JP7386088B2 - Adhesive composition and adhesive sheet using the adhesive composition - Google Patents
Adhesive composition and adhesive sheet using the adhesive composition Download PDFInfo
- Publication number
- JP7386088B2 JP7386088B2 JP2020007711A JP2020007711A JP7386088B2 JP 7386088 B2 JP7386088 B2 JP 7386088B2 JP 2020007711 A JP2020007711 A JP 2020007711A JP 2020007711 A JP2020007711 A JP 2020007711A JP 7386088 B2 JP7386088 B2 JP 7386088B2
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- Prior art keywords
- adhesive
- meth
- acrylate
- adhesive strength
- weight
- 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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- 239000000853 adhesive Substances 0.000 title claims description 198
- 230000001070 adhesive effect Effects 0.000 title claims description 198
- 239000000203 mixture Substances 0.000 title claims description 67
- 239000012790 adhesive layer Substances 0.000 claims description 53
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 48
- 239000010410 layer Substances 0.000 claims description 42
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 12
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 12
- 239000004642 Polyimide Substances 0.000 claims description 11
- 229920001721 polyimide Polymers 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- ZMDDERVSCYEKPQ-UHFFFAOYSA-N Ethyl (mesitylcarbonyl)phenylphosphinate Chemical group C=1C=CC=CC=1P(=O)(OCC)C(=O)C1=C(C)C=C(C)C=C1C ZMDDERVSCYEKPQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- 239000013464 silicone adhesive Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 80
- 239000000178 monomer Substances 0.000 description 60
- 239000003431 cross linking reagent Substances 0.000 description 39
- -1 polyimide Chemical compound 0.000 description 39
- 235000012431 wafers Nutrition 0.000 description 29
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 229920000178 Acrylic resin Polymers 0.000 description 16
- 239000004925 Acrylic resin Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 14
- 125000000524 functional group Chemical group 0.000 description 12
- 239000003999 initiator Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000012948 isocyanate Substances 0.000 description 10
- 239000011254 layer-forming composition Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 229920000058 polyacrylate Polymers 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229920005601 base polymer Polymers 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 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 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 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 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000004611 light stabiliser 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
- 150000002739 metals Chemical class 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 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 description 3
- 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 2
- 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 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- VHFGGWSXGDWGOY-UHFFFAOYSA-N 2-isocyanatoethyl 2-methylprop-2-enoate 5-isocyanato-2-methylpent-2-enoic acid Chemical compound N(=C=O)CCC=C(C(=O)O)C.C(C(=C)C)(=O)OCCN=C=O VHFGGWSXGDWGOY-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 125000002704 decyl 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])* 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 125000001421 myristyl 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])[H] 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl 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])[H] 0.000 description 2
- 125000002347 octyl 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])[H] 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 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 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000002889 tridecyl 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])[H] 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 125000002948 undecyl 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])[H] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- IAUGBVWVWDTCJV-UHFFFAOYSA-N 1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C=C IAUGBVWVWDTCJV-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- BFYSJBXFEVRVII-UHFFFAOYSA-N 1-prop-1-enylpyrrolidin-2-one Chemical compound CC=CN1CCCC1=O BFYSJBXFEVRVII-UHFFFAOYSA-N 0.000 description 1
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- QENRKQYUEGJNNZ-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(C)C(S(O)(=O)=O)NC(=O)C=C QENRKQYUEGJNNZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- 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
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- 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
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only 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
- C09J7/00—Adhesives in the form of films or foils
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- 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
- C09J2301/312—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 parameters being the characterizing feature
-
- 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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
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Description
本発明は、粘着剤組成物および該粘着剤組成物を用いた粘着シートに関する。 The present invention relates to an adhesive composition and an adhesive sheet using the adhesive composition.
大規模集積回路（ＬＳＩ）は、パーソナルコンピューター、スマートフォン、自動車等、様々な用途に用いられている。ＬＳＩ等の集積回路の製造過程では、加工時に表面を保護するために粘着シートが用いられている。近年、ＬＳＩの微細化、および、高機能化が進んでおり、ウエハの表面構造が複雑化している。例えば、銅およびアルミニウム等の金属配線、ポリイミド等の樹脂等の複数の材料を用いてウエハ表面が構成されており、はんだバンプ等によりウエハ表面の構造も複雑化している。そのため、ウエハ表面の材料および構造により粘着力の差が生じ、糊残りが発生する場合がある。糊残りを防止するために、紫外線硬化型粘着剤を用いた粘着シートが提案されている（特許文献１および２）。紫外線硬化型粘着剤を用いた場合であっても、ウエハ表面の組成および構造の違いによる紫外線照射後の粘着力の差が生じる場合がある。 Large-scale integrated circuits (LSIs) are used in various applications such as personal computers, smartphones, and automobiles. In the manufacturing process of integrated circuits such as LSIs, adhesive sheets are used to protect the surfaces during processing. In recent years, LSIs have become smaller and more sophisticated, and the surface structure of wafers has become more complex. For example, the wafer surface is constructed using a plurality of materials such as metal wiring such as copper and aluminum, and resin such as polyimide, and the structure of the wafer surface is also complicated by solder bumps and the like. Therefore, differences in adhesive strength may occur depending on the material and structure of the wafer surface, and adhesive residue may occur. In order to prevent adhesive residue, adhesive sheets using ultraviolet curable adhesives have been proposed (Patent Documents 1 and 2). Even when an ultraviolet curable adhesive is used, differences in adhesive strength after irradiation with ultraviolet rays may occur due to differences in the composition and structure of the wafer surface.
