardened|cured material of this invention can be used for each layer.

[Example]

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

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

Each component was thoroughly mixed by the formulation shown in following [Table 1] and [Table 2], and the curable composition of Examples 1-9 and the curable composition of Comparative Examples 1-5 were obtained, respectively. In addition, the unit of the compounding quantity of an Example and a comparative example is a mass part.

As the cationically polymerizable component (A), the following compound (A1-1), compound (A2-1), and compound (A3-1) were used.

Compound (A1-1): bisphenol type diglycidyl ether

Compound (A2-1): neopentyl glycol diglycidyl ether

Compound (A3-1): Aronoxetane OXT-221 (manufactured by Toa Synthesis Co., Ltd.)

The following compound (B-1) was used as a cationic polymerization initiator (B).

Compound (B-1): 50% solution of propylene carbonate of a mixture of a compound represented by the following formula (3) and a compound represented by the following formula (4)

As a radically polymerizable component (C), the following compound was used.

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

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

Compound (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 (polyfunctional acrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.)

Compound (C2-4): Viscote #150 (tetrahydrofurfuryl 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)

About each curable composition of the obtained Examples 1-9 and Comparative Examples 1-5, viscosity, adhesiveness, and sclerosis|hardenability were evaluated according to the following procedure. A result is written together in [Table 1] and [Table 2].

(Viscosity)

About each of the obtained curable compositions of Examples 1-9 and Comparative Examples 1-5, the viscosity in 25 degreeC was measured with the E-type viscometer. A result is written together in [Table 1] and [Table 2].

(Adhesiveness)

The curable compositions of Examples 1 to 9 and Comparative Examples 1 to 5 obtained above were respectively coated on a corona-treated PMMA film (Sumitomo Chemical Co., Ltd.: Technoroy 125S001), followed by corona discharge treatment of another sheet. COP (Cycloorepine Polymer, manufactured by Nippon Zeon: Part No. Zeonoa Film 14-060) Film and laminator are used to bond, and an electrodeless UV lamp is used to irradiate ^{light equivalent to 1000 mJ/cm 2} through the COP film. It adhered to obtain a test piece. A 90 degree peel test was performed on the obtained test piece.

(hardness test)

After applying the curable compositions of Examples 1 to 9 and Comparative Examples 1 to 5 obtained above on one TAC film (Fuji film: part number FT-TD60ULP), another COP ( Cycloorepine Polymer, manufactured by Nippon Zeon: Part No. Zeonoa Film 14-060) Film and laminator are used to bond, and 150mJ/cm ² light equivalent to 150mJ/cm 2 is irradiated through the COP film and adhered using an electrodeless UV lamp. The curing rate was evaluated. In less than 30 seconds of irradiation, the case where resistance was felt when peeling was evaluated as (circle), and the case where it could peel easily even if it was 30 second or more was evaluated as x. It means that sclerosis|hardenability is so good that hardening time is short.

[Table 1]

[Table 2]

※Measurable

From [Table 1] and [Table 2], it turns out that the curable composition of this invention is excellent in viscosity and adhesiveness.

Claims (8)

20 to 90 parts by mass of a cationically polymerizable component (A), 1 to 10 parts by mass of a cationic polymerization initiator (B), 1 to 30 parts by mass of a radically polymerizable component (C), and 0 to 10 parts by mass of a radical polymerization initiator (D) It contains a mass part so that the sum total of the said cationically polymerizable component (A) and the said radically polymerizable component (C) may become 100 mass parts,
The cationically polymerizable component (A) is an aromatic epoxy compound (A1), a glycidylated product of a polyhydric alcohol having a molecular weight of 200 or more, or a glycidylated product (A2) of a polyhydric alcohol alkylene oxide adduct, and an oxetane compound ( A3) as an essential component, and the aromatic epoxy compound (A1) is 35 to 50 parts by mass relative to 100 parts by mass in total of the cationically polymerizable component (A) and the radically polymerizable component (C),
The radically polymerizable component (C) is a compound (C1) having an epoxy group and an ethylenically unsaturated group, or an acrylic acid ester of an alcohol having 2 to 20 carbon atoms or a methacrylic acid ester of an alcohol having 2 to 20 carbon atoms (C2) ) as an essential component, the curable composition. According to claim 1,
The said aromatic epoxy compound (A1) is a polyfunctional aromatic epoxy compound, The curable composition. According to claim 1,
The curable composition, wherein the oxetane compound (A3) is a polyfunctional oxetane compound. According to claim 1,
The curable composition, wherein the acrylic acid ester of an alcohol having 2 to 20 carbon atoms or the methacrylic acid ester (C2) of an alcohol having 2 to 20 carbon atoms is an acrylic acid ester or a methacrylic acid ester having a cyclic structure. 5. The method of claim 4,
The cyclic structure is

At least one selected from the group consisting of, a curable composition. The hardening method of a curable composition which irradiates an active energy ray to the curable composition in any one of Claims 1-5. The curing method of a curable composition which heats the curable composition in any one of Claims 1-5. The hardened|cured material which is a hardened|cured material of the curable composition in any one of Claims 1-5.