TW201741360A - Curable composition, method for curing same, and cured product obtained thereby - Google Patents

Abstract

Provided is a curable composition that is useful in an optical film, has excellent adhesive properties, and has a low viscosity, as well as a method for curing said composition, and a cured product obtained through said method. The curable composition comprises 100 parts by mass of a cationic curable component (A), and 0.1 to 15 parts by mass of a cationic polymerization initiator (B), wherein the cationic curable component (A) includes, as essential components thereof, an alicyclic epoxy compound (A1), an aliphatic epoxy compound (A2), and an oxetane compound (A3). The cationic curable component (A) preferably further contains an aromatic epoxy compound (A4).

Description

Curable composition, hardening method thereof, and cured product obtained thereby

The present invention relates to a curable composition, a curing method thereof, and a cured product and an adhesive obtained thereby, and more particularly to a curable composition which is useful for an optical film, has excellent adhesion, and has low viscosity. The hardening method, and the hardened material obtained thereby.

A curable composition made of an epoxy resin or the like is excellent in adhesion to various substrates, and is a cured product obtained by curing an epoxy resin with a curing agent, and has heat resistance, chemical resistance, and electrical properties. Since it is excellent in mechanical properties and the like, it is used in the fields of inks, paints, various coating agents, adhesives, optical members, and the like.

For example, Patent Document 1 proposes a cationically polymerizable adhesive containing an oxetane compound, an aromatic glycidyl ether, and a cationic polymerization initiator. Further, Patent Document 2 proposes a photocurable composition as an adhesive for a polarizing plate, which contains a photocurable component, a decane coupling agent, and a photocationic polymerization initiator, and the photocurable component contains an alicyclic ring. An epoxy compound of the epoxy group. Further, Patent Document 3 proposes a cationic adhesive which is used as a cation for a polarizing plate. The adhesive contains an epoxy compound, an oxetane compound, and a photocationic polymerization initiator. Further, in Patent Document 4, a cationically polymerizable composition is proposed which contains an aromatic epoxy compound, an aliphatic epoxy compound or an alicyclic epoxy compound as a cationically polymerizable organic substance.

[Previous Technical Literature] [Patent Document]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2010-229392

Patent Document 2: Japanese Laid-Open Patent Publication No. 2013-210445

Patent Document 3: Japanese Patent Publication No. 2014-505274

Patent Document 4: International Publication No. 2015/005211

However, when the resin composition described in Patent Documents 1 to 4 is used for an optical film, the resin compositions described in Patent Documents 1 to 4 are difficult to obtain a high degree of balance between adhesion and coating properties, and thus the current situation is required. A new curable composition useful for optical films.

Accordingly, an object of the present invention is to provide a curable composition which is useful for an optical film, has excellent adhesion, and has a low viscosity, a curing method thereof, and a cured product obtained thereby.

As a result of intensive studies, the inventors of the present invention have found that a high degree of balance between adhesion and coating properties can be obtained by adjusting the composition of the cation-curable component in the curable composition, and the present invention has been completed.

In other words, the curable composition of the present invention contains a curable composition of 100 parts by mass of the cationic curable component (A) and 0.1 to 15 parts by mass of the cationic polymerization initiator (B), and is characterized in that the cationic hardening is carried out. The component (A) contains an alicyclic epoxy compound (A1), an aliphatic epoxy compound (A2), and an oxetane compound (A3) as essential components.

In the curable composition of the present invention, the cation curable component (A) further preferably contains an aromatic epoxy compound (A3). Further, the curable composition of the present invention preferably contains 0.1 to 15 parts by mass of the decane coupling agent (C) having an epoxy group (except for the cation curable component (A)). Furthermore, in the curable composition of the present invention, the alicyclic epoxy compound (A1) is preferably 1 to 30% by mass in 100% by mass of the cation curable component (A). Further, in the curable composition of the present invention, the alicyclic epoxy compound (A1) is selected from a 3',4'-epoxycyclohexylmethyl-3,4-epoxy ring. Hexane carboxylate, 7-oxabicyclo[4.1.0]heptane, poly[oxy-(1-o-oxy-1,6-hexanediyl)] derivative, adipic acid bis[( 7-oxabicyclo[4.1.0]heptan-3-yl)methyl]ester, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl At least one of a group of methacrylate and limonene dioxide is preferred. Further, in the curable composition of the present invention, the oxetane compound (A3) is selected from the group consisting of 3-ethyl-3-(hexyloxymethyl) Oxycyclobutane, 3-ethyl-3-(hydroxymethyl)oxetane, benzylenedioxybutane, 3-ethyl-3-(3-ethyl At least one of the group of 3-oxetanylmethyloxymethyl)oxetane is preferred.

