WO2018181846A1

WO2018181846A1 - Curable composition, method for producing cured product, cured product of same, and adhesive using same

Info

Publication number: WO2018181846A1
Application number: PCT/JP2018/013513
Authority: WO
Inventors: 和彦松土; 新之介関; 和幸板野; 一輝長坂
Original assignee: 株式会社Adeka
Priority date: 2017-03-31
Filing date: 2018-03-29
Publication date: 2018-10-04
Also published as: KR20190129830A; JP7641089B2; TW201900796A; CN110114376B; KR102756404B1; CN110114376A; KR20240095323A; JPWO2018181846A1; TWI855990B

Abstract

Provided are: a curable composition which has low viscosity and enables the achievement of a cured product that has excellent adhesiveness; a method for producing a cured product; a cured product of the curable composition; and an adhesive which uses the curable composition. A curable composition which contains 50-80 parts by mass of a radically polymerizable component (A), 1-10 parts by mass of a radical polymerization initiator (B), 20-50 parts by mass of a cationically polymerizable component (C) and 1-10 parts by mass of a cationic polymerization initiator (D), and wherein the total of the radically polymerizable component (A) and the cationically polymerizable component (C) is 100 parts by mass. The cationically polymerizable component (C) contains a glycidyl ether of an alcohol that has 11 or more carbon atoms.

Description

Curable composition, method for producing a cured product, cured product thereof, and adhesive using the same

The present invention relates to a curable composition, a method for producing a cured product, a cured product thereof, and an adhesive using the same, and more specifically, a curable composition having a low viscosity and a cured product having excellent adhesion, The present invention relates to a method for producing a cured product, the cured product, and an adhesive using the same.

The curable composition is used in the fields of inks, paints, various coating agents, adhesives, optical members, and the like, and includes an energy ray curable composition containing a cationic polymerizable component and a radical polymerizable component, and a cured product thereof. Has been proposed.

For example, Patent Document 1 proposes an adhesive composition for polarizing plates with improved initial curability and adhesiveness. Patent Document 2 proposes an active energy ray-curable composition that provides a cured product with reduced curl properties and excellent transparency while maintaining high surface hardness. Furthermore, the patent literature proposes an adhesive composition that is excellent in curability, adhesiveness, and water resistance and can be suitably used for the production of IT-related products.

JP 2014-037477 A JP 2016-102193 A International Publication No. 2014/178239

However, the curable compositions such as those proposed in Patent Documents 1 to 3 are not necessarily sufficient in viscosity and adhesion of the cured product to the substrate, and further improvement is desired at present. .

SUMMARY OF THE INVENTION An object of the present invention is to provide a curable composition capable of obtaining a cured product having low viscosity and excellent adhesion, a method for producing the cured product, the cured product, and an adhesive using the same. .

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

That is, the curable composition of the present invention comprises 50 to 80 parts by mass of the radical polymerizable component (A), 1 to 10 parts by mass of the radical polymerization initiator (B), 20 to 50 parts by mass of the cationic polymerizable component (C) and A curable composition containing 1 to 10 parts by mass of a cationic polymerization initiator (D), wherein the total of the radical polymerizable component (A) and the cationic polymerizable component (C) is 100 parts by mass,
The cationic polymerizable component (C) contains glycidyl ether of alcohol having 11 or more carbon atoms.

In the curable composition of the present invention, the radical polymerizable component (A) is an acrylate ester of an alcohol having 2 to 60 carbon atoms or a methacrylate ester (A1) of an alcohol having 2 to 60 carbon atoms. Or an acrylic ester of a phenol compound or a methacrylic ester (A2) of a phenol compound.

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

Furthermore, the cured product of the present invention is characterized by comprising the curable composition of the present invention.

Furthermore, the adhesive of the present invention is characterized by comprising the curable composition of the present invention.

According to the present invention, it is possible to provide a curable composition with a low viscosity and a cured product having excellent adhesion, a method for producing the cured product, the cured product, and an adhesive using the same.

Hereinafter, the curable composition of the present invention will be described in detail.
The curable composition of the present invention comprises 50 to 80 parts by mass of the radical polymerizable component (A), 1 to 10 parts by mass of the radical polymerization initiator (B), 20 to 50 parts by mass of the cationic polymerizable component (C), and cationic polymerization. 1 to 10 parts by mass of the initiator (D) is contained, and the total of the radical polymerizable component (A) and the cationic polymerizable component (C) is 100 parts by mass. In the curable composition of the present invention, the cationically polymerizable component (C) contains glycidyl ether of alcohol having 11 or more carbon atoms. By setting it as such a composition, it becomes a curable composition with a low viscosity and the hardened | cured material excellent in adhesiveness.

The radical polymerizable component (A) is not particularly limited as long as it is a compound that is polymerized or cross-linked by a radical polymerization initiator activated by irradiation with active energy rays or heating, and a known component can be used. For example, an acrylate of an alcohol having 2 to 60 carbon atoms, a methacrylate (A1) of an alcohol having 2 to 60 carbon atoms, an acrylic ester of a phenol compound or a methacrylic ester of a phenol compound (A2), acrylamide or methacryl Examples include amides, vinyl compounds, polyolefins, allyl urethane compounds, unsaturated polyester compounds, and styrene compounds.

Examples of the acrylate of an alcohol having 2 to 60 carbon atoms or the methacrylate (A1) of an alcohol having 2 to 60 carbon atoms include aromatic or aliphatic alcohols having at least one hydroxyl group in the molecule, and alkylenes 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, isoamyl acrylate, lauryl acrylate , Stearyl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, benzyl acrylate, 1,3-butanediol diacrylate, 1,4- Tandiol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, 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, tetrahydride Rofurfuryl methacrylate, isobornyl methacrylate, benzyl methacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neo Examples include pentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, and ε-caprolactone modified dipentaerythritol hexamethacrylate. Of these acrylates or methacrylates, polyhydric alcohol polyacrylates or polyhydric alcohol polymethacrylates are particularly preferred. Here, the acrylate of an alcohol having 2 to 60 carbon atoms or the methacrylate of an alcohol having 2 to 60 carbon atoms has 2 to 60 carbon atoms as an acrylate obtained by adding an acrylic group or a methacryl group to the alcohol. Means that.