また、ウエハの加工技術としても様々な方法が提案されている。例えば、レーザーでウエハに切り込みを入れた後、裏面を削り薄型化して個片化する技術（Ｓｔｅａｌｔｈ Ｄｉｃｉｎｇ Ｂｅｆｏｒｅ Ｇｒｉｎｄｉｎｇ、ＳＤＢＧ）が提案されている（例えば、特許文献３）。ＳＤＢＧは、半導体チップへ負荷を低減させることができるものの、加工時に個片化されたチップを保持可能な粘着力を有する粘着シートを用いる必要がある。表面が複雑化したウエハでは、粘着力の差が生じやすいため、個片化されたチップを適切に保持することが困難となる場合がある。そのため、ウエハの表面の材料および構造に影響されることなく粘着力を発揮し得る粘着剤組成物が求められている。 Furthermore, various methods have been proposed as wafer processing techniques. For example, a technology (Stealth Dicing Before Grinding, SDBG) has been proposed in which a wafer is cut with a laser and then the back surface is shaved to reduce the thickness and separate the wafer into pieces (Stealth Dicing Before Grinding, SDBG) (for example, Patent Document 3). Although SDBG can reduce the load on semiconductor chips, it is necessary to use an adhesive sheet that has adhesive strength that can hold chips that have been separated into pieces during processing. A wafer with a complex surface tends to have a difference in adhesive strength, so it may be difficult to properly hold the diced chips. Therefore, there is a need for an adhesive composition that can exhibit adhesive strength without being affected by the material and structure of the wafer surface.
本発明は、上記従来の課題を解決するためになされたものであり、被着体表面の組成および構造に関わらず紫外線照射前は被着体に対する優れた粘着力を、紫外線照射後には優れた剥離性を有する紫外線硬化型粘着剤組成物、および、この粘着剤組成物を用いた粘着シートを提供することにある。 The present invention has been made to solve the above-mentioned conventional problems, and it provides excellent adhesion to an adherend before irradiation with ultraviolet rays, and excellent adhesion to the adherend after irradiation with ultraviolet rays, regardless of the composition and structure of the surface of the adherend. An object of the present invention is to provide an ultraviolet curable pressure-sensitive adhesive composition having peelability and a pressure-sensitive adhesive sheet using this pressure-sensitive adhesive composition.
１つの実施形態においては、本発明の紫外線硬化型粘着剤組成物は、紫外線硬化型粘着剤と、フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルと、を含む。
１つの実施形態においては、上記フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルはフェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸エチルである。
本発明の別の局面においては、粘着シートが提供される。この粘着シートは、基材と、粘着剤層と、を含む。この該粘着剤層は上記紫外線硬化型粘着剤組成物から形成される。
１つの実施形態においては、粘着シートは上記粘着剤層を少なくとも１層含む。
１つの実施形態においては、上記粘着剤層の紫外線照射後のポリイミド粘着力とシリコン粘着力との比は２以下である。
１つの実施形態においては、粘着シートは中間層をさらに含む。
１つの実施形態においては、上記中間層は上記粘着剤層と同じフェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルを含む。
１つの実施形態においては、粘着シートは半導体ウエハ加工工程に用いられる。
１つの実施形態においては、粘着シートはバックグラインドシートとして用いられる。
In one embodiment, the ultraviolet curable adhesive composition of the present invention includes an ultraviolet curable adhesive and an alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate.
In one embodiment, the alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate is ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate.
In another aspect of the invention, a pressure-sensitive adhesive sheet is provided. This adhesive sheet includes a base material and an adhesive layer. This adhesive layer is formed from the above-mentioned ultraviolet curable adhesive composition.
In one embodiment, the adhesive sheet includes at least one of the above adhesive layers.
