JP4318743B1 - Ultraviolet curable removable pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet using the same - Google Patents
Ultraviolet curable removable pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet using the same Download PDFInfo
- Publication number
- JP4318743B1 JP4318743B1 JP2008261055A JP2008261055A JP4318743B1 JP 4318743 B1 JP4318743 B1 JP 4318743B1 JP 2008261055 A JP2008261055 A JP 2008261055A JP 2008261055 A JP2008261055 A JP 2008261055A JP 4318743 B1 JP4318743 B1 JP 4318743B1
- Authority
- JP
- Japan
- Prior art keywords
- group
- sensitive adhesive
- hydrogen atom
- ethylenically unsaturated
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 79
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 239000003522 acrylic cement Substances 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 230000009257 reactivity Effects 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 50
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 13
- 230000009477 glass transition Effects 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 45
- 230000001070 adhesive effect Effects 0.000 abstract description 45
- 235000012431 wafers Nutrition 0.000 abstract description 18
- 239000002313 adhesive film Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract 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 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 21
- 238000001723 curing Methods 0.000 description 19
- -1 acrylate ester Chemical class 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000003822 epoxy resin Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 229920000647 polyepoxide Polymers 0.000 description 14
- 239000000178 monomer Substances 0.000 description 12
- 238000003848 UV Light-Curing Methods 0.000 description 11
- 230000008859 change Effects 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 229920003986 novolac Polymers 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000005855 radiation Effects 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- IIQWTZQWBGDRQG-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C(C)=C IIQWTZQWBGDRQG-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Chemical class 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 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 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 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
- 239000011259 mixed solution Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QASBHTCRFDZQAM-UHFFFAOYSA-N (2-isocyanato-2-methyl-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(C)(COC(=O)C=C)N=C=O QASBHTCRFDZQAM-UHFFFAOYSA-N 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- FFBZKUHRIXKOSY-UHFFFAOYSA-N aziridine-1-carboxamide Chemical compound NC(=O)N1CC1 FFBZKUHRIXKOSY-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 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
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-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
- HUYKZYIAFUBPAQ-UHFFFAOYSA-N (2-hydroxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1O HUYKZYIAFUBPAQ-UHFFFAOYSA-N 0.000 description 1
- BWZAUXRKSMJLMH-UHFFFAOYSA-N 1,1-diethoxyethylbenzene Chemical compound CCOC(C)(OCC)C1=CC=CC=C1 BWZAUXRKSMJLMH-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-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
- UYEDESPZQLZMCL-UHFFFAOYSA-N 1,2-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(C)C(C)=CC=C3SC2=C1 UYEDESPZQLZMCL-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
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- FWWWRCRHNMOYQY-UHFFFAOYSA-N 1,5-diisocyanato-2,4-dimethylbenzene Chemical compound CC1=CC(C)=C(N=C=O)C=C1N=C=O FWWWRCRHNMOYQY-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- ZVEMLYIXBCTVOF-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-3-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC(C(C)(C)N=C=O)=C1 ZVEMLYIXBCTVOF-UHFFFAOYSA-N 0.000 description 1
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 1
- CTOHEPRICOKHIV-UHFFFAOYSA-N 1-dodecylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CCCCCCCCCCCC CTOHEPRICOKHIV-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- TXTIIWDWHSZBRK-UHFFFAOYSA-N 2,4-diisocyanato-1-methylbenzene;2-ethyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)CO.CC1=CC=C(N=C=O)C=C1N=C=O TXTIIWDWHSZBRK-UHFFFAOYSA-N 0.000 description 1
- ZDTLUUIYCAMIMQ-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.COC(O)COCCO ZDTLUUIYCAMIMQ-UHFFFAOYSA-N 0.000 description 1
- CMCLUJRFBZBVSW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(O)COCCO CMCLUJRFBZBVSW-UHFFFAOYSA-N 0.000 description 1
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-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
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical group COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- JEHFRMABGJJCPF-UHFFFAOYSA-N 2-methylprop-2-enoyl isocyanate Chemical compound CC(=C)C(=O)N=C=O JEHFRMABGJJCPF-UHFFFAOYSA-N 0.000 description 1
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 1
- NOIHCCJQOJZSKD-UHFFFAOYSA-N 2-n-(hexoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound CCCCCCOCNC1=NC(N)=NC(N)=N1 NOIHCCJQOJZSKD-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- LNNIPFBETXOKIA-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-9h-fluoren-2-yl]phenol Chemical compound C1=CC(O)=CC=C1C1=CC=C(C=2C(=CC=CC=2)C2)C2=C1C1=CC=C(O)C=C1 LNNIPFBETXOKIA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
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- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
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- 239000004840 adhesive resin Substances 0.000 description 1
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- 125000003282 alkyl amino group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
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- 238000005227 gel permeation chromatography Methods 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- KCNSDMPZCKLTQP-UHFFFAOYSA-N tetraphenylen-1-ol Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=CC=CC=C2C2=C1C=CC=C2O KCNSDMPZCKLTQP-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/54—Polycondensates of aldehydes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
- C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
- C08G18/683—Unsaturated polyesters containing cyclic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
- C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
- C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2463/00—Presence of epoxy resin
Abstract
【課題】
ウエハなどの集積回路形成に有用な成膜性のある紫外線硬化型粘着剤として、ダイシングテープに有用な硬化前後における粘着膜の強度の低減が好ましい範囲で、保持力が高く、硬化膜を剥離した際に、ウエハ表面に糊残りのない硬化膜を与える紫外線硬化型再剥離性粘着剤を提供する。
【解決手段】
本発明は、（ａ）アクリル系粘着性ポリマー、（ｂ）多官能エポキシアクリレート、（ｃ）光重合開始剤、（ｄ）水酸基、カルボキシル基又はエポキシ基に対して反応性を有する硬化剤からなる紫外線硬化型再剥離性粘着剤に関する。また、本発明は、前記紫外線硬化型再剥離性粘着剤組成物を用いた粘着シートに関する。
【選択図】 なし【Task】
As a UV-curable adhesive with film-forming properties useful for the formation of integrated circuits such as wafers, it is preferable to reduce the strength of the adhesive film before and after curing useful for dicing tape. In this case, an ultraviolet curable removable pressure-sensitive adhesive that gives a cured film having no adhesive residue on the wafer surface is provided.
[Solution]
The present invention comprises (a) an acrylic adhesive polymer, (b) a polyfunctional epoxy acrylate, (c) a photopolymerization initiator, (d) a curing agent having reactivity with a hydroxyl group, a carboxyl group or an epoxy group. The present invention relates to an ultraviolet curable removable adhesive. Moreover, this invention relates to the adhesive sheet using the said ultraviolet curable removable adhesive composition.
[Selection figure] None
Description
本発明は、ＩＣパッケージおよび半導体ウエハの集積回路形成等のダイシング加工に際し、半導体ウエハの表面を保護しつつ、素子小片に分離されるまで、該素子小片を固定・維持するために使用される仮止め用粘着シートに用いられる紫外線硬化型再剥離性粘着剤組成物に関する。 The present invention provides a temporary use for fixing and maintaining an element piece until it is separated into element pieces while protecting the surface of the semiconductor wafer during dicing processing such as IC package and semiconductor wafer integrated circuit formation. The present invention relates to an ultraviolet curable removable pressure-sensitive adhesive composition used for a pressure-sensitive adhesive sheet for fastening.
近年、半導体の製造工程において、ウエハの薄型化にともないダイシング時に発生するチッピングやクラックが一層問題視されるようになった。これらの原因はダイシング中に高速回転するブレードにより切断中のチップが振動してしまうことが主な原因だと考えられている。これらに用いられるダイシングテープはダイシング中のチップ振動が抑制されるような設計となり、粘着剤としては粘着力、保持力が高いことが要求される。 In recent years, chipping and cracks that occur during dicing are becoming more problematic in semiconductor manufacturing processes as wafers become thinner. It is considered that these causes are mainly caused by the vibration of the chip being cut by the blade rotating at high speed during dicing. The dicing tape used for these is designed to suppress chip vibration during dicing, and the adhesive is required to have high adhesive force and holding force.
このような中、例えば、基材フィルムと、この上に形成された放射線硬化型粘着剤層とからなるウェハ貼着用粘着シートであって、放射線硬化型粘着剤層が、アクリル酸エステルとＯＨ基含有重合性単量体とを共重合してなるアクリル系粘着剤と、不飽和結合を２個以上有する放射線重合性化合物とからなり、放射線重合性化合物の２０〜８０重量％が不飽和結合を４個以上有し、かつ、放射線硬化後における弾性率が１×１０９ｄｙｎ／ｃｍ２以上であるウェハ貼着用粘着シート（特許文献１）が開示されている。また、アクリル樹脂エマルジョン系粘着剤、多官能（メタ）アクリレート化合物および活性光線硬化型界面活性剤を含有することを特徴とする活性光線硬化型再剥離性粘着剤組成物（特許文献２）、さらには、重量平均分子量が１万〜２００万、ガラス転移温度が−１００〜１００℃であるポリマー、重合性の炭素−炭素二重結合を有するモノマー、重合性の炭素−炭素二重結合を有するオリゴマー、及び開始剤からなる粘着性樹脂組成物であって、紫外線硬化することにより、紫外線硬化前から紫外線硬化後の粘着剤層の粘着力が１／３以下となる粘着性樹脂組成物（特許文献３）が開示されている。 Among these, for example, a wafer sticking pressure-sensitive adhesive sheet comprising a base film and a radiation-curable pressure-sensitive adhesive layer formed thereon, wherein the radiation-curable pressure-sensitive adhesive layer comprises an acrylate ester and an OH group. It consists of an acrylic pressure-sensitive adhesive obtained by copolymerization with a polymerizable monomer and a radiation polymerizable compound having two or more unsaturated bonds, and 20 to 80% by weight of the radiation polymerizable compound has an unsaturated bond. A pressure-sensitive adhesive sheet for adhering to a wafer (Patent Document 1) having 4 or more and an elastic modulus after radiation curing of 1 × 10 9 dyn / cm 2 or more is disclosed. An actinic radiation curable releasable adhesive composition containing an acrylic resin emulsion-based adhesive, a polyfunctional (meth) acrylate compound and an actinic radiation curable surfactant (Patent Document 2), Is a polymer having a weight average molecular weight of 10,000 to 2,000,000 and a glass transition temperature of −100 to 100 ° C., a monomer having a polymerizable carbon-carbon double bond, and an oligomer having a polymerizable carbon-carbon double bond And an adhesive resin composition comprising an initiator, wherein the adhesive strength of the pressure-sensitive adhesive layer after ultraviolet curing becomes 1/3 or less by ultraviolet curing (Patent Document) 3) is disclosed.
