JP2009127023A - Photocurable composition for production of photocurable pressure-sensitive adhesive and photocurable pressure-sensitive adhesive sheet - Google Patents
Photocurable composition for production of photocurable pressure-sensitive adhesive and photocurable pressure-sensitive adhesive sheet Download PDFInfo
- Publication number
- JP2009127023A JP2009127023A JP2007306854A JP2007306854A JP2009127023A JP 2009127023 A JP2009127023 A JP 2009127023A JP 2007306854 A JP2007306854 A JP 2007306854A JP 2007306854 A JP2007306854 A JP 2007306854A JP 2009127023 A JP2009127023 A JP 2009127023A
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- Prior art keywords
- photocurable
- adhesive
- composition
- group
- meth
- Prior art date
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- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 97
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000000853 adhesive Substances 0.000 claims abstract description 121
- 230000001070 adhesive effect Effects 0.000 claims abstract description 118
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims abstract description 19
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 60
- 239000000463 material Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 15
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000002313 adhesive film Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000011907 photodimerization Methods 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000001723 curing Methods 0.000 description 36
- 239000010408 film Substances 0.000 description 34
- -1 methacryloyl group Chemical group 0.000 description 26
- 229920000139 polyethylene terephthalate Polymers 0.000 description 17
- 239000005020 polyethylene terephthalate Substances 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- 239000010703 silicon Substances 0.000 description 16
- 229910052710 silicon Inorganic materials 0.000 description 16
- 238000002156 mixing Methods 0.000 description 15
- 229920005862 polyol Polymers 0.000 description 15
- 150000003077 polyols Chemical class 0.000 description 15
- 229920002799 BoPET Polymers 0.000 description 14
- 238000000016 photochemical curing Methods 0.000 description 13
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 6
- 239000012788 optical film Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 239000011147 inorganic material Substances 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 description 4
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000006471 dimerization reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 101150065749 Churc1 gene Proteins 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 102100038239 Protein Churchill Human genes 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229960003424 phenylacetic acid Drugs 0.000 description 2
- 239000003279 phenylacetic acid Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- 229960000834 vinyl ether Drugs 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- HIYIGPVBMDKPCR-UHFFFAOYSA-N 1,1-bis(ethenoxymethyl)cyclohexane Chemical compound C=COCC1(COC=C)CCCCC1 HIYIGPVBMDKPCR-UHFFFAOYSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- SUDVPELGFZKOMD-UHFFFAOYSA-N 1,2-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(C(C)C)C(C(C)C)=CC=C3SC2=C1 SUDVPELGFZKOMD-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- JZLWSRCQCPAUDP-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;urea Chemical compound NC(N)=O.NC1=NC(N)=NC(N)=N1 JZLWSRCQCPAUDP-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- VDPSPUBXLOLDNB-UHFFFAOYSA-N 2-(1,3-dioxo-4,5,6,7-tetrahydroisoindol-2-yl)ethyl prop-2-enoate Chemical compound O=C1N(CCOC(=O)C=C)C(=O)C2=C1CCCC2 VDPSPUBXLOLDNB-UHFFFAOYSA-N 0.000 description 1
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- DSTZHSGHWUPNBW-UHFFFAOYSA-N 3-phenoxydodecyl prop-2-enoate Chemical group CCCCCCCCCC(CCOC(=O)C=C)OC1=CC=CC=C1 DSTZHSGHWUPNBW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
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- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
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- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
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- 238000006845 Michael addition reaction Methods 0.000 description 1
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Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、光硬化型粘接着剤製造用の光硬化型組成物に関し、これを使用した光硬化型粘接着シートに関するものであり、これら技術分野に属する。 The present invention relates to a photocurable composition for producing a photocurable adhesive, to a photocurable adhesive sheet using the composition, and belongs to these technical fields.
２つの材料を接着するための剤として、粘着剤は、液状の接着剤にはない特長を有している。
その特長の一つは流動しないことである。例えば、シート状の材料を別の固体に接着させる場合、予めシート状材料の接着させたい面に粘着剤を塗布しておけば、その状態で保管、運送及び加工することが可能となる。例えば、自動車の窓ガラスに貼り付ける紫外線カットフィルムは、その一方の面に予め粘着剤が塗布された形態で市販されている。このため、保管や運送が容易であり、又様々な形状に加工して、貼り付けることが可能である。
又、流動しないため、２つの材料を貼りあわせた際、隅の部分から液がはみ出さないという特長も有する。例えば、液晶ディスプレイやプロジェクションテレビ等の用途で光学フィルムを板状の材料に接着する場合、液状の接着剤を使用すると、隅の部分から接着剤がはみ出したり、逆に接着剤が足りないために隅の部分が接着されなかったりするといった問題が発生する。はみ出した場合、両方の材料がフィルム状であれば、隅の欠陥部分を切断して捨てることが比較的容易であるが、板状の場合は容易でなく、切断部分近傍での剥離や割れ等の欠陥を防ぐことが困難になる。しかし、このような光学フィルムに予め粘着剤を塗布しておき、離型フィルムを貼り付けて保護したものを使用すれば、フィルムの隅まで均一に貼り付けることができる。しかも、任意の時に、任意のサイズに切り出すことも可能となる。
さらに、流動しないため、凹凸を有する形状の凸部分のみを貼り付けることができるという特長を有する。粘着状態であれば、凸面の先端部が粘着剤の表面に接した状態、或いは粘着剤に少し食い込んだ状態で固定化することが可能であるが、液状の場合、凹面にも液が染み込むため、凹凸形状を残したまま貼り付ける場合には不向きである。
As an agent for bonding two materials, a pressure-sensitive adhesive has a feature not found in a liquid adhesive.
One of its features is that it does not flow. For example, when a sheet-like material is bonded to another solid, if a pressure-sensitive adhesive is previously applied to the surface of the sheet-like material to be bonded, it can be stored, transported and processed in that state. For example, an ultraviolet cut film to be attached to a window glass of an automobile is commercially available in a form in which an adhesive is previously applied to one surface thereof. For this reason, it is easy to store and transport, and it can be processed and pasted into various shapes.
Moreover, since it does not flow, it has the feature that the liquid does not protrude from the corner when two materials are bonded together. For example, when bonding an optical film to a plate-like material for applications such as liquid crystal displays and projection televisions, if a liquid adhesive is used, the adhesive will protrude from the corners, or conversely, the adhesive will be insufficient. There is a problem that corner portions are not adhered. When protruding, if both materials are film-like, it is relatively easy to cut and discard the defective part of the corner, but it is not easy if it is plate-like, peeling or cracking in the vicinity of the cut part, etc. It becomes difficult to prevent defects. However, if an adhesive is previously applied to such an optical film and a release film is applied and protected, the film can be uniformly applied to the corners of the film. Moreover, it is possible to cut out to any size at any time.
Furthermore, since it does not flow, it has the feature that only the convex part of the shape which has an unevenness | corrugation can be affixed. If it is in an adhesive state, it can be fixed in a state where the tip of the convex surface is in contact with the surface of the adhesive or in a state where it bites into the adhesive, but in the case of a liquid, the liquid soaks into the concave surface. It is unsuitable when pasting while leaving the uneven shape.
しかしながら、粘着剤は、貼り付け可能であるという本質的な性能を有するがために、必然的に軟らかい材料である。そのため、硬い接着剤に比べると、せん断方向の力に対して強度に劣ることが多い。
又、光学フィルムの接着等で、微細な凹凸形状の凸部分のみを別の被着体と貼り合せる場合、粘着剤では、荷重又は熱による力によって凹凸形状が粘着剤に埋没してしまい、希望する光学性能を発現することができなくなってしまう。そこで、貼り付け後に光照射すると硬くなる、所謂、光硬化型粘接着剤が必要とされる。例えば、液晶ディスプレイのレンズシートの凸面を、レンズ形状を保持したまま、導光板や拡散板等の板に接着する場合の好ましい方法として、板に粘接着剤を塗布した後、レンズの凸面を貼り合せ、最後に光照射して硬化させ、接着する方法が挙げられる。
このような背景から、近年、初期は粘着剤であるが、熱や光により硬くなって接着剤となる、いわゆる粘接着剤が注目されている。中でも、光照射で硬化する光硬化型粘接着剤は、熱硬化型に比べて、低エネルギー及び高生産性等の利点がある。
However, the adhesive is necessarily a soft material because it has the essential performance of being stickable. Therefore, compared to a hard adhesive, the strength is often inferior to the force in the shear direction.
In addition, when only a fine uneven-shaped convex part is bonded to another adherend by adhesion of an optical film or the like, with an adhesive, the uneven shape is buried in the adhesive by a force due to load or heat. It becomes impossible to express the optical performance. Therefore, a so-called photo-curing type adhesive that becomes hard when irradiated with light after bonding is required. For example, as a preferred method for adhering the convex surface of a lens sheet of a liquid crystal display to a plate such as a light guide plate or a diffusion plate while maintaining the lens shape, after applying an adhesive to the plate, the convex surface of the lens is A method of adhering, finally irradiating with light and curing and adhering may be mentioned.
From such a background, in recent years, attention has been focused on so-called adhesives, which are initially pressure-sensitive adhesives, but become hardened by heat and light to become adhesives. Among them, the photo-curing adhesive that cures by light irradiation has advantages such as low energy and high productivity as compared with the thermo-curing type.
粘接着剤用光硬化型組成物としては、具体的には、水酸基含有（メタ）アクリレート、エポキシ樹脂及び光カチオン重合開始剤からなる光カチオン硬化型粘接着剤組成物（特許文献１）や、ポリアクリレート等の粘着性重合体、エポキシ樹脂等のカチオン硬化性の化合物及び光カチオン重合開始剤からなる光カチオン硬化型粘接着剤組成物（特許文献２）が知られている（特許文献１及び特許文献２）。これら組成物は、光を照射するとカチオン重合が開始して硬化し、接着剤となるものである。
しかし、光カチオン硬化型粘接着剤組成物では、光カチオン重合そのものの欠点が避けられなかった。その欠点としては、高湿度環境下や吸水性又は親水性基材上では硬化性が悪くなること、光カチオン重合開始剤由来の酸、イオンに起因する腐食の問題等が挙げられる。
As a photocurable composition for adhesives, specifically, a photocationically curable adhesive composition comprising a hydroxyl group-containing (meth) acrylate, an epoxy resin, and a photocationic polymerization initiator (Patent Document 1). Also known is a photocationically curable adhesive composition (Patent Document 2) comprising a tacky polymer such as polyacrylate, a cationically curable compound such as an epoxy resin, and a photocationic polymerization initiator (Patent Document 2). Document 1 and Patent document 2). When these compositions are irradiated with light, cationic polymerization starts and cures to become an adhesive.
However, in the photocationic curable adhesive composition, the disadvantage of the photocationic polymerization itself cannot be avoided. The disadvantages include poor curability in a high humidity environment or on a water-absorbing or hydrophilic substrate, acid derived from a photocationic polymerization initiator, and corrosion problems caused by ions.
