JP5052792B2 - Resin composition and method for temporarily fixing and protecting surface of workpiece using the same - Google Patents
Resin composition and method for temporarily fixing and protecting surface of workpiece using the same Download PDFInfo
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- JP5052792B2 JP5052792B2 JP2006005597A JP2006005597A JP5052792B2 JP 5052792 B2 JP5052792 B2 JP 5052792B2 JP 2006005597 A JP2006005597 A JP 2006005597A JP 2006005597 A JP2006005597 A JP 2006005597A JP 5052792 B2 JP5052792 B2 JP 5052792B2
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- Prior art keywords
- acrylate
- meth
- resin composition
- mass
- processed
- 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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- 239000011342 resin composition Substances 0.000 title claims description 74
- 238000000034 method Methods 0.000 title claims description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 159
- -1 2-ethylhexyl Chemical group 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000000853 adhesive Substances 0.000 claims description 35
- 230000001070 adhesive effect Effects 0.000 claims description 35
- 238000012545 processing Methods 0.000 claims description 21
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 3
- TXZNVWGSLKSTDH-XCADPSHZSA-N (1Z,3Z,5Z)-cyclodeca-1,3,5-triene Chemical class C1CC\C=C/C=C\C=C/C1 TXZNVWGSLKSTDH-XCADPSHZSA-N 0.000 claims description 3
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 3
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 3
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 claims description 3
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 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 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 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 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- NTINFTOOVNKGIU-UHFFFAOYSA-N 2-(2-hydroxyethoxycarbonyl)benzoic acid Chemical compound OCCOC(=O)C1=CC=CC=C1C(O)=O NTINFTOOVNKGIU-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 239000000539 dimer Substances 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 description 36
- 238000012360 testing method Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000004927 fusion Effects 0.000 description 5
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000005297 pyrex Substances 0.000 description 4
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 2
- WLDMPODMCFGWAA-UHFFFAOYSA-N 3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione Chemical compound C1CCCC2C(=O)NC(=O)C21 WLDMPODMCFGWAA-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- JMIZWXDKTUGEES-UHFFFAOYSA-N 2,2-di(cyclopenten-1-yloxy)ethyl 2-methylprop-2-enoate Chemical compound C=1CCCC=1OC(COC(=O)C(=C)C)OC1=CCCC1 JMIZWXDKTUGEES-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- ZZYASVWWDLJXIM-UHFFFAOYSA-N 2,5-di-tert-Butyl-1,4-benzoquinone Chemical compound CC(C)(C)C1=CC(=O)C(C(C)(C)C)=CC1=O ZZYASVWWDLJXIM-UHFFFAOYSA-N 0.000 description 1
- QYXHDJJYVDLECA-UHFFFAOYSA-N 2,5-diphenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=C(C=2C=CC=CC=2)C(=O)C=C1C1=CC=CC=C1 QYXHDJJYVDLECA-UHFFFAOYSA-N 0.000 description 1
- KJSGODDTWRXQRH-UHFFFAOYSA-N 2-(dimethylamino)ethyl benzoate Chemical compound CN(C)CCOC(=O)C1=CC=CC=C1 KJSGODDTWRXQRH-UHFFFAOYSA-N 0.000 description 1
- ZUOBXYGNVPJKLK-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-methoxyethanol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.COC(O)COCCOCCOCCO ZUOBXYGNVPJKLK-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- WVQHODUGKTXKQF-UHFFFAOYSA-N 2-ethyl-2-methylhexane-1,1-diol Chemical compound CCCCC(C)(CC)C(O)O WVQHODUGKTXKQF-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- MRBKEAMVRSLQPH-UHFFFAOYSA-N 3-tert-butyl-4-hydroxyanisole Chemical group COC1=CC=C(O)C(C(C)(C)C)=C1 MRBKEAMVRSLQPH-UHFFFAOYSA-N 0.000 description 1
- IUDWGHRBQRGLDJ-UHFFFAOYSA-N 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-4-carboxylic acid Chemical compound C1CC2(C(O)=O)C(=O)C(=O)C1C2(C)C IUDWGHRBQRGLDJ-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- PLNRJAOPKDGABD-UHFFFAOYSA-N CC1=C(C(=O)C2=C(C=CC=C2)P(OC)(OC)=O)C(=CC(=C1)C)C Chemical compound CC1=C(C(=O)C2=C(C=CC=C2)P(OC)(OC)=O)C(=CC(=C1)C)C PLNRJAOPKDGABD-UHFFFAOYSA-N 0.000 description 1
- YWMSOIQUMJBHRP-UHFFFAOYSA-N CCOP(C1=CC=CC=C1)=O.Cl.Cl Chemical compound CCOP(C1=CC=CC=C1)=O.Cl.Cl YWMSOIQUMJBHRP-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
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- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 150000001634 bornane-2,3-dione derivatives Chemical class 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- TZAMQIAPGYOUKF-UHFFFAOYSA-N diethoxyphosphoryl(phenyl)methanone Chemical compound CCOP(=O)(OCC)C(=O)C1=CC=CC=C1 TZAMQIAPGYOUKF-UHFFFAOYSA-N 0.000 description 1
- XVKKIGYVKWTOKG-UHFFFAOYSA-N diphenylphosphoryl(phenyl)methanone Chemical compound C=1C=CC=CC=1P(=O)(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 XVKKIGYVKWTOKG-UHFFFAOYSA-N 0.000 description 1
- PODOEQVNFJSWIK-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethoxyphenyl)methanone Chemical compound COC1=CC(OC)=CC(OC)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 PODOEQVNFJSWIK-UHFFFAOYSA-N 0.000 description 1
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- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、いろいろな部材を加工するに際しての当該被加工部材の仮固定方法と表面保護方法に関し、またそれに好適な樹脂組成物と接着剤に関する。より詳細には、本発明は、光学用部材等を加工するに際し、被加工部材の表面にあって加工しない部分を加工時の汚れ等から保護することを目的とする被加工部材の表面保護方法を提示するとともに、基材に当該被加工物を接着し、被加工物を加工した後、接着部分を温水に浸漬して、硬化体を取り外すことで、被加工部材を回収することを特徴とする被加工部材の仮固定方法をも提示し、更に当該用途に好適な樹脂組成物並びに接着剤を提供するものである。 The present invention relates to a temporary fixing method and a surface protecting method for a workpiece when processing various members, and also relates to a resin composition and an adhesive suitable for the method. More specifically, the present invention relates to a method for protecting a surface of a member to be processed for the purpose of protecting a portion of the surface of the member to be processed that is not processed from dirt or the like during processing when processing an optical member or the like. The workpiece is bonded to the base material, the workpiece is processed, the bonded portion is immersed in warm water, and the cured body is removed to recover the workpiece. The present invention also provides a method for temporarily fixing a workpiece to be processed, and further provides a resin composition and an adhesive suitable for the application.
半導体ウエハ、光学部品等の薄型化を行う場合、表面保護シートでウエハの回路面や光学部品の非加工面を保護すると共に、前記表面保護シートを介して基材に仮固定され回路面とは反対側の裏面が研削される、いわゆる裏面研削方法で加工される。 When thinning a semiconductor wafer, optical component, etc., the surface protection sheet protects the circuit surface of the wafer and the non-processed surface of the optical component, and is temporarily fixed to the base material via the surface protection sheet. Processing is performed by a so-called back surface grinding method in which the opposite back surface is ground.
現在、産業レベルでのウエハの肉厚は一般的には１５０μｍであるが、益々、薄型化されたウエハが求められるようになっている。さらに薄い肉厚までウエハを薄型化していく場合、研削面（裏面）が回路面の凹凸の影響で不均一になる現象、すなわち、回路パターンの裏面転写現象が顕著になる。 At present, the thickness of a wafer at an industrial level is generally 150 μm, but a thinner wafer is increasingly required. When the wafer is made thinner to a thinner thickness, the phenomenon that the ground surface (back surface) becomes non-uniform due to the unevenness of the circuit surface, that is, the back surface transfer phenomenon of the circuit pattern becomes remarkable.
裏面転写現象が生じる原因は以下のように説明される。現在使用されている感圧接着性の表面保護シートは半導体ウエハの回路の凹凸に対する追従性には限界がある。このため、粘着剤層と回路面の間に隙間（空気ポケット）が介在することになり、ウエハはその領域では粘着剤（保護層）によって直接支持されていない。研削によりウエハを極薄化していくときに、支持されていないスクライブライン（ストリート）では空気ポケットを圧縮しながら回路ダイ間でウエハは垂直方向に移動して、結果としてこの領域では研削されず、他の部分より厚くなる。一方、バンプなどの硬い突起部がある場合には、ウエハはより削られて、結果として他の部分より薄くなる。 The cause of the back surface transfer phenomenon is explained as follows. The pressure-sensitive adhesive surface protective sheet currently used has a limit in the ability to follow the unevenness of the circuit of the semiconductor wafer. For this reason, a gap (air pocket) is interposed between the adhesive layer and the circuit surface, and the wafer is not directly supported by the adhesive (protective layer) in that region. When the wafer is thinned by grinding, the unsupported scribe line (street) moves the wafer vertically between circuit dies while compressing the air pockets, resulting in no grinding in this area, Thicker than other parts. On the other hand, when there are hard protrusions such as bumps, the wafer is more shaved and consequently thinner than the other parts.