Further, the method for curing a curable composition of the present invention is characterized in that the cured product of the present invention is cured by irradiation or heating of an active energy ray.

Further, the cured product of the present invention is characterized by being formed of the curable composition of the present invention.

According to the present invention, it is possible to provide a curable composition which is useful for an optical film, has excellent adhesion, and has a low viscosity, a curing method thereof, and a cured product obtained thereby.

[Best Practice for Carrying Out the Invention]

Hereinafter, the curable composition of the present invention, the method for curing the same, and the cured product and the adhesive obtained thereby will be described in detail.

The curable composition of the present invention contains 100 parts by mass of the cationic curable component (A) and 0.1 to 15 parts by mass of the cationic polymerization initiator (B) (hereinafter, also referred to as "(A) component" and "(B, respectively). )ingredient"). It is preferable to further contain 0.1 to 15 parts by mass of the decane coupling agent (C) having an epoxy group (except for the cation hardening component (A)). In the curable composition of the present invention, the component (A) is an alicyclic epoxide The compound (A1), the aliphatic epoxy compound (A2), and the oxetane compound (A3) are essential components, and further preferably contain an aromatic epoxy compound (A4). Hereinafter, the components (A) to (C) will be described in detail.

<Cationic hardening component (A)>

The component (A) used in the cured product of the present invention is a compound which causes polymerization or crosslinking reaction by using a cationic polymerization initiator which is activated by energy ray irradiation or heating, and is an alicyclic epoxy. The compound (A1), the aliphatic epoxy compound (A2) and the oxetane compound (A3) preferably contain an aromatic epoxy compound (A4) as an essential component.

Specific examples of the alicyclic epoxy compound (A1) include a polyglycidyl ether compound of a polyol having at least one alicyclic ring, or a cyclohexene or cyclopentene ring by using an oxidizing agent. A compound containing a cyclohexene oxide or a cyclopentene oxide obtained by epoxidation of a compound. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-lanyl Cyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxy Cyclohexane carboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy 5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, 3 , 4-epoxy-6-methylcyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4- Epoxycyclohexane), 2,2- Bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethyl bis(3,4-epoxycyclohexanecarboxylate), epoxy hexahydroortho Dioctyl phthalate, di-2-ethylhexyl hexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy Benz-2-epoxyethylcyclohexane, 7-oxabicyclo[4.1.0]heptane, poly[oxy-(1-o-oxy-1,6-hexanediyl)] derivative , adipic acid bis[(7-oxabicyclo[4.1.0]heptan-3-yl)methyl]ester, α-pinene oxide, limonene dioxide, 3',4'-epoxy Cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate Wait. Among these, in terms of adhesion improvement, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate Or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate is preferred.

For the alicyclic epoxy compound (A1), for example, Celloxide 2021P, Celloxide 2081, Celloxide 2000, Celloxide 3000, CYCLOMER M100 (manufactured by DAICEL), and CYRACURE UVR-6128 (manufactured by Dow Chemical Co., Ltd.) can be used. Wait.

In the curable composition of the present invention, the alicyclic epoxy compound (A1) is from 1 to 60% by mass, particularly from 5 to 50% by mass, based on 100% by mass of the component (A), viscosity, coatability and reaction. Sexual improvement is preferred.

The aliphatic epoxy compound (A2) means an aromatic epoxy compound which is not classified into an alicyclic epoxy compound (A1) or a later-described aromatic epoxy compound. The epoxy compound of the (A4), as a specific example of the aliphatic epoxy compound, may be a monofunctional epoxy compound such as a glycidyl ether compound of an aliphatic alcohol or a glycidyl ester of an alkyl carboxylic acid, or an aliphatic plural. A polyfunctional epoxy compound such as an alcohol or a polyglycidyl ether compound of the alkylene oxide adduct or a polyglycidyl ester of an aliphatic long-chain polybasic acid. Typical examples of the compound include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, and 1,4-butanediol dihydrate. Glycerol ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerol, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, a glycidyl ether of a polyhydric alcohol such as hexa-glycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol or diglycidyl ether of polypropylene glycol, and addition of one or more alkylene oxides A polyglycidyl ether ester of a polyether polyol obtained from an aliphatic polyol such as propylene glycol, trimethylolpropane or glycerin, or a diglycidyl ester of an aliphatic long-chain dibasic acid. Further, examples thereof include monoglycidyl ether of an aliphatic higher-order alcohol, glycidyl ester of a higher-order fatty acid, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized soybean oil, and epoxidized polycondensation. Butadiene, etc. Among these, it is preferred that the glycidyl ether compound of an aliphatic alcohol or an aliphatic polyhydric alcohol or a polyglycidyl ether compound of the alkylene oxide adduct is improved in viscosity, coatability and reactivity. Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether or 1,6-hexanediol diglycidyl ether is preferred.