光ラジカル硬化型粘接着剤用の組成物としては、具体的には、アクリル系樹脂、ウレタン（メタ）アクリレート系オリゴマー、光重合開始剤及び架橋剤からなる組成物が知られている（特許文献３）。これは、光照射前は粘着剤であり、光照射により硬化して接着剤となる組成物である。すなわち、光照射前は粘着剤であるため、基材に室温で塗工するためには溶剤が必要である。しかし、溶剤を使用することは、環境問題や作業環境の点から好ましくないため、無溶剤の光硬化型粘接着剤が求められている。 Specifically, a composition comprising an acrylic resin, a urethane (meth) acrylate oligomer, a photopolymerization initiator, and a crosslinking agent is known as a composition for a photo-radical curable adhesive (patent) Reference 3). This is a pressure-sensitive adhesive before light irradiation, and is a composition that is cured by light irradiation and becomes an adhesive. That is, since it is a pressure-sensitive adhesive before light irradiation, a solvent is required for coating on a substrate at room temperature. However, since it is not preferable to use a solvent from the viewpoint of environmental problems and working environment, a solvent-free photo-curing adhesive is demanded.
室温で塗工可能な粘度の無溶剤の光硬化型粘接着剤を製造する方法としては、光硬化型組成物を基材に塗布した後、光を適量照射して半硬化状態とすることで、粘着状態を得る方法がある。この状態は半硬化状態であるため、被着体と貼り合せて再度光照射すると、残存モノマーが重合して硬化し（本硬化し）、接着剤となる。
本発明者らは、このようないわゆる粘接着剤としての機能を有し、かつ型転写工程にも使用可能な無溶剤（メタ）アクリル系光硬化型組成物を発明した（特許文献４）。この組成物は、半硬化の制御が容易で、本硬化後のせん断接着力に優れるという特長があり、型転写を必要としない光硬化型粘接着剤としても使用することができる。しかしながら、凹凸形状の凸部を接着する場合、半硬化工程での反応率が低いと、本硬化時に空気が存在する凹部の硬化性が悪くなるという問題があった。
As a method for producing a solvent-free photo-curing adhesive having a viscosity that can be applied at room temperature, after applying a photo-curable composition to a substrate, it is irradiated with an appropriate amount of light to be in a semi-cured state. There is a method for obtaining a sticky state. Since this state is a semi-cured state, when it is attached to the adherend and irradiated again with light, the remaining monomer is polymerized and cured (mainly cured) to become an adhesive.
The present inventors have invented a solvent-free (meth) acrylic photocurable composition that has such a function as a so-called adhesive and can also be used in a mold transfer process (Patent Document 4). . This composition has the features that it is easy to control semi-curing and has excellent shear adhesive strength after main curing, and can also be used as a photo-curing adhesive that does not require mold transfer. However, when bonding convex and concave portions, if the reaction rate in the semi-curing step is low, there is a problem that the curability of the concave portions where air is present during the main curing deteriorates.
本発明者らは、無溶剤で塗工性に優れ、紫外線を照射した後の半硬化の制御が容易で、本硬化後の接着力に優れ、被着体を貼り合せて本硬化する際に空気が存在する部分でも硬化性に優れた光硬化型粘接着剤製造のための光硬化型組成物、及びこれを使用した光硬化型粘接着シートを見出すため、鋭意検討を行ったのである。 The inventors of the present invention are solventless and excellent in coating properties, easy to control semi-curing after irradiation with ultraviolet light, excellent in adhesive strength after main curing, and when the target is bonded and main cured. Since we have conducted intensive studies to find a photocurable composition for producing a photocurable adhesive with excellent curability even in the presence of air, and a photocurable adhesive sheet using this composition. is there.
本発明者らは、前記課題を解決するためには、マレイミド基及びエチレン性不飽和基を含有する化合物、エチレン性不飽和基を含有する化合物及び光重合開始剤を含む組成物が有効であることを見出し、本発明を完成した。
以下、本発明を詳細に説明する。
尚、本明細書においては、アクリロイル基又はメタクリロイル基を（メタ）アクリロイル基と表し、アクリレート又はメタクリレートを（メタ）アクリレートと表す。
In order to solve the above-mentioned problems, the present inventors effectively use a compound containing a maleimide group and an ethylenically unsaturated group, a compound containing an ethylenically unsaturated group, and a photopolymerization initiator. As a result, the present invention has been completed.
Hereinafter, the present invention will be described in detail.
In the present specification, an acryloyl group or a methacryloyl group is represented as a (meth) acryloyl group, and an acrylate or methacrylate is represented as a (meth) acrylate.
本発明の組成物によれば、被着体の接着や光硬化型粘接着シートの製造において、塗工性に優れる。又、この場合において、溶剤や熱を使用することなく、適量の光照射によって被着体の接着を行うことができ、又光硬化型粘接着シートを製造することができる。このとき、本発明の組成物は半硬化の制御が容易であるため、製造時の安定性に優れる。さらに、被着体を貼り合せて再度光照射し本硬化したものの接着力に優れるため、様々な接着用途に使用可能である。しかも、空気が存在する部分の硬化性にも優れるため、凹凸形状を有する被着体の凸部分のみを接着させる用途に対して、特に好適に使用することができる。 According to the composition of this invention, it is excellent in applicability | paintability in the adhesion | attachment of a to-be-adhered body, or manufacture of a photocurable adhesive sheet. In this case, the adherend can be adhered by irradiation with an appropriate amount of light without using a solvent or heat, and a photocurable adhesive sheet can be produced. At this time, the composition of the present invention is excellent in stability during production because it is easy to control the semi-curing. Furthermore, since the adherend is bonded and light-irradiated again to be fully cured, it has excellent adhesive strength and can be used for various bonding applications. And since it is excellent also in the sclerosis | hardenability of the part in which air exists, it can use especially suitably with respect to the use which adhere | attaches only the convex part of the to-be-adhered body which has an uneven | corrugated shape.
本発明は、不飽和二重結合に置換基を有することもあるマレイミド基及び当該マレイミド基以外のエチレン性不飽和基を有する化合物（Ａ）〔以下、（Ａ）成分という〕、（Ａ）成分以外のエチレン性不飽和基を有する化合物（Ｂ）〔以下、（Ｂ）成分という〕及び光重合開始剤（Ｃ）〔以下、（Ｃ）成分という〕を含む光硬化型粘接着剤製造用の光硬化型組成物に関する。
以下、（Ａ）成分〜（Ｃ）成分について説明する。
The present invention relates to a compound having a maleimide group which may have a substituent in an unsaturated double bond and an ethylenically unsaturated group other than the maleimide group (hereinafter referred to as component (A)), component (A) For producing a photocurable adhesive containing a compound (B) having an ethylenically unsaturated group other than the above (hereinafter referred to as component (B)) and a photopolymerization initiator (C) [hereinafter referred to as component (C)] It relates to a photo-curable composition.
Hereinafter, the components (A) to (C) will be described.
１．（Ａ）成分
（Ａ）成分は、不飽和二重結合に置換基を有することもあるマレイミド基（以下、単にマレイミド基という）及びマレイミド基以外のエチレン性不飽和基を有する化合物である。
1. Component (A) The component (A) is a compound having an ethylenically unsaturated group other than a maleimide group (hereinafter simply referred to as a maleimide group) and a maleimide group that may have a substituent in the unsaturated double bond.
前記（Ａ）成分におけるマレイミド基としては、下記一般式（１）で表される基が好ましい。 The maleimide group in the component (A) is preferably a group represented by the following general formula (1).
〔但し、一般式（１）において、Ｒ1及びＲ2は、それぞれ独立して水素原子、ハロゲン原子、アルキル基若しくはアリール基を表すか、又はＲ1及びＲ2は一つとなって５員環若しくは６員環を形成する炭化水素基を表す。〕 [However, in General Formula (1), R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, or R 1 and R 2 are combined to form a 5-membered ring. Alternatively, it represents a hydrocarbon group forming a 6-membered ring. ]
アルキル基としては、炭素数４以下のアルキル基が好ましい。
アルケニル基としては、炭素数４以下のアルケニル基が好ましい。
アリール基としてはフェニル基等を挙げることができる。
一つとなって５員環若しくは６員環を形成する炭化水素基としては、基−ＣＨ2ＣＨ2ＣＨ2−、基−ＣＨ2ＣＨ2ＣＨ2ＣＨ2−、基−ＣＨ＝ＣＨ−ＣＨ2ＣＨ2−等が挙げられる。
As the alkyl group, an alkyl group having 4 or less carbon atoms is preferable.
As the alkenyl group, an alkenyl group having 4 or less carbon atoms is preferable.
A phenyl group etc. can be mentioned as an aryl group.
Examples of the hydrocarbon group that forms a 5-membered ring or 6-membered ring together include a group —CH 2 CH 2 CH 2 —, a group —CH 2 CH 2 CH 2 CH 2 —, and a group —CH═CH—CH 2. CH 2 — and the like can be mentioned.
一般式（１）におけるマレイミド基の好ましい具体例を、以下の式（３）〜式（８）に示す。 Preferred specific examples of the maleimide group in the general formula (1) are shown in the following formulas (3) to (8).
アルキル基としては、炭素数４以下のアルキル基が好ましい。一つとなって５員環若しくは６員環を形成する飽和の炭化水素基としては、基−ＣＨ2ＣＨ2ＣＨ2−、基−ＣＨ2ＣＨ2ＣＨ2ＣＨ2−が挙げられ、不飽和の炭化水素基としては、基−ＣＨ＝ＣＨＣＨ2−、基−ＣＨ2ＣＨ＝ＣＨＣＨ2−等が挙げられる。尚、不飽和の炭化水素基において、マレイミド基が２量化反応するためには、最終的に得られる５員環又は６員環が芳香族性を有しないものを選択する必要がある。当該炭化水素基としては、飽和の炭化水素基が好ましい。 As the alkyl group, an alkyl group having 4 or less carbon atoms is preferable. Saturated hydrocarbon groups that together form a 5-membered or 6-membered ring include the group —CH 2 CH 2 CH 2 — and the group —CH 2 CH 2 CH 2 CH 2 —. Examples of the hydrocarbon group include a group —CH═CHCH 2 — and a group —CH 2 CH═CHCH 2 —. In the unsaturated hydrocarbon group, in order for the maleimide group to undergo a dimerization reaction, it is necessary to select a finally obtained 5-membered or 6-membered ring having no aromaticity. The hydrocarbon group is preferably a saturated hydrocarbon group.
Ｒ1及びＲ2としては、一方が水素原子で他方が炭素数４以下のアルキル基、Ｒ1及びＲ2の両方が炭素数４以下のアルキル基、並びにそれぞれが一つとなって炭素環を形成する飽和炭化水素基が、半硬化の制御が容易である点で好ましい。 As R 1 and R 2 , one is a hydrogen atom and the other is an alkyl group having 4 or less carbon atoms, both R 1 and R 2 are alkyl groups having 4 or less carbon atoms, and each forms one to form a carbocycle The saturated hydrocarbon group to be used is preferable in terms of easy semi-curing control.