また、エポキシ樹脂等で封止されたボール・グリッド・アレイ（ＢＧＡ）やチップ・サイズ・パッケージ（ＣＳＰ）などのＩＣパッケージを個別化するためのパッケージ用ダイシングテープにも同様な配慮が必要であり、例えば、紫外線及び／又は電子線に対し透過性を有するフィルム基材面上にベース樹脂、放射線重合性化合物、放射線重合性重合開始剤、並びに架橋剤からなる粘着剤を塗布してなる半導体基板加工用粘着テープであって、放射線重合性化合物が５官能以上のアクリレートモノマーからなる半導体基板加工用粘着テープ（特許文献４）が、開示されている。 Similar considerations are required for package dicing tape for individualizing IC packages such as ball grid array (BGA) and chip size package (CSP) sealed with epoxy resin. For example, a semiconductor substrate obtained by applying a base resin, a radiation-polymerizable compound, a radiation-polymerizable polymerization initiator, and a pressure-sensitive adhesive composed of a crosslinking agent on a film substrate surface that is transparent to ultraviolet rays and / or electron beams An adhesive tape for processing, which is a semiconductor substrate processing adhesive tape (Patent Document 4), in which a radiation polymerizable compound is composed of a pentafunctional or higher functional acrylate monomer, is disclosed.
本発明の目的は、ウエハなどの集積回路形成に有用な成膜性のある紫外線硬化型粘着剤として、ダイシングテープに有用な硬化前後における粘着膜の強度の低減が好ましい範囲で、保持力が高く、硬化膜を剥離した際に、ウエハ表面に糊残りのない硬化膜を与える紫外線硬化型再剥離性粘着剤を提供することにある。 The object of the present invention is to form a UV curable adhesive having a film forming property useful for forming an integrated circuit such as a wafer, and to reduce the strength of the adhesive film before and after curing useful for dicing tape, and has a high holding power. Another object of the present invention is to provide an ultraviolet curable removable pressure-sensitive adhesive that gives a cured film having no adhesive residue on the wafer surface when the cured film is peeled off.
そこで、本発明者らはかかる問題を解決するために、紫外線硬化型再剥離性粘着剤について鋭意研究を重ねた結果、（ａ）アクリル系粘着性ポリマー、（ｂ）多官能エポキシアクリレート、（ｃ）光重合開始剤、（ｄ）水酸基、カルボキシル基又はエポキシ基に対して反応性を有する硬化剤を含む紫外線硬化型再剥離性粘着剤が上記課題を解決することを見いだし、本発明を完成した。 Therefore, in order to solve such problems, the present inventors have conducted extensive research on ultraviolet curable removable pressure-sensitive adhesives. As a result, (a) acrylic pressure-sensitive polymer, (b) polyfunctional epoxy acrylate, (c It was found that an ultraviolet curable removable pressure-sensitive adhesive containing a photopolymerization initiator, (d) a curing agent reactive with a hydroxyl group, a carboxyl group or an epoxy group solves the above-mentioned problems, and completed the present invention. .
すなわち、本発明は、（ａ）アクリル系粘着性ポリマー、（ｂ）多官能エポキシアクリレート、（ｃ）光重合開始剤、（ｄ）水酸基、カルボキシル基又はエポキシ基に対して反応性を有する硬化剤からなり、（ｂ）多官能エポキシアクリレートが式（１）：
Ｘは、式（４）：
Ｒ２、Ｒ５、Ｒ７、Ｒ９又はＲ１１は、水素原子若しくは式（６）：
アクリル系粘着性ポリマー（ａ）１００質量部に対して、多官能エポキシアクリレート（ｂ）２０〜２００質量部からなることが好ましい。 It is preferable that it consists of 20-200 mass parts of polyfunctional epoxy acrylate (b) with respect to 100 mass parts of acrylic adhesive polymers (a).
アクリル系粘着性ポリマー（ａ）は、重量平均分子量２０万〜２００万で、ガラス転移温度が−５０℃〜１０℃であり、且つ水酸基を有する（メタ）アクリル酸エステル共重合体からなることが好ましい。 The acrylic pressure-sensitive adhesive polymer (a) has a weight average molecular weight of 200,000 to 2,000,000, a glass transition temperature of −50 ° C. to 10 ° C., and a (meth) acrylic acid ester copolymer having a hydroxyl group. preferable.
多官能エポキシアクリレート（ｂ）は、エポキシアクリレートとα，β−エチレン性不飽和モノイソシアナートとの反応性生成物であることが好ましい。 The polyfunctional epoxy acrylate (b) is preferably a reactive product of an epoxy acrylate and an α, β-ethylenically unsaturated monoisocyanate.
また、本発明は前記紫外線硬化型再剥離性粘着剤組成物を用いた粘着シートに関する。 Moreover, this invention relates to the adhesive sheet using the said ultraviolet curable removable adhesive composition.
本発明によれば、ウエハなどの集積回路形成に有用な成膜性のある紫外線硬化型粘着剤として、塗工後の粘着層の外観に優れ、ダイシングテープに有用な硬化前後における粘着膜の強度の低減が好ましい範囲で、保持力が高く、紫外線照射による硬化膜を剥離した際に、ウエハ表面に糊残りのない硬化膜を与える紫外線硬化型再剥離性粘着剤を提供することができる。 According to the present invention, as an ultraviolet curable pressure-sensitive adhesive having a film forming property useful for forming an integrated circuit such as a wafer, the pressure-sensitive adhesive layer has an excellent appearance after coating and is useful for a dicing tape. Therefore, it is possible to provide an ultraviolet curable removable pressure-sensitive adhesive that gives a cured film having no adhesive residue on the wafer surface when the cured film is peeled off by ultraviolet irradiation.
以下、本発明について具体的に説明する。本発明の紫外線硬化型再剥離性粘着剤組成物におけるアクリル系粘着性ポリマー（ａ）は、水酸基、カルボキシル基又はエポキシ基に対して反応性を有する硬化剤（ｄ）（以下、硬化剤（ｄ）という）と架橋反応を行ない、アクリル系粘着性ポリマーの凝集力を高める点から、分子中に水酸基を有することが好ましい。アクリル系粘着性ポリマー（ａ）は、具体的にはアクリル酸系アルキルエステル系あるいはメタクリル酸系アルキルエステル系の主モノマーと、水酸基を含有する（メタ）アクリレートとの共重合体である。特に水酸基を有するモノマーとしてはヒドロキシアルキル（メタ）アクリレート（２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート）が好ましい。 Hereinafter, the present invention will be specifically described. The acrylic pressure-sensitive adhesive polymer (a) in the ultraviolet curable removable pressure-sensitive adhesive composition of the present invention is a curing agent (d) (hereinafter referred to as a curing agent (d) having reactivity to a hydroxyl group, a carboxyl group or an epoxy group. )) And a hydroxyl group in the molecule from the viewpoint of increasing the cohesive strength of the acrylic adhesive polymer. The acrylic adhesive polymer (a) is specifically a copolymer of an acrylic acid alkyl ester-based or methacrylic acid alkyl ester-based main monomer and a (meth) acrylate containing a hydroxyl group. In particular, hydroxyalkyl (meth) acrylate (2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate) is preferable as the monomer having a hydroxyl group.
アクリル系粘着性ポリマー（ａ）を構成する主モノマーとしては、例えば、アクリル酸エステル（メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉｓｏ−ブチル（メタ）クリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボロニル（メタ）アクリレート等）、アルキルビニルエーテル化合物（アクリル酸２−メトキシエチル、メタクリル酸２−メトキシエチル、アクリル酸３−メトキシエチル、メタクリル酸３−メトキシエチル、アクリル酸メトキシジエチレングリコール、メタクリル酸メトキシジエチレングリコール）が用いられる。 Examples of the main monomer constituting the acrylic adhesive polymer (a) include acrylic acid esters (methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate), tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, etc.), alkyl vinyl ether compound (acrylic acid 2- Methoxyethyl, 2-methoxyethyl methacrylate, 3-methoxyethyl acrylate, 3-methoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate) It is.
また、前記共重合体には、本発明の主旨を逸脱しない範囲で上記以外の不飽和化合物（モノマー）を共重合することも可能で、このようなモノマーとしては、芳香族ビニル化合物（スチレン、α−メチルスチレン、ｐ−メチルスチレン、エチルビニルベンゼン等）、複素環式ビニル化合物（ビニルピロリドン等）、ポリアルキレンレングリコール（メタ）アクリレート（エチレングリコール（メタ）アクリレート、ブチレングリコール（メタ）アクリレート等）、アルキルアミノ（メタ）アクリレート（Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート等）、ビニルエステル化合物（蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル、バーサチツク酸ビニル）、アクリル酸、メタクリル酸が好ましい。 The copolymer can be copolymerized with an unsaturated compound (monomer) other than those described above without departing from the gist of the present invention. Examples of such a monomer include aromatic vinyl compounds (styrene, α-methylstyrene, p-methylstyrene, ethyl vinyl benzene, etc.), heterocyclic vinyl compounds (vinyl pyrrolidone, etc.), polyalkylene glycol (meth) acrylate (ethylene glycol (meth) acrylate, butylene glycol (meth) acrylate, etc.) ), Alkylamino (meth) acrylate (N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, etc.), vinyl ester compounds (vinyl formate, vinyl acetate, vinyl propionate, versatic) Acid vinyl), acrylic acid, metak Le acid is preferred.