In one embodiment, the ratio of the polyimide adhesive strength to the silicon adhesive strength of the adhesive layer after UV irradiation is 2 or less.
In one embodiment, the adhesive sheet further includes an intermediate layer.
In one embodiment, the intermediate layer includes the same alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate as the adhesive layer.
In one embodiment, the adhesive sheet is used in a semiconductor wafer processing process.
In one embodiment, the adhesive sheet is used as a backgrind sheet.
本発明の紫外線硬化型粘着剤組成物は、紫外線硬化型粘着剤と、フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルを含む。フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルは光重合性開始剤として機能し得る。本発明の紫外線硬化型粘着剤組成物は、紫外線照射前においては被着体表面が組成（例えば、金属等の無機物、樹脂等の有機物）の異なる部分を有する場合であっても優れた粘着力を発揮し得る。さらに、凹凸への追従性にも優れるため、被着体表面の構造（例えば、凹凸）が複雑な場合であっても優れた粘着力を発揮し得る。また、この紫外線硬化型粘着剤組成物は紫外線照射後においては、被着体表面の組成および構造に影響されず、軽剥離性を奏し得る。そのため、粘着シートの粘着剤層を形成する組成物として用いることにより、被着体表面への優れた粘着力と軽剥離性とを両立することが可能な粘着シートとすることができる。この粘着シートは、複雑な組成および構造を有し得る半導体ウエハの加工工程に好適に用いることができる。 The ultraviolet curable adhesive composition of the present invention includes an ultraviolet curable adhesive and an alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate. Alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate can function as a photopolymerization initiator. The ultraviolet curable adhesive composition of the present invention has excellent adhesive strength even when the surface of the adherend has different compositions (for example, inorganic substances such as metals, organic substances such as resins) before irradiation with ultraviolet rays. can be demonstrated. Furthermore, since it has excellent followability to irregularities, it can exhibit excellent adhesive strength even when the structure (for example, irregularities) of the surface of the adherend is complex. Further, after irradiation with ultraviolet rays, this ultraviolet curable pressure-sensitive adhesive composition is not affected by the composition and structure of the surface of the adherend and can exhibit easy releasability. Therefore, by using it as a composition for forming an adhesive layer of an adhesive sheet, it is possible to obtain an adhesive sheet that can have both excellent adhesion to the surface of an adherend and easy releasability. This pressure-sensitive adhesive sheet can be suitably used in the process of processing semiconductor wafers that may have complex compositions and structures.
Ａ．紫外線硬化型粘着剤組成物
１つの実施形態において、本発明の紫外線硬化型粘着剤組成物は、紫外線硬化型粘着剤と、フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルと、を含む。フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルは、光重合開始剤として機能し得る。光重合開始剤として、フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルを含むことにより、紫外線照射前においては、被着体表面が組成（例えば、金属等の無機物、樹脂等の有機物）の異なる部分を有する場合であっても優れた粘着力を発揮し得る。さらに、凹凸への追従性にも優れるため、被着体表面の構造（例えば、凹凸）が複雑な場合であっても優れた粘着力を発揮し得る。また、この紫外線硬化型粘着剤組成物は紫外線照射後においては、被着体表面の組成および構造に影響されることなく、粘着力が低下し、軽剥離性を奏し得る。そのため、被着体表面への糊残りを防止し得る。
A. Ultraviolet Curable Adhesive Composition In one embodiment, the ultraviolet curable adhesive composition of the present invention comprises an ultraviolet curable adhesive and an alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate. . Alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate can function as a photoinitiator. By including alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate as a photopolymerization initiator, the adherend surface has a composition (for example, inorganic substances such as metals, organic substances such as resins) before irradiation with ultraviolet rays. Excellent adhesive strength can be exhibited even when the adhesive has different portions. Furthermore, since it has excellent followability to irregularities, it can exhibit excellent adhesive strength even when the structure (for example, irregularities) of the surface of the adherend is complex. Furthermore, after irradiation with ultraviolet rays, this ultraviolet curable pressure-sensitive adhesive composition exhibits low adhesive strength and easy releasability without being affected by the composition and structure of the surface of the adherend. Therefore, it is possible to prevent adhesive from remaining on the surface of the adherend.
