JP6883020B2 - Curable composition, method for producing cured product, and cured product thereof - Google Patents

Description

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 having excellent viscosity and adhesion, a method for producing a cured product, and a cured product thereof.

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

For example, Patent Documents 1 to 3 below propose an energy ray-curable composition containing a cationically polymerizable component and a radically polymerizable component, and a cured product thereof. Specifically, Patent Document 1 proposes an adhesive composition for a polarizing plate having excellent initial curability and adhesiveness. Further, in Patent Document 2, when producing a polarizing plate using a resin film having a low moisture permeability as a protective film, it is excellent in curability even when the humidity of the coating environment is high, and the adhesive strength after a certain period of time is various. A low-viscosity photocurable adhesive that is good against force, does not cause problems even after the durability test, and has good adhesive strength after the completion of the moisture resistance test has been proposed. Further, Patent Document 3 proposes an active energy ray-polymerizable resin composition containing an unsaturated alicyclic epoxy ester compound, which can achieve both high heat resistance, high refractive index and transparency.

Japanese Unexamined Patent Publication No. 2014-105218 JP 2015-143352 Japanese Unexamined Patent Publication No. 2015-168757

However, even the curable compositions proposed in Patent Documents 1 to 3 may not always be satisfactory in terms of curability and adhesion, and it is possible to achieve a high degree of compatibility between viscosity and adhesion. At present, there is a demand for a new curable composition that can be produced.

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

As a result of diligent studies to solve the above problems, the present inventors have found that a curable composition having a specific composition can solve the above problems, and have completed the present invention.

That is, the curable composition of the present invention contains 70 to 90 parts by mass of the cationically polymerizable component (A), 1 to 10 parts by mass of the cationic polymerization initiator (B), and 10 to 30 parts by mass of the radically polymerizable component (C). A portion and 2 to 10 parts by mass of the radical polymerization initiator (D) are contained so that the total of the cationically polymerizable component (A) and the radically polymerizable component (C) is 100 parts by mass.
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). ), And the aromatic epoxy compound (A1) is 35 to 50 parts by mass with respect to a total of 100 parts by mass of the cationically polymerizable component (A) and the radically polymerizable component (C). Yes,
The radically polymerizable component (C) 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 an alcohol having 2 to 20 carbon atoms. It is characterized by containing a methacrylic acid ester (C2) as an essential component.

より選ばれる一種以上であることが好ましい。 In the curable composition of the present invention, the aromatic epoxy compound (A1) is preferably a polyfunctional aromatic epoxy compound. Further, in the curable composition of the present invention, the oxetane compound (A3) is preferably a polyfunctional oxetane compound. Further, in the curable composition of the present invention, the acrylic acid ester of the alcohol having 2 to 20 carbon atoms or the methacrylic acid ester (C2) of the alcohol having 2 to 20 carbon atoms is an acrylic having a cyclic structure. It is preferably an acid ester or a methacrylic acid ester. Furthermore, in the curable composition of the present invention, the cyclic structure is the following group.

It is preferable that it is one or more selected.

The method for producing a cured product of the present invention is characterized in that the curable composition of the present invention is irradiated with active energy rays or heated.

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

According to the present invention, it is possible to provide a curable composition having excellent viscosity 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 comprises 20 to 90 parts by mass of the cationically polymerizable component (A), 1 to 10 parts by mass of the cationic polymerization initiator (B), and 1 to 30 parts by mass of the radically polymerizable component (C). , The radical polymerization initiator (D) is contained in an amount of 0 to 10 parts by mass so that the total of the cationically polymerizable component (A) and the radically polymerizable component (C) is 100 parts by mass. In the curable composition of the present invention, the cationically polymerizable component (A) is a glycidyl compound of an aromatic epoxy compound (A1) and a polyhydric alcohol having a molecular weight of 200 or more, or a glycidyl compound of a polyhydric alcohol alkylene oxide adduct. (A2) and the oxetane compound (A3) are essential components, and the aromatic epoxy compound (A1) is based on 100 parts by mass of the total of the cationically polymerizable component (A) and the radically polymerizable component (C). It is 35 to 50 parts by mass. Further, the radically polymerizable component (C) 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 an alcohol having 2 to 20 carbon atoms. The methacrylic acid ester (C2) of the above is an essential component.