As the acrylate of alcohol having 2 to 60 carbon atoms or the methacrylate (A1) of alcohol having 2 to 60 carbon atoms, commercially available products may be used. For example, NK ester AM-90G, NK ester AM- 130G, NK ester A-SA, NK ester S-1800A, NK ester 701A, NK ester A-200, NK ester A-400, NK ester A-600, NK ester A-1000, NK ester A-DCP, NK ester A-DOD-N, NK ester A-HD-N, NK ester APG-100, NK ester APG-200, NK ester APG-400, NK ester APG-700, NK ester A-PTMG-65, NK ester A- 9300, NK ester A-9300-1C NK ester A-GLY-20E, NK ester A-TMM-3L, NK ester A-TMM-3LM-N, NK ester A-TMPT, NK ester AD-TMP, NK ester ATM-35E, NK ester A-TMMT NK Ester A-9550, NK Ester A-DPH, NK Ester M-90G, NK Ester M-230G, NK Ester S, NK Ester SA, NK Ester 1G, NK Ester 2G, NK Ester 3G, NK Ester 4G, NK Ester 9G, NK ester 14G, NK ester 23G, NK ester DCP, NK ester DOD-N, NK ester HD-N, NK ester NOD-N, NK ester NPG, NK ester 1206PE, NK ester 701, NK ester 9PG, NK Ester TMP (Manufactured by Shin-Nakamura Chemical Co., Ltd.); HEA, HPA, 4-HBA, AIB, TBA, NOAA, INAA, Biscote # 197, IDAA, LA, STA, ISTA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Light acrylate IAA, Light acrylate LA, Light acrylate SA, Light acrylate EC-A, Light acrylate MTG-A, Light acrylate EHDG-AT, Light acrylate 130A, Light acrylate DPM-A, Light acrylate IB-XA, Light ester HOA (N), light ester HOP-A (N), light acrylate HOB-A, HOA-MS (N), light acrylate HOA-HH (N), light acrylate 3EG-A, light acrylate 4EG-A, Light acrylate 9EG- A, Light acrylate 14EG-A, Light acrylate PTMGA-250, Light acrylate NP-A, Light acrylate MPD-A, Light acrylate 1,6HX-A, Light acrylate 1,9ND-A, Light acrylate DCP-A, Light acrylate HPP-A, light ester G-201P, light acrylate TMP-A, light acrylate PE-3A, light acrylate PE-4A, light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.); KAYARAD NPGDA, KAYARAD PEG400DA, KAYAARAD FM-400, KAYARAD R-167, KAYARAD HX-220, KAYARAD HX-620, KAYARAD R-604, KAYARAD R-68 , KAYARAD GPO-303, KAYARAD TMPTA, KAYARAD PET-30 (Nippon Kayaku Co., Ltd.) and the like.

As the above-mentioned acrylic ester of phenolic compound or methacrylic ester of phenolic compound (A2), phenol, cresol, butylphenol, resorcinol, hydroquinone, catechol, etc., a phenolic compound having at least one aromatic ring, or its alkylene oxide addition Mono / polyacrylate or methacrylate of the product, for example, bisphenol A, bisphenol F, or a diacrylate or dimethacrylate of a compound obtained by further adding an alkylene oxide thereto.

As the acrylic acid ester of the phenol compound or the methacrylic acid ester (A2) of the phenol compound, commercially available products can be used, for example, NK ester A-LEN-10, NK ester AMP-20GY, NK ester A-B1206PE. NK ester ABE-300, NK ester A-BPE-10, NK ester A-BPE-20, NK ester A-BPE-30, NK ester A-BPE-4, NK ester A-BPEF, NK ester A-BPE -3, NK ester PHE-1G, NK ester BPE-80N, NK ester BPE-100, NK ester BPE-200, NK ester BPE-500, NK ester BPE-900, NK ester BPE-1300N (Shin Nakamura Chemical Co., Ltd. ) Made by the company; Rate PO-A, light acrylate P2H-A, light acrylate P-200A (manufactured by Kyoeisha Chemical Co., Ltd.); KAYARAD R-128H, KAYARAD R-551, KAYARAD R-712 (manufactured by Nippon Kayaku Co., Ltd.) Etc.

In the radical polymerizable component (A), since the curability and adhesion of the cured product are improved, the proportion of the component (A1) is preferably 50 to 100% by mass, and preferably 60 to 100% by mass. Further preferred. The proportion of the component (A2) is preferably 0 to 50% by mass, and more preferably 0 to 30% by mass.

In the curable composition of the present invention, since the curability and the adhesion of the cured product are improved, the radical polymerizability with respect to the total 100 parts by mass of the radical polymerizable component (A) and the cationic polymerizable component (C). Component (A) is preferably 50 to 80 parts by mass, and more preferably 50 to 65 parts by mass.

Examples of the radical polymerization initiator (B) used in the present invention include a photo radical polymerization initiator or a thermal radical polymerization initiator.

Preferred examples of the photopolymerization initiator include acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds, bisimidazole compounds, acridine compounds, acylphosphine compounds, and oxime ester compounds. .

Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, and 2-hydroxymethyl. -2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiarybutyldichloroacetophenone, p-tertiarybutyltrichloroacetophenone, p-azide Benzalacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1, Nzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane -1-one and the like.

Examples of the benzylic compound include benzyl.

Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like. It is done.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and the like.

As the bisimidazole compound, hexaarylbisimidazole (HABI, dimer of triaryl-imidazole) can be used. Specifically, for example, 2,2′-bis (2-chlorophenyl) -4 , 4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-Ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophene) ) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,4,5,2 ′, 4 ′, 5′-hexaphenyl Bisimidazole, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenylbisimidazole, 2,2′-bis (2-bromophenyl) -4,5,4 ′, 5'-tetraphenylbisimidazole, 2,2'-bis (2,4-dichlorophen ) -4,5,4 ′, 5′-tetraphenylbisimidazole, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetrakis (3-methoxyphenyl) bisimidazole, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetrakis (3,4,5-trimethoxyphenyl) -bisimidazole, 2,5,2 ′, 5′-tetrakis ( 2-chlorophenyl) -4,4′-bis (3,4-dimethoxyphenyl) bisimidazole, 2,2′-bis (2,6-dichlorophenyl) -4,5,4 ′, 5′-tetraphenylbisimidazole 2,2′-bis (2-nitrophenyl) -4,5,4 ′, 5′-tetraphenylbisimidazole, 2,2′-di-o-tolyl-4,5,4 ′, 5′- Tetraphenylbisimidazo 2,2′-bis (2-ethoxyphenyl) -4,5,4 ′, 5′-tetraphenylbisimidazole and 2,2′-bis (2,6-difluorophenyl) -4,5 4 ′, 5′-tetraphenylbisimidazole, 5′-tetra (p-iodophenyl) biimidazole, 2,2′-bis (o-chlorophenyl-4,4 ′, 5,5′-tetra (m-methoxy) Phenyl) biimidazole), 2,2′-bis (p-methylthiophenyl) -4,5,4 ′, 5′-diphenyl-1,1′-biimidazole, bis (2,4,5-triphenyl) 1,1′-biimidazole, 5,5′-tetra (p-chloronaphthyl) biimidazole, etc., and 1,2′-, 1,4′-2, disclosed in Japanese Patent Publication No. 45-37377 , 4'- covalently linked to each other Isomers include compounds described in JP WO00 / 52529.