Ａ－１．紫外線硬化型粘着剤
紫外線硬化型粘着剤としては、任意の適切な粘着剤を用いることができる。例えば、アクリル系粘着剤、ゴム系粘着剤、シリコーン系粘着剤、ポリビニルエーテル系粘着剤等の任意の適切な粘着剤に紫外線硬化性のモノマーおよび／またはオリゴマーを添加した粘着剤であってもよく、ベースポリマーとして炭素－炭素二重結合を側鎖または末端に有するポリマーを用いた粘着剤であってもよい。
A-1. Ultraviolet Curing Adhesive Any suitable adhesive can be used as the ultraviolet curing adhesive. For example, the adhesive may be any suitable adhesive such as an acrylic adhesive, a rubber adhesive, a silicone adhesive, or a polyvinyl ether adhesive, to which an ultraviolet curable monomer and/or oligomer is added. Alternatively, it may be an adhesive using a polymer having a carbon-carbon double bond in a side chain or terminal as a base polymer.
紫外線硬化性モノマーおよびオリゴマーとしては、任意の適切なモノマーまたはオリゴマーを用いることができる。紫外線硬化性モノマーとしては、例えば、ウレタン（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリストールテトラ（メタ）アクリレート、ジペンタエリストールモノヒドロキシペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート等が挙げられる。放射線硬化性のオリゴマーとしては、ウレタン系オリゴマー、ポリエーテル系オリゴマー、ポリエステル系オリゴマー、ポリカーボネート系オリゴマー、ポリブタジエン系オリゴマー等が挙げられる。オリゴマーとしては、好ましくは分子量が１００～３００００程度のものが用いられる。モノマーおよびオリゴマーは１種のみを用いてもよく、２種以上を組み合わせて用いてもよい。 Any suitable monomer or oligomer can be used as the ultraviolet curable monomer and oligomer. Examples of UV-curable monomers include urethane (meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, Examples include dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and 1,4-butanediol di(meth)acrylate. Examples of radiation-curable oligomers include urethane oligomers, polyether oligomers, polyester oligomers, polycarbonate oligomers, and polybutadiene oligomers. The oligomer preferably has a molecular weight of about 100 to 30,000. Only one type of monomer and oligomer may be used, or two or more types may be used in combination.
モノマーおよび／またはオリゴマーは、用いる粘着剤の種類に応じて、任意の適切な量で用いられ得る。例えば、粘着剤を構成するベースポリマー１００重量部に対して、好ましくは５重量部～５００重量部、より好ましくは４０重量部～１５０重量部用いられる。 Monomers and/or oligomers may be used in any suitable amount depending on the type of adhesive used. For example, the amount used is preferably 5 to 500 parts by weight, more preferably 40 to 150 parts by weight, based on 100 parts by weight of the base polymer constituting the adhesive.
炭素－炭素二重結合を側鎖または末端を有するポリマーを用いた粘着剤を用いる場合、ベースポリマーとしては側鎖または末端に重合性炭素－炭素二重結合を有し、かつ、粘着性を有するポリマーが用いられる。このようなポリマーとしては、例えば、（メタ）アクリル系樹脂、ビニルアルキルエーテル系樹脂、シリコーン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ウレタン系樹脂、スチレン－ジエンブロック共重合体等の樹脂に重合性炭素－炭素二重結合を導入したポリマーが挙げられる。好ましくは、（メタ）アクリル系樹脂に重合性炭素－炭素二重結合が導入された（メタ）アクリル系ポリマーが用いられる。該（メタ）アクリル系ポリマーを用いることにより、粘着剤層の貯蔵弾性率および引っ張り弾性率の調整がしやすく、また、粘着力と剥離性とのバランスに優れた粘着シートを得ることができる。なお、「（メタ）アクリル」とは、アクリルおよび／またはメタクリルをいう。 When using a pressure-sensitive adhesive using a polymer having a carbon-carbon double bond in the side chain or end, the base polymer must have a polymerizable carbon-carbon double bond in the side chain or end, and be adhesive. Polymers are used. Examples of such polymers include (meth)acrylic resins, vinyl alkyl ether resins, silicone resins, polyester resins, polyamide resins, urethane resins, and styrene-diene block copolymers. Examples include polymers with carbon-carbon double bonds introduced therein. Preferably, a (meth)acrylic polymer in which a polymerizable carbon-carbon double bond is introduced into a (meth)acrylic resin is used. By using the (meth)acrylic polymer, the storage modulus and tensile modulus of the adhesive layer can be easily adjusted, and a pressure-sensitive adhesive sheet with an excellent balance between adhesive force and releasability can be obtained. Note that "(meth)acrylic" refers to acrylic and/or methacrylic.
（メタ）アクリル系樹脂としては、任意の適切な（メタ）アクリル系樹脂を用いることができる。（メタ）アクリル系樹脂としては、例えば、直鎖または分岐のアルキル基を有するアクリル酸またはメタクリル酸のエステルを１種または２種以上含むモノマー組成物を重合して得られる重合体が挙げられる。 As the (meth)acrylic resin, any suitable (meth)acrylic resin can be used. Examples of (meth)acrylic resins include polymers obtained by polymerizing a monomer composition containing one or more esters of acrylic acid or methacrylic acid having a linear or branched alkyl group.