The cationically polymerizable component (A) according to the curable composition of the present invention is a compound that undergoes a polymerization or cross-linking reaction by a cationic polymerization initiator activated by energy ray irradiation or heating. Epoxy compounds, oxetane compounds, vinyl ether compounds and the like can be mentioned.

The cationically polymerizable component (A) according to the curable composition of the present invention is a glycidyl compound of an aromatic epoxy compound (A1) and a polyhydric alcohol having a molecular weight of 200 or more, or a polyvalent component (A). The glycidyl compound (A2) of the alcohol alkylene oxide adduct and the oxetane compound (A3) are essential components, but as other epoxy compounds, an alicyclic epoxy compound, a vinyl ether compound and the like can also be used.

The aromatic epoxy compound (A1) refers to an epoxy compound containing an aromatic ring, and specific examples of the aromatic epoxy compound include polyhydric phenol having at least one aromatic ring such as phenol, cresol, and butylphenol. , A mono / polyglycidyl etherified product of the alkylene oxide adduct, for example, bisphenol A, bisphenol F, or a glycidyl etherified product or an epoxynovolac resin of a compound obtained by further adding an alkylene oxide to these; two such as resorcinol, hydroquinone, and catechol. Mono / polyglycidyl etherified product of the above aromatic compound having a phenolic hydroxyl group; glycidyl etherified product of an aromatic compound having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol, and phenyldibutanol; phthalic acid, terephthalate Examples thereof include glycidyl ester of a polybasic acid aromatic compound having two or more carboxylic acids such as acid and trimellitic acid, glycidyl ester of benzoic acid, and an epoxidized product of styrene oxide or divinylbenzene.

As the 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, On-Coat EX-1020, On-Coat EX-1030, On-Coat EX-1040, On-Coat EX-1050, On-Coat EX-1051, On-Coat EX-1010, On-Coat EX-1011, On-Coat 1012 (Nagase) Chemtex Co., Ltd.); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (DIC Co., Ltd.) (Manufactured by); ESN-475V (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.); Epicoat YX8800 (manufactured by Mitsubishi Chemical Co., Ltd.); Marproof G-0105SA, Marproof G-0130SP (manufactured by Nichiyu Co., Ltd.); Epicron N-665, Epicron HP-7200 (manufactured by DIC Co., Ltd.); 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.); Adecaledin EP-4000, Adecaledin EP-4005, Adecaledin EP-4100, Adecaledin EP-4901 (manufactured by ADEKA Co., Ltd.); TECHMORE VG-3101L (Manufactured by Printec Co., Ltd.) and the like. As the aromatic epoxy compound (A1), a polyfunctional compound is preferable because it has excellent curability.

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

Examples of the glycidyl product of a polyhydric alcohol having a molecular weight of 200 or more or the glycidyl product (A2) of a polyhydric alcohol alkylene oxide adduct include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neo. Pentyl glycol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, dicyclo Polyethers obtained by adding one or more alkylene oxides to glycidyl ethers of polyhydric alcohols such as pentadienedimethanol diglycidyl ethers and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin. Examples thereof include polyglycidyl ethers of polyols and diglycidyl esters of aliphatic long-chain dibasic acids.

As glycidylates of polyhydric alcohols or glycidylates of polyhydric alcohol alkylene oxide adducts (A1), monoglycidyl ethers of aliphatic higher alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxide stearate, Examples thereof include butyl epoxide stearate, epoxidized soybean oil, and epoxidized polybutadiene.

As the glycidyl product of a polyhydric alcohol having a molecular weight of 200 or more, or the glycidyl product (A2) of a polyhydric alcohol alkylene oxide adduct, one having a saturated condensed ring is preferable because the curability and adhesion of the cured product are improved.

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, commercially available products 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, 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 Corporation); Epolite M-1230 , Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.) Examples thereof include ADEKA Glycyrrol ED-503G, ADEKA Glycyrrol ED-506, ADEKA GRICILOL ED-523T, ADEKA REGIN EP-4088S, ADEKA REGIN EP-4080E (manufactured by ADEKA Corporation).