主モノマーと、水酸基を含有するモノマーの共重合比（質量比）は９９．９／０．１〜７０／３０が好ましく、９９．５／０．５〜９０／１０がより好ましい。共重合比がこの範囲外の場合は、再剥離時に粘着剤組成物が被着面に残存する傾向がある。 The copolymerization ratio (mass ratio) of the main monomer and the monomer containing a hydroxyl group is preferably 99.9 / 0.1 to 70/30, more preferably 99.5 / 0.5 to 90/10. When the copolymerization ratio is outside this range, the pressure-sensitive adhesive composition tends to remain on the adherend surface during re-peeling.
また、アクリル系粘着性ポリマー（ａ）を製造するにあたっては、特に制限されないが、有機溶媒中に主モノマー、水酸基を含有するモノマー、重合開始剤（アゾビスイソブチロニトリル、アゾビスイソバレロニトリル、過酸化ベンゾイル等）を混合あるいは滴下し、還流状態あるいは５０〜９０℃で４〜２０時間重合させる方法が好適に採用される。 Further, in producing the acrylic adhesive polymer (a), although not particularly limited, a main monomer, a monomer containing a hydroxyl group in an organic solvent, a polymerization initiator (azobisisobutyronitrile, azobisisovaleronitrile) Benzoyl peroxide, etc.) may be mixed or dropped and polymerized at reflux or at 50 to 90 ° C. for 4 to 20 hours.
得られるアクリル系粘着性ポリマー（ａ）の重量平均分子量は２０万〜２００万であることが必要で、好ましくは２０万〜１５０万、更には４０万〜１００万である。かかる重量平均分子量が２０万未満では、再剥離時に粘着剤組成物が被着面に残存する傾向がある。 The acrylic adhesive polymer (a) obtained should have a weight average molecular weight of 200,000 to 2,000,000, preferably 200,000 to 1,500,000, and more preferably 400,000 to 1,000,000. When the weight average molecular weight is less than 200,000, the pressure-sensitive adhesive composition tends to remain on the adherend surface during re-peeling.
また、アクリル系粘着性ポリマー（ａ）のガラス転移温度も−５０〜１０℃であることが好ましく、より好ましくは−４０〜−１５℃である。アクリル系粘着性ポリマー（ａ）のガラス転移温度が−５０℃未満では、多官能エポキシアクリレート（ｂ）との相溶性に劣り、紫外線あるいは放射線を照射した後の再剥離時の粘着力が十分に低下しないためにこの場合も粘着剤組成物が被着面に残存する傾向にあり、逆に１０℃を越えると十分な粘着力を得ることができない傾向にある。 The glass transition temperature of the acrylic adhesive polymer (a) is also preferably −50 to 10 ° C., more preferably −40 to −15 ° C. When the glass transition temperature of the acrylic adhesive polymer (a) is less than −50 ° C., the compatibility with the polyfunctional epoxy acrylate (b) is inferior, and the adhesive force upon re-peeling after irradiation with ultraviolet rays or radiation is sufficient. In this case as well, the pressure-sensitive adhesive composition tends to remain on the adherend surface, and when it exceeds 10 ° C., sufficient pressure-sensitive adhesive strength tends not to be obtained.
本発明において使用される多官能エポキシアクリレート（ｂ）はエポキシアクリレートの変性物である。すなわち、エポキシアクリレート中の２級水酸基とα，β−エチレン性不飽和モノイソシアナートを反応させることにより得られる。 The polyfunctional epoxy acrylate (b) used in the present invention is a modified product of epoxy acrylate. That is, it can be obtained by reacting a secondary hydroxyl group in an epoxy acrylate with an α, β-ethylenically unsaturated monoisocyanate.
エポキシアクリレートは、エポキシ樹脂とα，β−不飽和一塩基酸、例えばアクリル酸および／またはメタクリル酸とをエポキシ基に対して５０モル％以上、好ましくは８０モル％以上で公知の方法により反応させて得られる樹脂であり、例えば「滝山栄一郎著、ポリエステル樹脂ハンドブック」（日刊工業新聞社編、１９８８年刊）または「塗料用語辞典」（色材協会編、１９９３年刊）などに記載されている。なお、前記の如く、エポキシアクリレートは、α，β−不飽和一塩基酸をエポキシ樹脂のエポキシ基に対して５０モル％以上、好ましくは８０モル％以上反応させて得られたものであり、未反応のエポキシ基を有するものも含む概念である。 Epoxy acrylate is obtained by reacting an epoxy resin with an α, β-unsaturated monobasic acid such as acrylic acid and / or methacrylic acid by a known method at 50 mol% or more, preferably 80 mol% or more with respect to the epoxy group. For example, it is described in “Eiichiro Takiyama, Polyester Resin Handbook” (edited by Nikkan Kogyo Shimbun, published in 1988) or “Dictionary of Paint Terms” (edited by Color Material Association, published in 1993). As described above, the epoxy acrylate is obtained by reacting α, β-unsaturated monobasic acid with 50 mol% or more, preferably 80 mol% or more with respect to the epoxy group of the epoxy resin. It is a concept including those having an epoxy group of reaction.
エポキシ樹脂としてはビスフェノール型（例えばビフェノール、ビスフェノールＡ、水添ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ビスフェノールＳＨ、ビスフェノールＺ、４，４’−ジヒドロキシベンゾフェノン、２，４’−ジヒドロキシベンゾフェノン、ビス（４−ヒドロキシフェニル）フルオレン、カテコール、レゾルシン、ハイドロキノン、ジヒドロキシナフタレンなどのビスフェノール類、テトラクロロビスフェノールＡ等）、ノボラック型（フェノールノボラック、クレゾールノボラック、ビスフェノールＡノボラック、ジシクロペンタジエン−フェノールノボラック等）、ナフトールアラルキル型、フェノールアラルキル型、テトラフェニロールエタン型エポキシ樹脂、環状脂肪族エポキシ樹脂、トリグリシジルイソシアヌレート及びこれらに臭素原子などのハロゲン原子を導入したものなどが挙げられる。ここで紫外線を照射した後の再剥離時の粘着力を十分に低下させるために、これらの中で、ビスフェノールＡ型、ビスフェノールＦ型、水添ビスフェノールＡ型、フェノールノボラック型、クレゾールノボラック型エポキシ樹脂、トリグリシジルイソシアヌレートを使用することが好ましい。これらのエポキシ樹脂は１種または２種以上を併用しても良い。 Epoxy resins include bisphenol types (for example, biphenol, bisphenol A, hydrogenated bisphenol A, bisphenol F, bisphenol S, bisphenol SH, bisphenol Z, 4,4'-dihydroxybenzophenone, 2,4'-dihydroxybenzophenone, bis (4- Hydroxyphenyl) fluorene, catechol, resorcin, hydroquinone, dihydroxynaphthalene and other bisphenols, tetrachlorobisphenol A, etc.), novolak type (phenol novolac, cresol novolac, bisphenol A novolak, dicyclopentadiene-phenol novolak, etc.), naphthol aralkyl type , Phenol aralkyl type, tetraphenylol ethane type epoxy resin, cycloaliphatic epoxy resin, triglycy Such as Le isocyanurate and these obtained by introducing a halogen atom such as a bromine atom. Here, in order to sufficiently reduce the adhesive strength at the time of re-peeling after irradiation with ultraviolet rays, among them, bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, phenol novolac type, cresol novolac type epoxy resin It is preferable to use triglycidyl isocyanurate. These epoxy resins may be used alone or in combination of two or more.
エポキシアクリレート中の２級水酸基と反応させるα，β−エチレン性不飽和モノイソシアナートとしては、例えばＭＡＩ（メタクリロイルイソシアナート、日本ペイント（株）製）、カレンズＭＯＩ（イソシアナートエチルメタクリレート、昭和電工（株）製）、カレンズＡＯＩ（イソシアナートエチルアクリレート、昭和電工（株）製）、カレンズＢＥＩ（１，１-ビスアクリロイルオキシメチルエチルイソシアネート、昭和電工（株）製）が挙げられる。その他の重合性モノイソシアナートとしては、ｍ−ＴＭＩ（３−イソプロペニルーα，α’−ジメチルベンジルイソシアナート、アメリカンサイアナミド社製）も挙げられ、本発明の主旨を妨げぬ範囲で使用してもよい。中でも、紫外線硬化後に粘着力が十分に低下する点で、イソシアナートエチルアクリレート、イソシアナートエチルメタクリレート、１，１-ビスアクリロイルオキシメチルエチルイソシアネートが好ましい。 Examples of the α, β-ethylenically unsaturated monoisocyanate to be reacted with the secondary hydroxyl group in epoxy acrylate include MAI (methacryloyl isocyanate, manufactured by Nippon Paint Co., Ltd.), Karenz MOI (isocyanatoethyl methacrylate, Showa Denko ( Co., Ltd.), Karenz AOI (isocyanate ethyl acrylate, Showa Denko K.K.), Karenz BEI (1,1-bisacryloyloxymethylethyl isocyanate, Showa Denko K.K.). Examples of other polymerizable monoisocyanates include m-TMI (3-isopropenyl-α, α'-dimethylbenzyl isocyanate, manufactured by American Cyanamid Co., Ltd.). Also good. Among these, isocyanate ethyl acrylate, isocyanate ethyl methacrylate, and 1,1-bisacryloyloxymethyl ethyl isocyanate are preferable in that the adhesive strength is sufficiently lowered after ultraviolet curing.