さらに、これらの中でも、それぞれが一つとなって炭素環を形成する飽和炭化水素基が
半硬化の制御が特に容易であり、接着力にも優れる点でより好ましい。
Furthermore, among these, saturated hydrocarbon groups, each of which forms a carbocyclic ring, are more preferable in that they are particularly easy to control semi-curing and have excellent adhesion.
マレイミド基以外のエチレン性不飽和基としては、（メタ）アクリロイル基、ビニル基及びビニルエーテル基等が挙げられ、（メタ）アクリロイル基が好ましい。 Examples of the ethylenically unsaturated group other than the maleimide group include a (meth) acryloyl group, a vinyl group and a vinyl ether group, and a (meth) acryloyl group is preferable.
本発明の（Ａ）成分としては、前記したマレイミド基とマレイミド基以外のエチレン性不飽和基を有する化合物であれば種々の化合物を使用することができるが、下記一般式（２）で表される化合物が、製造が容易で、硬化性に優れるため好ましい。 As the component (A) of the present invention, various compounds can be used as long as they have a compound having an ethylenically unsaturated group other than the maleimide group and the maleimide group, and are represented by the following general formula (2). Is preferable because it is easy to produce and has excellent curability.
〔但し、式（２）において、Ｒ1及びＲ2は前記と同様の意味を示す。又、Ｒ3はアルキレン基を表し、Ｒ4は水素原子又はメチル基を表し、ｎは１から６の整数を表す。〕 [However, in Formula (2), R < 1 > and R < 2 > show the same meaning as the above. R 3 represents an alkylene group, R 4 represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6. ]
Ｒ3のアルキレン基としては、直鎖状であっても又は分岐状を有していても良い。より好ましくは炭素数１〜６のアルキレン基である。 The alkylene group for R 3 may be linear or branched. More preferably, it is a C1-C6 alkylene group.
（Ａ）成分の好ましい配合割合は、組成物中に１０〜７０重量％であり、より好ましくは２０〜６０重量％、特に好ましくは３０〜５０重量％である。配合割合が上記範囲であると、半硬化の制御が容易であること、本硬化後の接着力に優れること、及び被着体を貼り合せて再度光照射する際の空気存在部分の硬化性に優れることから好ましい。 A preferable blending ratio of the component (A) is 10 to 70% by weight in the composition, more preferably 20 to 60% by weight, and particularly preferably 30 to 50% by weight. When the blending ratio is in the above range, it is easy to control semi-curing, excellent adhesion after main curing, and curability of the air-existing part when the adherend is bonded and irradiated again with light. It is preferable because it is excellent.
２．（Ｂ）成分
（Ｂ）成分は、（Ａ）成分以外のエチレン性不飽和基を有する化合物である。
（Ｂ）成分としては、エチレン性不飽和基を有する化合物であれば種々の化合物を使用することができ、（メタ）アクリロイル基を有する化合物、ビニル系化合物及び（Ａ）成分以外の不飽和二重結合に置換基を有することもあるマレイミド基を含有する化合物〔以下、その他マレイミド化合物という〕等が挙げられる。
2. Component (B) The component (B) is a compound having an ethylenically unsaturated group other than the component (A).
As the component (B), various compounds can be used as long as the compound has an ethylenically unsaturated group, and a compound having a (meth) acryloyl group, a vinyl compound, and an unsaturated compound other than the component (A). Examples thereof include a compound containing a maleimide group that may have a substituent in a heavy bond (hereinafter referred to as other maleimide compound).
（メタ）アクリロイル基を有する化合としては、（メタ）アクリレートが好ましい。
（メタ）アクリレートとしては、１個の（メタ）アクリロイル基を有する化合物〔以下、単官能（メタ）アクリレートという〕及び２個以上の（メタ）アクリロイル基を有する化合物〔以下、多官能（メタ）アクリレートという〕を挙げることができる。
As the compound having a (meth) acryloyl group, (meth) acrylate is preferable.
As the (meth) acrylate, a compound having one (meth) acryloyl group [hereinafter referred to as monofunctional (meth) acrylate] and a compound having two or more (meth) acryloyl groups [hereinafter referred to as polyfunctional (meth) Acrylate)].
単官能（メタ）アクリレートの具体的としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート及び２−エチルヘキシル（メタ）アクリレート等のアルキル（メタ）アクリレート；シクロヘキシル（メタ）アクリレート及びイソボロニル（メタ）アクリレート等の脂環式アルキル（メタ）アクリレート；ベンジル（メタ）アクリレート等のアラルキル（メタ）アクリレート；フェノキシエチルアクリレート等のフェノールのアルキレンオキシド付加物の（メタ）アクリレート；ノニルフェノキシプロピルアクリレート、ｐ−クミルフェノキシエチル（メタ）アクリレート等の置換基を有するフェノールのアルキレンオキシド付加物の（メタ）アクリレート；２−メトキシエチル（メタ）アクリレート、２−エトキシエチル（メタ）アクリレート、エトキシエトキシエチル（メタ）アクリレート、２−エチルヘキシロキシエトキシエチル（メタ）アクリレート、等のアルコキシアルキル（メタ）アクリレート；ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート及びヒドロキシブチルアクリレート等のヒドロキシアルキル（メタ）アクリレート；２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、２−ヒドロキシ−３−ブトキシプロピル（メタ）アクリレート等の所謂単官能エポキシ（メタ）アクリレート；（メタ）アクリル酸、クロトン酸、桂皮酸又は（メタ）アクリル酸等の不飽和カルボン酸のマイケル付加反応生成物である２量体以上のオリゴマー；ω−カルボキシポリカプロラクトンモノ（メタ）アクリレート、フタル酸モノヒドロキシエチル（メタ）アクリレート及びコハク酸モノヒドロキシエチル（メタ）アクリレート等のカルボキシル基含有（メタ）アクリレート；アルコキシシリル基含有（メタ）アクリレートが挙げられる。 Specific examples of the monofunctional (meth) acrylate include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. Alicyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; (meta) of an alkylene oxide adduct of phenol such as phenoxyethyl acrylate ) Acrylate; (meth) acrylate of an alkylene oxide adduct of phenol having a substituent such as nonylphenoxypropyl acrylate, p-cumylphenoxyethyl (meth) acrylate; 2- Alkoxyalkyl (meth) acrylates such as toxiethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, 2-ethylhexyloxyethoxyethyl (meth) acrylate, and the like; hydroxyethyl (meth) acrylate , Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate and hydroxybutyl acrylate; so-called monofunctional such as 2-hydroxy-3-phenoxypropyl (meth) acrylate and 2-hydroxy-3-butoxypropyl (meth) acrylate Epoxy (meth) acrylate; oligomer of dimer or higher which is a Michael addition reaction product of unsaturated carboxylic acid such as (meth) acrylic acid, crotonic acid, cinnamic acid or (meth) acrylic acid Carboxy group-containing (meth) acrylates such as ω-carboxypolycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate and monohydroxyethyl (meth) acrylate succinate; alkoxysilyl group-containing (meth) acrylate It is done.
多官能（メタ）アクリレートとしては、モノマー及びオリゴマーが挙げられる。 Examples of the polyfunctional (meth) acrylate include monomers and oligomers.
モノマーとしては、エチレングリコールのジ（メタ）アクリレート、テトラエチレングリコールのジ（メタ）アクリレート及びトリプロピレングリコールのジ（メタ）アクリレート等のグリコールのジ（メタ）アクリレート；トリメチロールプロパントリ（メタ）アクリレート、トリヒドロキシエチルイソシアヌレートトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート及びジペンタエリスリトールヘキサアクリレート等のポリオールの（メタ）アクリレート、並びにこれらポリオールのアルキレンオキサイド付加物の（メタ）アクリレート等が挙げられる。 Monomers include di (meth) acrylates of ethylene glycol, di (meth) acrylates of tetraethylene glycol, di (meth) acrylates of tripropylene glycol, and the like; trimethylolpropane tri (meth) acrylate , (Meth) acrylates of polyols such as trihydroxyethyl isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexaacrylate, and alkylene oxide adducts of these polyols (Meth) acrylate and the like.
オリゴマーとしては、ウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレート及びエポキシ（メタ）アクリレート等が挙げられる。 Examples of the oligomer include urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate.
ウレタン（メタ）アクリレートオリゴマーとしては、ポリオールと有機ポリイソシアネート反応物に対して、さらにヒドロキシル基含有（メタ）アクリレートを反応させた反応物等が挙げられる。ここで、ポリオールとしては、低分子量ポリオール、ポリエーテルポリオール、ポリエステルポリオール及びポリカーボネートポリオール等がある。低分子量ポリオールとしては、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、シクロヘキサンジメタノール及び３−メチル−１，５−ペンタンジオール等が挙げられる。ポリエーテルポリオールとしては、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等が挙げられる。ポリエステルポリオールとしては、これら低分子量ポリオール又は／及びポリエーテルポリオールと、アジピン酸、コハク酸、フタル酸、ヘキサヒドロフタル酸及びテレフタル酸等の二塩基酸又はその無水物等の酸成分との反応物が挙げられる。ポリカーボネートポリオールとしては、１，６−ヘキサンジオールのポリカーボネートジオール等が挙げられる。有機ポリイソシアネートとしては、トリレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、ヘキサメチレンジイソシアネート及びイソホロンジイソシアネート等が挙げられる。ヒドロキシル基含有（メタ）アクリレートとしては、２−ヒドロキシエチル（メタ）アクリレート及び２−ヒドロキシプロピル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート等が挙げられる。 Examples of the urethane (meth) acrylate oligomer include a reaction product obtained by further reacting a hydroxyl group-containing (meth) acrylate with a polyol and an organic polyisocyanate reaction product. Here, examples of the polyol include a low molecular weight polyol, a polyether polyol, a polyester polyol, and a polycarbonate polyol. Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, neopentyl glycol, cyclohexanedimethanol and 3-methyl-1,5-pentanediol. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. As the polyester polyol, a reaction product of these low molecular weight polyols and / or polyether polyols and acid components such as dibasic acids such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid or anhydrides thereof. Is mentioned. Examples of the polycarbonate polyol include 1,6-hexanediol polycarbonate diol. Examples of the organic polyisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
ポリエステル（メタ）アクリレートオリゴマーとしては、ポリエステルポリオールと（メタ）アクリル酸との脱水縮合物が挙げられる。ポリエステルポリオールとしては、エチレングリコール、ポリエチレングリコール、シクロヘキサンジメタノール、３−メチル−１，５−ペンタンジオール、プロピレングリコール、ポリプロピレングリコール、１，６−ヘキサンジオール及びトリメチロールプロパン等の低分子量ポリオール、並びにこれらのアルキレンオキシド付加物等のポリオールと、アジピン酸、コハク酸、フタル酸、ヘキサヒドロフタル酸及びテレフタル酸等の二塩基酸又はその無水物等の酸成分とからの反応物等が挙げられる。 As a polyester (meth) acrylate oligomer, the dehydration condensate of a polyester polyol and (meth) acrylic acid is mentioned. Examples of the polyester polyol include low molecular weight polyols such as ethylene glycol, polyethylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol and trimethylolpropane, and these And a reaction product from a polyol such as an alkylene oxide adduct and an acid component such as a dipic acid such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or an anhydride thereof.