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 glycol bis (3-ethyl-3-oxetanylmethyl) ether , Triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, Bifunctional aliphatic oxetane compounds such as 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) Examples include monofunctional oxetane compounds such as oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, and 3-ethyl-3- (chloromethyl) oxetane. Be done. These can be used alone or in combination of two or more, and a polyfunctional oxetane compound is preferable because it enhances the curability and adhesion of the cured product.

As the oxetane compound (A3), a commercially available product can be used, for example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.); Aron oxetane OXT. -121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toa Synthetic Co., Ltd.), Ethanacole OXBP, OXTP (manufactured by Ube Industries, Ltd.) Be done.

The alicyclic epoxy compound refers to a compound in which an oxylane ring is directly bonded to a saturated ring without a bonding group. Specific examples of the alicyclic epoxy compound include a polyglycidyl etherified product of a polyhydric alcohol having at least one alicyclic ring, or a cyclohexene oxide obtained by epoxidizing a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. Cyclopentene oxide-containing compounds can be mentioned. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate. , 6-Methyl-3,4-Epoxycyclohexylmethyl-6-methyl-3,4-Epoxycyclohexanecarboxylate, 3,4-Epoxy-3-methylcyclohexylmethyl-3,4-Epoxy-3-methylcyclohexanecarboxylate , 3,4-Epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate , Methylenebis (3,4-epoxycyclohexane), Propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadienediepoxiside, Ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2 -Epoxy ethylcyclohexane, α-pinenooxide, limonendioxide and the like can be mentioned. Examples of the alicyclic epoxy compound include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-. 1-Methylhexanecarboxylate is preferable from the viewpoint of improving adhesion.

As the alicyclic epoxy compound, a commercially available product can be used, and examples thereof include celoxide 2021P, celoxide 2081, celoxide 2000, and celoxide 3000 (manufactured by Daicel Corporation).

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, and 2-. Examples thereof include hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, and 1,6-cyclohexanedimethanol divinyl ether.

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 ratio of the alicyclic epoxy compound and the vinyl ether compound used is 30 to 80 parts by mass of the aromatic epoxy compound (A1) with respect to 100 parts by mass of the total of the cationically polymerizable component (A) and the radically polymerizable component (C). A glycidyl compound of a polyhydric alcohol having a molecular weight of 200 or more, or a glycidyl compound of a polyhydric alcohol alkylene oxide adduct (A2) by 10 to 30 parts by mass, an oxetane compound (A3) by 10 to 30 parts by mass, an alicyclic epoxy compound 0 to 20 The parts by mass and 0 to 20 parts by mass of the vinyl ether compound are preferable because the viscosity, coatability, reactivity and curability are improved.

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. , Preferably a double salt, which is an onium salt that releases Lewis acid upon irradiation with energy rays, or a derivative thereof. Typical examples of such compounds include the following general formulas,
[A] ^{r +} [B] ^r-
Examples of salts of cations and anions 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 represented by.

Further, here, R ¹ is an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms. a is an integer of 1-5. The a R ^1s are independent and may be the same or different. Further, at least one is preferably an organic group as described above having an aromatic ring. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N = N. Further, when the valence of Q in the cation [A] ^{r +} is q, it is necessary that the relationship r = a−q holds (however, N = N is treated as having a valence of 0).

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

Further, 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 of 3 to 7. Further, when the valence of L in the anion [B] ^r− is p, it is necessary that the relationship r = bp is established.

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

The anion [B] ^r- is expressed by the following general formula.
[LY _b-1 (OH)] ^r-
The structure represented by is also preferably used. L, Y, b are the same as above. Other anions that can be used include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonic acid ion (FSO ₃ ) ⁻ , and toluene sulfonic acid anion. , Trinitrobenzene sulfonic acid anion, camphor sulfonate, nonafluorobutane sulfonate, 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. From these, one of them can be used alone, or two or more of them can be mixed and used.