As the aliphatic epoxy compound (A2), commercially available products such as Denacol EX-121 and Denacol EX-171 can be used. 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); Epolight M-1230, Epolight 40E, Epolight 100E, Epolight 200E , Epolight400E, Epolight70P, Epolight200P, Epolight400P, Epolight1500NP, Epolight1600, Epolight80MF, Epolight100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Adeka Glycirol ED-503, Adeka Glycirol ED-503G, Adeka Glycirol ED-506, Adeka Glycirol ED-523P (ADEKA Company system) and so on.

In the curable composition of the present invention, the aliphatic epoxy compound (A2) is 5 to 40% by mass, particularly 20 to 30% by mass, in terms of viscosity, coatability, and reactivity with respect to 100% by mass of the component (A). Upgrade is better.

Examples of the oxetane compound (A3) include 3,7-bis(3-oxetanyl)-5-oxa-decane and 1,4-bis[(3-ethyl-3). -oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-B Alkyl-3-oxetanyl Oxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, four Ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis (3) -ethyl-3-oxetanylmethoxy)hexane, 3-ethyl-3-(3-ethyl-3-oxetanylmethyloxymethyl)oxetane, benzophenone a difunctional oxetane compound such as methyl dioxetane (xylylenebisoxetane), 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3 -(hexyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl) a monofunctional oxetane compound such as oxetane or 3-ethyl-3-(chloromethyl)oxetane, and a monofunctional aliphatic oxetane compound for viscosity and reaction It is preferred in terms of sex. These may be used alone or in combination of two or more.

As the oxetane compound (A3), a commercially available product containing a cationically polymerizable monomer as a main component can be used, and examples thereof include 2-hydroxyethyl vinyl ether and diethylene glycol monovinyl ether. -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 Toagosei Co., Ltd.), ETERNACOLL OXBP, OX TP (made by Ube Industries Co., Ltd.).

In the curable composition of the present invention, the oxetane compound (A3) is 10 to 40% by mass, particularly 20 to 30% by mass, based on 100% by mass of the component (A), viscosity, coating property and reaction. Sexual ascension good.

The aromatic epoxy compound (A4) is an epoxy compound having a plurality of epoxy groups and containing an aromatic ring, and specific examples of the polyfunctional aromatic epoxy compound include at least phenol, cresol, butanol, and the like. a monocyclic phenol of one aromatic ring, or a mono/polyglycidyl ether compound of the alkylene oxide adduct, such as bisphenol A, bisphenol F, or glycidol of a compound which further adds alkylene oxide An ether compound or a phenolic novolak type epoxy compound; a glycidyl ether of an aromatic compound having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone or catechol; benzenedimethanol or phenylenediethanol; a polyglycidyl ether compound of an aromatic compound having two or more alcoholic hydroxyl groups such as phenylbutanol; and a dimer having two or more carboxylic acids such as phthalic acid, terephthalic acid or trimellitic acid Polyglycidyl ester of acid aromatic compound, polyglycidyl benzoate such as benzoic acid or toluic acid, naphthoic acid, glycidyl benzoate, styrene oxide or epoxide of divinylbenzene. Among these, polyglycidyl ether compound containing polyglycidyl ether selected from phenols, aromatic compound having two or more alcoholic hydroxyl groups, polyglycidyl ether compound of polyphenols, and polycondensation of benzoic acid At least one of the group of the glycidyl ester and the polyglycidyl ester of the polybasic acid is preferred from the viewpoint of low viscosity of the curable composition. In particular, as the aromatic epoxy compound, a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol E epoxy compound, or a phenol novolak epoxy compound is excellent in curability. It is better.