この現象は、ウエハの仕上げ厚みが１５０μｍ以上の場合は、問題にならないが、１００μｍを超えてウエハを薄くする場合（特に５０μｍ以下の厚みに仕上げる場合）や、バンプ等のウエハ回路面の高い突起が著しく大きい場合は（例えば、１００μｍ以上の場合）、ウエハの抗折強度を大きく下げるだけでなく、ひどい場合には研削中にウエハを破損させることさえある。 This phenomenon is not a problem when the finished thickness of the wafer is 150 μm or more, but when the wafer is made thinner than 100 μm (particularly when finished to a thickness of 50 μm or less), or a bump on the wafer circuit surface such as a bump is high. Is extremely large (for example, 100 μm or more), not only greatly reduces the bending strength of the wafer, but also severely damages the wafer during grinding.
また、５０μｍ付近までウエハを薄く削っていく場合、ウエハのエッジ欠けや、ウエハ・表面保護層間への研削水の進入等も問題となるが、この原因も、表面保護シートのウエハのエッジに対する密着性の欠如によるものであった。また、ウエハの薄型化と並び、バンプに代表される１００μｍ以上の突起を回路面上に有する半導体ウエハでは、典型的な半導体表面保護シートを貼り付けて行う研削そのものが困難であった。 In addition, when the wafer is thinned down to around 50 μm, chipping of the edge of the wafer and ingress of grinding water between the wafer and the surface protection layer also become problems. This is also caused by the adhesion of the surface protection sheet to the edge of the wafer. This was due to lack of sex. Further, along with the thinning of the wafer, the grinding itself performed by attaching a typical semiconductor surface protective sheet is difficult in a semiconductor wafer having protrusions of 100 μm or more typified by bumps on the circuit surface.
従来の表面保護シートは、一般に、ポリマーフィルム材料上に表面保護層として粘着剤層を有するシートである。粘着剤は回路面の凹凸に追従するように低弾性率を有するように設計されている。しかしながら、この傾向が強すぎると、シートをウエハからピール除去する際に、大きな応力がウエハに掛かり、破損につながる。 Conventional surface protective sheets are generally sheets having a pressure-sensitive adhesive layer as a surface protective layer on a polymer film material. The adhesive is designed to have a low elastic modulus so as to follow the irregularities of the circuit surface. However, if this tendency is too strong, a large stress is applied to the wafer when the sheet is peeled off from the wafer, leading to breakage.
そこで、シートをピールする前に、紫外線などのエネルギー線を照射することにより粘着剤を硬化し、ウエハ・保護シート間の接着力を低下させるエネルギー線易剥離型保護シートが開発された。しかしながら、研削の間に粘着剤層が未硬化の状態では柔軟すぎて研削中にウエハが破損するという問題がある。 Therefore, an energy ray easily peelable protective sheet has been developed that cures the adhesive by irradiating energy rays such as ultraviolet rays before peeling the sheet, and reduces the adhesive force between the wafer and the protective sheet. However, when the pressure-sensitive adhesive layer is uncured during grinding, it is too flexible and the wafer is damaged during grinding.
特許文献１は、上記のようなエネルギー線易剥離型保護シートを回路が形成されたウエハに貼り付け、エネルギー線で粘着剤層を硬化した後に、ウエハの裏面研削を行う、ウエハ研削方法を開示している。しかしながら、粘着剤は、流動体ではないため、ウエハ回路面の凹凸に対する追従性が十分ではない。
一方、特許文献２には、ホットメルト型の半導体表面保護シートが開示されている。６０〜１００℃に加熱することにより溶融し、流動性を示すホットメルト型シートは、回路面の凹凸に追従し、優れた研削性を示すことができる。しかしながら、このシートは、温度が融点を上回る度に溶融する性質がある。
一方、半導体ウエハは、一般に、保護シートと貼り合わされた後に、チップを固定するために使用するフィルム、すなわち、ダイアタッチメントフィルム（Die Attachment Film（以後、「ＤＡＦ」とも呼ぶ。）の貼り合わせ工程や、スパッタリングによる金属膜形成工程の間に加熱工程などを受けることがある。そのため、前記の工程における温度上昇によって、保護シートが再溶融するという不具合が発生していた。 On the other hand, a semiconductor wafer is generally bonded to a protective sheet and then a film used for fixing a chip, that is, a die attachment film (hereinafter also referred to as “DAF”) bonding process or the like. In some cases, the metal film forming process by sputtering may be subjected to a heating process, etc. For this reason, the protective sheet is remelted due to the temperature rise in the process.
切削加工後の部材の寸法精度を向上させるために、疎水性で高接着強度であり、かつ水中での剥離性に優れ、また、剥離後部材に糊残りのない環境的にも作業性に優れた光硬化型接着剤が望まれている。特に、裏面研削方法で半導体ウエハ、光学部品等の薄型化を行う場合に、ウエハの回路面や光学部品の非加工面を保護し、前記特性を有する光硬化型接着剤が熱望されている。 In order to improve the dimensional accuracy of the parts after cutting, it is hydrophobic, has high adhesive strength, has excellent releasability in water, and has excellent workability even in the environment where there is no adhesive residue on the parts after peeling. A photocurable adhesive is desired. In particular, when thinning a semiconductor wafer, an optical component, or the like by a back grinding method, a photocurable adhesive having the above-described characteristics that protects the circuit surface of the wafer and the non-processed surface of the optical component is desired.
本発明者は、従来技術の課題を解決し、前記産業界の要望を満足するために、ウエハ、光学部品の回路面の凹凸に対する追従性が十分にある材料であって、かつ研削時の支持体として十分な剛性を有する組成物を求めて、いろいろ検討した結果、（メタ）アクリルモノマーとシクロペンタジエン骨格を含有する樹脂とを成分とする樹脂組成物が、前記の目的を達成するものであるとの知見を得て、本発明に至ったものである。 In order to solve the problems of the prior art and satisfy the demands of the industry, the present inventor is a material that has sufficient followability to the unevenness of the circuit surface of the wafer and optical components, and supports during grinding. As a result of various investigations for a composition having sufficient rigidity as a body, a resin composition comprising a (meth) acrylic monomer and a resin containing a cyclopentadiene skeleton achieves the above object. The present invention has been obtained and the present invention has been achieved.