エポキシアクリレート中の２級水酸基と反応させるα，β−エチレン性不飽和モノイソシアナートの比率は、エポキシアクリレート中の２級水酸基１モルに対してα，β−エチレン性不飽和モノイソシアナート０．１モル以上、好ましくは０．３〜０．９モルが望ましい。α，β−エチレン性不飽和モノイソシアナートが０．１モル未満では、凝集力の低下および被着体から粘着フィルムを剥離した後の糊残りが発生する傾向にある。 The ratio of the α, β-ethylenically unsaturated monoisocyanate to be reacted with the secondary hydroxyl group in the epoxy acrylate is such that the α, β-ethylenically unsaturated monoisocyanate is 0. The amount is 1 mole or more, preferably 0.3 to 0.9 mole. When the α, β-ethylenically unsaturated monoisocyanate is less than 0.1 mol, there is a tendency that the cohesive strength is lowered and the adhesive residue after the adhesive film is peeled off from the adherend.
エポキシアクリレート中の２級水酸基とα，β−エチレン性不飽和モノイソシアナートとの付加反応は、通常のウレタン化反応の条件を用いれば良く、必要に応じてジブチル錫ジラウレート、ジアザビシクロオクタン（ＤＡＢＣＯ）などのいわゆるウレタン化触媒を使用して溶媒の存在下または不在下で反応させれば良い。 The addition reaction between the secondary hydroxyl group in the epoxy acrylate and the α, β-ethylenically unsaturated monoisocyanate may be carried out using the usual urethanization reaction conditions. Dibutyltin dilaurate, diazabicyclooctane ( The reaction may be performed in the presence or absence of a solvent using a so-called urethanization catalyst such as DABCO).
本発明において使用される多官能エポキシアクリレート（ｂ）には、式（１）：
ここで、Ｒ２は、水素原子又はエチレン性不飽和結合を有する基であるが、多官能エポキシアクリレート中の全ての分子において、Ｒ２がエチレン性不飽和結合を有する基で置換されていることを要するものではなく、Ｒ２が水素原子のまま置換されずに残存した分子が含まれていても良い。Ｒ２が水素原子の場合は、硬化剤（ｄ）を介してアクリル系粘着性ポリマー（ａ）と架橋構造をとるため、紫外線照射後の粘着性の低下速度を速める点で好ましい。 Here, R 2 is a group having a hydrogen atom or an ethylenically unsaturated bond, and R 2 is substituted with a group having an ethylenically unsaturated bond in all molecules in the polyfunctional epoxy acrylate. However, R 2 may be a molecule that remains without being replaced with a hydrogen atom. If R 2 is a hydrogen atom, to take the curing agent (d) and via an acrylic adhesive polymer (a) a crosslinked structure is preferable in that accelerate the rate of decrease in adhesiveness after ultraviolet irradiation.
Ｒ２は、水素原子又はエチレン性不飽和結合を有する基であるが、式（６）：
式（１）中、Ｘは、分子中に少なくとも２つのエポキシ基を有する化合物が重合することにより開環して得られる基であり、式（４）：
（式中、Ｒ８は水素原子又はメチル基であり、Ｒ９は水素原子又はエチレン性不飽和結合を有する基である）で表される基、又は式（５）：
In the formula, R 8 is a hydrogen atom or a methyl group, and R 9 is a hydrogen atom or a group having an ethylenically unsaturated bond, or a formula (5):
ここで、Ｒ９及びＲ１１は、Ｒ２と同様に、水素原子又はエチレン性不飽和結合を有する基であるが、多官能エポキシアクリレート中の全ての分子において、Ｒ９及びＲ１１がエチレン性不飽和結合を有する基で置換されていることを要するものではなく、Ｒ９及びＲ１１が水素原子のまま置換されずに残存した分子が含まれていても良い。 Here, R 9 and R 11 are a group having a hydrogen atom or an ethylenically unsaturated bond, as in R 2 , but R 9 and R 11 are ethylenic in all molecules in the polyfunctional epoxy acrylate. It is not required to be substituted with a group having an unsaturated bond, and a molecule in which R 9 and R 11 remain as hydrogen atoms without being substituted may be included.
Ｒ９及びＲ１１は、水素原子又はエチレン性不飽和結合を有する基であるが、前記式（６）で表される基であることが好ましい。式（６）で表される基は、イソシアナートエチルメタクリレート、イソシアナートエチルアクリレートをエポキシアクリレート中の２級水酸基と反応させることにより、導入される。 R 9 and R 11 are groups having a hydrogen atom or an ethylenically unsaturated bond, and are preferably a group represented by the formula (6). The group represented by the formula (6) is introduced by reacting isocyanate ethyl methacrylate or isocyanate ethyl acrylate with a secondary hydroxyl group in epoxy acrylate.
式（１）中、ｎは１〜１０であることが好ましく、１〜５であることがより好ましい。ｎが１０より大きくなると、アクリル系粘着性ポリマーとの相溶性が悪くなる傾向にある。 In formula (1), n is preferably 1 to 10, and more preferably 1 to 5. When n is larger than 10, the compatibility with the acrylic adhesive polymer tends to deteriorate.
また、本発明において使用される多官能エポキシアクリレート（ｂ）には、式（２）：
ここで、Ｒ５は少なくとも一つがエチレン性不飽和結合を有する基であれば良い。Ｒ５が水素原子である場合は、硬化剤（ｄ）を介してアクリル系粘着性ポリマー（ａ）と架橋構造をとるため、紫外線照射後の粘着性の低下速度を速める点で好ましい。 Here, at least one R 5 may be a group having an ethylenically unsaturated bond. When R 5 is a hydrogen atom, a cross-linked structure with the acrylic pressure-sensitive adhesive polymer (a) is taken through the curing agent (d), which is preferable from the viewpoint of increasing the speed of decreasing the pressure-sensitive adhesiveness.
Ｒ５は、エチレン性不飽和結合を有する基であるが、前記式（６）で表される基であることが好ましい。 R 5 is a group having an ethylenically unsaturated bond, and is preferably a group represented by the formula (6).
式（２）中、ｍは１〜１０であることが好ましく、１〜５であることがより好ましい。ｍが１０より大きくなると、アクリル系粘着性ポリマーとの相溶性が悪くなる傾向にある。 In formula (2), m is preferably 1 to 10, and more preferably 1 to 5. When m is larger than 10, the compatibility with the acrylic adhesive polymer tends to deteriorate.
さらには、本発明において使用される多官能エポキシアクリレート（ｂ）には、式（３）：
ここで、Ｒ７は少なくとも一つがエチレン性不飽和結合を有する基であれば良い。Ｒ７が水素原子の場合は、硬化剤（ｄ）を介してアクリル系粘着性ポリマー（ａ）と架橋構造をとるため、紫外線照射後の粘着性の低下速度を早める点で好ましい。 Here, at least one R 7 may be a group having an ethylenically unsaturated bond. In the case where R 7 is a hydrogen atom, a cross-linked structure is formed with the acrylic pressure-sensitive adhesive polymer (a) via the curing agent (d).
Ｒ７は、エチレン性不飽和結合を有する基であるが、前記式（６）で表される基であることが好ましい。 R 7 is a group having an ethylenically unsaturated bond, and is preferably a group represented by the formula (6).
多官能エポキシアクリレート（ｂ）の使用量は、通常、アクリル系粘着性ポリマー（ａ）１００質量部に対して２０〜２００質量部、好ましくは４０〜１５０質量部の範囲とするのがよい。多官能エポキシアクリレート（ｂ）の使用量が２０質量部未満では、粘着剤層の活性光線照射による三次元網状化が不充分であり、チップに対する接着力の低下の程度が小さすぎて好ましくない。一方、２００質量部を超える使用量では、粘着剤層の可塑化が著しく凝集力が低下し半導体ウエハ切断時に必要な接着力が得られず好ましくない。 The amount of the polyfunctional epoxy acrylate (b) used is usually 20 to 200 parts by mass, preferably 40 to 150 parts by mass with respect to 100 parts by mass of the acrylic adhesive polymer (a). When the amount of the polyfunctional epoxy acrylate (b) used is less than 20 parts by mass, the pressure-sensitive adhesive layer is insufficiently formed into a three-dimensional network by actinic ray irradiation, and the degree of decrease in the adhesive force to the chip is too small. On the other hand, the use amount exceeding 200 parts by mass is not preferable because the pressure-sensitive adhesive layer is plasticized so that the cohesive force is lowered and the adhesive force required for cutting the semiconductor wafer cannot be obtained.
本発明の紫外線硬化型再剥離性粘着剤組成物では、必要に応じて、光重合開始剤（ｃ）を含有させることができ、光重合開始剤（ｃ）の共存下、活性光線を使用することが可能である。使用される光重合開始剤（ｃ）としては、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンゾフェノン、ミヒラーズケトン、クロロチオキサントン、ドデシルチオキサントン、ジメチルチオキサントン、ジエチルチオキサントン、アセトフェノンジエチルケタール、ベンジルジメチルケタール、１−ヒドロキシー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−オンなどが挙げられる。殊にベンジルジメチルケタール、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−オンが表面硬化性に優れることから好ましい。 In the ultraviolet curable releasable pressure-sensitive adhesive composition of the present invention, a photopolymerization initiator (c) can be contained as necessary, and an actinic ray is used in the presence of the photopolymerization initiator (c). It is possible. Examples of the photopolymerization initiator (c) used include benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, Michler's ketone, chlorothioxanthone, dodecyl thioxanthone, dimethylthioxanthone, diethylthioxanthone, acetophenone diethyl ketal, benzyl dimethyl ketal, 1-hydroxycyclohexyl Examples include phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one. In particular, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one are preferable because of excellent surface curability.