A commercially available product can be used as the aromatic epoxy compound (A4), and examples thereof include Denacol EX-121 and Denacol EX-145. Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, On Court EX-1020, On Court EX-1030, On Court EX-1040, On Court EX-1050, On Court EX-1051, On Court EX-1010, On Court EX-1011, On Court 1012 (manufactured by Nagase ChemteX); OGSOL PG-100, OGSOL EG-200, OGSOL EG-210, OGSOL EG- 250 (manufactured by Osaka Gas Chemicals Co., Ltd.); HP 4032, HP4032D, HP4700 (manufactured by DIC Corporation); ESN-475V (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); Epikote YX8800 (manufactured by Mitsubishi Chemical Corporation); Marr proof G-0105SA, Marr proof G-0130SP (manufactured by Nippon Oil Co., Ltd.); EPICLON N-665, EPICLON 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 (manufactured by Nippon Kayaku Co., Ltd.); ADEKA RESIN EP-4000, ADEKA RESIN EP-4005, ADEKA RESIN EP-4100, ADEKA RESIN EP-4901 (made by ADEKA) ;TECHMORE VG-3101L (manufactured by PRINTEC).

In the curable composition of the present invention, the aromatic epoxy compound (A4) is 20 to 60% by mass based on 100% by mass of the component (A), and particularly 30 to 50% by mass, from the viewpoint of improvement in hardenability. It is better.

In the curable composition of the present invention, a vinyl ether compound (A5) may be further added as the cation curable component (A). As the vinyl ether compound (A5), for example, diethylene glycol monovinyl group 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-cyclohexane dimethanol monovinyl ether, ethylene Alcohol divinyl ether, 1,4-butanediol divinyl ether, 1,6-cyclohexane dimethanol divinyl ether, and the like.

In the curable composition of the present invention, the alicyclic epoxy compound (A1), the aliphatic epoxy compound (A2), the oxetane compound (A3), and the aromatic epoxy compound in the component (A) ( The ratio of the use of the A4) and the vinyl ether compound (A5) is 1 to 30% by mass of the alicyclic epoxy compound (A1) and the aliphatic epoxy compound (A2) 5 to 100% by mass of the component (A). 40% by mass, oxetane compound (A3) 10 to 40% by mass, aromatic epoxy compound (A4) 20 to 60% by mass, and vinyl ether compound (A5) 1 to 15 parts by mass, viscosity, Improvement in coatability, reactivity, and hardenability is preferred.

<Cationic polymerization initiator (B)>

The component (B) used in the curable composition of the present invention may be any compound as long as it is a compound which can initiate cationic polymerization by light irradiation or heating, and is preferably released by a substance. The double salt of the cerium salt of the Lewis acid, or a derivative thereof, is released by irradiation of the wire. Representative examples of the related compound include a salt of a cation and an anion represented by the following general formula.

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

Here, the cation [A]r+ is preferably 鎓, and its structure can be represented, for example, by the following general formula.

[(R ² ) _a Q] ^r+

Further, the R ² -based carbon atom may have from 1 to 60 carbon atoms, and may contain several organic groups other than carbon atoms. a is an integer from 1 to 5. Each of R ² is independent and may be the same or different. Further, at least one organic group having an aromatic ring as described above is preferred. Q is selected from the group consisting of atoms, or groups of atoms formed 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 q, the relationship of r = aq must be established (however, N = N is treated as the valence of 0).

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

[LY _b ] ^r-

Further, the metal or semimetal of the central atom of the L-based halide complex is B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V. , Cr, Mn, Co, etc. Y is a halogen atom. B is an integer from 3 to 7. Further, when the valence of L in the anion [B] ^r- is p, the relationship of r = bp must be established.

Specific examples of the general anion [LY _b ] ^r- include quinone (pentafluorophenyl) borate, tetrakis(3,5-difluoro-4-methoxyphenyl)borate, and tetrafluoroethylene. Boric acid (BF ₄ ) ^- , hexafluorophosphate (PF ₆ ) ^- , hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarsenate (AsF ₆ ) ^- , hexachloroantimonate (SbCl ₆ ) ^- and the like.

Further, as the anion [B] ^r- system, a structure represented by the following general formula can be preferably used.