Examples of the acridine compounds include acridine, 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (p-ethylphenyl) acridine, 9- (p-iso-propylphenyl) acridine, 9- (p -N-butylphenyl) acridine, 9- (p-tert-butylphenyl) acridine, 9- (p-methoxyphenyl) acridine, 9- (p-ethoxyphenyl) acridine, 9- (p-acetylphenyl) acridine 9- (p-dimethylaminophenyl) acridine, 9- (p-cyanophenylphenyl) acridine, 9- (p-chlorophenyl) acridine, 9- (p-bromophenyl) acridine, 9- (m-methyl) Phenyl) acridine, 9- (mn-propylphenyl) acridine, 9- (m- so-propylphenyl) acridine, 9- (mn-butylphenyl) acridine, 9- (m-tert-butylphenyl) acridine, 9- (m-methoxyphenyl) acridine, 9- (m-ethoxyphenyl) Acridine, 9- (m-acetylphenyl) acridine, 9- (m-dimethylaminophenyl) acridine, 9- (m-diethylaminophenyl) acridine, 9- (cyanophenyl) acridine, 9- (m-chlorophenyl) acridine 9- (m-bromophenyl) acridine, 9-methylacridine, 9-ethylacridine, 9-n-propylacridine, 9-iso-propylacridine, 9-cyanoethylacridine, 9-hydroxyethylacridine, 9-chloroethyl Acridine, 9-bromoacridine, 9 Hydroxyacridine, 9-nitroacridine, 9-aminoacridine, 9-methoxyacridine, 9-ethoxyacridine, 9-n-propoxyacridine, 9-iso-propoxyacridine, 9-chloroethoxyacridine, 4,6-bis (dimethyl) Amino) acridine, 10-acetate acridine, 10-methyl acetate acridine, 3,6-dimethylacridine, 7,13-dimethylacridine, 7,13-bis (dimethylamino) acridine, 3,6-dimethyl-10-acetidine acridine 3,5-dimethyl-10-methyl acetate acridine, 7,13-dimethyl-10-acetate acridine, 7,13-dimethyl-10-methyl acetate acridine, 1,7-bis (9-acridinyl) heptane, 1, 5-bis (9-acridini ) Pentane, 1,3-bis (9-acridinyl) propane, 2,7-dibenzoyl-9-phenylacridine, 2,7-bis (α-hydroxybenzyl) -9-phenylacridine, 2,7-bis ( α-acetoxybenzyl) -9-phenylacridine, 2,7-dimethyl-9- (4-methylphenyl) acridine, 2,7-dimethyl-9-phenylacridine, 2,7-bis (3,4-dimethyl- Benzoyl) -9- (3,4-dimethylphenyl) acridine, 2,7-bis (α-acetoxy-4-tert-butylbenzyl) -9- (4-tert-butylphenyl) acridine, 2,7-dimethyl -9- (3,4-dichlorophenyl) acridine, 2,7-dimethyl-9- (4-benzoylphenyl) acridine, 2,7-bis (2- Lolobenzoyl) -9- (2-chlorophenyl) acridine, 2- (α-hydroxy-3-bromobenzyl) -6-methyl-9- (3-bromophenyl) acridine, 2,5-bis (4-tert- Butylbenzoyl) -9- (4-tert-butylphenyl) acridine, 1,4-bis (2,7-dimethyl-9-acridinyl) benzene, 2,7-bis (α-phenylaminocarbonyloxy-3,4) -Dimethylbenzyl) -9- (3,4-dimethylphenyl) acridine and 2,7-bis (3,5-dimethyl-4-hydroxy-4'-fluorodiphenylmethyl) -9- (4-fluorophenyl) acridine 9,10-dihydroacridine, 1-methylacridine, 4-methylacridine, 2,3-dimethylacridine, 1-pheny Acridine, 4-phenylacridine, 1-benzylacridine, 4-benzylacridine, 1-chloroacridine, 2,3-dichloroacridine, 10-butyl-2-chloroacridine-9 (10H) -one, 10-propyl-2 -Chloroacridin-9 (10H) -one, 10-butyl-2-chloroacridine-9 (10H) -one 1,2-bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, 1,4-bis (9-acridinyl) butane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane, 9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) Undecane, 1,12-bis (9-acridinyl) dodecane, 1,14-bis (9-acridinyl) tetradecane, 1,16-bis (9-acridinyl) hexadecane, 1,18-bis (9-acridinyl) octadecane, 1,20-bis (9-acridinyl) eicosane, 1,3-bis (9-acridinyl) -2-thiapropane, 1,5-bis (9-acridinyl) -3-thiapentane 7-methyl-benzo [c] acridine 7-ethyl-benzo [c] acridine, 7-propyl-benzo [c] acridine, 7-butyl-benzo [c] acridine, 7-pentyl-benzo [c] acridine, 7-hexyl-benzo [c] acridine 7-heptyl-benzo [c] acridine, 7-octyl-benzo [c] acridine, 7-nonyl-benzo [ c) acridine, 7-decyl-benzo [c] acridine, 7-undecyl-benzo [c] acridine, 7-dodecyl-benzo [c] acridine, 7-tridecyl-benzo [c] acridine, 7-tetradecyl-benzo [ c] acridine, 7-pentadecyl-benzo [c] acridine, 7-hexadecyl-benzo [c] acridine, 7-heptadecyl-benzo [c] acridine, 7-octadecyl-benzo [c] acridine, 7-nonadecyl-benzo [C] acridine, 1,1-bis (7-benzo [c] acridinyl) methane, 1,2-bis (7-benzo [c] acridinyl) ethane, 1,3-bis (7-benzo [c] acridinyl ) Propane, 1,4-bis (7-benzo [c] acridinyl) butane, 1,5-bis (7-benzo [c] actene Dinyl) pentane, 1,6-bis (7-benzo [c] acridinyl) hexane, 1,7-bis (7-benzo [c] acridinyl) heptane, 1,8-bis (7-benzo [c] acridinyl) Octane, 1,9-bis (7-benzo [c] acridinyl) nonane, 1,10-bis (7-benzo [c] acridinyl) decane, 1,11-bis (7-benzo [c] acridinyl) undecane, 1,12-bis (7-benzo [c] acridinyl) dodecane, 1,13-bis (7-benzo [c] acridinyl) tridecane, 1,14-bis (7-benzo [c] acridinyl) tetradecane, 15-bis (7-benzo [c] acridinyl) pentadecane, 1,16-bis (7-benzo [c] acridinyl) hexadecane, 1,17-bis (7-benzo c] acridinyl) heptadecane, 1,18-bis (7-benzo [c] acridinyl) octadecane, 1,19-bis (7-benzo [c] acridinyl) nonadecane, 1,20-bis (7-benzo [c] Acridinyl) eicosane, 7-phenyl-benzo [c] acridine, 7- (2-chlorophenyl) -benzo [c] acridine, 7- (4-methylphenyl) -benzo [c] acridine, 7- (4-nitro Phenyl) -benzo [c] acridine, 1,3-bis (7-benzo [c] acridinyl) benzene, 1,4-bis (7-benzo [c] acridinyl) benzene, 7- [1-propene-3- Yl (benzo [c] acridine)], 7- [1-ethylpentyl- (benzo [c] acridine)], 7- [8-heptadecenyl- (benzo [c] a Klysine)], 7,8-diphenyl-1,14-bis (7-benzo [c] acridinyl) tetradecane, 1,2-bis (7-benzo [c] acridinyl) ethylene, 1-methyl-1,2- Bis (7-benzo [c] acridinyl) ethylene, 7-styryl-benzo [c] acridine, 7- (1-propenyl) -benzo [c] acridine, 7- (1-pentenyl) -benzo [c] acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridyl) acridine, 9- (4-pyrimidinyl) acridine, 9- (2-pyrazinyl) acridine, 9 (5-methyl) -2-pyrazinyl) acridine, 9- (2-quinolinyl) acridine, 9- (2-pyridyl) -2-methyl-acridine, 9- (2-pyridyl) -2-e Luacridine, 9- (3-pyridyl) -2-methyl-acridine, 9- (3-pyridyl) -2,4-diethyl-acridine, 3,6-diamino-acridine sulfonate, 3,6-bis- ( Dimethylamino) -acridine sulfonate, 3,6-diamino-10-methyl-acridinium chloride, 9-acridinecarboxylic acid and the like.