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

(B) Diaryl such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, trilucmil iodonium tetrakis (pentafluorophenyl) borate, etc. Iodonium salt

(C) Sulfonium cations represented by Group I or Group II below and sulfonium salts such as hexafluoroantimon ion, hexafluorophosphate ion, and tetrakis (pentafluorophenyl) borate ion.

<Group I>

<Group II>

Also, those other preferred, (eta ^{5-2,4-cyclopentadiene-1-yl)} [(1,2,3,4,5,6-η) - (1- methylethyl) benzene] - Iron -Iron-arene complexes such as hexafluorophosphate, aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salitylaldehidato) aluminum, and silanols such as triphenylsilanol. Mixtures of; salts such as thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, hydrazinium salt; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine; 1,2-diaminocyclohexane, 1,4-diamino Alicyclic polyamines such as -3,6-diethylcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylene diamine, diaminodiphenylmethane and diaminodiphenylsulfone; Polyepoxy addition-modified product produced by reacting with various epoxy resins such as glycidyl ethers such as bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether or glycidyl esters of carboxylic acid by a conventional method; the above organic Amidation modified products produced by reacting polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimeric acid by a conventional method; the above polyamines and aldehydes such as formaldehyde and phenols, cresols, xylenols, etc. Mannig-modified products produced by reacting tributylphenol, resorcin and other phenols having at least one aldehyde reaction-reactive site with a nucleus by a conventional method; polyvalent carboxylic acids (succinic acid, malonic acid, succinic acid). , Glutalic acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladiponic acid, 3-methyladiponic acid, 3-methylpentanedioic acid, 2-methyl Aliphatic dicarboxylic acids such as octanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid; phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc. Aromatic dicarboxylic acids; cyclohexanedicarbo Alicyclic dicarboxylic acids such as acids; tricarboxylic acids such as trimellitic acid, trimesic acid, trimer of castor oil fatty acid; tetracarboxylic acids such as pyromellitic acid) acid anhydrides; dicyandiamides, imidazoles, carboxylic acid esters , Sulphonic acid ester, amineimide and the like.

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

ここで、式中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９およびＲ^２０は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基または炭素原子数２〜１０のエステル基を表し、Ｒ^２１、Ｒ^２２、Ｒ^２３およびＲ^２４は、それぞれ独立に、水素原子、ハロゲン原子または炭素原子数１〜１０のアルキル基を表し、Ｒ^２５は、水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基または下記化学式（Ａ）〜（Ｃ）より選択されるいずれかの置換基を表し、Ａｎ^ｑ−はｑ価の陰イオンを表し、ｐは電荷を中性にする係数を表す。

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 are independently hydrogen atoms, halogen atoms, and carbon atoms, respectively. It represents an alkyl group of 1 to 10, an alkoxy group having 1 to 10 carbon atoms, or an ester group having 2 to 10 carbon atoms, and R ²¹ , R ²² , R ^23, and R ²⁴ are independently hydrogen atoms and halogens, respectively. represents an atom or an alkyl group having 1 to 10 carbon ^{atoms, R 25} is a hydrogen atom, a halogen atom, an alkyl group, or the following chemical formula 1 to 10 carbon atoms (a) ~ one selected from (C) It represents a substituent, An ^q− represents a q-valent anion, and p represents a coefficient for neutralizing the charge.

ここで、式中、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およびＲ^３９は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基または炭素原子数２〜１０のエステル基を表し、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３およびＲ^３４は、それぞれ独立に、水素原子、ハロゲン原子または炭素原子数１〜１０のアルキル基を表す。

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 are independently hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms and 1 carbon atom. Represents an alkoxy group of 10 or an ester group of 2 to 10 carbon atoms, and R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ independently represent hydrogen atoms, halogen atoms or 1 to 10 carbon atoms, respectively. Represents the alkyl group of.