エポキシアクリレートは、エポキシ樹脂に（メタ）アクリル酸を付加反応させたもので、ビスフェノールＡ型エポキシ樹脂の（メタ）アクリレート、フェノール又はクレゾールノボラック型エポキシ樹脂の（メタ）アクリレート及びポリエーテルのジグリシジルエーテルの（メタ）アクリル酸付物等が挙げられる。 Epoxy acrylate is obtained by addition reaction of (meth) acrylic acid to epoxy resin, (meth) acrylate of bisphenol A type epoxy resin, (meth) acrylate of phenol or cresol novolac type epoxy resin and diglycidyl ether of polyether (Meth) acrylic acid adducts and the like.
（メタ）アクリレート以外の（メタ）アクリロイル基を有する化合物としては、（メタ）アクリロイルモルホリン、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド等の（メタ）アクリルアミド等を挙げることができる。 Examples of the compound having a (meth) acryloyl group other than (meth) acrylate include (meth) acryloyl such as (meth) acryloylmorpholine and N, N-dimethyl (meth) acrylamide.
ビニル系化合物の例としては、N−ビニルピロリドン、N−ビニルカプロラクタム、無水マレイン酸、スチレン、ジアリルフタレート及びジビニルエーテル等が挙げられる。
ジビニルエーテルとしては、トリエチレングリコールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル等が挙げられる。
Examples of vinyl compounds include N-vinyl pyrrolidone, N-vinyl caprolactam, maleic anhydride, styrene, diallyl phthalate and divinyl ether.
Examples of divinyl ether include triethylene glycol divinyl ether and cyclohexane dimethanol divinyl ether.
その他マレイミド化合物としては、シトラコンイミドアルコール、シトラコンイミドアルコールとポリイソシアネートからなるウレタン化合物、シトラコンイミドアルコールとポリイソシアネートとポリオールからなるウレタン化合物等が挙げられる。 Other maleimide compounds include citraconic imide alcohol, urethane compounds composed of citraconic imide alcohol and polyisocyanate, urethane compounds composed of citraconic imide alcohol, polyisocyanate and polyol, and the like.
（Ｂ）成分としては、（メタ）アクリレートを主成分とするものが好ましい。この場合、（メタ）アクリレート以外のエチレン性不飽和基を有する化合物の割合としては、組成物中に０〜３０重量％であることが好ましく、より好ましくは０〜２０重量％、さらに好ましくは０〜１０重量％である。 (B) As a component, what has (meth) acrylate as a main component is preferable. In this case, the ratio of the compound having an ethylenically unsaturated group other than (meth) acrylate is preferably 0 to 30% by weight in the composition, more preferably 0 to 20% by weight, and still more preferably 0. -10% by weight.
（Ｂ）成分が（メタ）アクリレートである場合において、アクリレートが５０モル％以上であることが好ましく、８０モル％以上であることがより好ましく、９０モル％以上であることが特に好ましい。（Ｂ）成分としてアクリレートが５０モル％以上であると、被着体を貼り合せて再度光照射する際の空気存在部分の硬化性に優れるため好ましい。 When the component (B) is (meth) acrylate, the acrylate is preferably 50 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more. It is preferable that acrylate is 50 mol% or more as the component (B) because the air-existing portion is excellent in curability when the adherend is bonded and irradiated again with light.
さらに、（Ｂ）成分としては、（Ｂ）成分中に、単官能アクリレートを５０重量％以上含むことが好ましく、８０重量％以上であることがより好ましく、９０重量％以上であることが特に好ましい。（Ｂ）成分中に単官能アクリレートを５０重量％以上含むものは、半硬化状態を制御しやすく、本硬化後の接着力にも優れるため好ましい。 Furthermore, as the component (B), the component (B) preferably contains 50% by weight or more of monofunctional acrylate, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. . A component containing 50% by weight or more of a monofunctional acrylate in the component (B) is preferable because the semi-cured state can be easily controlled and the adhesive strength after the main curing is excellent.
（Ｂ）成分の好ましい配合割合は、組成物中に２０〜７０重量％であり、より好ましくは３０〜６０重量％である。配合割合が上記範囲であると、半硬化の制御が容易であること、及び被着体を貼り合せて再度光照射する際の空気存在部分の硬化性に優れることから好ましい。 (B) The preferable mixture ratio of a component is 20 to 70 weight% in a composition, More preferably, it is 30 to 60 weight%. The blending ratio within the above range is preferable because it is easy to control semi-curing and is excellent in curability of the air-existing portion when the adherend is bonded and irradiated again with light.
３．（Ｃ）成分
本発明の（Ｃ）成分は、光ラジカル重合開始剤であり、光照射でラジカルを発生する化合物であれば種々の化合物が使用できる。光としては紫外線又は可視光が使用される。
3. Component (C) The component (C) of the present invention is a photo radical polymerization initiator, and various compounds can be used as long as they generate a radical upon irradiation with light. As light, ultraviolet light or visible light is used.
（Ｃ）成分の具体例としては、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、１−〔４−（２−ヒドロキシエトキシ）−フェニル〕−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−メチル−１−〔４−（メチルチオ）フェニル〕−２−モルフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタン−１−オン、ジエトキシアセトフェノン、オリゴ〔２−ヒドロキシ−２−メチル−１−〔４−（１−メチルビニル）フェニル〕プロパノン〕及び２−ヒドロキシ−１−｛４−〔４−（２−ヒドロキシ−２−メチル−プロピオニル）−ベンジル〕−フェニル｝−２−メチル−プロパン−１−オン等のアセトフェノン系化合物；ベンゾフェノン、４−フェニルベンゾフェノン、２，４，６−トリメチルベンゾフェノン及び４−ベンゾイル−４’−メチル−ジフェニルスルファイド等のベンゾフェノン系化合物；メチルベンゾイルフォルメート、オキシ−フェニル−アセチックアシッド２−〔２−オキソ−２−フェニル−アセトキシ−エトキシ〕−エチルエステル及びオキシ−フェニル−アセチックアシッド２−〔２−ヒドロキシ−エトキシ〕−エチルエステル等のα−ケトエステル系化合物；２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、ビス（２，６−ジメトキシベンゾイル）−２，４，４−トリメチル−ペンチルフォスフィンオキサイド等のフォスフィンオキサイド系化合物；ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル及びベンゾインイソブチルエーテル等のベンゾイン系化合物；チタノセン系化合物；１−(４−（４−ベンゾイルフェニルスルファニル）フェニル〕−２−メチル−２−（４−メチルフェニルスルフィニル）プロパン−１−オン等のアセトフェノン／ベンゾフェノンハイブリッド系光開始剤；１，２−オクタンジオン、１−〔４−（フェニルチオ）−，２−（Ｏ−ベンゾイルオキシム））等のオキシムエステル系光開始剤；並びにカンファーキノン等が挙げられる。 Specific examples of the component (C) include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane. -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, diethoxyacetophenone, oligo [2-hydroxy-2-methyl- 1- [4- (1-methylvinyl) phenyl] propanone] and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -be Acetophenone compounds such as [zyl] -phenyl} -2-methyl-propan-1-one; benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-4′-methyl-diphenylsulfide, etc. Benzophenone compounds: methyl benzoylformate, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy- Α-ketoester compounds such as ethoxy] -ethyl ester; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6 -Dimethoxybe Nzoyl) -2,4,4-trimethyl-pentylphosphine oxide and other phosphine oxide compounds; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanocene compounds; Acetophenone / benzophenone hybrid photoinitiators such as 1- (4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfinyl) propan-1-one; 1,2-octanedione Oxime ester photoinitiators such as 1- [4- (phenylthio)-, 2- (O-benzoyloxime)); and camphorquinone.
これらのうち、より好ましい化合物はフォスフィンオキサイド系化合物であり、特に好ましくはビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド等のビスアシルフォスフィンオキサイドである。 Of these, more preferred compounds are phosphine oxide compounds, and particularly preferred are bisacylphosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
（Ｃ）成分の好ましい配合割合は、組成物中に０．０１〜１０重量％であり、より好ましくは０．１〜５重量％、特に好ましくは０．５〜３重量％である。配合割合が上記範囲であると、半硬化の制御が容易であること、及び被着体を貼り合せて再度光照射する際の硬化性に優れることから、好ましい。 A preferred blending ratio of the component (C) is 0.01 to 10% by weight in the composition, more preferably 0.1 to 5% by weight, and particularly preferably 0.5 to 3% by weight. The blending ratio within the above range is preferable because it is easy to control semi-curing and is excellent in curability when the adherend is bonded and irradiated again with light.
４．（Ｄ）成分
本発明の組成物は、前記（Ａ）〜（Ｃ）成分を必須とするものであるが、空気による硬化阻害を受ける用途においては、光二量化反応を増感する化合物〔（Ｄ）成分〕を配合することが好ましい。これにより、空気による硬化阻害を受ける被着体の接着用途、具体的には、凹凸部を有する被着体の接着に使用する場合、優れた硬化性を発揮する。
（Ｄ）成分は、（Ａ）成分の光二量化反応を増感する化合物である。好適な具体例としては、ジエチルチオキサントン及びジイソプロピルチオキサントン等のチオキサントン、並びにアセトフェノン及びベンゾフェノン等のフェニルケトンが挙げられる。これらの中でも、（Ａ）成分の光二量化反応を増感する効果が大きいため、チオキサントン系化合物がより好ましい。
4). Component (D) The composition of the present invention essentially comprises the components (A) to (C). However, in applications subject to curing inhibition by air, the compound [(D ) Component] is preferably blended. Thereby, when it uses for the adhesion | attachment use of the to-be-adhered body which receives the hardening inhibition by air, specifically, the adherend which has an uneven | corrugated | grooved part, it exhibits outstanding curability.
The component (D) is a compound that sensitizes the photodimerization reaction of the component (A). Suitable specific examples include thioxanthones such as diethyl thioxanthone and diisopropyl thioxanthone, and phenyl ketones such as acetophenone and benzophenone. Among these, a thioxanthone compound is more preferable because it has a great effect of sensitizing the photodimerization reaction of the component (A).
（Ｄ）成分の好ましい配合割合は、組成物中に０．１〜３重量％であり、特に好ましくは０．３〜２重量％である。配合割合が３重量％以下であると、硬化後の黄変が目立たなくなるため好ましい。又、配合割合が０．１重量％以上であると、被着体を貼り合せて再度光照射する際の空気存在部分の硬化性に優れるため好ましい。 A preferable blending ratio of the component (D) is 0.1 to 3% by weight in the composition, and particularly preferably 0.3 to 2% by weight. A blending ratio of 3% by weight or less is preferable because yellowing after curing does not stand out. Moreover, it is preferable for the blending ratio to be 0.1% by weight or more because the curability of the air-existing portion is excellent when the adherend is bonded and irradiated again with light.