Examples of the acylphosphine compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO; manufactured by BASF), isobutyryl-methylphosphinic acid methyl ester, isobutyryl-phenylphosphinic acid methyl ester, and pivaloyl-phenylphosphinic acid methyl. Ester, 2-ethylhexanoyl-phenylphosphinic acid methyl ester, pivaloyl-phenylphosphinic acid isopropyl ester, p-toluyl-phenylphosphinic acid methyl ester, o-toluyl-phenylphosphinic acid methyl ester, 2,4-dimethylbenzoyl-phenyl Phosphinic acid methyl ester, p-tert-butylbenzoyl-phenylphosphinic acid isopropyl ester, acryloyl-phenylphosphite Acid methyl ester, isobutyryl-diphenylphosphine oxide, 2-ethylhexanoyl-diphenylphosphine oxide, o-toluyl-diphenylphosphine oxide, p-tertiarybutylbenzoyl-diphenylphosphine oxide, 3-pyridylcarbonyl-diphenylphosphine oxide, acryloyl- Diphenylphosphine oxide, benzoyl-diphenylphosphine oxide, pivaloyl-phenylphosphinic acid vinyl ester, adipoyl-bis-diphenylphosphine oxide, pivaloyl-diphenylphosphine oxide, p-toluyl-diphenylphosphine oxide, 4- (tertiarybutyl) -benzoyl- Diphenylphosphine oxide, 2-methylbenzoyl-diphenylphosphine Oxide, 2-methyl-2-ethylhexanoyl-diphenylphosphine oxide, 1-methyl-cyclohexanoyl-diphenylphosphine oxide, pivaloyl-phenylphosphinic acid methyl ester and pivaloyl-phenylphosphinic acid isopropyl ester, 4-octylphenylphosphine oxide Terephthaloyl-bis-diphenylphosphine oxide, 1-methyl-cyclohexylcarbonyldiphenylphosphine oxide, versatoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-diisobutoxyphenylphosphine oxide, bis (2 , 4,6-Trimethylbenzoyl) phenylphosphine oxide (Irgacure 819; manufactured by BASF), bis (2,4,6-trimethylbenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis ( 2,6-dichloro-3,4,5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methyl- 1-naphthoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2-naphthylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2 -Methyl-1-naphthoyl) -2,5-dimethylphenylphospho Fin oxide, bis (2-methoxy-1-naphthoyl) -4-ethoxyphenylphosphine oxide, bis (2-chloro-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dioctyloxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4- Diisopropoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dihexyloxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2-propoxy-4-methylphenylphosphine Oxide, bis (2 4,6-trimethylbenzoyl) -2,4-diisopentyloxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine Oxide, bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-biphenylylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide Bis (2,6-dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl -Pencil And phosphine oxide (CGI403), 6-trimethylbenzoyl-ethyl-phenyl-phosphinate (SPEEDCURE TPO-L; manufactured by Lambson), and the like.

Examples of the oxime ester compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl-9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl]. -6-benzoyl-9H-carbazol-3-yl-octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethane- 1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime , Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9- Ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl- 4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2 -Methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like.

Examples of the thermal radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (methylisobutyrate), 2,2′-azobis-2,4-dimethylvaleronitrile, Azo initiators such as 1′-azobis (1-acetoxy-1-phenylethane); benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butylperoxypivalate, di (4-t-butylcyclohexyl) ) Peroxide initiators such as peroxydicarbonate, and persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. These can be used alone or in combination of two or more.

In the curable composition of the present invention, since the curability and the adhesion of the cured product are improved, the radical polymerization initiator (B) is a total of 100 of the radical polymerizable component (A) and the cationic polymerizable component (C). The amount is preferably 1 to 10 parts by mass, more preferably 2 to 5 parts by mass with respect to parts by mass.

The cationic polymerizable component (C) is a compound that is polymerized or crosslinked by a cationic polymerization initiator activated by irradiation with active energy rays or heating, and is an essential component of an alcohol having 11 or more carbon atoms. In addition to glycidyl ether, aromatic epoxy compound (C1), aliphatic epoxy compound (C2), alicyclic epoxy compound (C3), oxetane compound (C4), vinyl ether compound (C5), and the following formula (I) A polymer obtained from a monomer represented by formula (II), a polymer obtained from a monomer represented by formula (II) below, and two or more monomers selected from monomers represented by formula (I) below A polymer obtained from the body, a polymer obtained from two or more monomers selected from monomers represented by the following formula (II), or a single monomer represented by the following formula (I) And a polymer (C6) having a weight average molecular weight of 1,000 to 30,000 selected from the group of polymers obtained from monomers represented by the following formula (II) (hereinafter also referred to as polymer (C6)), etc. Can be used.