Among the compounds represented by the above general formulas, 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. ^{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 halogen atom include fluorine, chlorine, bromine, iodine and the like.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ as alkyl groups with 1 to 10 carbon atoms. Methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3- Methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl , Bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tridecafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl , Methoxymethyl, 1,2-epoxyethyl, methoxyethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, t-butylthiomethyl, 4-pentenyloxymethyl, trichloroethoxymethyl, bis (2-chloroethoxy) Methyl, methoxycyclohexyl, 1- (2-chloroethoxy) ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl, trimethylsilylethyl, t-butyldimethylsilyloxymethyl, 2- (trimethylsilyl) ethoxymethyl, t-butoxy Carbonylmethyl, ethyloxycarbonylmethyl, ethylcarbonylmethyl, t-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl, acetylethyl, 2-methoxy-1-propenyl, hydroxymethyl , 2-Hydroxyethyl, 1-Hydroxyethyl, 2-Hydroxypropyl, 3-Hydroxypropyl, 3-Hydroxybutyl, 4-Hi Examples thereof include droxybutyl and 1,2-dihydroxyethyl.

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 alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, s-butyloxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethyloxy, 3-methoxypropyloxy, 4- Examples thereof include 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 ester groups with 2 to 10 carbon atoms include methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy and propionyl. Examples thereof include oxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, t-butylcarbonyloxy, methoxyacetyloxy, benzoyloxy and the like.

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, or an acrylic acid ester of an alcohol having 2 to 20 carbon atoms or an alcohol having 2 to 20 carbon atoms. The methacrylic acid ester (C2) of alcohol, which is 2 to 20, is an essential component. Among (C2), an acrylic acid ester or a methacrylic acid ester having a cyclic structure is preferable, and it is more preferable that the cyclic structure is one or more selected from the following group.

Examples of the compound (C1) having an epoxy group and an ethylenically unsaturated group include epoxy acrylate and epoxy methacrylate. Specific examples thereof include conventionally known aromatic epoxy resins and alicyclic epoxy resins. It is an acrylate obtained by reacting an aliphatic epoxy resin or the like with acrylic acid or methacrylic acid. Of these epoxy acrylates or epoxy methacrylates, particularly preferred are acrylates or methacrylates of glycidyl ethers of alcohols.

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 thereof. Examples thereof include acrylates or methacrylates obtained by reacting an oxide adduct 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, isobonyl 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, Trimethylol propantriacrylate, Pentaerythritol tetraacrylate, Dipentaerythritol 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, isobonyl methacrylate, benzyl methacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanedioldi. Methacrylate, Diethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, Neopentyl glycol dimethacrylate, Polyethylene glycol dimethacrylate, Polypropylene glycol dimethacrylate, Trimethylol propantrimethacrylate, Pentaerythritol tetramethacrylate, Dipentaerythritol hexamethacrylate, ε-caprolactone-modified dimethacrylate Pentaerythritol hexamethacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, ε-caprolactone-modified tris- (2-acryroxyethyl) isocyanurate, ε-caprolactone-modified tris- (2-methacryloxyethyl) isocyanurate. And so on. Of these acrylates or methacrylates, polyacrylates of polyhydric alcohols or polymethacrylates of polyhydric alcohols are particularly preferable.

As the radically polymerizable component (C), a compound other than (C1) or (C2) that undergoes a polymerization or cross-linking reaction with a radical polymerization initiator activated by energy ray irradiation or heating can also be used, for example, allyl. Examples thereof include urethane compounds, unsaturated polyester compounds, and styrene compounds. The ratio of the component (C1) and the component (C2) in the radically polymerizable component (C) is preferably 50% by mass or more.

The radical initiator (D) according to the curable composition of the present invention is not particularly limited, and known radical initiators can be used. For example, a ketone compound such as an acetophenone compound, a benzyl compound, a benzophenone compound, a thioxanthone compound, an oxime compound, or the like can be used.

In the curable composition of the present invention, the cationically 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, and the radical polymerization is carried out. The sex component (C) is 1 to 30 parts by mass, and the radical polymerization initiator (D) is 0 to 10 parts by mass. If the blending ratio is other than the above, the curability and adhesion of the cured product may deteriorate. The total of the cationically polymerizable component (A) and the radically polymerizable component (C) is 100 parts by mass. The amount of the component (A1) is 35 to 50 parts by mass with respect to a total of 100 parts by mass of the cationically polymerizable component (A) and the radically polymerizable component (C).