即ち、本発明は、被加工部材の表面に被覆し硬化させた後、該被加工部材を加工後に９０℃以下の温水に浸漬して、樹脂組成物の硬化体を取り外すことを特徴とする被加工部材の加工方法に使用する樹脂組成物であり、かつ、（Ａ）多官能（メタ）アクリレート、（Ｂ）単官能（メタ）アクリレート、（Ｃ）シクロペンタジエン骨格樹脂を含有することを特徴とする樹脂組成物であり、被加工部材の表面に被覆し硬化させた後、該被加工部材を加工後に９０℃以下の温水に浸漬して、樹脂組成物の硬化体を取り外すことを特徴とする被加工部材の加工方法に使用する樹脂組成物であり、かつ、（Ａ）多官能（メタ）アクリレート、（Ｂ）単官能（メタ）アクリレート、（Ｃ）シクロペンタジエン骨格樹脂、（Ｄ）光重合開始剤、（Ｅ）アルコールを含有することを特徴する樹脂組成物であり、（Ｃ）シクロペンタジエン骨格樹脂が、分子内にエステル基と水酸基とのいずれかを含有することを特徴とする該樹脂組成物であり、（Ａ）及び（Ｂ）成分の合計量１００質量部中、（Ａ）成分を１〜９５質量部、（Ｂ）成分を５〜９９質量部、（Ａ）及び（Ｂ）成分の合計量１００質量部に対して、（Ｃ）成分を０．１〜５０質量部、（Ｄ）成分を０．１〜２０質量部、必要に応じて（Ｅ）成分を０．５〜１０質量部含有することを特徴とする該樹脂組成物であり、更に、重合禁止剤を含有することを特徴とする該樹脂組成物であり、（Ａ）成分が、多官能（メタ）アクリレートオリゴマー／ポリマーと２個以上の（メタ）アクロイル基を有するモノマーからなる群のうちの１種以上であることを特徴とする該樹脂組成物であり、（Ｂ）成分が、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソデシル（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、フェニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニロキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、メトキシ化シクロデカトリエン（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、３−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、グリシジル（メタ）アクリレート、カプロラクトン変性テトラヒドロフルフリル（メタ）アクリレート、３−クロロ−２−ヒドロキシプロピル（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−ジエチルアミノエチル（メタ）アクリレート、ｔ−ブチルアミノエチル（メタ）アクリレート、エトキシカルボニルメチル（メタ）アクリレート、フェノールエチレンオキサイド変性アクリレート、フェノール（エチレンオキサイド２モル変性）アクリレート、フェノール（エチレンオキサイド４モル変性）アクリレート、パラクミルフェノールエチレンオキサイド変性アクリレート、ノニルフェノールエチレンオキサイド変性アクリレート、ノニルフェノール（エチレンオキサイド４モル変性）アクリレート、ノニルフェノール（エチレンオキサイド８モル変性）アクリレート、ノニルフェノール（プロピレンオキサイド２．５モル変性）アクリレート、２−エチルヘキシルカルビトールアクリレート、エチレンオキシド変性フタル酸（メタ）アクリレ−ト、エチレンオキシド変性コハク酸（メタ）アクリレート、トリフロロエチル（メタ）アクリレート、アクリル酸、メタクリル酸、マレイン酸、フマル酸、ω−カルボキシ−ポリカプロラクトンモノ（メタ）アクリレート、フタル酸モノヒドロキシエチル（メタ）アクリレート、（メタ）アクリル酸ダイマー、β−（メタ）アクロイルオキシエチルハイドロジェンサクシネート、ｎ−（メタ）アクリロイルオキシアルキルヘキサヒドロフタルイミド、ベンジル（メタ）クリレートからなる群のうちの１種以上であることを特徴とする該樹脂組成物であり、樹脂組成物の硬化体が８０℃以下の温水と接触して膨潤し、フィルム状に部材から回収することにより樹脂組成物の硬化体を取り外すことを特徴とする該樹脂組成物である。 That is, the present invention is characterized in that after the surface of a workpiece is coated and cured, the workpiece is immersed in warm water of 90 ° C. or lower after processing to remove the cured body of the resin composition. It is a resin composition used for the processing method of a processed member, and contains (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, and (C) cyclopentadiene skeleton resin. The resin composition is a resin composition that is coated on the surface of the workpiece and cured, and then the workpiece is immersed in warm water of 90 ° C. or lower after processing to remove the cured body of the resin composition. It is a resin composition used in a method for processing a workpiece, and (A) polyfunctional (meth) acrylate, (B) monofunctional (meth) acrylate, (C) cyclopentadiene skeleton resin, (D) photopolymerization Initiator, (E) Al A resin composition characterized by containing Lumpur, a resin composition, characterized by containing either the (C) cyclopentadiene skeleton resin, an ester group and a hydroxyl group in the molecule, In 100 parts by mass of the total amount of the components (A) and (B), the component (A) is 1 to 95 parts by mass, the component (B) is 5 to 99 parts by mass, and the total amount 100 of the components (A) and (B) is 100. 0.1 to 50 parts by mass of component (C), 0.1 to 20 parts by mass of component (D), and 0.5 to 10 parts by mass of component (E) as necessary with respect to parts by mass The resin composition is characterized in that it further contains a polymerization inhibitor, and the component (A) is composed of two polyfunctional (meth) acrylate oligomers / polymers. One or more members selected from the group consisting of monomers having the above (meth) acryloyl groups The resin composition is characterized in that component (B) is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl ( (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Roxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) Acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, t- Butylaminoethyl (meth) acrylate, ethoxycarbonylmethyl (meth) acrylate, phenol ethylene oxide modified acrylate, phenol (ethylene oxide 2 mol modified) acrylate , Phenol (ethylene oxide 4 mol modified) acrylate, paracumylphenol ethylene oxide modified acrylate, nonylphenol ethylene oxide modified acrylate, nonylphenol (ethylene oxide 4 mol modified) acrylate, nonylphenol (ethylene oxide 8 mol modified) acrylate, nonylphenol (propylene oxide 2) .5 mol modified) acrylate, 2-ethylhexyl carbitol acrylate, ethylene oxide modified phthalic acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, trifluoroethyl (meth) acrylate, acrylic acid, methacrylic acid, maleic acid , Fumaric acid, ω-carboxy-polycaprolactone mono (meth) acrylate, phthalic acid monohydro Of the group consisting of ciethyl (meth) acrylate, (meth) acrylic acid dimer, β- (meth) acryloyloxyethyl hydrogen succinate, n- (meth) acryloyloxyalkylhexahydrophthalimide, benzyl (meth) acrylate One or more types of the resin composition, wherein the cured resin composition swells in contact with hot water of 80 ° C. or less, and is recovered from the member in a film form to cure the resin composition It is this resin composition characterized by removing a body .
本発明は、前記の樹脂組成物からなることを特徴とする接着剤であり、また、表面に、前記の樹脂組成物からなる硬化体を設けてなることを特徴とする被加工部材である。 The present invention is an adhesive characterized by comprising the above resin composition, also on the surface, a workpiece characterized by comprising providing a cured product made of the resin composition.
更に、本発明は、前記の樹脂組成物を用いて被加工部材の表面に被覆し硬化させた後、該被加工部材を加工後に９０℃以下の温水に浸漬して、前記樹脂組成物の硬化体を取り外すことを特徴とする被加工部材の表面保護方法であり、また、前記の樹脂組成物を用いて被加工部材を基材に接着し、硬化させた後、該被加工部材を加工後に９０℃以下の温水に浸漬して、前記樹脂組成物の硬化体を取り外すことを特徴とする被加工部材の仮固定方法である。 Further, in the present invention, the surface of the workpiece is coated and cured using the resin composition, and the workpiece is then immersed in warm water of 90 ° C. or less after processing to cure the resin composition. A method for protecting a surface of a workpiece, wherein the body is removed, and the workpiece is bonded to a substrate using the resin composition and cured, and then the workpiece is processed. It is a method for temporarily fixing a workpiece by immersing in warm water of 90 ° C. or less and removing the cured body of the resin composition.
本発明の樹脂組成物は、その組成故に光硬化性を有し、可視光または紫外線によって硬化する。このために、従来のホットメルト接着剤に比べ、省力化、省エネルギー化、作業短縮の面で著しい効果が得られる。また、その硬化体は、加工時に用いる切削水などに影響せずに高い接着強度を発現できるので、部材の加工時にずれを生じ難く、寸法精度面で優れた部材が容易に得られるという効果が得られる。更に、当該硬化体は、特に９０℃以下の温水に接触することで接着強度を低下させ部材間の或いは部材と治具との接合力を低下するので容易に部材の回収ができる特徴があり、従来の接着剤の場合に比べ、高価で、発火性の強い、或いは人体に有害なガスを発生する有機溶媒を用いる必要がないという格段の効果が得られる。更に、特定の好ましい組成範囲の樹脂組成物においては、硬化体が９０℃以下の温水と接触して膨潤し、フィルム状に部材から回収できるので、作業性に優れるという効果が得られる。 The resin composition of the present invention has photocurability because of its composition and is cured by visible light or ultraviolet light. For this reason, compared with the conventional hot melt adhesive, a remarkable effect is acquired in terms of labor saving, energy saving, and work shortening. In addition, since the cured body can exhibit high adhesive strength without affecting the cutting water used at the time of processing, there is an effect that a member excellent in dimensional accuracy can be easily obtained without being displaced during the processing of the member. can get. Furthermore, the cured body has a feature that the member can be easily recovered because the adhesive strength is lowered by contact with warm water of 90 ° C. or less, and the bonding force between the members or between the member and the jig is lowered. Compared to the case of conventional adhesives, it is possible to obtain a remarkable effect that it is not necessary to use an organic solvent that is expensive, strongly ignitable, or generates a gas harmful to the human body. Furthermore, in the resin composition having a specific preferable composition range, the cured body comes into contact with hot water of 90 ° C. or less and swells and can be recovered from the member in the form of a film, so that an effect of excellent workability can be obtained.
本発明の部材の仮固定方法並びに表面保護方法は、前述した通りに、９０℃以下の温水に接触することで接着強度を低下させる樹脂組成物を用いているので、温水に接触させるのみで容易に部材の回収ができる特徴があり、従来の接着剤の場合に比べ、高価で、発火性の強い、或いは人体に有害なガスを発生する有機溶媒を用いる必要がないという格段の効果が得られる。 As described above, the temporary fixing method and the surface protecting method of the member of the present invention use the resin composition that reduces the adhesive strength by contacting with hot water of 90 ° C. or less, and thus can be easily performed only by contacting with warm water. There is a feature that can recover the member, and it is possible to obtain a remarkable effect that it is not necessary to use an organic solvent that is expensive, strongly ignitable, or generates a gas harmful to the human body as compared with the case of a conventional adhesive. .