(Wherein X is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, or a carbon atom) An alicyclic hydrocarbon group of 6 to 10 or a hydrogen atom in these groups substituted with one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group is there.)

(Wherein R ¹ represents a hydrogen atom, a methyl group or a halogen atom, and X ′ represents an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a group having 6 to 10 carbon atoms) An alicyclic hydrocarbon group or a hydrogen atom in these groups is substituted with one or more groups selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group and a carboxyl group.

Examples of the glycidyl ether of alcohol having 11 or more carbon atoms include triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, One or more alkylene oxides such as glycidyl ethers of polyhydric alcohols such as diglycidyl ether of polypropylene glycol and dicyclopentadiene dimethanol diglycidyl ether, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin And polyglycidyl ether of polyether polyol obtained by adding. Here, the glycidyl ether of an alcohol having 11 or more carbon atoms means that the residue part has 11 or more carbon atoms in the glycidyl ether obtained by adding a glycidyl group to the alcohol. As the glycidyl ether of alcohol having 11 or more carbon atoms, those having a saturated condensed ring are preferable because the curability and adhesion of the cured product are improved.

As the glycidyl ether of alcohol having 11 or more carbon atoms, commercially available products can be used. For example, Denacol EX-171, Denacol EX-192, Denacol EX-830, Denacol EX-832, Denacol EX- 841, Denacol EX-861, Denacol EX-931 (manufactured by Nagase ChemteX Corp.); Epolite M-1230, Epolite 400E, Epolite 400P (Kyoeisha Chemical Co., Ltd.), Adeka Glycilol ED-506, Adeka Resin EP-4088S (manufactured by ADEKA Corporation) and the like.

The aromatic epoxy compound (C1) refers to an epoxy compound containing an aromatic ring. Specific examples of the aromatic epoxy compound (C1) include monohydric / polyglycidyl etherified products of polyhydric phenols having at least one aromatic ring such as phenol, cresol, butylphenol, or alkylene oxide adducts thereof, such as bisphenol A. , Bisphenol F, or a glycidyl etherified compound or epoxy novolac resin of a compound obtained by further adding an alkylene oxide to these; a mono / polyglycidyl etherified compound of an aromatic compound having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, or catechol; Glycidyl etherified products of aromatic compounds having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol, phenyldibutanol; phthalic acid, terephthalic acid, trimellitic acid Glycidyl esters of polybasic acid aromatic compound having two or more carboxylic acids, glycidyl esters of benzoic acid, epoxides and the like of styrene oxide or divinylbenzene.

As the aromatic epoxy compound (C1), 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 Chem Tex Co., Ltd.); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (DIC Corporation) ); ESN-475V ( YX8800 (manufactured by Mitsubishi Chemical Corporation); Marproof G-0105SA, Marproof G-0130SP (manufactured by NOF Corporation); Epicron N-665, Epicron 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 (Japan) Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (manufactured by ADEKA); TECHMORE VG-3101L (manufactured by Printec Co., Ltd.) Etc. As the aromatic epoxy compound (C1), a polyfunctional one is preferable because of its excellent curability.

The aliphatic epoxy compound (C2) refers to an epoxy compound that is not classified as an aromatic epoxy compound (C1) or an alicyclic epoxy compound (C3) described later. Specific examples of the aliphatic epoxy compound (C2) include monofunctional epoxy compounds such as glycidyl ethers of aliphatic alcohols and glycidyl esters of alkyl carboxylic acids, and polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. And polyfunctional epoxy compounds such as polyglycidyl esters of aliphatic long-chain polybasic acids. Representative compounds include glycidyl ethers of polyhydric alcohols such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and aliphatic long-chain dibases. The diglycidyl ester of an acid is mentioned. Furthermore, monoglycidides of higher aliphatic alcohols, further ethers, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized polybutadiene and the like can be mentioned. As the aliphatic epoxy compound (C2), a glycidyl etherified product of an aliphatic alcohol other than a glycidyl ether of an alcohol having 11 or more carbon atoms, a polyglycidyl etherified product of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof, Viscosity, coatability and reactivity are improved, which is preferable.

As the aliphatic epoxy compound (C2), commercially available products can be used. For example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX- 313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, 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 X-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.), Adeka Glycilol ED-503, Adeka Glycilol ED-503G, Adeka Glycilol ED 506, Adekaglycil ED-523T, Adeka Resin EP-4088S (manufactured by ADEKA Corporation) and the like.

The alicyclic epoxy compound (C3) refers to a compound in which an oxirane ring is directly bonded to a saturated ring without a bonding group. Specific examples of the alicyclic epoxy compound (C3) are obtained by epoxidizing a polyglycidyl etherified product of a polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. Examples include cyclohexene oxide and cyclopentene oxide-containing compounds. 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-methylcyclohexane Ruboxylate, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadiene diepoxide , Ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy Examples include 2-epoxyethylcyclohexane, α-pinene oxide, limonene dioxide and the like.

Examples of the alicyclic epoxy compound (C3) include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, or 3,4-epoxy-1-methylcyclohexyl-3,4. -Epoxy-1-methylhexanecarboxylate is preferred from the viewpoint of improving adhesion.

Commercially available products can be used as the alicyclic epoxy compound (C3), and examples thereof include Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxa such as Id 3000 (manufactured by Daicel Corporation), and the like.

Examples of the oxetane compound (C4) 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, , 6-bis (3-ethyl-3-oxetanylmethoxy) hexane and other bifunctional aliphatic oxes Compounds, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl- And monofunctional oxetane compounds such as 3- (hydroxymethyl) oxetane and 3-ethyl-3- (chloromethyl) oxetane. These can be used singly or in combination of two or more, and a polyfunctional oxetane compound is preferable because the curability and adhesion of the cured product are increased.

As the oxetane compound (C4), commercially available products can be used. For example, Aron oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (Toagosei Co., Ltd.) Co., Ltd.), Etanacol OXBP, OXTP (manufactured by Ube Industries, Ltd.) and the like.

Examples of the vinyl ether compound (C5) 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, Examples include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-cyclohexanedimethanol divinyl ether, and the like.

Commercially available products may be used as the vinyl ether compound (C5), and examples thereof include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.).