５．（Ｅ）成分
本発明の組成物には、接着力を低下させることなく粘度を適度に増加させること等を目的として、（メタ）アクリル系のポリマー〔（Ｅ）成分〕を配合することが好ましい。
（Ｅ）成分の重量平均分子量としては、１，０００〜５００，０００が好ましく、より好ましくは１０，０００〜１５０，０００である。ここで重量平均分子量とは、ＧＰＣのポリスチレン換算の重量平均分子量である。
5). Component (E) The composition of the present invention preferably contains a (meth) acrylic polymer [component (E)] for the purpose of appropriately increasing the viscosity without decreasing the adhesive strength. .
(E) As a weight average molecular weight of a component, 1,000-500,000 are preferable, More preferably, it is 10,000-150,000. Here, the weight average molecular weight is a weight average molecular weight of GPC in terms of polystyrene.
（Ｅ）成分の構成モノマーとしては、（メタ）アクリレートを主成分とするものであれば良く、具体例としては、前記した単官能（メタ）アクリレートと同様のものが挙げられる。モノマーとしては、メチルメタクリレートを含むものが好ましい。 The constituent monomer of the component (E) is not particularly limited as long as it has (meth) acrylate as a main component, and specific examples thereof include those similar to the above-described monofunctional (meth) acrylate. As the monomer, those containing methyl methacrylate are preferable.
（Ｅ）成分の好ましい配合割合は、組成物中に２〜４０重量％であり、より好ましくは５〜３０重量％、特に好ましくは１０〜２５重量％である。配合割合が上記範囲であると、塗工性、半硬化の制御しやすさ、本硬化後の接着力、及び被着体を貼り合せて再度光照射する際の空気存在部分の硬化性がさらに優れたものとなるため、好ましい。 (E) The preferable mixture ratio of a component is 2-40 weight% in a composition, More preferably, it is 5-30 weight%, Most preferably, it is 10-25 weight%. When the blending ratio is in the above range, the coating property, the ease of control of semi-curing, the adhesive force after the main curing, and the curability of the air-existing part when the adherend is bonded and irradiated again with light are further added. Since it becomes excellent, it is preferable.
６．その他の成分
本発明の組成物には、必要に応じて後記するその他の成分を配合することもできる。具体的には、無機材料、レベリング剤、シランカップリング剤、重合禁止剤又は／及び酸化防止剤、耐光性向上剤、並びに有機溶剤及び／又は水等を挙げることができる。
以下これらの成分について説明する。
6). Other Components Other components described later can be blended in the composition of the present invention as necessary. Specific examples include inorganic materials, leveling agents, silane coupling agents, polymerization inhibitors or / and antioxidants, light resistance improvers, organic solvents and / or water.
Hereinafter, these components will be described.
●無機材料
無機材料は、組成物の硬化時のひずみを緩和させたり、接着力を向上させる目的で配合することもできる。
無機材料としては、コロイダルシリカ、シリカ、アルミナ、タルク及び粘土等が挙げられる。
無機材料の配合割合は、組成物中に０〜５０重量％であることが好ましく、より好ましくは０〜３０重量％、さらに好ましくは０〜１０重量％である。
● Inorganic materials Inorganic materials can be blended for the purpose of alleviating strain at the time of curing of the composition or improving adhesive strength.
Examples of the inorganic material include colloidal silica, silica, alumina, talc, and clay.
The blending ratio of the inorganic material is preferably 0 to 50% by weight in the composition, more preferably 0 to 30% by weight, and still more preferably 0 to 10% by weight.
●レベリング剤
レベリング剤としては、シリコン系化合物及びフッ素系化合物等が挙げられる。
レベリング剤の配合割合は、組成物中に０．５重量％以下であることが、接着性能への悪影響が小さいため好ましい。
● Leveling agent Examples of the leveling agent include silicon compounds and fluorine compounds.
The blending ratio of the leveling agent is preferably 0.5% by weight or less in the composition because the adverse effect on the adhesive performance is small.
●シランカップリング剤
シランカップリング剤は、ガラス、金属、金属酸化物等の無機物への接着性能を高める目的等で添加することもできる。
シランカップリング剤は、１分子中に１個以上のアルコキシシリル基と１個以上の有機官能基を有する化合物であり、有機官能基としては、（メタ）アクリロイル基、エポキシ基、アミノ基、チオール基が好ましく、より好ましくは（メタ）アクリロイル基である。
シランカップリング剤の配合割合は、組成物中に５重量％以下であることが、アウトガス低減の点から好ましい。
Silane coupling agent A silane coupling agent can also be added for the purpose of improving the adhesion performance to inorganic substances such as glass, metal, and metal oxide.
A silane coupling agent is a compound having one or more alkoxysilyl groups and one or more organic functional groups in one molecule. Examples of the organic functional groups include (meth) acryloyl groups, epoxy groups, amino groups, and thiols. Group is preferred, more preferably a (meth) acryloyl group.
The blending ratio of the silane coupling agent is preferably 5% by weight or less in the composition from the viewpoint of reducing outgas.
●重合禁止剤又は／及び酸化防止剤
本発明の組成物には、重合禁止剤又は／及び酸化防止剤を添加することが、本発明の組成物及び光硬化型粘接着シートの保存安定性を向上させことができ、好ましい。
重合禁止剤としては、ハイドロキノン、ハイドロキノンモノメチルエーテル、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール、並びに種々のフェノール系酸化防止剤が好ましいが、イオウ系二次酸化防止剤、リン系二次酸化防止剤、クロペン系酸化防止剤等を添加することもできる。
これら重合禁止剤又は／及び酸化防止剤の総配合割合は、組成物中に０．００１〜３重量％であることが好ましく、さらに好ましくは０．０１〜０．５重量％である。
● Polymerization inhibitor or / and antioxidant The composition of the present invention may be added with a polymerization inhibitor or / and an antioxidant to preserve the storage stability of the composition of the present invention and the photocurable adhesive sheet. Can be improved.
As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, and various phenolic antioxidants are preferable. Subsequent antioxidants, clopene antioxidants and the like can also be added.
The total blending ratio of these polymerization inhibitors or / and antioxidants is preferably 0.001 to 3% by weight, more preferably 0.01 to 0.5% by weight in the composition.
●耐光性向上剤
本発明の組成物には、用途に応じて、紫外線吸収剤や光安定剤を添加することができる。
耐光性向上剤の配合割合は、組成物中に０〜１０重量％であることが好ましく、さらに好ましくは０〜５重量％である。
-Light resistance improver An ultraviolet absorber and a light stabilizer can be added to the composition of the present invention depending on the application.
The blending ratio of the light resistance improver is preferably 0 to 10% by weight in the composition, and more preferably 0 to 5% by weight.
●有機溶剤及び／又は水
本発明の組成物には、塗工性や密着性を高める目的で少量添加しても良いが、本発明の組成物の特長である「無溶剤」であることが損なわれるため、添加しないことが好ましい。
● Organic solvent and / or water A small amount may be added to the composition of the present invention for the purpose of improving the coatability and adhesion, but it should be “solvent-free” which is a feature of the composition of the present invention. Since it will be damaged, it is preferable not to add.
７．光硬化型粘接着剤製造用の光硬化型組成物
本発明の光硬化型粘接着剤製造用の光硬化型組成物は、上記必須成分及び必要に応じてその他の成分を常法に従い、攪拌・混合することにより得ることができる。本発明の組成物は、均一透明であるものが好ましい。
本発明の組成物の粘度は、室温で厚さ数μｍ〜数１０μｍに塗布することが容易な粘度であることが好ましく、具体的には、２５℃の粘度が５０〜２０，０００ｍＰａ・ｓであることが好ましく、より好ましくは１００〜１０，０００ｍＰａ・ｓである。
7). Photocurable composition for producing a photocurable adhesive The photocurable composition for producing a photocurable adhesive of the present invention is prepared by adding the above essential components and other components according to conventional methods. It can be obtained by stirring and mixing. The composition of the present invention is preferably uniform and transparent.
The viscosity of the composition of the present invention is preferably a viscosity that can be easily applied to a thickness of several μm to several tens of μm at room temperature. Specifically, the viscosity at 25 ° C. is 50 to 20,000 mPa · s. It is preferable that there is, more preferably 100 to 10,000 mPa · s.
８．光硬化型粘接着シート
本発明の組成物は、接着を目的とする材料（以下、被着体という）の一方に直接塗布して使用することが可能であるが、光硬化型粘接着シート（以下、粘接着シートということもある）の製造にも使用できる。
8). Photocurable Adhesive Sheet The composition of the present invention can be used by directly applying to one of materials for adhesion (hereinafter referred to as adherend). It can also be used for production of a sheet (hereinafter sometimes referred to as an adhesive sheet).
光硬化型粘接着シートの製造方法としては、常法に従えば良く、基材に組成物を塗布した後、光照射により半硬化させ、粘接着性硬化膜を形成する方法等が挙げられる。
光硬化型粘接着シートは、製造工程上液体を使用したくない場合等で好適に使用できる。
As a method for producing a photo-curing adhesive sheet, a conventional method may be followed, for example, a method of applying a composition to a substrate and then semi-curing by light irradiation to form an adhesive-cured cured film. It is done.
The photocurable adhesive sheet can be suitably used when it is not desired to use a liquid in the production process.
基材としては、被着体であっても良く、被着体とは無関係の剥離可能な材料（以下、剥離材という）であっても良い。 The substrate may be an adherend or may be a peelable material (hereinafter referred to as a release material) unrelated to the adherend.
被着体としては、ポリマー材料、ガラス、金属や金属酸化物が蒸着されたポリマーやガラス、セラミックス、金属、シリコン、木、紙等、種々のものが適用できる。
ポリマー材料としては、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステル、ポリアミド、ポリイミド、ポリカーボネート、ユリア・メラミン樹脂、エポキシ樹脂、ポリウレタン、ポリ乳酸、ポリエチレン、ポリプロピレン、シクロオレフィンポリマー、アクリル樹脂、メタクリル樹脂、ポリ塩化ビニル、ポリスチレン、ポリビニルアセテート、ポリビニルアルコール、トリアセチルセルロース、ヒドロキシプロピルセルロース、ポリエーテルサルホン、セロハン、液晶ポリマー、上記ポリマーの共重合体やブレンド材料等が挙げられる。ポリマーが難接着性である場合は、密着性を高めるために、コロナ処理等の易接着処理をすることが好ましい。
As the adherend, various materials such as polymer material, glass, polymer or glass on which a metal or metal oxide is deposited, ceramics, metal, silicon, wood, paper, and the like can be applied.