本発明で使用する（Ａ）多官能（メタ）アクリレートとしては、オリゴマー／ポリマー末端又は側鎖に２個以上（メタ）アクロイル化された多官能（メタ）アクリレートオリゴマー／ポリマーや２個以上の（メタ）アクロイル基を有するモノマーを使用することができる。例えば、多官能（メタ）アクリレートオリゴマー／ポリマーとしては１，２-ポリブタジエン末端ウレタン（メタ）アクリレート（例えば、日本曹達社製ＴＥ−２０００、ＴＥＡ−１０００）、前記水素添加物（例えば、日本曹達社製ＴＥＡＩ−１０００）、１，４−ポリブタジエン末端ウレタン（メタ）アクリレート（例えば、大阪有機化学社製ＢＡＣ−４５）、ポリイソプレン末端（メタ）アクリレート、ポリエステル系ウレタン（メタ）アクリート、ポリエーテル系ウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレート、ビスＡ型エポキシ（メタ）アクリレート（例えば、大阪有機化学社製ビスコート＃５４０、昭和高分子社製ビスコートＶＲ−７７）などが挙げられる。 As (A) polyfunctional (meth) acrylate used in the present invention, two or more (meth) acryloylated polyfunctional (meth) acrylate oligomer / polymer or two or more ( A monomer having a (meth) acryloyl group can be used. For example, as the polyfunctional (meth) acrylate oligomer / polymer, 1,2-polybutadiene-terminated urethane (meth) acrylate (for example, TE-2000, TEA-1000 manufactured by Nippon Soda Co., Ltd.), the hydrogenated product (for example, Nippon Soda Co., Ltd.) TEAI-1000), 1,4-polybutadiene-terminated urethane (meth) acrylate (for example, BAC-45 manufactured by Osaka Organic Chemical Co., Ltd.), polyisoprene-terminated (meth) acrylate, polyester-based urethane (meth) acrylate, polyether-based urethane (Meth) acrylate, polyester (meth) acrylate, bis-A type epoxy (meth) acrylate (for example, Biscoat # 540 manufactured by Osaka Organic Chemical Co., Ltd., Biscoat VR-77 manufactured by Showa High Polymer Co., Ltd.), and the like.
さらに２官能（メタ）アクリレートモノマーとして、１，３−ブチレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、２−エチル−２−ブチル−プロパンジオール（メタ）アクリレート、ネオペンチルグリコール変性トリメチロールプロパンジ（メタ）アクリレート、ステアリン酸変性ペンタエリストールジアクリレート、ポリプロピレングリコールジ（メタ）アクリレート、２，２−ビス（４−（メタ）アクリロキシジエトキシフェニル）プロパン、２，２−ビス（４−（メタ）アクリロキシプロポキシフェニル）プロパン、２，２−ビス（４−（メタ）アクリロキシテトラエトキシフェニル）プロパン等が挙げられ、３官能（メタ）アクリレートモノマーとしては、トメチロールプロパントリ（メタ）アクリレート、トリス［（メタ）アクリロイキシエチル］イソシアヌレート等が挙げられ、４官能以上の（メタ）アクリレートモノマーとしては、ジメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールエトキシテトラ（メタ）アクリレート、ジペンタエリストールペンタ（メタ）アクリレート、ジペンタエリストールヘキサ（メタ）アクリレート等が挙げられる Furthermore, as a bifunctional (meth) acrylate monomer, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, 1,9- Nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 2-ethyl-2-butyl-propanediol (meth) acrylate, neopentyl glycol modified trimethylolpropane di (Meth) acrylate, stearic acid modified pentaerythritol diacrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- ( (Meta) acryloxypro Xylphenyl) propane, 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) propane, and the like. Examples of the trifunctional (meth) acrylate monomer include tomethylolpropane tri (meth) acrylate, tris [(meta ) Acryloylethyl] isocyanurate, etc., and the tetrafunctional or higher (meth) acrylate monomers include dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate. , Dipentaerystol penta (meth) acrylate, dipentaerystol hexa (meth) acrylate, etc.
本発明で使用する（Ａ）多官能（メタ）アクリレートは、疎水性のものがより好ましく、水溶性の場合、切削加工時に樹脂組成物の硬化体が膨潤することにより位置ずれを起こし加工精度が劣る恐れがあるため好ましくない。親水性であっても、その樹脂組成物の硬化体が水によって大きく膨潤もしくは一部溶解することがなければ、使用しても差し支えない。 The (A) polyfunctional (meth) acrylate used in the present invention is more preferably a hydrophobic one, and when it is water-soluble, the cured product of the resin composition swells at the time of cutting, causing positional displacement and processing accuracy. Since it may be inferior, it is not preferable. Even if it is hydrophilic, it can be used as long as the cured product of the resin composition is not greatly swollen or partially dissolved by water.
本発明で使用する（Ａ）多官能（メタ）アクリレートの添加量は、（Ａ）及び（Ｂ）成分の合計量１００質量部中、１〜５０質量部が好ましい。１質量部未満だと剥離性が低下し樹脂組成物の硬化体がフィルム状でない恐れがあり、５０質量部を越えると、硬化収縮が大きくなり初期の接着性が低下する恐れがある。 As for the addition amount of (A) polyfunctional (meth) acrylate used by this invention, 1-50 mass parts is preferable in 100 mass parts of total amounts of (A) and (B) component. If the amount is less than 1 part by mass, the peelability may be reduced and the cured product of the resin composition may not be in the form of a film. If the amount exceeds 50 parts by mass, the curing shrinkage may increase and the initial adhesiveness may be reduced.
本発明で使用する（Ｂ）成分の単官能（メタ）アクリレートモノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソデシル（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、フェニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニロキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、メトキシ化シクロデカトリエン（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、３−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、グリシジル（メタ）アクリレート、カプロラクトン変性テトラヒドロフルフリル（メタ）アクリレート、３−クロロ−２−ヒドロキシプロピル（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−ジエチルアミノエチル（メタ）アクリレート、ｔ−ブチルアミノエチル（メタ）アクリレート、エトキシカルボニルメチル（メタ）アクリレート、フェノールエチレンオキサイド変性アクリレート、フェノール（エチレンオキサイド２モル変性）アクリレート、フェノール（エチレンオキサイド４モル変性）アクリレート、パラクミルフェノールエチレンオキサイド変性アクリレート、ノニルフェノールエチレンオキサイド変性アクリレート、ノニルフェノール（エチレンオキサイド４モル変性）アクリレート、ノニルフェノール（エチレンオキサイド８モル変性）アクリレート、ノニルフェノール（プロピレンオキサイド２．５モル変性）アクリレート、２−エチルヘキシルカルビトールアクリレート、エチレンオキシド変性フタル酸（メタ）アクリレ−ト、エチレンオキシド変性コハク酸（メタ）アクリレート、トリフロロエチル（メタ）アクリレート、アクリル酸、メタクリル酸、マレイン酸、フマル酸、ω−カルボキシ−ポリカプロラクトンモノ（メタ）アクリレート、フタル酸モノヒドロキシエチル（メタ）アクリレート、（メタ）アクリル酸ダイマー、β−（メタ）アクロイルオキシエチルハイドロジェンサクシネート、ｎ−（メタ）アクリロイルオキシアルキルヘキサヒドロフタルイミド、ベンジル（メタ）アクリレート等が挙げられる。 As the monofunctional (meth) acrylate monomer of the component (B) used in the present invention, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, Glycidyl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) Acrylate, t-butylaminoethyl (meth) acrylate, ethoxycarbonylmethyl (meth) acrylate, phenol ethylene oxide modified acrylate, phenol (ethylene oxide 2 mol) ) Acrylate, phenol (ethylene oxide 4 mol modified) acrylate, paracumylphenol ethylene oxide modified acrylate, nonylphenol ethylene oxide modified acrylate, nonylphenol (ethylene oxide 4 mol modified) acrylate, nonylphenol (ethylene oxide 8 mol modified) acrylate, nonylphenol ( Propylene oxide 2.5 mol modified) acrylate, 2-ethylhexyl carbitol acrylate, ethylene oxide modified phthalic acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, trifluoroethyl (meth) acrylate, acrylic acid, methacrylic acid , Maleic acid, fumaric acid, ω-carboxy-polycaprolactone mono (meth) acrylate, Le acid mono-hydroxyethyl (meth) acrylate, (meth) acrylic acid dimer, beta-(meth) acryloyloxyethyl hydrogen succinate, n-(meth) acryloyloxy alkyl hexahydrophthalimide, benzyl (meth) acrylate Can be mentioned.