[LY _b-1 (OH)] ^r-

The L, Y, and b systems are the same as described above. Further, examples of other anions which can be used include perchloric acid ions (ClO ₄ ) ^- , trifluoromethyl sulfite ions (CF ₃ SO ₃ ) ^- , fluorosulfonic acid ions (FSO ₃ ) ^- , toluenesulfonic acid. Anion, trinitrobenzenesulfonic acid anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraarylborate, ruthenium (pentafluorophenyl)sulfonate, and the like.

In the present invention, among the above-mentioned sulfonium salts, the aromatic sulfonium salts of the following (i) to (iii) are particularly preferred. In the curable composition of the present invention, one of these may be used alone or two or more of them may be used in combination.

(i) aryldiazonium salt such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate or 4-methylphenyldiazonium hexafluorophosphate

(ii) diphenylphosphonium hexafluoroantimonate, bis(4-methylphenyl)phosphonium hexafluorophosphate, bis(4-tert-butylphenyl)phosphonium hexafluorophosphate, tolylcumene Diarylsulfonium salt of quinone (pentafluorophenyl) borate

(iii) a phosphonium salt of a phosphonium cation represented by the following group I or group II, and a hexafluoroantimonium ion, a hexafluorophosphate ion, or a quinone (pentafluorophenyl) borate ion;

Further, as another preferred one, (η ⁵ -2,4-cyclopentadien-1-yl)[(1,2,3,4,5,6-η)-(1-methyl An iron-aromatic hydrocarbon complex such as ethyl)benzene]-iron-hexafluorophosphate or an aluminum miscide such as aluminum acetylate, aluminum ginseng or aluminum ginseng (salicylic acid) a mixture of a decyl alcohol such as a triphenyl decyl alcohol; a salt of a thiophene sulfonium salt, a thiolanium salt, a benzyl ammonium salt, a pyridinium salt, a phosphonium salt or the like; a diethylenetriamine, a triethylamine Polyalkyl polyamines such as triamine, tetraethylenepentamine, etc.; 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophorone II An alicyclic polyamine such as an amine; an aromatic polyamine such as m-xylylenediamine, diaminodiphenylmethane or diaminodiphenylphosphonium; and the above polyamines by a usual method And various epoxy resins such as glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, or glycidyl esters of carboxylic acid a polyepoxy group produced by reacting a compound to form a modified substance; by using a conventional method to make the above organic polyamines, and adjacent An amide-modified product produced by reacting a carboxylic acid such as phthalic acid, isophthalic acid or a dimer acid; and the above-mentioned polyamines and aldehydes such as formaldehyde and phenol, cresol, and the like by a conventional method Mannich modified product produced by reacting phenols having at least one hydroformylation site on the nucleus such as cresol, tromide, resorcin, etc.; polycarboxylic acid (oxalic acid, C Diacid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid , 3-methyladipate, 3-methylglutaric acid, 2-methyloctanedioic acid, 3,8-dimethylsebacic acid, 3,7-dimethylsebacic acid, hydrogenated dimerization An aliphatic dicarboxylic acid such as an acid or a dimer acid; an aromatic dicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid or naphthalene dicarboxylic acid; or an alicyclic ring such as cyclohexane dicarboxylic acid. a dicarboxylic acid; a tricarboxylic acid such as trimellitic acid, trimesic acid, a trimer of a castor oil fatty acid; a tetracarboxylic acid such as pyromic acid; or an acid anhydride; dicyandiamide, an imidazole, Carboxylic ester, sulfonate Ester, amine (PEI) and the like.

Among these, in view of the improvement of the practical surface and the light sensitivity, it is preferred to use an aromatic onium salt, an aromatic onium salt, or an iron-aromatic hydrocarbon complex.

The ratio of use of the component (B) of the component (A) is not particularly limited, and may be used in an approximate usual use ratio within a range not inhibiting the object of the present invention, for example, 100 parts by mass relative to the component (A). The component (B) is 0.1 to 15 parts by mass, preferably 1 to 10 by mass. Share. When the amount is too small, the hardening is likely to be insufficient, and if it is too large, the physical properties such as the water absorption rate of the cured product and the strength of the cured product may be adversely affected.

<Centane coupling agent (C) having an epoxy group>

The component (C) used in the present invention is a decane coupling agent having an epoxy group, but does not contain a component corresponding to the component (A). As the component (C), an epoxy-functional alkoxydecane can be used, and examples thereof include γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, and γ. - glycidoxypropylmethyldimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane Wait.