直鎖または分岐のアルキル基は、好ましくは炭素数が３０個以下のアルキル基であり、より好ましくは炭素数１個～２０個のアルキル基であり、さらに好ましくは炭素数４個～１８個のアルキル基である。アルキル基としては、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｔ－ブチル基、イソブチル基、アミル基、イソアミル基、へキシル基、ヘプチル基、シクロヘキシル基、２－エチルヘキシル基、オクチル基、イソオクチル基、ノニル基、イソノニル基、デシル基、イソデシル基、ウンデシル基、ラウリル基、トリデシル基、テトラデシル基、ステアリル基、オクタデシル基、ドデシル基等が挙げられる。 The straight chain or branched alkyl group is preferably an alkyl group having 30 or less carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, and even more preferably an alkyl group having 4 to 18 carbon atoms. It is an alkyl group. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, and cyclohexyl group. , 2-ethylhexyl group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, lauryl group, tridecyl group, tetradecyl group, stearyl group, octadecyl group, dodecyl group and the like.
（メタ）アクリル系樹脂を形成するモノマー組成物は、任意の適切な他のモノマーを含んでいてもよい。他のモノマーとしては、例えば、アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸等のカルボキシル基含有モノマー；無水マレイン酸、無水イタコン酸等の酸無水物モノマー；（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸６－ヒドロキシヘキシル、（メタ）アクリル酸８－ヒドロキシオクチル、（メタ）アクリル酸１０－ヒドロキシデシル、（メタ）アクリル酸１２－ヒドロキシラウリル、（４－ヒドロキシメチルシクロヘキシル）－メチルアクリレート、２－ヒドロキシエチルビニルエーテル、４－ヒドロキシブチルビニルエーテル、ジエチレングリコールモノビニルエーテル等のヒドロキシル基含有モノマー；スチレンスルホン酸、アリルスルホン酸、２－（メタ）アクリルアミド－２－メチルプロパンスルホン酸、（メタ）アクリルアミドプロパンスルホン酸、スルホプロピル（メタ）アクリレート、（メタ）アクリロイルオキシナフタレンスルホン酸等のスルホン酸基含有モノマー；２－ヒドロキシエチルアクリロイルホスフェート等のリン酸基含有モノマー等の官能基含有モノマーが挙げられる。官能基含有モノマーを含むことにより、重合性炭素－炭素二重結合が導入されやすい（メタ）アクリル系樹脂を得ることができる。官能基含有モノマーの含有割合は、モノマー組成物の全モノマー１００重量部に対して、好ましくは４重量部～３０重量部であり、より好ましくは６重量部～２０重量部である。 The monomer composition forming the (meth)acrylic resin may contain any suitable other monomers. Examples of other monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; acids such as maleic anhydride and itaconic anhydride. Anhydride monomer; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (meth)acrylic acid 8 -Hydroxyoctyl, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)-methyl acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether Hydroxyl group-containing monomers such as styrene sulfonic acid, allyl sulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloyloxynaphthalene Examples include monomers containing a sulfonic acid group such as sulfonic acid; monomers containing a functional group such as a monomer containing a phosphoric acid group such as 2-hydroxyethyl acryloyl phosphate. By including a functional group-containing monomer, a (meth)acrylic resin into which polymerizable carbon-carbon double bonds are easily introduced can be obtained. The content of the functional group-containing monomer is preferably 4 to 30 parts by weight, more preferably 6 to 20 parts by weight, based on 100 parts by weight of all monomers in the monomer composition.
他のモノマーとして、多官能モノマーを用いてもよい。多官能モノマーを用いることにより、粘着剤の凝集力、耐熱性、接着性等を高めることができる。また、粘着剤層中の低分子量成分が少なくなるため、被着体を汚染し難い粘着シートを得ることができる。多官能性モノマーとしては、例えば、ヘキサンジオール（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）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、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、エポキシ(メタ)アクリレート、ポリエステル(メタ)アクリレート、ウレタン(メタ)アクリレート等が挙げられる。多官能モノマーの含有割合は、上記モノマー組成物の全モノマー１００重量部に対して、好ましくは１重量部～1００重量部であり、より好ましくは５重量部～５０重量部である。 A polyfunctional monomer may be used as the other monomer. By using a polyfunctional monomer, the cohesive force, heat resistance, adhesiveness, etc. of the adhesive can be improved. Furthermore, since the amount of low molecular weight components in the adhesive layer is reduced, it is possible to obtain an adhesive sheet that is less likely to contaminate adherends. Examples of polyfunctional monomers include hexanediol (meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and pentaerythritol di(meth)acrylate. (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy(meth)acrylate, polyester(meth)acrylate, urethane(meth)acrylate, etc. Can be mentioned. The content of the polyfunctional monomer is preferably 1 part by weight to 100 parts by weight, more preferably 5 parts by weight to 50 parts by weight, based on 100 parts by weight of all monomers in the monomer composition.