光重合開始剤（ｃ）の使用量としては、多官能エポキシアクリレート（ｂ）１００質量部に対して０．１〜５質量部の範囲が好ましい。光重合開始剤（ｃ）の使用量が０．１質量部未満では、粘着剤組成物の活性光線照射による硬化速度が遅く、また粘着力の低減の程度が小さすぎる。逆に使用量が５質量部を超える量を使用しても、それに見合う効果が見られないのみならず、ウェハの表面に光重合開始剤が残留し易いまた使用する光重合開始剤によっては、アミンを併用することにより、感光領域の幅を広げることにより、相対的に感度を高められることができる。使用されるアミンとしては例えばＮ，Ｎ−ジメチルエタノールアミン、Ｎ−メチルジエタノールアミンなどが好ましく用いられる。アミンを併用する場合には、光重合開始剤（ｃ）と同量以下である。 As the usage-amount of a photoinitiator (c), the range of 0.1-5 mass parts is preferable with respect to 100 mass parts of polyfunctional epoxy acrylate (b). If the usage-amount of a photoinitiator (c) is less than 0.1 mass part, the cure rate by actinic ray irradiation of an adhesive composition will be slow, and the grade of reduction of adhesive force will be too small. On the contrary, even if the amount used exceeds 5 parts by mass, not only an effect commensurate with it is seen, but also depending on the photopolymerization initiator used, the photopolymerization initiator tends to remain on the surface of the wafer. By using an amine in combination, the sensitivity can be relatively increased by widening the width of the photosensitive region. As the amine used, for example, N, N-dimethylethanolamine, N-methyldiethanolamine and the like are preferably used. When an amine is used in combination, the amount is equal to or less than that of the photopolymerization initiator (c).
更に、本発明に用いる硬化剤（ｄ）としては、２， ４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、水素化トリレンジイソシアネート、１，３−キシリレンジイソシアネート、１，４−キシリレンジイソシアネート、ジフェニルメタン−４，４−ジイソシアネート、イソホロンジイソシアネート、１，３−ビス（イソシアナトメチル）シクロヘキサン、テトラメチルキシリレンジイソシアネート、１，５−ナフタレンジイソシアネート、トリメチロールプロパンのトリレンジイソシアネート付加物、トリメチロールプロパンのキシリレンジイソシアネート付加物、トリフェニルメタントリイソシアネート、メチレンビス（４−フェニルメタン）トリイソシアネート等のイソシアネート系化合物、ビスフェノールＡ・エピクロルヒドリン型のエポキシ樹脂、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエリスリトール、ジグリセロールポリグリシジルエーテル等のエポキシ系化合物、テトラメチロールメタン−トリ−β−アジリジニルプロピオネート、トリメチロールプロパン−トリ−β−アジリジニルプロピオネート、Ｎ，Ｎ′−ジフェニルメタン−４，４′−ビス（１−アジリジンカルボキシアミド）、Ｎ，Ｎ′−ヘキサメチレン−１，６−ビス（１−アジリジンカルボキシアミド）等のアジリジン系化合物、ヘキサメトキシメチルメラミン、ヘキサエトキシメチルメラミン、ヘキサプロポキシメチルメラミン、ヘキサプトキシメチルメラミン、ヘキサペンチルオキシメチルメラミン、ヘキサヘキシルオキシメチルメラミン等のメラミン系化合物等が挙げられ、中でも、トリメチロールプロパンのトリレンジイソシアネート付加物が、アクリルポリマーとの反応性が良好な点で好ましい。硬化剤（ｄ）は、水酸基、カルボキシル基又はエポキシ基に対して反応性を有するものであれば特に限定されず、その他の官能基と反応することを制限するものではない。例えば、アクリル系粘着性ポリマー（ａ）がアミン基を有しているような場合は、このアミン基と硬化剤（ｄ）が反応しても良い。 Furthermore, as the curing agent (d) used in the present invention, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diene Isocyanate, diphenylmethane-4,4-diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, tolylene diisocyanate adduct of trimethylolpropane, trimethylol Xylene diisocyanate adducts of propane, isocyanate compounds such as triphenylmethane triisocyanate, methylenebis (4-phenylmethane) triisocyanate, bisphenol A / epi Chlorhydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, Epoxy compounds such as polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl erythritol, diglycerol polyglycidyl ether, tetramethylolmethane-tri-β-aziridinylpropionate, trimethylolpropane-tri-β-aziridinylpro Pionate, N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), N, N ′ -Aziridine compounds such as hexamethylene-1,6-bis (1-aziridinecarboxamide), hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexaptoxymethyl melamine, hexapentyloxymethyl melamine, hexa Examples include melamine compounds such as hexyloxymethylmelamine, and among them, a tolylene diisocyanate adduct of trimethylolpropane is preferable in terms of good reactivity with an acrylic polymer. A hardening | curing agent (d) will not be specifically limited if it has reactivity with respect to a hydroxyl group, a carboxyl group, or an epoxy group, and does not restrict | limit reacting with another functional group. For example, when the acrylic adhesive polymer (a) has an amine group, the amine group and the curing agent (d) may react.
硬化剤（ｄ）の使用量としては、アクリル系粘着性ポリマー（ａ）と多官能エポキシアクリレート（ｂ） の合計量１００質量部に対して、０．０５〜１０質量部とすることが好ましく、更には０．１〜５質量部が好ましい。硬化剤（ｄ）の使用量が０．０５質量部未満では、紫外線あるいは放射線を照射させた後の再剥離時に被着面に粘着剤組成物が残存して汚染の原因となり、特に半導体ウエハのダイシング工程の一時的接着用途に用いた場合には、チップ上に粘着剤組成物が残留する恐れがあり、逆に１０質量部を越えると、紫外線あるいは放射線を照射させる前に硬化が進行してしまい、紫外線あるいは放射線の照射後の粘着力の低下が望めなくなる傾向にある。 The amount of the curing agent (d) used is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the total amount of the acrylic adhesive polymer (a) and the polyfunctional epoxy acrylate (b). Furthermore, 0.1-5 mass parts is preferable. When the amount of the curing agent (d) used is less than 0.05 parts by mass, the pressure-sensitive adhesive composition remains on the adherend surface during re-peeling after irradiation with ultraviolet rays or radiation, causing contamination. When used for temporary bonding in the dicing process, there is a risk that the pressure-sensitive adhesive composition may remain on the chip. Conversely, if it exceeds 10 parts by mass, curing proceeds before irradiation with ultraviolet rays or radiation. Therefore, there is a tendency that a decrease in adhesive strength after irradiation with ultraviolet rays or radiation cannot be expected.
このように構成される再剥離性粘着剤組成物を用いて粘着シートを作製するには、この粘着剤組成物を公知の方法で基材上に塗布した後、必要に応じて乾燥して、通常１０〜１００μｍ、好ましくは１０〜５０μｍ程度の厚さを有する粘着剤層を形成すればよい。基材としては、活性光線が透過する透明フィルムで、エキスパンド時に延伸性のよい材質であれば特に制限はなく、具体的には、ポリ塩化ビニル、ポリブテン、ポリブタジエン、ポリウレタン、エチレン−酢酸ビニル共重合体、ポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、ポリメチルペンテン−１、ポリウレタン、ポリエチレンテレフタレート、ポリブチレンテレフタレートなどのフィルムが用いられる。 In order to produce a pressure-sensitive adhesive sheet using the releasable pressure-sensitive adhesive composition configured as described above, the pressure-sensitive adhesive composition is applied onto a substrate by a known method, and then dried as necessary. What is necessary is just to form the adhesive layer which has a thickness of about 10-100 micrometers normally, Preferably it is about 10-50 micrometers. The base material is not particularly limited as long as it is a transparent film that transmits actinic rays and has good stretchability during expansion. Specifically, polyvinyl chloride, polybutene, polybutadiene, polyurethane, ethylene-vinyl acetate copolymer Films such as coalescence, polyethylene, polypropylene, ethylene-propylene copolymer, polymethylpentene-1, polyurethane, polyethylene terephthalate, and polybutylene terephthalate are used.
本発明の再剥離性粘着剤組成物は、ウエハダイシング工程用の粘着シートとして好適に用いられるが、該用途では粘着シートに半導体ウエハを貼付固定した後、回転丸刃で半導体ウエハをチップに切断する。その後、粘着シートの基材側から紫外線あるいは電子線のような活性光線を照射して硬化する。 The releasable pressure-sensitive adhesive composition of the present invention is suitably used as a pressure-sensitive adhesive sheet for a wafer dicing process. In this application, after a semiconductor wafer is stuck and fixed to the pressure-sensitive adhesive sheet, the semiconductor wafer is cut into chips with a rotating round blade. To do. Then, it hardens | cures by irradiating actinic light rays, such as an ultraviolet-ray or an electron beam, from the base material side of an adhesive sheet.
紫外線照射を行う時の光源としては、高圧水銀灯、超高圧水銀灯カーボンアーク灯、キセノン灯、メタルハライドランプ、ケミカルランプ、ブラックライトなどが用いられる。高圧水銀ランプの場合は、紫外線照射量が５０〜３０００ｍＪ／ｃｍ２ 、好ましくは１００〜６００ｍＪ／ｃｍ２ の条件で行われる。電子線照射の場合には、例えば、５０〜１０００ＫｅＶの範囲のエネルギーを持つ電子線を用い、２〜５０Ｍｒａｄの照射線量とするのがよい。紫外線照射量または電子線照射線量が過不足の時には、何れも光重合開始剤量が過不足の時と同様な状況を生ずることから好ましくない。 A high pressure mercury lamp, an ultrahigh pressure mercury lamp carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, a black light, or the like is used as a light source for ultraviolet irradiation. In the case of a high-pressure mercury lamp, the irradiation is performed under the condition that the ultraviolet irradiation amount is 50 to 3000 mJ / cm 2 , preferably 100 to 600 mJ / cm 2 . In the case of electron beam irradiation, for example, an electron beam having an energy in the range of 50 to 1000 KeV is used, and the irradiation dose is preferably 2 to 50 Mrad. When the amount of ultraviolet irradiation or the amount of electron beam irradiation is excessive or insufficient, the same situation as when the amount of photopolymerization initiator is excessive or insufficient is undesirable.