In the cationically polymerizable component (C), the content of glycidyl ether of alcohol having 11 or more carbon atoms improves the adhesion and low moisture permeability of the cured product, so that the radically polymerizable component (A) and the cationically polymerizable component are improved. The amount is preferably 25 to 45 parts by weight, more preferably 28 to 43 parts by weight, based on 100 parts by weight in total with the component (C). In addition to glycidyl ether of alcohol having 11 or more carbon atoms, which is an essential component, aromatic epoxy compound (C1), aliphatic epoxy compound (C2), alicyclic epoxy compound (C3), oxetane compound (C4) The vinyl ether compound (C5) and the polymer (C6) are used in a proportion of 1 to 10 parts by weight of the aromatic epoxy compound (C1) with respect to 100 parts by mass in total of the radical polymerizable component (A) and the cationic polymerizable component (C). 20 parts by mass, aliphatic epoxy compound (C2) 20-40 parts by mass, alicyclic epoxy compound (C3) 0-20 parts by mass, oxetane compound (C4) 10-30 parts by mass, vinyl ether compound (C5) 0-20 The amount by weight and the polymer (C6) of 0 to 15 parts by weight are preferred because the viscosity, coatability, reactivity and curability are improved. The component (C) is 20 to 50 parts by mass with respect to a total of 100 parts by mass of the components (A) and (C).

In addition to the radical polymerizable component (A) and the cationic polymerizable component (C), a compound having an epoxy group and an ethylenically unsaturated group can also be used. Examples of these compounds include epoxy acrylate or epoxy methacrylate. Specifically, conventionally known aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins and the like, acrylic acid or methacrylic acid. Is an acrylate obtained by reacting Among these epoxy acrylates or epoxy methacrylates, particularly preferred are acrylates or methacrylates of glycidyl ethers of alcohols.

The cationic polymerization initiator (D) according to the curable composition of the present invention may be any compound that can release a substance that initiates cationic polymerization by irradiation with active energy rays or heating. Is preferably a double salt which is an onium salt that releases a Lewis acid by irradiation with active energy rays, or a derivative thereof. Representative examples of such compounds include the following general formula:
[A] ^{r +} [B] ^r-
And cation and anion salts represented by the formula:

Here, the cation [A] ^{r +} is preferably onium, and the structure thereof is, for example, the following general formula:
[(R ² ) _a Q] ^{r +}
Can be expressed as

Further, R ² is an organic group having 1 to 60 carbon atoms and any number of atoms other than carbon atoms. a is an integer of 1 to 5. The a R ^{2 s} 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, and 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 (where N = N is treated as a valence of 0).

The anion [B] ^r- is preferably a halide complex, and the structure thereof is, for example, the following general formula:
[LY _b ] ^r-
Can be expressed as

Here, L is a metal or metalloid which is a central atom of a 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, the relationship r = b−p needs to be established.

Specific examples of the anion [LY _b ] ^{r- in} the above general formula include halogen ion, perchlorate ion (ClO ₄ ) ⁻ , tetrafluoroborate ion (BF ₄ ) ⁻ , hexafluorophosphate ion (PF ₆ ). ^- , Inorganic ions such as hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarsenate (AsF ₆ ) ^- , hexachloroantimonate (SbCl ₆ ) ^- ; trifluoromethanesulfonate ion, methanesulfonate ion, butanesulfonate ion , fluorosulfonic acid ion (FSO ₃₎ ^-, a benzenesulfonate anion, toluenesulfonate ion, trinitrobenzene sulfonate ion, camphor sulfonate ion, nonafluorobutanesulfonate ion, such as hexa decafluoro octanoic acid ion scan Phosphonic acid ion; boric acid ion such as tetraaryl borate ion, tetrakis (pentafluorophenyl) borate ion; methane carboxylate ion, ethane carboxylate ion, propane carboxylate ion, butane carboxylate ion, octane carboxylate ion, trifluoromethanecarboxyl Carboxylate ions such as acid ion, benzenecarboxylate ion, p-toluenecarboxylate ion; trifluoromethylsulfite ion (CF ₃ SO ₃ ) ⁻ , methylsulfate ion (CH ₃ OSO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) Imido ion, tris (trifluoromethanesulfonyl) methide ion, (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , ((CF ₃ ) ₂ C ₆ In addition to H ₃ ) ₄ Ga ^— , there may be mentioned those selected from the following group.

Further, the anion [B] ^r- is represented by the following general formula:
[LY _b-1 (OH)] ^r-
The thing of the structure represented by can also be used preferably. L, Y, and b are the same as described above. Other anions that can be used include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethylsulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , and toluenesulfonate anion. , Trinitrobenzenesulfonate anion, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.

In the curable composition of the present invention, among the onium salts, it is particularly effective to use the following aromatic onium salts (a) to (c). Among these, one of them can be used alone, or two or more of them can be mixed and used.

(I) Aryl diazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, etc.

(B) Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, and tricumyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt

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

Other preferable examples include (η ⁵ -2,4-cyclopentadien-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 (salicylaldehyde) aluminum, and silanols such as triphenylsilanol A mixture of: thiophenium salt, thioranium salt, benzylammonium, pyridinium salt, hydrazinium salt, etc .; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine; 1,2-diaminocyclohexane, 1,4-diamino -3,6-Di Cycloaliphatic polyamines such as tilcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone; the above polyamines and phenylglycidyl ether, butylglycidyl ether, bisphenol A-diglycidyl Polyepoxy addition-modified products produced by reacting ethers, glycidyl ethers such as bisphenol F-diglycidyl ether, or various epoxy resins such as glycidyl esters of carboxylic acids; the above organic polyamines and phthalates An amidation-modified product produced by reacting a carboxylic acid such as acid, isophthalic acid or dimer acid by a conventional method; Mannich-modified products produced by reacting phenols having at least one aldehyde-reactive site with nuclei such as diol, cresol, xylenol, tert-butylphenol, and resorcin; Acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methyl Aliphatic dicarboxylic acids such as pentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid; phthalic acid, terephthalic acid, isophthalic acid Aromatic dicarboxylic acids such as acid and naphthalenedicarboxylic acid; cyclohexanedicarboxylic acid Alicyclic dicarboxylic acids such as: trimellitic acid, trimesic acid, trimeric acid such as trimer of castor oil fatty acid; tetracarboxylic acids such as pyromellitic acid] acid anhydrides; dicyandiamide, imidazoles, carboxylic acid ester, sulfone Examples include acid esters and amine imides.