本発明で使用する（Ｂ）単官能（メタ）アクリレートは、（Ａ）成分同様に疎水性のものがより好ましく、水溶性の場合、切削加工時に樹脂組成物の硬化体が膨潤することにより位置ずれを起こし加工精度が劣る恐れがあるため好ましくない。また、親水性であっても、その樹脂組成物の硬化体が水によって膨潤もしくは一部溶解することがなければ、使用しても差し支えない。 The (B) monofunctional (meth) acrylate used in the present invention is more preferably hydrophobic as in the case of the component (A). In the case of water solubility, the position of the resin composition cured by swelling during the cutting process. This is not preferable because there is a possibility of causing displacement and inferior processing accuracy. Even if it is hydrophilic, it can be used if the cured product of the resin composition does not swell or partially dissolve with water.
本発明で使用する（Ｂ）単官能（メタ）アクリレートの添加量は、（Ａ）及び（Ｂ）成分の合計量１００質量部中、５〜９５質量部が好ましい。５質量部未満だと初期の接着性が低下す恐れがあり、９５質量部を越えると、剥離性が低下し、樹脂組成物の硬化体がフィルム状でない恐れがある。 As for the addition amount of (B) monofunctional (meth) acrylate used by this invention, 5-95 mass parts is preferable in 100 mass parts of total amounts of (A) and (B) component. If it is less than 5 parts by mass, the initial adhesiveness may be reduced, and if it exceeds 95 parts by mass, the peelability may be reduced, and the cured product of the resin composition may not be in the form of a film.
また、前記（Ａ）及び（Ｂ）成分の配合組成に、（メタ）アクリロイルオキシエチルアシッドフォスフェート、ジブチル２−（メタ）アクリロイルオキシエチルアシッドフォスフェート、ジオクチル２−（メタ）アクリロイルオキシエチルフォスフェート、ジフェニル２−（メタ）アクリロイルオキシエチルフォスフェート、（メタ）アクリロイルオキシエチルポリエチレングリコールアシッドフォスフェート等のビニル基又は（メタ）アクリル基を有するリン酸エステルを併用することで、金属面への密着性をさらに向上させることができる。 In addition, the composition of the components (A) and (B) includes (meth) acryloyloxyethyl acid phosphate, dibutyl 2- (meth) acryloyloxyethyl acid phosphate, dioctyl 2- (meth) acryloyloxyethyl phosphate. , Diphenyl 2- (meth) acryloyloxyethyl phosphate, (meth) acryloyloxyethyl polyethylene glycol acid phosphate, etc. The property can be further improved.
本発明で使用する（Ｃ）シクロペンタジエン骨格樹脂は、シクロペンタジエン骨格を有する樹脂ならばどのようなものでも構わないが、軟化点が５０℃から２００℃が好ましく、さらに数平均分子量（Ｍｎ）３００から６００のものが（Ａ）や（Ｂ）への溶解性の面で望ましい。 The (C) cyclopentadiene skeleton resin used in the present invention may be any resin as long as it has a cyclopentadiene skeleton, but the softening point is preferably 50 ° C. to 200 ° C., and the number average molecular weight (Mn) 300 To 600 are desirable in terms of solubility in (A) and (B).
本発明で使用する（Ｃ）シクロペンタジエン骨格樹脂は、（Ａ）及び（Ｂ）成分の合計量１００質量部に対して、０．５〜５０質量部が好ましい。０．５質量部以上であれば、フィルムを形成せずに糊残りすることもなく、５０質量部以下であれば接着性が低下することもない。 As for (C) cyclopentadiene frame | skeleton resin used by this invention, 0.5-50 mass parts is preferable with respect to 100 mass parts of total amounts of (A) and (B) component. If it is 0.5 parts by mass or more, no adhesive remains without forming a film, and if it is 50 parts by mass or less, the adhesiveness does not decrease.
本発明で使用する（Ｄ）光重合開始剤としては、可視光線や紫外線の活性光線により増感させて樹脂組成物の光硬化を促進するために配合するものであり、公知の各種光重合開始剤が使用可能である。具体的にはベンゾフェノン及びその誘導体、ベンジル及びその誘導体、エントラキノン及びその誘導体、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタール等のベンゾイン誘導体、ジエトキシアセトフェノン、４−ｔ−ブチルトリクロロアセトフェノン等のアセトフェノン誘導体、２−ジメチルアミノエチルベンゾエート、ｐ−ジメチルアミノエチルベンゾエート、ジフェニルジスルフィド、チオキサントン及びその誘導体、カンファーキノン、７，７−ジメチル−２，３−ジオキソビシクロ［２．２．１］ヘプタン−１−カルボン酸、７，７−ジメチル−２，３−ジオキソビシクロ［２．２．１］ヘプタン−１−カルボキシ−２−ブロモエチルエステル、７，７−ジメチル−２，３−ジオキソビシクロ［２．２．１］ヘプタン−１−カルボキシ−２−メチルエステル、７，７−ジメチル−２，３−ジオキソビシクロ［２．２．１］ヘプタン−１−カルボン酸クロライド等のカンファーキノン誘導体、２−メチル−１−［４-（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１等のα−アミノアルキルフェノン誘導体、ベンゾイルジフェニルホスフィンオキサイド、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド、ベンゾイルジエトキシポスフィンオキサイド、２，４，６−トリメチルベンゾイルジメトキシフェニルホスフィンオキサイド、２，４，６−トリメチルベンゾイルジエトキシフェニルホスフィンオキサイド等のアシルホスフィンオキサイド誘導体等が挙げられる。光重合開始剤は１種又は２種以上を組み合わせて用いることができる。 The (D) photopolymerization initiator used in the present invention is blended to accelerate photocuring of the resin composition by sensitizing with actinic rays of visible light or ultraviolet rays. The agent can be used. Specifically, benzophenone and derivatives thereof, benzyl and derivatives thereof, enthraquinone and derivatives thereof, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin derivatives such as benzyl dimethyl ketal, diethoxyacetophenone, Acetophenone derivatives such as 4-t-butyltrichloroacetophenone, 2-dimethylaminoethyl benzoate, p-dimethylaminoethyl benzoate, diphenyl disulfide, thioxanthone and derivatives thereof, camphorquinone, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] Heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2 Bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2 2.1] Camphorquinone derivatives such as heptane-1-carboxylic acid chloride, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Α-aminoalkylphenone derivatives such as amino-1- (4-morpholinophenyl) -butanone-1, benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, 2, 4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, 2 Acylphosphine oxide derivatives such as 4,6-trimethylbenzoyl dichloride ethoxyphenyl phosphine oxide. A photoinitiator can be used 1 type or in combination of 2 or more types.
（Ｄ）光重合開始剤の添加量は、（Ａ）及び（Ｂ）の合計１００質量部に対して、０．１〜２０質量部が好ましい。より好ましくは３〜２０質量部が好ましい。０．１質量部以上であれば、硬化促進の効果が確実に得られるし、２０質量部以下で充分な硬化速度が達成できる。より好ましい形態として（Ｄ）成分を３質量部以上添加することで、光照射量に依存なく硬化可能となり、さらに樹脂組成物の硬化体の架橋度が高くなり、切削加工時に位置ずれ等を起こさなくなる点や剥離性が向上する点でより好ましい。 (D) As for the addition amount of a photoinitiator, 0.1-20 mass parts is preferable with respect to a total of 100 mass parts of (A) and (B). More preferably, 3-20 mass parts is preferable. If it is 0.1 mass part or more, the effect of hardening acceleration | stimulation will be acquired reliably and sufficient curing speed can be achieved by 20 mass parts or less. By adding 3 parts by mass or more of component (D) as a more preferable form, it becomes possible to cure without depending on the amount of light irradiation, and further, the degree of cross-linking of the cured product of the resin composition is increased, causing misalignment during cutting. It is more preferable at the point which loses and the peelability improves.
本発明で使用する（Ｅ）成分のアルコールとしては、メタノール、エタノール、イソプロパノール、ブタノールが挙げられ、沸点として１００℃以下を有するアルコールが好ましく選択される。沸点が１００℃以下で充分な剥離性が得られるからである。特に臭気があまりなく、医薬用劇物と指定されていないエタノール、イソプロパノールが好ましい。 Examples of the (E) component alcohol used in the present invention include methanol, ethanol, isopropanol, and butanol, and an alcohol having a boiling point of 100 ° C. or lower is preferably selected. This is because sufficient peelability can be obtained when the boiling point is 100 ° C. or lower. Particularly preferred are ethanol and isopropanol, which have little odor and are not designated as pharmaceutical deleterious substances.