Further, a sensitizer and / or a sensitizing aid can be used in the curable composition of the present invention, if necessary. The sensitizer is a compound that exhibits maximum absorption at a wavelength longer than the maximum absorption wavelength indicated by the cationic polymerization initiator (B) and promotes the polymerization initiation reaction by the cationic polymerization initiator (B). The sensitizer is a compound that further promotes the action of the sensitizer.

Examples of the sensitizer and the sensitizer aid include anthracene compounds and naphthalene compounds.

Examples of the anthracene-based compound include those represented by the following formula (1).

ここで、式（１）中、Ｒ^５０およびＲ^５１は、各々独立に水素原子、炭素原子数１〜６のアルキル基または炭素原子数２〜１２のアルコキシアルキル基を表し、Ｒ^５２は水素原子または炭素原子数１〜６のアルキル基を表す。

Here, in the formula (1), R ⁵⁰ and R ⁵¹ independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy alkyl group having 2 to 12 carbon atoms, and R ⁵² is a hydrogen atom. Alternatively, it represents an alkyl group having 1 to 6 carbon atoms.

Specific examples of the anthracene-based compound represented by the above 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 Examples thereof include 2-ethyl-9,10-dipentyloxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene.

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

ここで、式（２）中、Ｒ^５３およびＲ^５４は各々独立に炭素原子数１〜６のアルキル基を表す。

Here, in the 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 above 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, Examples thereof include 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene and 1,4-dibutoxynaphthalene.

The ratio of the sensitizer and the sensitizer to the cationically polymerizable component (A) is not particularly limited, and the sensitizer and the sensitizer may be used at a generally normal ratio as long as the object of the present invention is not impaired. From the viewpoint of improving curability, it is preferable that the sensitizer and the sensitizer aid are each 0.1 to 3 parts by mass with respect to 100 parts by mass of the cationically polymerizable component (A).

A silane coupling agent can be used in the curable composition of the present invention, if necessary. Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkenyl-functional alkoxysilanes such as alkyl-functional alkoxysilanes, vinyltrichlorosilanes, vinyltrimethoxysilanes, vinyltriethoxysilanes, and allyltrimethoxysilanes, 3-methacryloxybropyrriethoxysilanes, 3-methacryloxybropyrtrimethoxys. Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and other epoxy-functional alkoxysilanes, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl Amino-functional alkoxysilanes such as −γ-aminopropyltrimethoxysilane, mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, titanium alkoxides such as titaniumtetraisopropoxide, titaniumtetranormalbutoxide, and titanium diocties. Titanium chelates such as loxybis (octylene glycolate) and titanium diisopropoxybis (ethylacetoacetate), zirconium chelates such as zircounium tetraacetylacetonate and zirconiumtributoxymonoacetylacetonate, zirconiumtributoxymono Zirconic acylates such as stearate, isocyanate silanes such as methyltriisocyanate silane, and the like can be used.

The amount of the silane coupling agent used is not particularly limited, but is usually in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of solids in the 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, if necessary. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate ethyl acrylate copolymer, methyl methacrylate glycidyl methacrylate copolymer, poly (meth) acrylic acid, and styrene- (meth) acrylic acid copolymer. Examples thereof include (meth) acrylic acid-methyl methacrylate copolymer, glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester and the like.

In the curable composition of the present invention, if necessary, the protective group is further desorbed and activated by an ultraviolet absorber, an inactive material at room temperature, heating to a predetermined temperature, light irradiation, acid, or the like. It is also possible to use a compound that exhibits an ultraviolet absorbing ability.

Further, as long as the effects of the present invention are not impaired, colorants such as polyols, inorganic fillers, organic fillers, pigments and dyes, antifoaming agents, thickeners, surfactants, leveling agents and difficulties are required. Various resin additives such as flame retardants, tinctures, diluents, plasticizers, stabilizers, polymerization inhibitors, UV absorbers, antioxidants, antistatic agents, flow conditioners, and adhesion promoters can be added. it can.