Polymer materials include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamide, polyimide, polycarbonate, urea melamine resin, epoxy resin, polyurethane, polylactic acid, polyethylene, polypropylene, cycloolefin polymer, acrylic resin, methacrylic resin, polychlorinated resin Examples thereof include vinyl, polystyrene, polyvinyl acetate, polyvinyl alcohol, triacetyl cellulose, hydroxypropyl cellulose, polyethersulfone, cellophane, liquid crystal polymer, and a copolymer or blend material of the above polymer. When the polymer is difficult to adhere, it is preferable to perform easy adhesion treatment such as corona treatment in order to improve adhesion.
剥離材としては、シリコン剥離処理ＰＥＴフィルムが特に好ましいが、テフロン（登録商標）、ポリオレフィン等の難接着性フィルムや、シリコン剥離処理した紙等も使用可能である。 As the release material, a silicon release-treated PET film is particularly preferable, but a hard-to-adhere film such as Teflon (registered trademark) or polyolefin, a paper subjected to silicon release treatment, or the like can also be used.
本発明の組成物の半硬化及び本硬化に使用する光の光源としては、種々のものが使用可能である。好適な光源としては、高圧水銀ランプ、メタルハライドランプ、ＵＶ無電極ランプ及び紫外線及び／又は可視光を放射するＬＥＤ等が挙げられる。
光照射における、照射強度等の照射条件は、使用する組成物、基材及び目的等に応じて適宜設定すれば良い。
Various light sources can be used for the semi-curing and the main curing of the composition of the present invention. Suitable light sources include high pressure mercury lamps, metal halide lamps, UV electrodeless lamps, and LEDs that emit ultraviolet and / or visible light.
What is necessary is just to set suitably irradiation conditions, such as irradiation intensity | strength in light irradiation, according to the composition to be used, a base material, the objective, etc.
光硬化型粘接着シートの具体例を挙げる。
例えば、被着体／粘接着性硬化膜／剥離材から構成される粘接着シートが挙げられる。
当該粘接着シートの製造方法としては、主に以下の２つの方法がある。まず、本発明の組成物を被着体に塗布し、塗布面に光を適量照射して粘接着性硬化膜を形成し、この上に剥離材をラミネートして製造する方法が挙げられる。又、本発明の組成物を被着体に塗布し、塗布面に剥離材をラミネートした後、光を適量照射して製造する方法が挙げられる。
又、剥離材／粘接着性硬化膜／剥離材から構成される粘接着シートが挙げられる。
当該粘接着シートの製造方法としては、本発明の組成物を剥離材に塗布し、塗布面に別の剥離材をラミネートして光を適量照射して製造する方法が挙げられる。
Specific examples of the photocurable adhesive sheet will be given.
For example, the adhesive sheet comprised from a to-be-adhered body / adhesive adhesive cured film / release material is mentioned.
There are mainly the following two methods for producing the adhesive sheet. First, a method of applying the composition of the present invention to an adherend, irradiating an appropriate amount of light on the coated surface to form an adhesive-cured cured film, and laminating a release material thereon to produce the method. Moreover, after apply | coating the composition of this invention to a to-be-adhered body, laminating a peeling material on an application | coating surface, the method of irradiating a suitable amount of light and manufacturing can be mentioned.
Moreover, the adhesive sheet comprised from a release material / adhesive adhesive cured film / release material is mentioned.
Examples of the method for producing the adhesive sheet include a method of applying the composition of the present invention to a release material, laminating another release material on the coated surface, and irradiating an appropriate amount of light.
粘接着性硬化膜の厚さとしては、２〜４０μｍが好ましく、より好ましくは５〜３０μｍ、特に好ましくは８〜２０μｍである。粘接着性硬化膜の厚さを上記範囲とすると、貼り易さ、接着力、硬化性等の性能が優れるため、好ましい。 As thickness of an adhesive adhesive cured film, 2-40 micrometers is preferable, More preferably, it is 5-30 micrometers, Most preferably, it is 8-20 micrometers. When the thickness of the adhesive-cured cured film is within the above range, it is preferable because performance such as ease of sticking, adhesive strength, and curability is excellent.
９．接着方法
本発明の組成物を使用した好ましい接着方法の一例を以下に示す。但し、以下に示した接着方法に限定されるものではない。
9. Adhesion method An example of a preferred adhesion method using the composition of the present invention is shown below. However, it is not limited to the adhesion method shown below.
●被着体に、組成物を直接塗布して使用する場合
本発明の組成物を使用して基材（被着体）を接着する方法としては、好ましくは下記工程１〜工程４を含む基材（被着体）の接着方法が挙げられる。
工程１：基材（被着体）に、本発明の組成物を塗布する。
工程２：基材（被着体）側又は塗布面側から光照射して、前記組成物を半硬化させ粘接着性硬化膜を形成させる。
工程３：粘接着性硬化膜と他の基材（被着体）を密着させる。
工程４：基材（被着体）のいずれか一方から光照射して、前記硬化膜を完全硬化させる。
When using the composition directly applied to an adherend, the method of adhering a substrate (adherend) using the composition of the present invention is preferably a group comprising the following steps 1 to 4 Examples include a method for bonding a material (adhered body).
Step 1: The composition of the present invention is applied to a substrate (adhered body).
Step 2: Light irradiation is performed from the substrate (adhered body) side or the application surface side, and the composition is semi-cured to form an adhesive-cured cured film.
Process 3: Adhesive adhesive film and another base material (adherent body) are stuck.
Step 4: Irradiate light from any one of the base materials (adhered bodies) to completely cure the cured film.
工程１において、被着体の一方に、本発明の組成物を塗布する方法としては、ロールコータやダイコータ等が挙げられる。
工程２においては、被着体側又は塗布面側から光を適量照射して、粘着状態を有する粘接着性硬化膜を形成させる。
この場合、塗布面に剥離材でラミネートし、光を照射する方法が好ましい。粘接着性硬化膜を形成した後、直ちに被着体を貼り合せる場合には、剥離材のラミネート工程は省略しても良い。透明な剥離材でラミネートした場合、剥離材側から光を照射することができる。
このときの厚さとしては、２〜４０μｍが好ましく、より好ましくは５〜３０μｍ、特に好ましくは８〜２０μｍである。
工程３においては、工程２で形成した粘接着性硬化膜ともう一方の被着体を貼り合せる。剥離材を使用した場合は剥離材を剥離した後、もう一方の被着体を貼り合せる。
工程４においては、被着体のいずれか一方から再度光照射して、前記硬化膜を完全硬化させる（本硬化）。光照射は、紫外線をより透過する被着体の側から照射することが好ましい。
In step 1, examples of the method of applying the composition of the present invention to one of the adherends include a roll coater and a die coater.
In step 2, an appropriate amount of light is irradiated from the adherend side or the application surface side to form an adhesive-cured cured film having an adhesive state.
In this case, a method of laminating the coated surface with a release material and irradiating light is preferable. If the adherend is to be bonded immediately after forming the adhesive-cured cured film, the release material laminating step may be omitted. When laminated with a transparent release material, light can be irradiated from the release material side.
As thickness at this time, 2-40 micrometers is preferable, More preferably, it is 5-30 micrometers, Most preferably, it is 8-20 micrometers.
In step 3, the adhesive adhesive cured film formed in step 2 is bonded to the other adherend. When the release material is used, after the release material is peeled off, the other adherend is bonded.
In step 4, either one of the adherends is irradiated again with light to completely cure the cured film (main curing). The light irradiation is preferably performed from the side of the adherend that transmits more ultraviolet rays.
●光硬化型粘接着シートを使用する場合
被着体／粘接着性硬化膜／剥離材から構成される光硬化型粘接着シートの場合、剥離材を剥がして、粘接着シートをもう一方の被着体を貼り付け、最後に、再度光照射して硬化させる（本硬化）方法が挙げられる。
剥離材／粘接着性硬化膜／剥離材から構成される光硬化型粘接着シートの場合、剥離材を剥がして、被着体の一方に、粘接着シートを貼り付け、もう一方の剥離材を剥がして、粘接着シートの他方の面に、もう一方の被着体を貼り付ける。最後に、再度光照射して硬化させる（本硬化）方法が挙げられる。
● When using a photo-curing adhesive sheet In the case of a photo-curing adhesive sheet composed of an adherend / adhesive cured film / release material, remove the release material and remove the adhesive sheet. There is a method in which the other adherend is attached and finally cured by light irradiation again (main curing).
In the case of a photo-curing type adhesive sheet composed of a release material / adhesive cured film / release material, the release material is peeled off and an adhesive sheet is attached to one of the adherends. The release material is peeled off, and the other adherend is attached to the other surface of the adhesive sheet. Finally, there is a method of curing by irradiating light again (main curing).
被着体の一方は、光を透過する材料であることが好ましい。被着体の両方が光を透過しない場合、粘接着剤の断面方向から光を入れる必要があるが、この場合、小さな部品の接着に限られてしまうため、あまり好適ではない。
被着体の形状としては種々のものが使用可能であるが、板やフィルム形状の被着体に対して、より好適に使用できる。とりわけ、一方の被着体が平滑な板又はフィルム、他方の被着体が１ｍｍ以下（より好ましくは５〜１００μｍ）の凹凸形状を有する場合に特に好適に使用できる。
One of the adherends is preferably a material that transmits light. When both of the adherends do not transmit light, it is necessary to enter light from the cross-sectional direction of the adhesive, but in this case, since it is limited to adhesion of small parts, it is not very suitable.
Various shapes can be used for the adherend, but it can be more suitably used for a plate or film-shaped adherend. In particular, it can be particularly suitably used when one adherend has a smooth plate or film and the other adherend has an uneven shape of 1 mm or less (more preferably 5 to 100 μm).
本発明の組成物の半硬化及び本硬化に使用する光の光源としては、前記と同様のものが挙げられ、前記と同様のものが好ましい。
光照射における、照射強度等の照射条件は、使用する組成物、基材及び目的等に応じて適宜設定すれば良い。
Examples of the light source used for the semi-curing and the main curing of the composition of the present invention include those described above, and those similar to the above are preferable.
What is necessary is just to set suitably irradiation conditions, such as irradiation intensity | strength in light irradiation, according to the composition to be used, a base material, the objective, etc.
１０．用途
本発明の組成物は、一方の被着体が光を透過する材料である場合、様々な部品の接着に使用することができる。とりわけ、凹凸形状を有する被着体の凸部分の接着に特に適している。
具体的には、以下の用途が挙げられる。液晶ディスプレイやプロジェクションテレビ等のレンズシートのレンズ部分を他の板或いはフィルムに接着する用途に特に好適である。又、レンズ以外のパターン形状を有する光学フィルムを、液晶ディスプレイの拡散板や導光板等に、パターン形状を埋没させることなく接着させる用途に特に好適である。
10. Application The composition of the present invention can be used for bonding various parts when one adherend is a material that transmits light. In particular, it is particularly suitable for adhesion of the convex portion of the adherend having an uneven shape.