（メタ）アクリル系樹脂の重量平均分子量は、好ましくは３０万以上であり、より好ましくは５０万以上であり、さらに好ましくは８０万～３００万である。このような範囲であれば、低分子量成分のブリードを防止し、低汚染性の粘着シートを得ることができる。（メタ）アクリル系樹脂の分子量分布(重量平均分子量／数平均分子量)は、好ましくは１～２０であり、より好ましくは３～１０である。分子量分布の狭い（メタ）アクリル系樹脂を用いることにより、低分子量成分のブリードを防止し、低汚染性の粘着シートを得ることができる。なお、重量平均分子量および数平均分子量は、ゲルパーミエーションクロマトグラフィ測定（溶媒：テトラヒドロフラン、ポリスチレン換算）により求めることができる。 The weight average molecular weight of the (meth)acrylic resin is preferably 300,000 or more, more preferably 500,000 or more, and even more preferably 800,000 to 3,000,000. Within this range, bleeding of low molecular weight components can be prevented and a pressure-sensitive adhesive sheet with low staining properties can be obtained. The molecular weight distribution (weight average molecular weight/number average molecular weight) of the (meth)acrylic resin is preferably 1 to 20, more preferably 3 to 10. By using a (meth)acrylic resin with a narrow molecular weight distribution, bleeding of low molecular weight components can be prevented and a pressure-sensitive adhesive sheet with low staining properties can be obtained. Note that the weight average molecular weight and number average molecular weight can be determined by gel permeation chromatography measurement (solvent: tetrahydrofuran, polystyrene equivalent).
側鎖または末端に重合性炭素－炭素二重結合を有するポリマーは、任意の適切な方法により得ることができる。例えば、任意の適切な重合方法により得られた樹脂と、重合性炭素－炭素二重結合を有する化合物とを反応（例えば、縮合反応、付加反応）させることにより得られ得る。具体的には、（メタ）アクリル系樹脂を用いる場合、任意の適切な官能基を有するモノマー由来の構成単位を有する（メタ）アクリル系樹脂（共重合体）を任意の適切な溶媒中で重合し、その後、該アクリル系樹脂の官能基と、該官能基と反応し得る重合性炭素－炭素二重結合を有する化合物とを反応させることにより、上記ポリマーを得ることができる。反応させる重合性炭素－炭素二重結合を有する化合物の量は、上記樹脂１００重量部に対して、好ましくは４重量部～３０重量部であり、より好ましくは４重量部～２０重量部である。溶媒としては任意の適切な溶媒を用いることができ、例えば、酢酸エチル、メチルチルケトン、トルエン等の各種有機溶剤が挙げられる。 Polymers having polymerizable carbon-carbon double bonds in side chains or terminals can be obtained by any suitable method. For example, it can be obtained by reacting a resin obtained by any appropriate polymerization method with a compound having a polymerizable carbon-carbon double bond (eg, condensation reaction, addition reaction). Specifically, when using a (meth)acrylic resin, a (meth)acrylic resin (copolymer) having structural units derived from a monomer having any appropriate functional group is polymerized in any appropriate solvent. Then, the above polymer can be obtained by reacting the functional group of the acrylic resin with a compound having a polymerizable carbon-carbon double bond that can react with the functional group. The amount of the compound having a polymerizable carbon-carbon double bond to be reacted is preferably 4 parts by weight to 30 parts by weight, more preferably 4 parts by weight to 20 parts by weight, based on 100 parts by weight of the resin. . Any suitable solvent can be used as the solvent, and examples thereof include various organic solvents such as ethyl acetate, methyl thyl ketone, and toluene.
上記のようにして樹脂と重合性炭素－炭素二重結合を有する化合物とを反応させる場合、樹脂および重合性炭素－炭素二重結合を有する化合物はそれぞれ、互いに反応可能な官能基を有することが好ましい。官能基の組み合わせとしては、例えば、カルボキシル基／エポキシ基、カルボキシル基／アジリジン基、ヒドロキシル基／イソシアネート基等が挙げられる。これらの官能基の組み合わせの中でも、反応追跡の容易さから、ヒドロキシル基とイソシアネート基との組み合わせが好ましい。 When a resin and a compound having a polymerizable carbon-carbon double bond are reacted as described above, the resin and the compound having a polymerizable carbon-carbon double bond each have a functional group that can react with each other. preferable. Examples of the combination of functional groups include carboxyl group/epoxy group, carboxyl group/aziridine group, hydroxyl group/isocyanate group, and the like. Among these combinations of functional groups, a combination of a hydroxyl group and an isocyanate group is preferred from the viewpoint of ease of tracking the reaction.