For the component (C), for example, D2632, G0261, G0210, and T2675 (manufactured by Tokyo Chemical Industry Co., Ltd.); KBM-303, KBM-402, KBM-403, KBE-402, and KBE-403 (Shin) can be used. -Etsu Silicone Co., Ltd.).

The amount of the component (C) to be used is not particularly limited. For example, the component (C) is 0.1 to 15 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the component (A).

<Other ingredients>

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

Examples of the sensitizer and the sensitizing agent include an anthraquinone compound and a naphthalene compound.

The oxime compound is, for example, represented by the following formula (1).

(wherein R ¹ and R ² are each independently represented by an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 12 carbon atoms; and R ^{3 is} represented by a hydrogen atom or a carbon number of 1 to 6; alkyl).

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

9,10-Dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-dibutoxyanthracene , 9,10-dipentyloxy fluorene, 9,10-dihexyloxy fluorene, 9,10-bis(2-methoxyethoxy) fluorene, 9,10-bis(2-ethoxylated Oxy) ruthenium, 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-dipropoxy Bismuth, 2-methyl- or 2-ethyl-9,10-diisopropoxy oxime, 2-methyl- or 2-ethyl-9,10-dibutoxyanthracene, 2-methyl- Or 2-ethyl-9,10-dipentyloxy guanidine, 2-methyl- or 2-ethyl-9,10-dihexyloxyfluorene or the like.

The naphthalene compound is, for example, represented by the following formula (2).

(wherein R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).

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

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 or the like.

The ratio of use of the sensitizer and the sensitizing agent to the component (A) is not particularly limited, and may be used in an approximate usual use ratio as long as it does not inhibit the object of the present invention, for example, relative to ( 100 parts by mass of the component A), the sensitizer and the sensitizer are each 0.1 to 3 parts by mass, and it is preferable from the viewpoint of improvement in hardenability.

The curable composition of the present invention can also improve the properties of the cured product by using a thermoplastic organic polymer as needed. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, and poly(methyl) propylene. Acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, glycidyl (meth)acrylate-poly(methyl) methacrylate copolymer, polyvinyl Butyral, cellulose ester, polypropylene decylamine, saturated polyester, and the like.

The curable composition of the present invention is not particularly limited, and a solvent which can be used for dissolving or dispersing the components (A), (B) and (C) can be used, and examples thereof include methyl ethyl ketone. a ketone such as methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone or 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, An ether solvent such as 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether or dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid - An ester-based solvent such as n-propyl ester, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, or texanol; Solvent-based solvent such as base ether or ethylene glycol monoethyl ether; alcohol-based solvent such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol or pentanol; Methyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl Ether esters such as acetoxyacetate and ethoxyethyl propionate a solvent; a BTX-based solvent such as benzene, toluene or xylene; an aliphatic hydrocarbon-based solvent such as hexane, heptane, octane or cyclohexane; or a terpene-based hydrocarbon oil such as turpentine, D-limonene or decene; Paraffin-based solvent such as mineral spirits, Swasol #310 (Cosmo Matsuyama Oil), Solvesso # 100 (Exxon Chemical), carbon tetrachloride, chloroform, trichloroethylene, dichloromethane, 1 Halogenation of 2-dichloroethane An aliphatic hydrocarbon solvent; a halogenated aromatic hydrocarbon solvent such as chlorobenzene; propylene carbonate, carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N - dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylhydrazine, water, etc., one or two of these solvents may be used. The above mixed solvent is used.

Further, in the curable composition of the present invention, other monomers, other energy ray-sensitive polymerization initiators, inorganic fillers, organic fillers, pigments, dyes, and the like may be added as needed, as long as the effects of the present invention are not impaired. Coloring agent, defoaming agent, thickener, surfactant, leveling agent, flame retardant, thixotropic agent, diluent, plasticizer, stabilizer, polymerization inhibitor, ultraviolet absorber, antioxidant, static electricity prevention Various resin additives such as a solvent, a flow regulator, and a subsequent accelerator.

The curable composition of the present invention can be applied to a support substrate by well-known means such as roll coating, curtain coating, various printing, and immersion. Further, it can be temporarily applied to a support substrate such as a film and then transferred to another support substrate, and the method of application is not limited.