In the curable composition of the present invention, a solvent capable of dissolving or dispersing each of the above-mentioned components (A), (B), (C) and (D), which is not particularly limited and is usually 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; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1 , 2-Diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether and other ether solvents; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, succinic acid Ester-based solvents such as dimethyl and texanol; Cellosolve-based solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol-based solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol. Aether ester type such as 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. Solvents; BTX-based solvents such as benzene, toluene, xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane; terpene hydrocarbon oils such as terepine oil, D-lymonen, pinen; mineral spirit, swazole # Paraffinic solvents such as 310 (manufactured by Cosmo Matsuyama Oil Co., Ltd.) and Solbesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane, etc. Solvents: Halogenized 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, dimethylsulfoxide, water and the like. These solvents can be used as one kind or a mixed solvent of two or more kinds.

Since the curable composition of the present invention improves curability, adhesiveness, and liquid storage stability, the water content is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. If there is too much water, it may become cloudy or the components may precipitate, which is not preferable.

The curable composition of the present invention is applied onto a support substrate by known means such as a roll coater, a curtain coater, various types of printing, and immersion. Further, once applied on a support substrate such as a film, it can be transferred onto another support substrate, and there is no limitation on the application method.

The material of the support substrate is not particularly limited, and a commonly used material can be used. For example, an inorganic material such as glass; diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl, etc. can be used. Cellulose esters such as cellulose and nitrocellulose; polyamide; polyimide; polyurethane; epoxy resin; polycarbonate; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxy Polyesters such as ethane-4,4'-dicarboxylate, polybutylene terephthalate; polystyrene; polyolefins such as polyethylene, polypropylene, polymethylpentene; vinyl compounds such as polyvinyl acetate, polyvinyl chloride, polyvinyl fluoride; polymethylmethacrylate , Polyacrylate and other acrylic resins; polycarbonate; polysulfone; polyethersulfone; polyetherketone; polyetherimide; polyoxyethylene, norbornene resin, cycloolefin polymer (COP) and other polymer materials. The support substrate may be subjected to surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.

In the method of curing the curable composition of the present invention by irradiation with energy rays, examples of the energy rays include ultraviolet rays, electron beams, X-rays, radiation, high frequencies and the like, and ultraviolet rays are the most economically preferable. Examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.

The conditions in the method of curing the curable composition of the present invention by heating are 70 to 250 ° C. for 1 to 100 minutes. It may be pre-baked (PAB) and then pressurized to post-bake (PEB), or it may be baked at several different temperatures. The heating conditions vary depending on the type and blending ratio of each component, but are, for example, 70 to 180 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Then, a cured film can be obtained by heat-treating the coating film at 180 to 250 ° C., preferably 200 to 250 ° C. for 30 to 90 minutes in an oven and 5 to 30 minutes in a hot plate.

Specific applications of the curable composition of the present invention or a cured product thereof include adhesives, glasses, optical materials typified by imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, and printing. Plates, color TVs, PC monitors, mobile information terminals, digital cameras, organic EL, display elements such as touch panels, insulating varnish, insulating sheets, laminated boards, printed boards, semiconductor devices, LED packages, liquid crystal inlets, organic Encapsulants for EL, optical elements, electrical insulation, electronic parts, separation films, etc., molding materials, putty, glass fiber impregnants, sealants, passivation films for semiconductors, solar cells, etc., layers Insulating film, protective film, prism lens sheet used for backlight of liquid crystal display device, Frenel lens sheet used for screen of projection TV, lens part of lens sheet such as lenticular lens sheet, or such sheet Examples thereof include the used backlight and the like, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, casting agents for optical modeling, and the like.

As a display device, a transparent support is provided with various layers 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, if necessary. A film made of the cured product of the present invention can be used for each layer.

Hereinafter, the present invention will be described in more detail with reference to 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 sufficiently mixed with the formulations shown in [Table 1] and [Table 2] below to obtain a curable composition of Examples 1 to 9 and a curable composition of Comparative Examples 1 to 5, respectively. The unit of the blending amount of Examples and Comparative Examples is parts by mass.

The following compounds (A1-1), (A2-1) and (A3-1) were 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 Toa Synthetic Co., Ltd.)