本発明で使用する（Ｅ）成分のアルコールの添加量は、（Ａ）及び（Ｂ）成分の合計量１００質量部に対して、０．５〜１０質量部が好ましい。０．５質量部以上ならば充分な剥離性が達成できるし、１０質量部以下で接着性が低下する恐れもなく、硬化体がフィルムを形成して糊残りする可能性が少ない。 The amount of the (E) component alcohol used in the present invention is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the (A) and (B) components. If it is 0.5 parts by mass or more, sufficient peelability can be achieved, and if it is 10 parts by mass or less, there is no possibility of the adhesiveness being lowered, and the cured body is less likely to form a film and leave glue.
本発明の樹脂組成物は、その貯蔵安定性向上のため少量の重合禁止剤を使用することができる。例えば重合禁止剤としては、メチルハイドロキノン、ハイドロキノン、２，２−メチレン−ビス（４−メチル−６−ターシャリーブチルフェノール）、カテコール、ハイドロキノンモノメチルエーテル、モノターシャリーブチルハイドロキノン、２，５−ジターシャリーブチルハイドロキノン、ｐ−ベンゾキノン、２，５−ジフェニル−ｐ−ベンゾキノン、２，５−ジターシャリーブチル−ｐ−ベンゾキノン、ピクリン酸、クエン酸、フェノチアジン、ターシャリーブチルカテコール、２−ブチル−４−ヒドロキシアニソール及び２，６−ジターシャリーブチル−ｐ−クレゾール等が挙げられる。 The resin composition of the present invention can use a small amount of a polymerization inhibitor in order to improve its storage stability. For example, polymerization inhibitors include methylhydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol), catechol, hydroquinone monomethyl ether, monotertiarybutylhydroquinone, 2,5-ditertiarybutyl. Hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertiarybutyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary butylcatechol, 2-butyl-4-hydroxyanisole and Examples include 2,6-ditertiary butyl-p-cresol.
これらの重合禁止剤の使用量は、（メタ）アクリル酸エステルモノマー１００質量部に対し、０．００１〜３質量部が好ましく、０．０１〜２質量部がより好ましい。０．００１質量部以上で貯蔵安定性が充分であるし、３質量部以下で確実な接着性が得られ、未硬化になるおそれもない。 0.001-3 mass parts is preferable with respect to 100 mass parts of (meth) acrylic acid ester monomers, and, as for the usage-amount of these polymerization inhibitors, 0.01-2 mass parts is more preferable. Storage stability is sufficient at 0.001 parts by mass or more, and reliable adhesion is obtained at 3 parts by mass or less, and there is no possibility of becoming uncured.
本発明の樹脂組成物は、本発明の目的を損なわない範囲で、一般に使用されているアクリルゴム、ウレタンゴム、アクリロニトリル−ブタジエン−スチレンゴムなどの各種エラストマー、無機フィラー、溶剤、増量材、補強材、可塑剤、増粘剤、染料、顔料、難燃剤、シランカップリング剤及び界面活性剤等の添加剤を使用してもよい。 The resin composition of the present invention includes various elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, inorganic filler, solvent, filler, reinforcing material, etc., which are generally used within the range not impairing the object of the present invention. Additives such as plasticizers, thickeners, dyes, pigments, flame retardants, silane coupling agents and surfactants may be used.
次に、本発明は、９０℃以下の温水と接触して接着強度を低下させる樹脂組成物を用いて被加工部材を基材に接着し、樹脂組成物を硬化して、仮固定し、該仮固定された部材を加工後、該加工された部材を必要なら基材ごと温水に浸漬して硬化した接着剤を取り外す部材の仮固定方法であり、これにより、有機溶剤を用いることなく、光学用部材などのいろいろな部材を加工精度高く加工することができる。 Next, the present invention uses a resin composition that comes into contact with warm water of 90 ° C. or lower to lower the adhesive strength, adheres the workpiece to the substrate, cures the resin composition, temporarily fixes, After the temporarily fixed member is processed, the processed member is temporarily fixed with a base material by removing the cured adhesive by immersing it in warm water together with the base material. It is possible to process various members such as members for use with high processing accuracy.
また、本発明の好ましい実施態様によれば、部材を取り外すときに、樹脂組成物の硬化体が８０℃以下の温水と接触して膨潤し、フィルム状に部材から回収できるようにすることで、作業性に優れるという効果が得られる。 Further, according to a preferred embodiment of the present invention, when the member is removed, the cured body of the resin composition swells in contact with warm water of 80 ° C. or less, and can be recovered from the member in a film shape. The effect of excellent workability can be obtained.
本発明の仮固定方法において、前記本発明の樹脂組成物からなる接着剤を用いると、前記発明の効果が確実に得られるので、好ましい。 In the temporary fixing method of the present invention, it is preferable to use an adhesive comprising the resin composition of the present invention because the effects of the present invention can be obtained with certainty.
本発明に於いて、適度に加熱した９０℃以下の温水を用いる時、水中での剥離性が短時間に達成でき、生産性の面から好ましい。前記温水の温度に関しては、３０℃〜９０℃、好ましくは４０〜８０℃、の温水を用いると短時間で接着剤の硬化物が少し膨潤し、接着強度が低下するとともに、（Ｃ）成分のアルコールの蒸気圧が剥離力として働き、被着体のフィルム状に接着剤硬化体を取り外すことができるので、好ましい。尚、硬化体と水との接触の方法については、水中に接合体ごと浸漬する方法が簡便であることから推奨される。 In the present invention, when warm water of 90 ° C. or less heated moderately is used, releasability in water can be achieved in a short time, which is preferable from the viewpoint of productivity. Regarding the temperature of the warm water, when using warm water of 30 ° C. to 90 ° C., preferably 40 to 80 ° C., the cured product of the adhesive slightly swells in a short time, and the adhesive strength decreases. The vapor pressure of alcohol works as a peeling force, and the cured adhesive can be removed in the form of an adherend, which is preferable. In addition, about the method of contact with a hardening body and water, since the method of immersing the whole joined body in water is simple, it is recommended.
本発明において、仮固定することのできる部材並びに基材の材質に特に制限はなく、紫外線硬化型接着剤として用いる場合には、紫外線を透過できる材料からなる部材や基材が好ましい。このような材質として、例えば、水晶部材、ガラス部材、プラスチック部材、ウエハが挙げられる。本発明の仮固定方法は、ガラスレンズ、プラスチックレンズ、ウエハ及び光ディスクの加工における仮固定に適用可能である。 In the present invention, the material that can be temporarily fixed and the material of the substrate are not particularly limited, and when used as an ultraviolet curable adhesive, a member or substrate made of a material that can transmit ultraviolet rays is preferable. Examples of such a material include a crystal member, a glass member, a plastic member, and a wafer. The temporary fixing method of the present invention can be applied to temporary fixing in the processing of glass lenses, plastic lenses, wafers, and optical disks.
仮固定方法において接着剤の使用方法に関しては、接着剤として光硬化性接着剤を用いる場合を想定すると、例えば、固定する一方の部材又は支持基板の接着面に接着剤を適量塗布し、該部材を可視光または紫外線を照射して、光硬化性接着剤を硬化させ仮固定する方法等が例示される。 Assuming that a photocurable adhesive is used as the adhesive in the temporary fixing method, for example, an appropriate amount of adhesive is applied to one of the members to be fixed or the adhesive surface of the support substrate. Examples of the method include irradiating visible light or ultraviolet light to cure and temporarily fix the photocurable adhesive.
その後、仮固定された部材を所望の形状に切断、研削、研磨、孔開け等の加工を施した後、該部材を水好ましくは温水に浸漬することにより、接着剤の硬化物を部材から剥離することができる。 Thereafter, the temporarily fixed member is cut into a desired shape, ground, polished, drilled, etc., and then the cured product of the adhesive is peeled off from the member by immersing the member in water, preferably warm water. can do.
また、本発明は、前記の樹脂組成物を用いて被加工部材の表面に被覆し硬化させた後、該被加工部材を加工後に９０℃以下の温水に浸漬して、前記樹脂組成物の硬化体を取り外すことを特徴とする被加工部材の表面保護方法である。即ち、被加工部材の加工されない表面に前記樹脂組成物を塗布し硬化させることで、加工時に当該表面が汚れたり、チッピングを発生するのを防ぐことができる。 In the present invention, the surface of the workpiece is coated and cured using the resin composition, and the workpiece is then immersed in warm water of 90 ° C. or less after the workpiece is cured to cure the resin composition. A method for protecting a surface of a workpiece, wherein the body is removed. That is, by applying and curing the resin composition on the surface of the workpiece to be processed, it is possible to prevent the surface from becoming dirty or chipping during processing.
以下に実施例及び比較例をあげて本発明を更に詳細に説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.