上記重合性炭素－炭素二重結合を有する化合物としては、例えば、２－イソシアネートエチルメタクリレート、メタクリロイソシアネート、２－メタクリロイルオキシエチルイソシアネート（２－イソシアナトエチルメタクリレート）、ｍ－イソプロペニル－α，α－ジメチルベンジルイソシアネート等が挙げられる。 Examples of the compound having a polymerizable carbon-carbon double bond include 2-isocyanate ethyl methacrylate, methacryloisocyanate, 2-methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate), m-isopropenyl-α,α -dimethylbenzylisocyanate and the like.
Ａ－２．フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキル
フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルは、光重合性開始剤として機能し、紫外線照射により上記紫外線硬化型粘着剤を硬化させ、粘着力を低下させ得る。フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルは、室温では液体である。そのため、粘着剤組成物中により均一に分散し、より均一に光重合開始剤が分散した粘着剤層が形成される。それにより、紫外線照射後には、粘着剤層の硬化反応のバラつきが抑えられ、軽剥離性が発揮され、その結果、被着体表面への糊残りを防止し得る。
A-2. Alkyl phenyl (2,4,6-trimethylbenzoyl)phosphinate The alkyl phenyl (2,4,6-trimethylbenzoyl) phosphinate functions as a photopolymerization initiator and cures the above-mentioned ultraviolet curable adhesive by irradiating it with ultraviolet light. and reduce adhesion. Alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate is a liquid at room temperature. Therefore, a pressure-sensitive adhesive layer is formed in which the photopolymerization initiator is more uniformly dispersed in the pressure-sensitive adhesive composition. Thereby, after irradiation with ultraviolet rays, variations in the curing reaction of the adhesive layer are suppressed, and easy releasability is exhibited, and as a result, it is possible to prevent adhesive from remaining on the surface of the adherend.
フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルが有するアルキル基としては、任意の適切なアルキル基が挙げられる。好ましくは炭素数１～５のアルキル基であり、より好ましくはメチル基またはエチル基である。すなわち、フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルとしては、好ましくはフェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸メチルまたはフェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸エチルを用いることができ、より好ましくはフェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸エチルを用いることができる。このようなフェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルを用いることにより、より均一に光重合開始剤が分散した紫外線硬化型粘着剤組成物が得られ得る。フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルは１種のみを用いてもよく、２種以上を組み合わせて用いてもよい。 The alkyl group possessed by the alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate includes any suitable alkyl group. Preferably it is an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group. That is, the alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate is preferably methyl phenyl(2,4,6-trimethylbenzoyl)phosphinate or ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate. More preferably, ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate can be used. By using such alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, an ultraviolet curable pressure-sensitive adhesive composition in which the photopolymerization initiator is more uniformly dispersed can be obtained. One type of alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate may be used, or two or more types may be used in combination.
フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルは、任意の適切な量で用いられる。フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルの含有量は、上記紫外線硬化型粘着剤１００重量部に対して、好ましくは０．５重量部～１０重量部であり、より好ましくは１重量部～７重量部である。 The alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate is used in any suitable amount. The content of alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate is preferably 0.5 parts by weight to 10 parts by weight, more preferably 1 part by weight, based on 100 parts by weight of the UV-curable adhesive. Parts by weight to 7 parts by weight.
Ａ－３．架橋剤
紫外線硬化型粘着剤組成物は、好ましくは架橋剤をさらに含む。架橋剤としては、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、メラミン系架橋剤、過酸化物系架橋剤、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、カルボジイミド系架橋剤、アミン系架橋剤等が挙げられる。
A-3. Crosslinking Agent The ultraviolet curable pressure-sensitive adhesive composition preferably further includes a crosslinking agent. Examples of crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, melamine crosslinking agents, peroxide crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, Examples include metal chelate crosslinking agents, metal salt crosslinking agents, carbodiimide crosslinking agents, and amine crosslinking agents.