Of these, aromatic iodonium salts, aromatic sulfonium salts, and iron-arene complexes are preferably used from the viewpoint of practical use and improvement of photosensitivity, and an aromatic sulfonium salt having the following structure is converted into a cationic polymerization initiator (D ) It is more preferable to contain at least 0.1% by mass with respect to 100% by mass.

In the curable composition of the present invention, the proportion of the cationic polymerization initiator (D) used is 1 to 10 parts by weight, preferably 100 parts by weight in total of the radical component (A) and the cationic polymerization component (C). 2 to 5 parts by mass. If the amount is too small, curing tends to be insufficient, and if the amount is too large, various physical properties such as the water absorption rate and the strength of the cured product may be adversely affected.

In the curable composition of the present invention, a sensitizer and / or a sensitization aid can be further used as 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 (D) and promotes the polymerization initiation reaction by the cationic polymerization initiator (D). The sensitization aid is a compound that further promotes the action of the sensitizer.

Sensitizers and sensitizers include anthracene compounds and naphthalene compounds.

Examples of the anthracene compound include those represented by the following formula (IIIa).

In the formula (IIIa), R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 12 carbon atoms, and R ⁵ represents a hydrogen atom. Or an alkyl group having 1 to 6 carbon atoms.

Specific examples of the anthracene compound represented by the formula (IIIa) 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-dipropoxyanthra 2-methyl- or 2-ethyl-9,10-diisopropoxyanthracene, 2-methyl- or 2-ethyl-9,10-dibutoxyanthracene, 2-methyl- or 2-ethyl-9,10- Examples include dipentyloxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene.

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

Here, in formula (IIIb), R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms.

Specific examples of the naphthalene compound represented by the above formula (IIIb) 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, 1,4-dibutoxynaphthalene and the like.

The use ratio of the sensitizer and the sensitization aid to the cationic polymerizable component (C) is not particularly limited, and may be used at a generally normal use ratio within a range not impairing the object of the present invention. From the viewpoint of improving curability, the sensitizer and the sensitization agent are each preferably 0.1 to 3 parts by mass or more with respect to 100 parts by mass of the polymerizable component (C).

In the curable composition of the present invention, a silane coupling agent can be used as necessary. Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkyl-functional alkoxysilanes, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and other alkenyl-functional alkoxysilanes, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ Epoxy-functional alkoxysilanes such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl) -γ Aminofunctional alkoxysilanes such as aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, titanium Titanium alkoxides such as tetraisopropoxide and titanium tetranormal butoxide, titanium chelates such as titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethyl acetoacetate), zirconi Arm tetraacetyl acetonate, zirconium chelates such as zirconium tributoxy monoacetylacetonate, zirconium acylates such as zirconium tributoxy monostearate, an isocyanate silane such as methyl triisocyanate silane.

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.

In the curable composition of the present invention, the properties of the cured product can be improved by using a thermoplastic organic polymer as 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, styrene- (meth) acrylic acid copolymer, Examples include (meth) acrylic acid-methyl methacrylate copolymer, glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.

The curable composition of the present invention is not particularly limited, and a solvent that can dissolve or disperse the components (A), (B), (C), and (D) that are usually used can be used. , Ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxy Ether solvents such as ethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol, etc. Beauty treatment System solvents; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol and amyl alcohol; ethylene glycol monomethyl acetate; Ether ester solvents such as ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate; benzene, toluene, BTX solvents such as xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane; turpentine oil, D-limonene, pinet Terpene hydrocarbon oils such as mineral spirits, paraffinic solvents such as mineral spirits, Swazol # 310 (Cosmo Matsuyama Petroleum), Solvesso # 100 (Exxon Chemical), carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2- Halogenated aliphatic hydrocarbon solvents such as dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Propylene carbonate, carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N- Examples thereof include dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water and the like, and these solvents can be used as one or a mixture of two or more.

In the curable composition of the present invention, the water content is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less because the curability, adhesiveness, and liquid storage stability are improved. Too much moisture is not preferred because it may cause cloudiness or components may precipitate.

In the curable composition of the present invention, if necessary, the UV-absorbing agent is inactivated at room temperature, and the protective group is released by heating to a predetermined temperature, light irradiation, acid, etc. and activated. In addition, a compound exhibiting ultraviolet absorbing ability can also be used.

In addition, as long as the effects of the present invention are not impaired, coloring agents such as polyols, inorganic fillers, organic fillers, pigments, dyes, antifoaming agents, thickeners, surfactants, leveling agents, difficulty Various resin additives such as flame retardants, thixotropic agents, diluents, plasticizers, stabilizers, polymerization inhibitors, UV absorbers, antioxidants, antistatic agents, flow regulators, adhesion promoters, etc. may be added. it can.

The curable composition of the present invention is applied onto a support substrate by a known means such as a roll coater, a curtain coater, various types of printing, and immersion. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

The material for the support substrate is not particularly limited and those usually used can be used. For example, inorganic materials such as glass; diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetylpropionyl cellulose Polyester; Polyurethane; Epoxy resin; Polycarbonate; Polyethylene terephthalate, Polyethylene naphthalate, Polybutylene terephthalate, Poly-1,4-cyclohexanedimethylene terephthalate, Polyethylene-1,2-diphenoxyethane -4,4'-dicarboxylate, polyester such as polybutylene terephthalate; polystyrene; polyethylene, polypropylene, polymethylpentene, etc. Polyolefins; Vinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; Acrylic resins such as polymethyl methacrylate and polyacrylate; Polycarbonates; Polysulfones; Polyether sulfones; Polyether ketones; Polyether imides; Examples thereof include polymer materials such as norbornene resin and cycloolefin polymer (COP).

Note that 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, laser treatment and the like.

In the method of curing the curable composition of the present invention by irradiation with active energy rays, examples of the active energy rays include ultraviolet rays, electron beams, X-rays, radiation, high frequencies, and the like, and ultraviolet rays are 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 for the method of curing the curable composition of the present invention by heating are 70 to 250 ° C. and 1 to 100 minutes. After performing pre-baking (PAB), pressurization and post-baking (PEB) may be performed, or baking may be performed at several different temperatures. The heating conditions vary depending on the type and mixing 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. Thereafter, in order to cure the coating film, a cured film can be obtained by heat treatment at 180 to 250 ° C., preferably 200 to 250 ° C., for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate.