（実施例１）（Ａ）多官能（メタ）アクリレートとして、日本曹達社製ＴＥ-２０００（１，２-ポリブタジエン末端ウレタンメタクリレート、以下「ＴＥ−２０００」と略す。）２０質量部、ジシクロペンタニルジアクリレート（日本化薬社製ＫＡＹＡＲＡＤ Ｒ−６８４、以下「Ｒ−６８４」と略す。）１５質量部、（Ｂ）単官能（メタ）アクリレートとして、ｎ−アクリロイルオキシエチルヘキサヒドロフタルイミド（東亜合成社製ＴＯ−１４２９、以下「ＴＯ−１４２９」と略す。）４０質量部、フェノールエチレンオキサイド２モル変成アクリレート（東亜合成社製アロニックスＭ−１０１Ａ、以下「Ｍ−１０１Ａ」と略す。）２５質量部、合計１００質量部、（Ｃ）シクロペンタジエン樹脂（日本ゼオン製クイントン１７００）１質量部、（Ｄ）光重合開始剤として、ベンジルジメチルケタール（以下、「ＢＤＫ」と略す。）１０質量部、（Ｅ）アルコールとして、イソプロピルアルコール（以下、「ＩＰＡ」と略す。）２質量部、重合禁止剤として２，２−メチレン−ビス（４−メチル−６−ターシャリーブチルフェノール）（以下、「ＭＤＰ」と略す。）０．１質量部を配合して樹脂組成物を作成した。得られた樹脂組成物を使用して、以下に示す評価方法にてその硬化体の引張せん断接着強さの測定及び剥離試験を行った。それらの結果を表１に示す。 (Example 1) (A) a polyfunctional (meth) acrylate, manufactured by Nippon Soda Co., Ltd. TE-2000 (1,2-polybutadiene-terminated urethane methacrylate, hereinafter abbreviated as "TE-2000".) 20 parts by mass, dicyclohexyl Bae printer Nyl diacrylate (Nippon Kayaku Co., Ltd. KAYARAD R-684, hereinafter abbreviated as “R-684”) 15 parts by mass, (B) As monofunctional (meth) acrylate, n-acryloyloxyethyl hexahydrophthalimide (Toagosei) 40 parts by mass of TO-1429 manufactured by Toyo Gosei Co., Ltd., hereinafter referred to as “TO-1429”), 25 parts by mass of 2 mol of phenol ethylene oxide modified acrylate (Aronix M-101A manufactured by Toagosei Co., Ltd., hereinafter referred to as “M-101A”). , 100 parts by mass in total, (C) cyclopentadiene resin (Quinton 1700 manufactured by Zeon Corporation) Parts, (D) 10 parts by mass of benzyl dimethyl ketal (hereinafter abbreviated as “BDK”) as a photopolymerization initiator, and (E) 2 parts by mass of isopropyl alcohol (hereinafter abbreviated as “IPA”) as alcohol. A resin composition was prepared by blending 0.1 part by mass of 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol) (hereinafter abbreviated as “MDP”) as a polymerization inhibitor. Using the obtained resin composition, the tensile shear bond strength of the cured product and a peel test were performed by the following evaluation methods. The results are shown in Table 1.
（評価方法）
引張せん断接着強さ：ＪＩＳ Ｋ ６８５０に従い測定した。具体的には被着材として、耐熱パイレックス（商標登録）ガラス（２５ｍｍ×２５ｍｍ×２．０ｍｍ）を用いて、接着部位を直径８ｍｍとして、作成した樹脂組成物にて、２枚の耐熱パイレックス（商標登録）ガラスを貼り合わせ、無電極放電ランプを使用したフュージョン社製硬化装置により、３６５ｎｍの波長の積算光量２０００ｍＪ／ｃｍ２の条件にて硬化させ、引張せん断接着強さ試験片を作成した。作成した試験片は、万能試験機を使用して、温度２３℃、湿度５０％の環境下、引張速度１０ｍｍ／ｍｉｎで引張せん断接着強さを測定した。
剥離試験：上記耐熱パイレックス（登録商標）ガラスに樹脂組成物を塗布し、無電極放電ランプを使用したフュージョン社製硬化装置により、３６５ｎｍの波長の積算光量２０００ｍＪ／ｃｍ２の条件にて樹脂組成物を硬化させ、剥離試験体を作成した。得られた試験体を、温水（８０℃）に浸漬し、耐熱パイレックス（登録商標）ガラスから剥離する時間を測定し、また剥離状態も観察した。
(Evaluation method)
Tensile shear bond strength: measured in accordance with JIS K 6850. Specifically, using heat resistant Pyrex (registered trademark) glass (25 mm × 25 mm × 2.0 mm) as the adherend, the bonded portion having a diameter of 8 mm, the two resin Pyrex ( Trademark registration) Glass was laminated, and cured by a fusion device made by Fusion Corporation using an electrodeless discharge lamp under the condition of an integrated light amount of 2000 mJ / cm 2 at a wavelength of 365 nm, to prepare a tensile shear bond strength test piece. The prepared test piece was measured for tensile shear bond strength at a tensile speed of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a universal testing machine.
Peel test: The resin composition was applied to the above heat-resistant Pyrex (registered trademark) glass, and the resin composition was used under a condition of an integrated light amount of 2000 mJ / cm 2 at a wavelength of 365 nm using a curing device manufactured by Fusion Corporation using an electrodeless discharge lamp. Was cured to prepare a peel test specimen. The obtained test body was immersed in warm water (80 ° C.), the time for peeling from the heat-resistant Pyrex (registered trademark) glass was measured, and the peeled state was also observed.
（実施例２〜２１）
表１、表２に示す種類の原材料を表１、表２に示す組成で使用したこと以外は実施例１と同様にして樹脂組成物を作成した。得られた樹脂組成物に関して、実施例１と同様に引張せん断接着強さの測定及び剥離試験を行った。それらの結果を表１、表２に示す
(Examples 2 to 21)
Resin compositions were prepared in the same manner as in Example 1 except that the raw materials of the types shown in Tables 1 and 2 were used in the compositions shown in Tables 1 and 2. With respect to the obtained resin composition, the measurement of the tensile shear bond strength and the peel test were performed in the same manner as in Example 1. The results are shown in Tables 1 and 2.
（使用材料）
ＴＰＯ：２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド（ＢＡＳＦ社製ルシリンＴＰＯ）
Ｉ−９０７：２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン（チバ・スペシャルティ・ケミカルズ社製ＩＲＧＡＣＵＲＥ９０７）
ＱＭ：ジシクロペンテニルオキシエチルメタクリレート（ローム＆ハース社製ＱＭ−６５７）
ＢＺ：ベンジルメタクリレート（共栄社化学社製ライトエステルＢＺ）
ＩＢＸ：イソボルニルメタクリレート（共栄社化学社製ライトエステルＩＢ−Ｘ）
(Materials used)
TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO manufactured by BASF)
I-907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (IRGACURE907 manufactured by Ciba Specialty Chemicals)
QM: Dicyclopentenyloxyethyl methacrylate (Rohm & Haas QM-657)
BZ: benzyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester BZ)
IBX: Isobornyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester IB-X)
（比較例１〜６）
表３に示す種類の原材料を表３に示す組成で使用したこと以外は実施例１と同様にして樹脂組成物を作成した。得られた樹脂組成物に関して、実施例１と同様に引張せん断接着強さの測定及び剥離試験を行った。それらの結果を表３に示す。
(Comparative Examples 1-6)
A resin composition was prepared in the same manner as in Example 1 except that the raw materials of the type shown in Table 3 were used in the composition shown in Table 3. With respect to the obtained resin composition, the measurement of the tensile shear bond strength and the peel test were performed in the same manner as in Example 1. The results are shown in Table 3.
（使用材料）
２−ＨＥＭＡ：２-ヒドロキシエチルメタクリレート
ＭＴＥＧＭＡ：メトシキテトラエチレングリコールモノメタクリレート（新中村化学社製ＮＫエステルＭ−９０Ｇ）
(Materials used)
2-HEMA: 2-hydroxyethyl methacrylate MTEGMA: methoxytetraethylene glycol monomethacrylate (NK Nakamura Chemical Co., Ltd. NK ester M-90G)
（実施例２２、比較例７）
実施例１及び比較例８の樹脂組成物をそれぞれ用いて、無電極放電ランプを使用したフュージョン社製硬化装置により、３６５ｎｍの波長の積算光量を５００，１０００，２０００，４０００ｍＪ/ｃｍ2と変えて接着剤組成物を硬化させ、剥離試験体、引張せん断接着強さ試験片を作成したこと以外は、実施例1と同様に引張せん断接着強さの測定及び剥離試験を行った。それらの結果を表４に示す。
(Example 22, Comparative Example 7)
Using each of the resin compositions of Example 1 and Comparative Example 8, the integrated light quantity at a wavelength of 365 nm was changed to 500, 1000, 2000, and 4000 mJ / cm 2 by a fusion device manufactured by Fusion Corporation using an electrodeless discharge lamp. Except that the adhesive composition was cured and a peel test specimen and a tensile shear bond strength test piece were prepared, the measurement of the tensile shear bond strength and the peel test were performed in the same manner as in Example 1. The results are shown in Table 4.