The following compound (B-1) was used as the cationic polymerization initiator (B).
Compound B-1: A 50% propylene carbonate solution of a mixture of a compound represented by the following formula (3) and a compound represented by the following formula (4).

The following compounds were used as the radically polymerizable component (C).
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; Shin Nakamura Chemical Industry Co., Ltd.) Made)
Compound (C2-4): Viscote # 150 (Tetrahydrofurfuryl Acrylate; manufactured by Osaka Organic Chemical Industry Co., Ltd.)

The following compound (D-1) was used as the radical polymerization initiator (D).
Compound (D-1): Irgacure 184 (manufactured by BASF)

The viscosity, adhesion and curability of each of the obtained curable compositions of Examples 1 to 9 and Comparative Examples 1 to 5 were evaluated according to the following procedure. The results are shown together in [Table 1] and [Table 2].

(viscosity)
The viscosities of each of the obtained curable compositions of Examples 1 to 9 and Comparative Examples 1 to 5 at 25 ° C. were measured with an E-type viscometer. The results are shown together in [Table 1] and [Table 2].

(Adhesion)
The curable compositions of Examples 1 to 9 and Comparative Examples 1 to 5 obtained above are applied to one corona-treated PMMA film (Sumitomo Chemical Co., Ltd .: Technoroy 125S001), and then another corona. A COP (cycloolefin polymer, manufactured by Nippon Zeon: product number Zeonoa film 14-060) film that has been subjected to discharge treatment and a laminator are used to bond them together, and an electrodeless ultraviolet lamp is used to emit light equivalent to ^{1000 mJ / cm 2 to the COP film.} A test piece was obtained by irradiating through and adhering. The obtained test piece was subjected to a 90-degree peel test.

(Curing test)
After applying the curable compositions of Examples 1 to 9 and Comparative Examples 1 to 5 obtained above to one TAC film (Fuji film: product number FT-TD60ULP), another corona discharge treatment is performed. The applied COP (cycloolefin polymer, manufactured by Nippon Zeon: product number Zeonoa film 14-060) film and laminator are used to bond them together, and an electrodeless ultraviolet lamp is used to irradiate light equivalent to ^{150 mJ / cm 2 through the COP film.} And adhered to evaluate the curing rate. The case where the irradiation felt resistance when peeled off in less than 30 seconds was evaluated as ◯, and the case where the irradiation was easily peeled off in 30 seconds or more was evaluated as x. The shorter the curing time, the better the curing property.

※測定不能

* Cannot be measured

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

Claims (8)

70 to 90 parts by mass of the cationically polymerizable component (A), 1 to 10 parts by mass of the cationic polymerization initiator (B), 10 to 30 parts by mass of the radically polymerizable component (C), and the radical polymerization initiator (D) 2. 10 parts by mass is contained so that the total of the cationically polymerizable component (A) and the radically polymerizable component (C) is 100 parts by mass.
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). ), And the aromatic epoxy compound (A1) is 35 to 50 parts by mass with respect to a total of 100 parts by mass of the cationically polymerizable component (A) and the radically polymerizable component (C). Yes,
The radically polymerizable component (C) 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 an alcohol having 2 to 20 carbon atoms. A curable composition containing a methacrylic acid ester (C2) as an essential component. The curable composition according to claim 1, wherein the aromatic epoxy compound (A1) is a polyfunctional aromatic epoxy compound. The curable composition according to claim 1, wherein the oxetane compound (A3) is a polyfunctional oxetane compound. The first aspect of claim 1, wherein the acrylic acid ester of the alcohol having 2 to 20 carbon atoms or the methacrylic acid ester (C2) of the alcohol having 2 to 20 carbon atoms is an acrylic acid ester or a methacrylic acid ester having a cyclic structure. Curable composition. The annular structure is the following group,

The curable composition according to claim 4, which is one or more selected from the above. A method for curing a curable composition, which comprises irradiating the curable composition according to any one of claims 1 to 5 with active energy rays. A method for curing a curable composition, which comprises heating the curable composition according to any one of claims 1 to 5. A cured product according to any one of claims 1 to 5, which is a cured product of the curable composition.