Specifically, the following uses are mentioned. It is particularly suitable for applications in which a lens portion of a lens sheet such as a liquid crystal display or a projection television is bonded to another plate or film. Further, it is particularly suitable for an application in which an optical film having a pattern shape other than a lens is adhered to a diffusion plate or a light guide plate of a liquid crystal display without burying the pattern shape.
以下に、実施例及び比較例を示し、本発明をより具体的に説明する。尚、本発明は、これらの実施例によって限定されるものではない。
尚、以下において「部」とは、重量部を意味する。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, this invention is not limited by these Examples.
In the following, “parts” means parts by weight.
●実施例及び比較例における略号
実施例及び比較例における略号の意味を、以下に記載する。
（Ａ）成分
・ＴＯ−１５３４：下記式（７）で表される化合物、東亞合成(株)製アロニックスＴＯ−１５３４。
● Abbreviations in Examples and Comparative Examples The meanings of the abbreviations in Examples and Comparative Examples are described below.
(A) Component · TO-1534: Compound represented by the following formula (7), Aronix TO-1534 manufactured by Toagosei Co., Ltd.
（Ｂ）成分
・ビスコート１９０：エトキシエトキシエチルアクリレート、大阪有機化学工業(株)製ビスコート１９０。
・Ｍ−２４０：ポリエチレングリコール（平均繰り返し数４）ジアクリレート、東亞合成(株)製アロニックスＭ−２４０。
・ＢｚＭＡ：ベンジルメタクリレート、三菱レイヨン(株)製アクリエステルＢＺ。
・Ｍ−１６００：ポリエーテル系ウレタンアクリレート、東亞合成(株)製アロニックスＭ−１６００。
・Ｍ−４０２：ジペンタエリスリトールペンタ及びヘキサアクリレート、東亞合成(株)製アロニックスＭ−４０２。
(B) Component / Biscoat 190: Ethoxyethoxyethyl acrylate, Biscoat 190 manufactured by Osaka Organic Chemical Industry Co., Ltd.
M-240: Polyethylene glycol (average number of repetitions 4) diacrylate, Aronix M-240 manufactured by Toagosei Co., Ltd.
BzMA: benzyl methacrylate, acrylate ester BZ manufactured by Mitsubishi Rayon Co., Ltd.
M-1600: Polyether urethane acrylate, Aronix M-1600 manufactured by Toagosei Co., Ltd.
M-402: Dipentaerythritol penta and hexaacrylate, Aronix M-402 manufactured by Toagosei Co., Ltd.
（Ｃ）成分
・Ｉｒｇ８１９：ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、チバ・スペシャルティ・ケミカルズ(株)製イルガキュア８１９。
・Ｉｒｇ１８４：１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、チバ・スペシャルティ・ケミカルズ(株)製イルガキュア１８４。
Component (C) Irg819: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure 819 manufactured by Ciba Specialty Chemicals Co., Ltd.
Irg184: 1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure 184 manufactured by Ciba Specialty Chemicals.
（Ｄ）成分
・ＤＥＴＸ：２，４−ジエチルチオキサントン、日本化薬(株)製カヤキュアＤＥＴＸ−Ｓ。
Component (D) DETX: 2,4-diethylthioxanthone, Nippon Kayaku Co., Ltd. Kayacure DETX-S.
（Ｅ）成分
・ＢＲ−６０：メタクリル系ポリマー（分子量７０，０００）、三菱レイヨン(株)製ダイヤナールＢＲ−６０。
(E) Component · BR-60: Methacrylic polymer (molecular weight 70,000), Mitsubishi Rayon Co., Ltd. Dianal BR-60.
＜実施例１〜４、比較例１＞
●組成物の調製と塗工性の評価
表１に示す成分を常法に従い撹拌・混合して光硬化型組成物を調製した。尚、表中の配合組成の数値は、部数を表す。
得られた組成物を室温でバーコータにより塗布し、８〜１２μｍ厚さに容易に塗工可能であったものを○と評価した。
<Examples 1-4, Comparative Example 1>
Preparation of Composition and Evaluation of Coating Property The components shown in Table 1 were stirred and mixed according to a conventional method to prepare a photocurable composition. In addition, the numerical value of the compounding composition in a table | surface represents a number of parts.
The obtained composition was applied with a bar coater at room temperature, and a film that could be easily applied to a thickness of 8 to 12 μm was evaluated as “good”.
●粘接着性硬化膜の作成と評価
得られた組成物の光照射後の粘接着性硬化膜について、光硬化型粘接着シート（被着体／粘接着性硬化膜／剥離材）を製造して評価した。
表１記載の組成物を、一方の被着体としてのＰＥＴフィルム（東洋紡(株)製コスモシャインＡ４３００、厚さ５０μｍ）に、バーコータ＃７で塗布した後、シリコン剥離処理ＰＥＴフィルム（シリコンＰＥＴ）をラミネートした。次いで、シリコンＰＥＴの上から、アイグラフィックス(株)製のコンベア式ＵＶ照射機（８０Ｗ／ｃｍ高圧水銀ランプ、平行光コールドミラー付き、ランプ高さ３０ｃｍ、ＵＶ−Ａの照射強度１４０ｍＷ／ｃｍ2（ＥＩＴ社製ＵＶ ＰＯＷＥＲ ＰＵＣＫの測定値））により、コンベア速度を調整して表２記載の照射量（ｍＪ／ｃｍ2）を照射した。得られた粘接着シートの粘接着性硬化膜の厚さは、８〜１２μｍであった。
得られた粘接着シートを１インチ幅の短冊状に切り出し、シリコンＰＥＴを剥離し、もう一方の被着体としてのコロナ処理ＰＭＭＡに貼り付け、貼り付け直後の剥離強度（Ｎ／インチ）を測定した（引張速度２００ｍｍ／分）。
剥離強度の測定結果を、照射量と共に、表２に示した。但し、照射量が少なすぎてシリコンＰＥＴに液移りした場合や、逆に照射量が多すぎてタックフリーとなった場合には、測定を省略した。
半硬化制御性について、貼り付け可能な照射量幅に基づき、下記基準に従い評価した。
○：３００ｍＪ／ｃｍ2以上であるもの
△：１００〜３００ｍＪ／ｃｍ2であるもの
×：１００ｍＪ／ｃｍ2未満又は場所による不均一性が見られたもの
● Creation and evaluation of adhesive-cured cured film About the adhesive-cured cured film after light irradiation of the obtained composition, a photo-curable adhesive sheet (adhered body / adhesive-cured cured film / release material) ) Was evaluated.
After applying the composition shown in Table 1 to a PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd., thickness 50 μm) as one adherend with a bar coater # 7, a silicon release-treated PET film (silicon PET) Was laminated. Next, a conveyor type UV irradiator (80 W / cm high-pressure mercury lamp, with a parallel light cold mirror, lamp height of 30 cm, UV-A irradiation intensity of 140 mW / cm 2 made by iGraphics Co., Ltd. from above silicon PET. (Measured value of UV POWER PUCK manufactured by EIT Co.) was used to adjust the conveyor speed and irradiate the irradiation amount (mJ / cm 2 ) described in Table 2. The thickness of the adhesive adhesive cured film of the obtained adhesive sheet was 8-12 micrometers.
The obtained adhesive sheet is cut into a 1-inch strip, the silicon PET is peeled off, and is attached to the corona-treated PMMA as the other adherend, and the peel strength (N / inch) immediately after being attached is determined. Measured (tensile speed 200 mm / min).
The measurement results of the peel strength are shown in Table 2 together with the irradiation amount. However, the measurement was omitted when the amount of irradiation was too small and the liquid was transferred to silicon PET, or when the amount of irradiation was too large and tack-free.
The semi-curing controllability was evaluated according to the following criteria based on the dose width that can be pasted.
○: 300mJ / cm 2 or more at which those △: 100~300mJ / cm 2 at which those ×: those heterogeneity by 100 mJ / cm 2 or less than the location was observed
表２の組成物はすべて、半硬化状態を制御することが可能であった。特に、（Ｂ）成分の全てが単官能アクリレートである実施例１〜３の組成物は、半硬化の制御が特に容易であった。 All the compositions in Table 2 were able to control the semi-cured state. In particular, the compositions of Examples 1 to 3 in which all of the component (B) were monofunctional acrylates were particularly easy to control semi-curing.
●本硬化後の接着力
粘接着シートの粘接着性硬化膜を被着体に貼り付け、再度光照射して硬化させたもの（本硬化させたもの）の接着力を、以下のようにして評価した。
表２において、粘接着性硬化膜の剥離強度が最大となる照射量で粘接着シートを作成した（基材は先の実験と同じＰＥＴフィルム）。この粘接着シートを、シリコンＰＥＴを剥離してコロナ処理ＰＭＭＡ板に貼り付けた。このとき、接着部分が１インチ四方となるようにした。
次いで、ＰＥＴ基材の側より、先の実験と同様に紫外線照射して本硬化させた。但し、コンベア速度は、１パスで１，０００ｍＪ／ｃｍ2となるよう調整し、３パス照射した（ＵＶ−Ａで合計３，０００ｍＪ／ｃｍ2）。
得られた接着物のせん断接着力を、引張速度１０ｍｍ／分で測定し、以下の基準で評価した。結果を表３に示す。
○：一方の被着体であるＰＥＴフィルムが伸びるまで剥離しなかったもの（１３０Ｎ／平方インチ以上）、
△：１００〜１３０Ｎ／平方インチのもの
×：１００Ｎ／平方インチ未満のもの
● Adhesive strength after main curing Adhesive strength of adhesives that have been cured by applying light-irradiated light again after applying the adhesive adhesive film of the adhesive sheet to the adherend is as follows. And evaluated.
In Table 2, a pressure-sensitive adhesive sheet was prepared with an irradiation amount at which the peel strength of the pressure-sensitive adhesive cured film was maximized (the base material was the same PET film as in the previous experiment). The adhesive sheet was affixed to a corona-treated PMMA plate by peeling off the silicon PET. At this time, the bonded portion was set to be 1 inch square.
Next, UV curing was performed from the side of the PET base material in the same manner as in the previous experiment, and main curing was performed. However, the conveyor speed was adjusted to 1,000 mJ / cm 2 in one pass and irradiated for 3 passes (total of 3000 mJ / cm 2 with UV-A).
The adhesive strength of the obtained adhesive was measured at a tensile speed of 10 mm / min and evaluated according to the following criteria. The results are shown in Table 3.