The material of the support substrate is not particularly limited and can be used as a general user, and examples thereof include inorganic materials such as glass; diacetyl cellulose, triethyl cellulose (TAC), and propyl cellulose. Cellulose esters of butyl sulfonium cellulose, acetyl hydrazine cellulose, nitrocellulose, etc.; polydecylamine; poly phthalimide; polyurethane; epoxy resin; polycarbonate; Ethylene glycol, polyethylene naphthalate, polybutylene terephthalate, dimethyl 1,4-cyclohexane terephthalate, polyethylene -1,2-diphenoxyethane-4,4'-dicarboxylate, polyester such as polybutylene terephthalate; polystyrene; polyethylene, polypropylene, polymethylpentene Polyolefins such as polyvinyl acetate, polyvinyl chloride, polyvinyl fluoride, etc.; acrylic resins such as polymethyl methacrylate and polyacrylate; polycarbonate; polyfluorene; polyether oxime; Polyether ketone; polyether quinone imine; polymer material such as polyoxyethylene, norbornene resin, cycloolefin polymer (COP). Further, the support substrate may be subjected to surface activation treatment such as corona discharge treatment, fireworks treatment, ultraviolet treatment, high-frequency treatment, glow discharge treatment, active plasma treatment, or laser treatment.

Specific examples of the use of the curable composition of the present invention and the cured product thereof include optical materials, paints, coating agents, lining agents, inks, and resists represented by optical films, adhesives, glasses, and photographic lenses. Agent, liquid resist, printing plate, insulating varnish, insulating sheet, laminate, printed circuit board, semiconductor device, LED package, liquid crystal injection port, organic EL, optical component, electrical insulation, electronic component ‧Use of sealing agent for forming film, molding material, putty, glass fiber impregnating agent, filler, passivation film for semiconductor, solar cell, etc., interlayer insulating film, protective film, and backlight for liquid crystal display device a lens portion of a lens sheet such as a Fresnel lens sheet or a lenticular lens sheet used for a screen such as a lenticular lens sheet or a projection television, or an optical lens or an optical element such as a microlens or the like using such a sheet-like backlight; An optical coupler, an optical waveguide, an optical molding agent, and the like.

For example, when it is used as an optical film, metal, wood, rubber, plastic, glass, ceramics, etc. are used as a substrate. The above-described means applies the curable composition of the present invention to a substrate, and is cured by light irradiation or heating by the above means. As a typical configuration of the optical film, each layer such as an undercoat layer, an antireflection layer, a hard coat layer, a gas barrier layer, a lubricant layer, and an adhesive layer may be provided on the transparent support.

Further, as the support substrate, an inorganic material may be used as the substrate, and a film coated by the above method may be used, or a vacuum deposition method, an ion plating method, a plasma CVD method, an ion assist method, or a reaction may be used. A film produced by various vapor deposition methods such as a sputtering method or a chemical vapor deposition method is laminated.

When the film is laminated by a vapor deposition method, it is preferable to use glass as the substrate, and the film thickness varies depending on the type of the inorganic material to be used, and is, for example, 5 to 300 nm. The vapor deposition film may be formed only on one side of the substrate or may be formed on both sides of the substrate. As the inorganic material, for example, bismuth (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), indium (In), sodium (Na), boron (B) can be used. ), oxides of titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), yttrium (Sb), or indium ‧ tin composite oxide (abbreviated as ITO), yttrium-tin composite oxide ( A composite oxide such as ATO).

When the curable composition of the present invention is cured by irradiation with an energy ray, ultraviolet rays, electron beams, X-rays, radiation, high frequency, and the like are exemplified as energy rays, and ultraviolet rays are economically preferable. Examples of the light source of the ultraviolet light include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.

The condition in which the curable composition of the present invention is cured by heating is 1 to 100 minutes at 70 to 250 °C. After prebaking (PAB; Pre applied bake), pressurization, post exposure bake (PEB; Post exposure bake), or baking at different stages of temperature.

The heating conditions vary depending on the type of each component and the blending ratio. For example, at 70 to 180 ° C, the oven is 5 to 15 minutes, and when the plate is heated, it is 1 to 5 minutes. Thereafter, in order to cure the coating film to 180 to 250 ° C, it is preferably 200 to 250 ° C, 30 to 90 minutes in an oven, and 5 to 30 minutes in a hot plate to obtain a cured film by heat treatment.

[Examples]

Hereinafter, the cured product obtained by curing the curable composition of the present invention and the curable composition thereof will be described in detail by using examples and comparative examples, but the present invention is not limited to the examples. in. In the examples and comparative examples, the parts mean the parts by mass.