硬化前後の粘着力は、基材の種類、ウエハの種類によっても変わるが、硬化前はＪＩＳ Ｚ ２３０７による１８０°剥離粘着力が１５０〜２５００ｇ／２５ｍｍ、照射後の粘着力が５〜５０ｇ／２５ｍｍ程度が好ましい。次いで、ウエハ拡張装置を用いて粘着シートをエキスパンド（延伸）し、チップ間隔を一定間隔に広げた後、チップをニードル等で突き上げると共に、エアピンセット等で吸着する方法等によりピックアップし、チップを基盤に接着し、金線で電極を接続し製品となる半導体チップとなる。 The adhesive strength before and after curing varies depending on the type of substrate and the type of wafer, but before curing, the 180 ° peel adhesive strength according to JIS Z 2307 is 150 to 2500 g / 25 mm, and the adhesive strength after irradiation is 5 to 50 g / 25 mm. The degree is preferred. Next, the adhesive sheet is expanded (stretched) using a wafer expansion device, and the chip interval is expanded to a fixed interval, and then the chip is picked up by a method such as pushing up with a needle and adsorbing with air tweezers, etc. A semiconductor chip is obtained by bonding the electrodes to each other and connecting the electrodes with gold wires.
次に、実施例および比較例により本発明について具体的に説明する。但し本発明は以下の実施例により制限されるものではない。なお、以下の記述で「％」、「部」とあるのは特に断りのない限り質量基準である。 Next, the present invention will be specifically described with reference to examples and comparative examples. However, the present invention is not limited by the following examples. In the following description, “%” and “part” are based on mass unless otherwise specified.
以下の実施例および比較例における再剥離型粘着シートの評価は次のように行なった。得られた粘着シートをＳＵＳ３０４の表面に荷重１ｋｇの加圧ロールを用いて貼着し、２３℃、６５％ＲＨに調整された室内に１時間放置した後、コンベヤー型紫外線照射装置（アイグラフィックス社製、２ＫＷランプ、８０Ｗ／ｃｍ）で１００ｍＪ／ｃｍ２ および３００ｍＪ／ｃｍ ２の紫外線照射を行い、照射前後での粘着力、保持力の変化をＪＩＳ０２３７に準じて以下の方法で測定した。 The re-peelable pressure-sensitive adhesive sheets in the following examples and comparative examples were evaluated as follows. The obtained pressure-sensitive adhesive sheet was adhered to the surface of SUS304 using a pressure roll having a load of 1 kg and left in a room adjusted to 23 ° C. and 65% RH for 1 hour, and then a conveyor type ultraviolet irradiation device (eye graphics). 100 mJ / cm 2 and 300 mJ / cm 2 were irradiated with ultraviolet rays using a 2KW lamp (80 W / cm), and changes in adhesive strength and holding power before and after irradiation were measured by the following method according to JIS0237.
（イ）粘着力：粘着テープ又は粘着シートを試験板又は背面に貼り付け、圧着後、ＵＶ照射前後で粘着テープ又は粘着シートを１８０°の角度で引き剥がすのに要する力を測定した。 (A) Adhesive strength: Adhesive tape or adhesive sheet was affixed to the test plate or the back surface, and after pressing, the force required to peel off the adhesive tape or adhesive sheet at an angle of 180 ° before and after UV irradiation was measured.
（ロ）保持力：試験板の一端に、試験片の２５×２５ｍｍの面積が接するように貼り付け、貼り付いていない部分は、粘着面を内側にして折り重ねた。試験片の上から、ローラを１往復させて圧着した。２０分以上経過した後、試験板の一端を止め金で止め、試験板及び試験片が鉛直に垂れ下がるようにし、折り重ねた部分の端に、１ｋｇの重りを取り付けた。試験温度８０℃にてテープが試験板から落下するまでの時間を計った。 (B) Holding force: The test plate was attached to one end of the test plate so that the area of 25 × 25 mm was in contact with it, and the non-attached portion was folded with the adhesive surface inside. From the top of the test piece, the roller was reciprocated once and pressed. After 20 minutes or more, one end of the test plate was stopped with a stopper, the test plate and the test piece were allowed to hang vertically, and a 1 kg weight was attached to the end of the folded portion. The time until the tape dropped from the test plate at a test temperature of 80 ° C. was measured.
（ハ）外観：基材に粘着剤を塗工して乾燥させた後に、粘着層にハジキや気泡、異物等によるブツブツがなくきれいな状態となっているかを目視で確認した。
○：きれいな状態の粘着層。
△：ハジキやブツブツが少し見られる。
×：ハジキやブツブツがはっきりと見られる。
(C) Appearance: After the adhesive was applied to the substrate and dried, it was visually confirmed that the adhesive layer was clean and free of repellency, bubbles, and foreign matter.
○: Adhesive layer in a clean state.
Δ: Slight repellency and splatter are observed.
X: The repellency and the buzz are clearly seen.
（ニ）糊残り：被着体に粘着フィルムを貼り付け、ＵＶ照射（５００ｍＪ／ｃｍ２）を行なった後に、粘着フィルムを剥し、被着体に粘着剤が残っているかどうかを目視で確認した。
○：被着体に粘着剤が残らない。
△：被着体に粘着剤が僅かに残る。
×：被着体に粘着剤がはっきりと残る。
(D) Adhesive residue: Adhesive film was attached to the adherend, and after UV irradiation (500 mJ / cm 2 ), the adhesive film was peeled off to confirm whether the adhesive remained on the adherend. .
○: No adhesive remains on the adherend.
Δ: Slight adhesive remains on the adherend.
X: Adhesive remains clearly on the adherend.
製造例１＜アクリル系粘着剤（１）＞
攪拌機、温度調節器、還流冷却器、滴下ロート、温度計を付した反応装置に、アクリル酸ｎ−ブチル８０部、アクリル酸エチル６０部、メタクリル酸メチル６．３部、アクリル酸１部、アクリル酸２−ヒドロキシエチル０．８部及び酢酸エチル１３０部を仕込み、加熱還流開始後、重合開始剤としてアゾビスイソブチロニトリル０．１部を加え、酢酸エチル還流温度で３時間反応後、アゾビスイソブチロニトリル０．１部をトルエン４部に溶解させたものを加え、還流温度にて更に４時間反応させ、トルエンにて希釈することにより樹脂分４０％、重量平均分子量５５万、ガラス転移温度−３５．２℃のアクリル系粘着剤（１）を得た。尚、重量平均分子量はゲルパーミションクロマトグラフィー法で、ガラス転移温度は示差走査熱量計（ＤＳＣ）によって求めた。
Production Example 1 <Acrylic Adhesive (1)>
In a reactor equipped with a stirrer, temperature controller, reflux condenser, dropping funnel, thermometer, 80 parts of n-butyl acrylate, 60 parts of ethyl acrylate, 6.3 parts of methyl methacrylate, 1 part of acrylic acid, acrylic After charging 0.8 parts of 2-hydroxyethyl acid and 130 parts of ethyl acetate, heating and refluxing were started, 0.1 part of azobisisobutyronitrile was added as a polymerization initiator, and the reaction was performed at ethyl acetate refluxing temperature for 3 hours. A solution obtained by dissolving 0.1 part of bisisobutyronitrile in 4 parts of toluene, reacting at reflux temperature for further 4 hours, and diluting with toluene, the resin content is 40%, the weight average molecular weight is 550,000, glass An acrylic pressure-sensitive adhesive (1) having a transition temperature of −35.2 ° C. was obtained. The weight average molecular weight was determined by gel permeation chromatography, and the glass transition temperature was determined by a differential scanning calorimeter (DSC).
製造例２＜アクリル系粘着剤（２）＞
攪拌機、温度調節器、還流冷却器、滴下ロート、温度計を付した反応装置に、アクリル酸ｎ−ブチル８０部、アクリル酸メチル６０部、メタクリル酸メチル６．３部、アクリル酸１部、アクリル酸２−ヒドロキシエチル０．８部及び酢酸エチル１３０部を仕込み、加熱還流開始後、重合開始剤としてアゾビスイソブチロニトリル０.２部を加え、酢酸エチル還流温度で８時間反応後、トルエンにて希釈することにより樹脂分４０％、重量平均分子量６１万、ガラス転移温度−２５．３℃のアクリル系粘着剤（２）を得た。
Production Example 2 <Acrylic Adhesive (2)>
In a reactor equipped with a stirrer, temperature controller, reflux condenser, dropping funnel, thermometer, 80 parts of n-butyl acrylate, 60 parts of methyl acrylate, 6.3 parts of methyl methacrylate, 1 part of acrylic acid, acrylic After charging 0.8 parts of 2-hydroxyethyl acid and 130 parts of ethyl acetate, heating and refluxing were started, 0.2 parts of azobisisobutyronitrile was added as a polymerization initiator, and the reaction was conducted at ethyl acetate refluxing temperature for 8 hours. The acrylic pressure-sensitive adhesive (2) having a resin content of 40%, a weight average molecular weight of 610,000, and a glass transition temperature of −25.3 ° C. was obtained.