Specific applications of the curable composition of the present invention or a cured product thereof include adhesives, glasses, optical materials represented by imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, printing Plates, color TVs, PC monitors, personal digital assistants, digital cameras, organic EL, touch panels and other display elements, insulating varnishes, insulating sheets, laminates, printed boards, semiconductor devices, LED packages, liquid crystal inlets, organic Sealants for EL, optical elements, electrical insulation, electronic parts, separation membranes, molding materials, putty, glass fiber impregnating agents, sealants, passivation films for semiconductors and solar cells, interlayers Insulating film, protective film, prism lens sheet used for backlight of liquid crystal display device, Fresnel label used for screen of projection TV, etc. Lens parts of lens sheets such as lens sheets, lenticular lens sheets, or backlights using such sheets, optical lenses such as micro lenses, optical elements, optical connectors, optical waveguides, castings for optical modeling, etc. Can be mentioned.

As a display device, a transparent support, an undercoat layer, an antireflection layer, a polarizing element layer, a retardation layer, a birefringence layer, a light scattering layer, a hard coating layer, a lubricating layer, a protective layer, etc., as necessary The film which consists of hardened | cured material of this invention can be used for each layer.

Hereinafter, the present invention will be described in more detail using examples and comparative examples. In Examples and Comparative Examples, “part” means “part by mass”.

[Examples 1 to 11, Comparative Examples 1 to 4]
The components shown in [Table 1] to [Table 3] below were mixed thoroughly to obtain curable compositions of Examples 1 to 11 and Comparative Examples 1 to 4. About each obtained curable composition, the evaluation regarding a viscosity and adhesiveness was performed according to the following procedure.

(viscosity)
About each obtained curable composition, the viscosity was measured with the E-type viscosity meter in 25 degreeC. The results are also shown in [Table 1] to [Table 3].

(Adhesion)
Each obtained curable composition was applied to one acrylic film (Sumitomo Chemical Co., Ltd .: Technoloy 125S001) subjected to corona discharge treatment, and then subjected to another corona discharge treatment COP ( Cycloolefin polymer, manufactured by Nippon Zeon Co., Ltd .: Product No. ZEONOR Film 14-060) A film and a laminator were bonded together, and an electrodeless ultraviolet lamp was used to irradiate light equivalent to 1000 mJ / cm ² through the COP film. And bonded to obtain a test piece. About the obtained test piece, the 90 degree | times peel test was done. The initial adhesion is a value after 3 minutes from the exposure, and the adhesion after curing is a value after 6 hours or more have elapsed from the exposure. Evaluation was performed according to the following criteria.

<Initial adhesion>
A: An adhesive force of more than 0.5 N / 2 cm is shown.
X: Adhesive strength of 0.5 N / 2 cm or less is shown.
<Adhesion after curing>
(Circle): The adhesive force exceeding 1.5 N / 2cm is shown.
X: Adhesive strength of 1.5 N / 2 cm or less is shown.

(Moisture permeability)
Each of the obtained curable compositions was applied to a single corona discharge-treated acrylic film (Sumitomo Chemical Co., Ltd .: Technoloy 75S001), and then 500 mJ / cm using an electrodeless ultraviolet lamp. ^A test piece was obtained by irradiation with light corresponding to ² . Further, the test piece was left in a 23 ° C. (humidity 50%) environment for 6 hours or more. The moisture permeability of the obtained test piece was measured with a water vapor transmission rate measuring device 7002 (manufactured by ILLINOIS INSTRUMENTS, INC.). The test environment was 40 ° C./90% RH. Evaluation was performed according to the following criteria. The moisture permeability of the acrylic film alone was 50 g / m ² / day.
A: ≦ 40 g / m ² / day.
A: <50 g / m ² / day is indicated.
X: Indicates ≧ 50 g / m ² / day.

As the radical polymerizable component (A), the following compounds (A1-1) to (A1-5) and (A2-1) were used.
Compound A1-1: 1,6-hexanediol diacrylate Compound A1-2: Biscote # 150 (tetrahydrofurfuryl acrylate; manufactured by Osaka Organic Chemical Co., Ltd.)
Compound A1-3: NK ester A-DCP (tricyclodecane dimethanol diacrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.)
Compound A1-4: NK ester APG-200 (tripropylene glycol diacrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.)
Compound A1-5: A-9300S (polyfunctional acrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.)
Compound A2-1: NK ester BPE-500 (ethoxylated bisphenol A dimethacrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.)

The following compound (B-1) was used as the radical polymerization initiator (B).
Compound B1-1: Irgacure 184 (manufactured by BASF)

The following compounds (C1-1), (C2-1) to (C2-4), (C3-1) and (C6-1) were used as the cationic polymerizable component (C).
Compound C1-1: EP-4100 (bisphenol A type diglycidyl ether: manufactured by ADEKA Corporation)
Compound C2-1: Adeka Resin EP-4088L (diglycidyl ether of alcohol having 11 or more carbon atoms; manufactured by ADEKA Corporation)
Compound C2-2: 1,4-butanediol diglycidyl ether compound C2-3: Neopentyl glycol diglycidyl ether compound C2-4: Epiklone HP-7200 (dicyclopentadiene type glycidyl ether; manufactured by DIC Corporation)
Compound C3-1: Celoxide 2021P (alicyclic epoxy compound; manufactured by Daicel Corporation)
Compound C6-1: copolymer of 70 parts by weight of methyl methacrylate and 30 parts by weight of glycidyl methacrylate (weight average molecular weight 8000)

The following compound D-1 was used as the cationic polymerization initiator (D).
Compound D-1: 50% propylene carbonate solution of a mixture of two compounds represented by the following structure

[Table 1] to [Table 3] show that the curable composition of the present invention is excellent in curability and adhesion of the cured product.

Claims

Radical polymerizable component (A) 50-80 parts by mass, radical polymerization initiator (B) 1-10 parts by mass, cationic polymerizable component (C) 20-50 parts by mass and cationic polymerization initiator (D) 1-10 parts by mass A total of 100 parts by mass of the radical polymerizable component (A) and the cationic polymerizable component (C),
The curable composition characterized in that the cationic polymerizable component (C) contains a glycidyl ether of alcohol having 11 or more carbon atoms.
The radical polymerizable component (A) is an acrylate ester of an alcohol having 2 to 60 carbon atoms or an methacrylic acid ester (A1) of an alcohol having 2 to 60 carbon atoms, or an acrylate ester or phenol of a phenol compound. The curable composition of Claim 1 containing the methacrylic acid ester (A2) of a compound.
A method for producing a cured product, wherein the curable composition according to any one of claims 1 and 2 is cured by irradiation with active energy rays.
A method for producing a cured product, wherein the curable composition according to any one of claims 1 and 2 is cured by heating.
Hardened | cured material of the curable composition as described in any one of Claim 1 or 2.
An adhesive comprising the curable composition according to any one of claims 1 and 2.