○: one that was not peeled off until the PET film as one adherend stretched (130 N / in 2 or more),
Δ: 100 to 130 N / square inch ×: less than 100 N / square inch
●空気が存在する部分の硬化性
本発明の組成物を使用して、微細な凹凸形状を有する光学フィルムの凸面を接着する場合、凹部には空気が存在する。光学フィルムの基材としてよく使用されるＰＥＴフィルムは、エネルギーの高い低波長の紫外線（ＵＶ−Ｂ及びＵＶ−Ｃ）をほぼ完全に吸収する。そのため、凹部の硬化条件は、「空気下ＰＥＴ越し」という（メタ）アクリル系光硬化型接着剤組成物にとって非常に不利な条件であるが、ここではこの条件下における硬化性を、以下のようにして評価した。
表２において、粘接着性硬化膜の剥離強度が最大となる照射量で粘接着シートを作成し、シリコンＰＥＴを剥離し、粘接着性硬化膜を上にしてトレイの上に置いた。この上に、ＰＥＴフィルムを、ＰＥＴフィルムが粘接着性硬化膜に接しないように覆い被せ、先の粘接着性硬化膜の作成実験と同様にして紫外線を照射した。但し、コンベア速度は、１パスで５００ｍＪ／ｃｍ2となるよう調整し、１パスごとに塗膜の硬化性を指触で評価した。そして、タックフリーとなったときの照射量に基づき、以下の基準で評価し、結果を表３に記載した。
◎：１，０００ｍＪ／ｃｍ2以下であったもの
○：１，０００〜２，０００ｍＪ／ｃｍ2であったもの
△：２，０００〜３，０００ｍＪ／ｃｍ2であったもの
×：３，０００ｍＪ／ｃｍ2以上であったもの
表３の結果は、次のことを示している。すなわち、本発明である実施例の組成物は、（Ａ）成分が有するマレイミド基の二量化反応は空気阻害を受けないため、空気下ＰＥＴ越しの硬化性が良好になり、マレイミドの二量化反応を増感する化合物を含む組成物（実施例２〜４）では、空気下ＰＥＴ越しの硬化性が特に良好になる。
● Curability of the portion where air exists When using the composition of the present invention to bond the convex surface of an optical film having a fine concavo-convex shape, air exists in the concave portion. PET films that are often used as optical film substrates absorb almost completely high energy, low wavelength ultraviolet (UV-B and UV-C). Therefore, the curing condition of the recess is a very disadvantageous condition for the (meth) acrylic photocurable adhesive composition called “through PET under air”. Here, the curability under this condition is as follows. And evaluated.
In Table 2, a pressure-sensitive adhesive sheet was prepared with an irradiation dose that maximized the peel strength of the pressure-sensitive adhesive cured film, and the silicon PET was peeled off and placed on the tray with the pressure-sensitive adhesive cured film facing up. . On top of this, the PET film was covered so that the PET film did not contact the adhesive-cured cured film, and irradiated with ultraviolet rays in the same manner as in the previous experiment for producing the adhesive-cured cured film. However, the conveyor speed was adjusted to 500 mJ / cm 2 in one pass, and the curability of the coating film was evaluated by touch with each pass. And based on the irradiation amount when it became tack-free, it evaluated on the following references | standards, and the result was described in Table 3.
◎: 1,000mJ / cm 2 or less a thing ○: 1,000~2,000mJ / cm 2 and was the thing △: 2,000~3,000mJ / cm 2 and it was the thing ×: 3,000mJ What was more than / cm < 2 > The result of Table 3 has shown the following. That is, since the dimerization reaction of the maleimide group of the component (A) is not subject to air inhibition in the composition of the example of the present invention, the curability through PET under air is improved, and the maleimide dimerization reaction In the compositions (Examples 2 to 4) containing a compound that sensitizes the curable resin, the curability through PET under air is particularly good.
●粘接着剤としての評価結果のまとめ
表３に、凹凸形状を有する被着体の接着に使用する場合の総合評価を付記した。総合評価は、以下の基準で評価した。
◎：△も×もないもの
○：△が１つのもの
△：×はないが△が複数あるもの
×：１項目でも×があったもの
● Summary of Evaluation Results as Adhesives Table 3 shows the comprehensive evaluation when used for bonding adherends having uneven shapes. The overall evaluation was based on the following criteria.
◎: No △ or × ○: △ is one △: There is no x, but there are multiple △ ×: One item has x
表３の結果から、本発明の組成物は、凹凸形状を有する被着体の接着に好適であった。特に、成分（Ｄ）を含む実施例２〜実施例４は、空気存在部分の硬化性が優れていた。又、成分（Ｂ）の全てが単官能アクリレートである実施例２及び実施例３は、半硬化制御性や本硬化後の接着力の点でも優れていた。 From the results of Table 3, the composition of the present invention was suitable for adhesion of adherends having uneven shapes. In particular, Examples 2 to 4 including the component (D) were excellent in curability of the air-existing portion. In addition, Example 2 and Example 3 in which all of the component (B) is a monofunctional acrylate were also excellent in terms of semi-curing controllability and adhesive strength after main curing.
＜実施例５＞
●光硬化型粘接着シート（剥離材／粘接着性硬化膜／剥離材）の製造
実施例３の組成物を、シリコンＰＥＴにバーコータ＃７で塗布した後、シリコンＰＥＴをラミネートし、アイグラフィックス(株)製のコンベア式ＵＶ照射機（８０Ｗ／ｃｍ高圧水銀ランプ、平行光コールドミラー付き、ランプ高さ３０ｃｍ、ＵＶ−Ａの照射強度１４０ｍＷ／ｃｍ2（ＥＩＴ社製ＵＶ ＰＯＷＥＲ ＰＵＣＫの測定値））により、コンベア速度を調整して３００ｍＪ／ｃｍ2ＵＶ照射し、本発明の光硬化型粘接着シートを作成した。得られた粘接着シートの厚さは、８〜１２μｍであった。
<Example 5>
● Manufacture of photo-curing type adhesive sheet (peeling material / adhesive cured film / peeling material) The composition of Example 3 was applied to silicon PET with a bar coater # 7, and then silicon PET was laminated. Conveyor type UV irradiator manufactured by Graphics Co., Ltd. (80 W / cm high-pressure mercury lamp, with parallel light cold mirror, lamp height 30 cm, UV-A irradiation intensity 140 mW / cm 2 (measurement of UV POWER PUCK manufactured by EIT) Value)), the conveyor speed was adjusted and 300 mJ / cm 2 UV irradiation was performed to prepare the photo-curing adhesive sheet of the present invention. The thickness of the obtained adhesive sheet was 8 to 12 μm.
●ＰＥＴフィルムとＰＭＭＡ板の接着と評価
まず、上記した光硬化型粘接着シートの一方のシリコンＰＥＴを剥離した後、ＰＥＴフィルム（東洋紡(株)製コスモシャインＡ４３００、厚さ５０μｍ）にローラーで貼り付けた。これを、１インチ幅の短冊状に切り出し、残ったもう一方のシリコンＰＥＴを剥離し、コロナ処理ＰＭＭＡ板にローラーで貼り付けた。このとき、接着部分が1インチ四方となるようにした。最後に、実施例１等と同様にして３，０００ｍＪ／ｃｍ2のＵＶ照射を行って硬化し接着した。
得られた接着物のせん断接着力を、実施例１等と同様に評価した。その結果、一方の被着体であるＰＥＴフィルムが伸びるまで剥離せず、表３で「○」と表記される良好な接着力であった。
● Adhesion and evaluation of PET film and PMMA plate First, after peeling off one silicon PET of the above-mentioned photo-curing type adhesive sheet, a PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd., 50 μm thick) with a roller Pasted. This was cut into a 1-inch wide strip, the other remaining silicon PET was peeled off, and attached to a corona-treated PMMA plate with a roller. At this time, the bonded portion was set to be 1 inch square. Finally, UV irradiation of 3,000 mJ / cm 2 was performed and cured and adhered in the same manner as in Example 1 and the like.
The shear adhesive strength of the obtained adhesive was evaluated in the same manner as in Example 1. As a result, it did not peel until the PET film as one adherend was stretched, and the adhesive strength indicated as “◯” in Table 3 was obtained.
●空気が存在する部分の硬化性
上記した光硬化型粘接着シートの一方のシリコンＰＥＴを剥離した後、ＰＥＴフィルムに貼り付け、残ったもう一方のシリコンＰＥＴを剥離した。この上に、ＰＥＴフィルムを、ＰＥＴフィルムが粘着塗膜に接しないように覆い被せ、実施例１等と同様にＵＶ照射して硬化性を評価した。その結果、タックフリーとなったときの照射量は１，０００ｍＪ／ｃｍ2以下であり、表３で「◎」と表記される良好な硬化性であった。
● Curability of the portion where air is present After peeling one silicon PET of the above-mentioned photo-curing adhesive sheet, it was attached to a PET film, and the other remaining silicon PET was peeled. On top of this, a PET film was covered so that the PET film did not come into contact with the adhesive coating film, and the curability was evaluated by UV irradiation in the same manner as in Example 1 and the like. As a result, the irradiation amount when tack-free was 1,000 mJ / cm 2 or less, and good curability expressed as “◎” in Table 3.
本発明の光硬化型粘接着剤製造用の光硬化型組成物及び光硬化型粘接着シートは、広範な接着用途に使用でき、特に、凹凸形状を有する被着体の凸部分の接着に好適に使用できる。より具体的には、ディスプレイ材料等の光学部品の製造に好ましく使用できる。 The photocurable composition and the photocurable adhesive sheet for producing the photocurable adhesive of the present invention can be used for a wide range of adhesive applications, and in particular, adhesion of the convex portion of an adherend having an uneven shape. Can be suitably used. More specifically, it can be preferably used for the production of optical parts such as display materials.
Claims (13)
〔但し、一般式（１）において、Ｒ1及びＲ2は、それぞれ独立して水素原子、ハロゲン原子、アルキル基若しくはアリール基を表すか、又はＲ1及びＲ2は一つとなって５員環若しくは６員環を形成する炭化水素基を表す。〕 The photocurable composition for producing a photocurable adhesive according to claim 1, wherein the maleimide group in the component (A) is a group represented by the following general formula (1).
[However, in General Formula (1), R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, or R 1 and R 2 are combined to form a 5-membered ring. Alternatively, it represents a hydrocarbon group forming a 6-membered ring. ]
〔但し、式（２）において、Ｒ1及びＲ2は前記と同様の意味を示す。又、Ｒ3はアルキレン基を表し、Ｒ4は水素原子又はメチル基を表し、ｎは１から６の整数を表す。〕 The photocurable composition for producing a photocurable adhesive according to claim 2, wherein the component (A) is a compound represented by the following general formula (2).
[However, in Formula (2), R < 1 > and R < 2 > show the same meaning as the above. R 3 represents an alkylene group, R 4 represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6. ]
工程１：基材に、請求項１〜請求項９のいずれかに記載の組成物を塗布する。
工程２：基材側又は塗布面側から光照射して、前記組成物を半硬化させ粘接着性硬化膜を形成させる。
工程３：粘接着性硬化膜と他の基材を密着させる。
工程４：基材のいずれか一方から光照射して、前記硬化膜を完全硬化させる。 A bonding method of a substrate including the following steps 1 to 4.
Process 1: The composition in any one of Claims 1-9 is apply | coated to a base material.
Process 2: Light irradiation is performed from the substrate side or the coating surface side, and the composition is semi-cured to form an adhesive-adhesive cured film.
Process 3: Adhesive adhesive film and another base material are stuck.
Step 4: Irradiate light from any one of the substrates to completely cure the cured film.
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