製造例３＜多官能エポキシアクリレート（１）＞
攪拌機、温度調節器、還流冷却器、滴下ロート、温度計を付した反応装置に、ビスフェノールＡ型エポキシ樹脂（旭化成エポキシ株式会社製、商品名アラルダイトＡＥＲ２６０３ 、エポキシ当量１８９）１００部（１．０当量）、アクリル酸３７部（１．０モル）、トリフェニルフォスフィン０．６部、メチルハイドロキノン０．１２部を仕込み、空気を吹き込みながら、１２０℃で８時間反応を続け、酸価０．５ＫＯＨｍｇ／ｇの反応物を得た。次に温度を６０℃まで下げ、滴下ロートを通じてイソシアナートエチルメタクリレート（昭和電工株式会社製、商品名カレンズＭＯＩ）６２部とジブチル錫ジラウレート０．０２部の混合液を滴下し、滴下終了後反応系を７０℃で４時間保持することにより、イソシアナート基を消失させ、重量平均分子量１３００の多官能エポキシアクリレート（１）を得た。
Production Example 3 <Polyfunctional Epoxy Acrylate (1)>
A reactor equipped with a stirrer, a temperature controller, a reflux condenser, a dropping funnel, and a thermometer, 100 parts (1.0 equivalent) of a bisphenol A type epoxy resin (Asahi Kasei Epoxy Co., Ltd., trade name Araldite AER2603, epoxy equivalent 189) ), 37 parts (1.0 mol) of acrylic acid, 0.6 part of triphenylphosphine, and 0.12 part of methylhydroquinone were added, and the reaction was continued at 120 ° C. for 8 hours while blowing air. / G of reaction product was obtained. Next, the temperature was lowered to 60 ° C., and a mixed solution of 62 parts of isocyanate ethyl methacrylate (trade name Karenz MOI, manufactured by Showa Denko KK) and 0.02 part of dibutyltin dilaurate was added dropwise through a dropping funnel, and the reaction system after completion of the addition Was maintained at 70 ° C. for 4 hours to eliminate the isocyanate group and obtain a polyfunctional epoxy acrylate (1) having a weight average molecular weight of 1300.
製造例４＜多官能エポキシアクリレート（２）＞
攪拌機、温度調節器、還流冷却器、滴下ロート、温度計を付した反応装置に、クレゾールノボラック型エポキシ樹脂（東都化成株式会社製、商品名ＹＤ−７０４Ｌ 、エポキシ当量２０９）１００部（１．０当量）、アクリル酸３３部（１．０モル）、トリフェニルフォスフィン０．４部、メチルハイドロキノン０．０８部を仕込み、空気を吹き込みながら、１２０℃で８時間反応を続け、酸価０．５ＫＯＨｍｇ／ｇの反応物を得た。次に温度を６０℃まで下げ、滴下ロートを通じてイソシアナートエチルメタクリレート（昭和電工株式会社製、商品名カレンズＭＯＩ）５６部とジブチル錫ジラウレート０．０２部の混合液を滴下し、滴下終了後反応系を７０℃で４時間保持することにより、イソシアナート基を消失させ、重量平均分子量４０００の多官能エポキシアクリレート（２）を得た。
Production Example 4 <Polyfunctional Epoxy Acrylate (2)>
To a reaction apparatus equipped with a stirrer, a temperature controller, a reflux condenser, a dropping funnel, and a thermometer, 100 parts of cresol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name YD-704L, epoxy equivalent 209) (1.0 Equivalent), 33 parts (1.0 mol) of acrylic acid, 0.4 part of triphenylphosphine, 0.08 part of methylhydroquinone, and the reaction was continued at 120 ° C. for 8 hours while blowing air. A reaction product of 5 KOH mg / g was obtained. Next, the temperature is lowered to 60 ° C., and a mixed solution of 56 parts of isocyanate ethyl methacrylate (trade name Karenz MOI, manufactured by Showa Denko KK) and 0.02 part of dibutyltin dilaurate is added dropwise through a dropping funnel. Was maintained at 70 ° C. for 4 hours to eliminate the isocyanate group and obtain a polyfunctional epoxy acrylate (2) having a weight average molecular weight of 4000.
製造例５＜多官能エポキシアクリレート（３）＞
攪拌機、温度調節器、還流冷却器、滴下ロート、温度計を付した反応装置に、トリアジン核を骨格にもつ３価のエポキシ化合物（日産化学工業株式会社製、商品名ＴＥＰＩＣ−Ｓ 、エポキシ当量１００）１００部（１．０当量）、アクリル酸７２部（１．０モル）、トリフェニルフォスフィン０．６部、メチルハイドロキノン０．１２部を仕込み、空気を吹き込みながら、１２０℃で８時間反応を続け、酸価０．５ＫＯＨｍｇ／ｇの反応物を得た。次に温度を６０℃まで下げ、滴下ロートを通じてイソシアナートエチルメタクリレート（昭和電工株式会社製、商品名カレンズＭＯＩ）７０部とジブチル錫ジラウレート０．０２部の混合液を滴下し、滴下終了後反応系を７０℃で４時間保持することにより、イソシアナート基を消失させ、重量平均分子量１１００の多官能エポキシアクリレート（３）を得た。
Production Example 5 <Polyfunctional Epoxy Acrylate (3)>
A reactor equipped with a stirrer, a temperature controller, a reflux condenser, a dropping funnel, a thermometer, and a trivalent epoxy compound having a triazine nucleus as a skeleton (manufactured by Nissan Chemical Industries, Ltd., trade name TEPIC-S, epoxy equivalent 100) ) 100 parts (1.0 equivalent), 72 parts (1.0 mol) of acrylic acid, 0.6 part of triphenylphosphine, 0.12 part of methylhydroquinone, and reacted at 120 ° C. for 8 hours while blowing air. Then, a reaction product having an acid value of 0.5 KOH mg / g was obtained. Next, the temperature is lowered to 60 ° C., and a mixed solution of 70 parts of isocyanate ethyl methacrylate (trade name Karenz MOI, manufactured by Showa Denko KK) and 0.02 part of dibutyltin dilaurate is added dropwise through a dropping funnel. Was held at 70 ° C. for 4 hours to eliminate the isocyanate group and obtain a polyfunctional epoxy acrylate (3) having a weight average molecular weight of 1100.
実施例１＜再剥離性粘着剤および再剥離型粘着シートの製造＞
紫外線の遮断された室内にて、プラスチック製容器に、アクリル系粘着剤（１）７０部、多官能エポキシアクリレート（１）３０部、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・ケミカルズ社製、イルガキュア１８４）１．２部、トリメチロールプロパンのトリレンジイソシアネート付加物の４５％酢酸エチル溶液（日本ポリウレタン工業株式会社製、コロネートＬ−４５Ｅ）２．０部を加えて攪拌し、再剥離性粘着剤とし、さらにこれを厚さ５０μｍのポリエチレンテレフタレートフィルムに乾燥後の膜厚が２０μｍになるように塗工し、１０５℃で２分間、加熱乾燥させて再剥離型粘着シートを作製した。次に、前述の方法で紫外線硬化前後の性能変化を評価した。測定結果を表１に示す。
Example 1 <Production of Removable Adhesive and Removable Adhesive Sheet>
In a room protected from ultraviolet rays, 70 parts of acrylic adhesive (1), 30 parts of polyfunctional epoxy acrylate (1), 1-hydroxy-cyclohexyl-phenyl-ketone (Ciba Specialty Chemicals) Manufactured by Irgacure 184) 1.2 parts, 2.0 parts of 45% ethyl acetate solution of trimethylolpropane tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L-45E), stirred and re-peeled Further, this was applied to a polyethylene terephthalate film having a thickness of 50 μm so that the film thickness after drying was 20 μm, and dried by heating at 105 ° C. for 2 minutes to prepare a releasable adhesive sheet. Next, the change in performance before and after UV curing was evaluated by the method described above. The measurement results are shown in Table 1.
実施例２
実施例１の再剥離型粘着シートの製造において、アクリル系粘着剤（１）の使用量を６０部、多官能エポキシアクリレート（１）の使用量を４０部に変更した他は実施例１と同様の方法で再剥離型粘着シートを製造し、紫外線硬化前後の性能変化を評価した。測定結果を表１に示す。
Example 2
In the production of the re-peelable pressure-sensitive adhesive sheet of Example 1, the same as Example 1 except that the amount of acrylic pressure-sensitive adhesive (1) used was changed to 60 parts and the amount of polyfunctional epoxy acrylate (1) used was changed to 40 parts. A re-peelable pressure-sensitive adhesive sheet was produced by this method, and the performance change before and after UV curing was evaluated. The measurement results are shown in Table 1.
実施例３
実施例１の再剥離型粘着シートの製造において、アクリル系粘着剤（１）の使用量を５０部、多官能エポキシアクリレート（１）の使用量を５０部に変更した他は実施例１と同様の方法で再剥離型粘着シートを製造し、紫外線硬化前後の性能変化を評価した。測定結果を表１に示す。
Example 3
In the production of the re-peelable pressure-sensitive adhesive sheet of Example 1, the same as Example 1 except that the amount of acrylic pressure-sensitive adhesive (1) used was changed to 50 parts and the amount of polyfunctional epoxy acrylate (1) used was changed to 50 parts. A re-peelable pressure-sensitive adhesive sheet was produced by this method, and the performance change before and after UV curing was evaluated. The measurement results are shown in Table 1.
実施例４
実施例１の再剥離型粘着シートの製造において、アクリル系粘着剤（２）の使用量を６０部、多官能エポキシアクリレート（１）の使用量を４０部に変更した他は実施例１と同様の方法で再剥離型粘着シートを製造し、紫外線硬化前後の性能変化を評価した。測定結果を表１に示す。
Example 4
In the production of the re-peelable pressure-sensitive adhesive sheet of Example 1, the same as Example 1 except that the amount of acrylic pressure-sensitive adhesive (2) used was changed to 60 parts and the amount of polyfunctional epoxy acrylate (1) used was changed to 40 parts. A re-peelable pressure-sensitive adhesive sheet was produced by this method, and the performance change before and after UV curing was evaluated. The measurement results are shown in Table 1.
実施例５
実施例１の再剥離型粘着シートの製造において、アクリル系粘着剤（２）の使用量を５０部、多官能エポキシアクリレート（１）の使用量を５０部に変更した他は実施例１と同様の方法で再剥離型粘着シートを製造し、紫外線硬化前後の性能変化を評価した。測定結果を表１に示す。
Example 5
In the production of the re-peelable pressure-sensitive adhesive sheet of Example 1, the same as Example 1 except that the amount of acrylic pressure-sensitive adhesive (2) used was changed to 50 parts and the amount of polyfunctional epoxy acrylate (1) used was changed to 50 parts. A re-peelable pressure-sensitive adhesive sheet was produced by this method, and the performance change before and after UV curing was evaluated. The measurement results are shown in Table 1.