（実施例２３、２４）
実施例１及び７の樹脂組成物を使用し、実施例１と同様に剥離試験体を作成し、温水の温度４０℃、５０℃、６０、７０℃を変えて剥離試験を行った。その結果を表５に示す。その結果、いずれの温度でも剥離性を有する。
(Examples 23 and 24)
Using the resin compositions of Examples 1 and 7, peel test bodies were prepared in the same manner as in Example 1, and peel tests were performed while changing the temperature of hot water at 40 ° C, 50 ° C, 60, and 70 ° C. The results are shown in Table 5. As a result, it has peelability at any temperature.
本発明の樹脂組成物は、その組成故に光硬化性を有し、可視光または紫外線によって硬化し、その硬化体は切削水などに影響されずに、高い接着強度を発現できるので、部材の加工時にずれを生じ難く、寸法精度面で優れた部材が容易に得られるという効果が得られるし、更に、温水に接触することで接着強度を低下させ、部材間の或いは部材と治具との接合力を低下するので、容易に部材の回収ができる特徴があるので、光学レンズ、プリズム、アレイ、シリコンウエハ、半導体実装部品等の仮固定用接着剤として、産業上有用である。 The resin composition of the present invention has photocurability because of its composition, is cured by visible light or ultraviolet light, and the cured product can exhibit high adhesive strength without being affected by cutting water or the like. There is an effect that a member excellent in dimensional accuracy can be easily obtained with little time deviation, and further, the adhesive strength is lowered by contact with hot water, and the bonding between the members or between the member and the jig is performed. Since the force is reduced, the member can be easily recovered, so that it is industrially useful as an adhesive for temporarily fixing optical lenses, prisms, arrays, silicon wafers, semiconductor mounting parts and the like.
本発明の部材の仮固定方法並びに表面保護方法は、前記特徴ある樹脂組成物を用いているので、従来技術に於いて必要であった有機溶媒を用いる必要がなく、またフィルム状に部材から回収できるので作業性に優れるという特徴があるので、産業上非常に有用である。更に、本発明はその好ましい実施態様に於いて、基板に一時的に付着したまま部材から剥がれ、後に基板からもフィルム上に剥がれることから、加工部材の回収が効率的にでき、また基材の再使用も容易となることから、産業上非常に有用である。 The temporary fixing method and the surface protecting method of the member of the present invention use the characteristic resin composition, so that it is not necessary to use an organic solvent required in the prior art, and the film is recovered from the member. Since it has a feature that it is excellent in workability, it is very useful industrially. Furthermore, in the preferred embodiment of the present invention, since the material is peeled off from the member while temporarily adhering to the substrate, and then peeled off from the substrate onto the film, the processed member can be efficiently recovered, and the substrate Since reuse becomes easy, it is very useful industrially.
Claims (12)
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006005597A JP5052792B2 (en) | 2006-01-13 | 2006-01-13 | Resin composition and method for temporarily fixing and protecting surface of workpiece using the same |
| US12/159,231 US20080289750A1 (en) | 2006-01-13 | 2007-01-11 | Curable Resin Composition, Surface Protection Method, Temporary Fixation Method, and Separation Method |
| CN200780002262.XA CN101370879B (en) | 2006-01-13 | 2007-01-11 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
| CN201010622598XA CN102161732B (en) | 2006-01-13 | 2007-01-11 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
| KR1020087013075A KR101447298B1 (en) | 2006-01-13 | 2007-01-11 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
| EP07706620A EP1972663A4 (en) | 2006-01-13 | 2007-01-11 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
| PCT/JP2007/050273 WO2007080936A1 (en) | 2006-01-13 | 2007-01-11 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
| KR1020137014159A KR101320823B1 (en) | 2006-01-13 | 2007-01-11 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
| TW096101311A TWI405831B (en) | 2006-01-13 | 2007-01-12 | A hardening resin composition, a surface protection method, a temporary fixing method, and a peeling method |
| MYPI20082032A MY145362A (en) | 2006-01-13 | 2008-06-10 | Curable resin composition, surface-protecting method, temporary fixing method and removing method |
| US13/181,031 US8338526B2 (en) | 2006-01-13 | 2011-07-12 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
| US13/436,025 US8415425B2 (en) | 2006-01-13 | 2012-03-30 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
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| JP2006005597A JP5052792B2 (en) | 2006-01-13 | 2006-01-13 | Resin composition and method for temporarily fixing and protecting surface of workpiece using the same |
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| JP2007186587A JP2007186587A (en) | 2007-07-26 |
| JP5052792B2 true JP5052792B2 (en) | 2012-10-17 |
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| KR101447298B1 (en) | 2006-01-13 | 2014-10-06 | 덴끼 가가꾸 고교 가부시키가이샤 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
Families Citing this family (11)
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| JPWO2009096459A1 (en) * | 2008-02-01 | 2011-05-26 | 電気化学工業株式会社 | Resin composition and method for temporarily fixing workpiece |
| KR101555729B1 (en) | 2008-05-12 | 2015-09-25 | 덴끼 가가꾸 고교 가부시키가이샤 | Method for protection of surface of material to be processed, and temporary fixing method |
| WO2012005169A1 (en) * | 2010-07-08 | 2012-01-12 | 電気化学工業株式会社 | Curable resin composition |
| CN102898959B (en) * | 2011-07-25 | 2016-07-06 | 汉高股份有限及两合公司 | A kind of photo curable adhesive composition and application thereof |
| JP6030560B2 (en) * | 2011-09-14 | 2016-11-24 | デンカ株式会社 | Composition and method for temporarily fixing member using the same |
| JP5596205B2 (en) * | 2013-04-17 | 2014-09-24 | 電気化学工業株式会社 | Material transport method |
| JP5901808B2 (en) * | 2014-08-05 | 2016-04-13 | 古河電気工業株式会社 | Curable hygroscopic resin composition for sealing electronic device, sealing resin and electronic device |
| CN104974310B (en) * | 2015-06-12 | 2017-09-05 | 长沙市汇华胶粘剂科技有限公司 | A kind of Decal peelable film oil resin and preparation method thereof |
| CN109415473B (en) * | 2016-07-01 | 2021-12-10 | 电化株式会社 | Composition comprising a metal oxide and a metal oxide |
| JP2019137555A (en) * | 2018-02-14 | 2019-08-22 | 住友化学株式会社 | Film roll |
| CN111138966B (en) * | 2019-12-20 | 2021-11-09 | 江苏乘鹰新材料股份有限公司 | Flexible UV (ultraviolet) photocureable coating and preparation method and application thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61207476A (en) * | 1985-03-12 | 1986-09-13 | Hitachi Chem Co Ltd | Radiation-curable self-adhesive for surface protective film used for drawing process |
| US4717700A (en) * | 1986-06-16 | 1988-01-05 | Exxon Research & Engineering Co. | Catalyst drying and activation methods |
| JPH01110584A (en) * | 1987-10-22 | 1989-04-27 | Nichiban Co Ltd | Curable adhesive tape or sheet |
| CN1028433C (en) * | 1989-02-01 | 1995-05-17 | 北京大学 | Photo-curing composition and preparation method and application thereof |
| JPH04178482A (en) * | 1990-11-09 | 1992-06-25 | Nitto Denko Corp | Pressure-sensitive adhesive and surface-protective member using the same |
| US5288807A (en) * | 1991-07-02 | 1994-02-22 | Rohm And Haas Company | Vinyl monomer compositions with accelerated surface cure |
| JPH06240176A (en) * | 1993-02-18 | 1994-08-30 | Mitsui Petrochem Ind Ltd | Resin composition for coating |
| JPH101523A (en) * | 1996-06-14 | 1998-01-06 | Japan Synthetic Rubber Co Ltd | Radiation-curable resin composition |
| JP2003128714A (en) * | 2001-10-26 | 2003-05-08 | Arakawa Chem Ind Co Ltd | Method for producing partially polymerized acrylic polymer composition, partially polymerized acrylic polymer composition produced by the production method and adhesive composition produced by ultraviolet polymerization of the composition |
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| KR101447298B1 (en) | 2006-01-13 | 2014-10-06 | 덴끼 가가꾸 고교 가부시키가이샤 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
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| JP2007186587A (en) | 2007-07-26 |
| CN101370879B (en) | 2015-06-24 |
| CN101370879A (en) | 2009-02-18 |
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