[Examples 1 to 7 and Comparative Examples 1 to 4] The components shown in the following Tables 1 and 2 were sufficiently mixed, and the compositions of Examples 1 to 7 and Comparative Examples 1 to 4 were obtained. As the component (A), the following compounds (A1-1), (A2-1) to (A2-3), (A3-1), (A3-2), and (A4-1) were used as (B). The component (C) is the following compound (B), and the compound (C-1) and the compound (C-2).

Compound A1-1: Celloxide 2021P (alicyclic epoxy: manufactured by DAICEL Co., Ltd.)

Compound A2-1: 1,4-butanediol diglycidyl ether

Compound A2-2: Adeka Glycirol ED-523T (aliphatic epoxy: manufactured by ADEKA)

Compound A2-2: Neopentyl glycol diglycidyl ether

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

Compound A3-2: Aron Oxetane OXT-101 (oxetane: manufactured by Toagosei Co., Ltd.)

Compound A4-1: ADEKA RESIN EP-4100 (bisphenol A type polyfunctional epoxy: manufactured by ADEKA Corporation)

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

Compound C-1: KBM-403 (decane coupling agent: manufactured by Shin-Etsu Silicone Co., Ltd.)

Compound C-2: KBE-403 (decane coupling agent: manufactured by Shin-Etsu Silicone Co., Ltd.)

The following evaluations were performed on the curable compositions of Examples 1 to 7 and Comparative Examples 1 to 4 thus obtained. The results of the evaluation are combined and recorded in Tables 1 and 2.

(viscosity)

The obtained curable compositions of Examples 1 to 7 and Comparative Examples 1 to 4 were each measured for viscosity at 25 ° C by an E-type viscometer. The results are combined and recorded in Tables 1 and 2.

(Adhesiveness 1)

The obtained curable compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were respectively applied to a glass substrate (5 cm × 10 cm) by a bar coating #3, and cut into a COP of 2 cm width ( The cycloolefin polymer film was bonded, and a test piece was obtained by irradiating an energy of 1000 mJ/cm ² at an illuminance of 250 mW/cm ² using a metal halide lamp. A 90 degree peel test of the obtained test piece was performed. The results are combined and recorded in Tables 1 and 2.

(Adhesiveness 2)

The obtained compositions of Examples 6 and 7 and Comparative Example 4 were applied to a single TAC film, and then bonded to a COP (cycloolefin polymer) film to which corona discharge treatment was applied using a bonding machine. The test piece was obtained by irradiating an energy of 1000 mJ/cm ² with an electrodeless ultraviolet lamp. A 90 degree peel test of the obtained test piece was performed. The results are combined and recorded in Tables 1 and 2.

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

Claims (9)

A curable composition containing 100 parts by mass of a cationic curable component (A) and 0.1 to 15 parts by mass of a cationic polymerization initiator (B), wherein the cationically curable component (A) The alicyclic epoxy compound (A1), the aliphatic epoxy compound (A2), and the oxetane compound (A3) are essential components. The curable composition of claim 1, wherein the cation curable component (A) further contains an aromatic epoxy compound (A4). The curable composition of claim 1, further comprising 0.1 to 15 parts by mass of the decane coupling agent (C) having an epoxy group (except for the cation hardening component (A)). The curable composition of claim 1, wherein the alicyclic epoxy compound (A1) is from 1 to 30% by mass based on 100% by mass of the cation curable component (A). The sclerosing composition of claim 1, wherein the alicyclic epoxy compound (A1) is selected from the group consisting of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate Acid ester, 7-oxabicyclo[4.1.0]heptane, poly[oxy-(1-sideoxy-1,6-hexanediyl)] derivative, adipic acid bis[(7-oxygen) Heterobicyclo[4.1.0]heptan-3-yl)methyl]ester, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate At least one of a group of esters and limonene dioxide. The sclerosing composition of claim 1, wherein the aforementioned oxygen heterocycle The butane compound (A3) is selected from the group consisting of 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane, and benzophenone At least one of a group of methyl dioxetane and 3-ethyl-3-(3-ethyl-3-oxetanylmethyloxymethyl)oxetane. A method of curing a curable composition, characterized in that the curable composition according to any one of claims 1 to 6 is cured by irradiation with an active energy ray. A method of curing a curable composition, characterized in that the curable composition according to any one of claims 1 to 6 is cured by heating. A cured product characterized by the curable composition of any one of claims 1 to 6.