実施例６
実施例１の再剥離型粘着シートの製造において、アクリル系粘着剤（１）の使用量を７０部、多官能エポキシアクリレート（２）の使用量を３０部に変更した他は実施例１と同様の方法で再剥離型粘着シートを製造し、紫外線硬化前後の性能変化を評価した。測定結果を表１に示す。
Example 6
In the production of the re-peelable pressure-sensitive adhesive sheet of Example 1, the same as Example 1 except that the amount of acrylic pressure-sensitive adhesive (1) used was changed to 70 parts and the amount of polyfunctional epoxy acrylate (2) used was changed to 30 parts. A re-peelable pressure-sensitive adhesive sheet was produced by this method, and the performance change before and after UV curing was evaluated. The measurement results are shown in Table 1.
実施例７
実施例１の再剥離型粘着シートの製造において、アクリル系粘着剤（１）の使用量を７０部、多官能エポキシアクリレート（３）の使用量を３０部に変更した他は実施例１と同様の方法で再剥離型粘着シートを製造し、紫外線硬化前後の性能変化を評価した。測定結果を表１に示す。
Example 7
In the production of the re-peelable pressure-sensitive adhesive sheet of Example 1, the same as Example 1 except that the amount of acrylic adhesive (1) used was changed to 70 parts and the amount of polyfunctional epoxy acrylate (3) used was changed to 30 parts. A re-peelable pressure-sensitive adhesive sheet was produced by this method, and the performance change before and after UV curing was evaluated. The measurement results are shown in Table 1.
比較例１
実施例１の再剥離型粘着シートの製造において、多官能エポキシアクリレート（１）をビスフェノールＡ型エポキシアクリレート（昭和高分子株式会社製、商品名ＶＲ−７７）に変更した他は実施例１と同様の方法で再剥離型粘着シートを製造し、紫外線硬化前後の性能変化を評価した。測定結果を表２に示す。
Comparative Example 1
In the production of the re-peelable pressure-sensitive adhesive sheet of Example 1, the same as Example 1 except that the polyfunctional epoxy acrylate (1) was changed to bisphenol A type epoxy acrylate (product name VR-77, manufactured by Showa Polymer Co., Ltd.). A re-peelable pressure-sensitive adhesive sheet was produced by this method, and the performance change before and after UV curing was evaluated. The measurement results are shown in Table 2.
比較例２
実施例１の再剥離型粘着シートの製造において、アクリル系粘着剤（１）の使用量を６０部とし、多官能エポキシアクリレート（１）の代わりにビスフェノールＡ型エポキシアクリレート４０部とした他は実施例１と同様の方法で再剥離型粘着シートを製造し、紫外線硬化前後の性能変化を評価した。測定結果を表２に示す。
Comparative Example 2
The production of the re-peelable pressure-sensitive adhesive sheet of Example 1 was carried out except that the amount of the acrylic pressure-sensitive adhesive (1) used was 60 parts, and 40 parts of bisphenol A type epoxy acrylate was used instead of the polyfunctional epoxy acrylate (1). A re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1, and the change in performance before and after UV curing was evaluated. The measurement results are shown in Table 2.
比較例３
実施例１の再剥離型粘着シートの製造において、アクリル系粘着剤（１）の使用量を７０部とし、多官能エポキシアクリレート（１）の代わりにジペンタエリスリトールヘキサアクリレート（日本化薬株式会社製、商品名ＫＡＹＡＲＡＤ ＤＰＨＡ）３０部に変更した他は実施例１と同様の方法で再剥離型粘着シートを製造し、紫外線硬化前後の性能変化を評価した。測定結果を表２に示す。
Comparative Example 3
In the production of the re-peelable pressure-sensitive adhesive sheet of Example 1, the amount of the acrylic pressure-sensitive adhesive (1) used was 70 parts, and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) instead of the polyfunctional epoxy acrylate (1). The trade name KAYARAD DPHA) was changed to 30 parts, and a re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1, and the performance change before and after UV curing was evaluated. The measurement results are shown in Table 2.
比較例４
実施例１の再剥離型粘着シートの製造において、アクリル系粘着剤（１）の使用量を６０部とし、多官能エポキシアクリレート（１）の代わりにビスフェノールＡ型エポキシアクリレート２０部、及びジペンタエリスリトールヘキサアクリレート２０部に変更した他は実施例１と同様の方法で再剥離型粘着シートを製造し、紫外線硬化前後の性能変化を評価した。測定結果を表２に示す。
Comparative Example 4
In the production of the releasable pressure-sensitive adhesive sheet of Example 1, the amount of the acrylic pressure-sensitive adhesive (1) used was 60 parts, 20 parts of bisphenol A type epoxy acrylate and dipentaerythritol instead of the polyfunctional epoxy acrylate (1). Except for changing to 20 parts of hexaacrylate, a re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1, and the change in performance before and after UV curing was evaluated. The measurement results are shown in Table 2.
実施例及び比較例の比較から、本発明にかかる紫外線硬化型再剥離性粘着剤組成物は、塗工後の粘着層の外観に優れ、また、紫外線照射前の粘着力、保持力に優れ、且つ紫外線照射後は糊残りのない硬化膜を得ることができるものであることがわかる。 From the comparison of Examples and Comparative Examples, the ultraviolet curable removable pressure-sensitive adhesive composition according to the present invention is excellent in the appearance of the pressure-sensitive adhesive layer after coating, and is excellent in adhesive strength before ultraviolet irradiation, holding power, It can also be seen that a cured film having no adhesive residue can be obtained after irradiation with ultraviolet rays.
Claims (6)
PSA sheet using the ultraviolet-curable removable pressure sensitive adhesive composition according to any one of claims 1, 2, 3, 4 or 5.
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| JP2008261055A JP4318743B1 (en) | 2008-10-07 | 2008-10-07 | Ultraviolet curable removable pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet using the same |
| CN2008801314456A CN102177214B (en) | 2008-10-07 | 2008-12-05 | Ultraviolet curing removable adhesive composition and adhesive sheet using the same |
| KR1020117008009A KR101547378B1 (en) | 2008-10-07 | 2008-12-05 | Ultraviolet curable-type removable pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet using the ultraviolet curable-type removable pressure-sensitive adhesive composition |
| PCT/JP2008/003617 WO2010041299A1 (en) | 2008-10-07 | 2008-12-05 | Ultraviolet curable-type removable pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet using the ultraviolet curable-type removable pressure-sensitive adhesive composition |
| TW097150440A TWI441889B (en) | 2008-10-07 | 2008-12-24 | A UV-curable releasable adhesive composition, and an adhesive sheet using the same |
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| JP2008261055A JP4318743B1 (en) | 2008-10-07 | 2008-10-07 | Ultraviolet curable removable pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet using the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101240622B1 (en) * | 2010-10-29 | 2013-03-14 | 주식회사 영우 | Manufacturing method of double pressure sensitive adhesive without substrate using dual cure method |
| KR101293887B1 (en) * | 2010-01-29 | 2013-08-06 | 주식회사 엘지화학 | Photocurable adhesive compositon |
| KR20190021286A (en) | 2019-02-20 | 2019-03-05 | (주)한성비씨씨 | Manufacturing method of airsol spray type can including peelable rubber paint |
Families Citing this family (23)
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| JP5858347B2 (en) * | 2014-02-05 | 2016-02-10 | 大日本印刷株式会社 | Adhesive composition and adhesive film using the same |
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| WO2020049829A1 (en) * | 2018-09-03 | 2020-03-12 | 昭和電工株式会社 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| WO2020116101A1 (en) | 2018-12-07 | 2020-06-11 | 昭和電工株式会社 | Adhesive composition and adhesive sheet |
| KR102356750B1 (en) * | 2019-01-03 | 2022-01-27 | 삼성에스디아이 주식회사 | Adhesive laminate and optical member comprising the same |
| WO2021065517A1 (en) * | 2019-09-30 | 2021-04-08 | 昭和電工マテリアルズ株式会社 | Adhesive for semiconductors, adhesive sheet for semiconductors, and method for manufacturing semiconductor device |
| JP7168820B2 (en) * | 2020-05-25 | 2022-11-09 | 日東電工株式会社 | Adhesive tape for optical components |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3410202B2 (en) * | 1993-04-28 | 2003-05-26 | 日本テキサス・インスツルメンツ株式会社 | Adhesive sheet for attaching wafer and method for manufacturing semiconductor device using the same |
| JP2002317155A (en) * | 2001-04-23 | 2002-10-31 | Nippon Kayaku Co Ltd | Energetic ray curing adhesive composition and adhesive sheet |
| JP4059497B2 (en) * | 2003-06-24 | 2008-03-12 | 日東電工株式会社 | Die bonding adhesive film, dicing die bonding adhesive film, and semiconductor device |
| TW200613903A (en) * | 2004-05-26 | 2006-05-01 | Showa Denko Kk | Photosensitive resin composition, and cured product and use thereof |
| JP5250202B2 (en) * | 2006-12-18 | 2013-07-31 | 電気化学工業株式会社 | A multilayer adhesive sheet and a method for producing an electronic component. |
-
2008
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101293887B1 (en) * | 2010-01-29 | 2013-08-06 | 주식회사 엘지화학 | Photocurable adhesive compositon |
| KR101240622B1 (en) * | 2010-10-29 | 2013-03-14 | 주식회사 영우 | Manufacturing method of double pressure sensitive adhesive without substrate using dual cure method |
| KR20190021286A (en) | 2019-02-20 | 2019-03-05 | (주)한성비씨씨 | Manufacturing method of airsol spray type can including peelable rubber paint |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI441889B (en) | 2014-06-21 |
| JP2010090249A (en) | 2010-04-22 |
| TW201014892A (en) | 2010-04-16 |
| CN102177214A (en) | 2011-09-07 |
| KR101547378B1 (en) | 2015-08-25 |
| KR20110067119A (en) | 2011-06-21 |
| CN102177214B (en) | 2013-09-25 |
| WO2010041299A1 (en) | 2010-04-15 |
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