１つの実施形態においては、イソシアネート系架橋剤が好ましく用いられる。イソシアネート系架橋剤は、多種の官能基と反応し得る点で好ましい。上記イソシアネート系架橋剤の具体例としては、ブチレンジイソシアネート、ヘキサメチレンジイソシアネート等の低級脂肪族ポリイソシアネート類；シクロペンチレンジイソシアネート、シクロへキシレンジイソシアネート、イソホロンジイソシアネート等の脂環族イソシアネート類；２，４－トリレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、キシリレンジイソシアネート等の芳香族イソシアネート類；トリメチロールプロパン／トリレンジイソシアネート３量体付加物（具体的には、東ソー社製、商品名「コロネートＬ」）、トリメチロールプロパン／へキサメチレンジイソシアネート３量体付加物（具体的には、日本ポリウレタン工業社製、商品名「コロネートＨＬ」）、ヘキサメチレンジイソシアネートのイソシアヌレート体（具体的には、日本ポリウレタン工業社製、商品名「コロネートＨＸ」）等のイソシアネート付加物；等が挙げられる。好ましくは、イソシアネート基を３個以上有する架橋剤が用いられる。 In one embodiment, isocyanate-based crosslinking agents are preferably used. Isocyanate-based crosslinking agents are preferred in that they can react with various functional groups. Specific examples of the isocyanate-based crosslinking agents include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate; 2,4- Aromatic isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylolpropane/tolylene diisocyanate trimer adduct (specifically, manufactured by Tosoh Corporation, product name "Coronate L") ), trimethylolpropane/hexamethylene diisocyanate trimer adduct (specifically, manufactured by Nippon Polyurethane Industry Co., Ltd., product name "Coronate HL"), isocyanurate of hexamethylene diisocyanate (specifically, Nippon Polyurethane Isocyanate adducts such as "Coronate HX" (trade name, manufactured by Kogyo Co., Ltd.); and the like. Preferably, a crosslinking agent having three or more isocyanate groups is used.
架橋剤の含有量は、任意の適切な量に調整することができる。例えば、紫外線硬化型粘着剤１００重量部に対して好ましくは０．００５重量部～２０重量部であり、より好ましくは０．０２重量部～１０重量部である。 The content of the crosslinking agent can be adjusted to any appropriate amount. For example, the amount is preferably 0.005 parts by weight to 20 parts by weight, more preferably 0.02 parts by weight to 10 parts by weight, based on 100 parts by weight of the ultraviolet curable adhesive.
Ａ－４．他の成分
紫外線硬化型粘着剤組成物は、任意の適切な添加剤をさらに含んでいてもよい。添加剤としては、例えば、フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキル以外の重合開始剤、活性エネルギー線重合促進剤、ラジカル捕捉剤、粘着付与剤、可塑剤（例えば、トリメリット酸エステル系可塑剤、ピロメリット酸エステル系可塑剤）、顔料、染料、充填剤、老化防止剤、導電材、帯電防止剤、紫外線吸収剤、光安定剤、剥離調整剤、軟化剤、界面活性剤、難燃剤、酸化防止剤等が挙げられる。他の添加剤は任意の適切な量で用いることができる。
A-4. Other Components The ultraviolet curable pressure-sensitive adhesive composition may further contain any appropriate additives. Examples of additives include polymerization initiators other than alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, active energy ray polymerization accelerators, radical scavengers, tackifiers, plasticizers (for example, trimellitic acid ester plasticizer, pyromellitic acid ester plasticizer), pigment, dye, filler, anti-aging agent, conductive material, antistatic agent, ultraviolet absorber, light stabilizer, release modifier, softener, surfactant , flame retardants, antioxidants, etc. Other additives can be used in any suitable amounts.
Ｂ．粘着シート
Ｂ－１．粘着シートの概要
図１は、本発明の１つの実施形態による粘着シートの概略断面図である。図示例の粘着シート１００は、基材１０と、基材１０の一方の面に配置された粘着剤層２０とを備える。粘着剤層は、上記紫外線硬化型粘着剤組成物で形成される。実用的には、使用までの間、粘着剤層２０を適切に保護するために、粘着剤層２０にはセパレータが剥離可能に仮着される。１つの実施形態においては、粘着剤シート１００は、基材１０と粘着剤層２０と間に中間層が形成され得る（図示せず）。
B. Adhesive sheet B-1. Overview of Adhesive Sheet FIG. 1 is a schematic cross-sectional view of an adhesive sheet according to one embodiment of the present invention. The illustrated example
本発明の別の実施形態においては、粘着剤層は２層構成であり、粘着シートは、基材と第１の粘着剤層と第２の粘着剤層とをこの順に備える（図示せず）。 In another embodiment of the present invention, the adhesive layer has a two-layer structure, and the adhesive sheet includes a base material, a first adhesive layer, and a second adhesive layer in this order (not shown). .
粘着シートの厚みは任意の適切な範囲に設定され得る。好ましくは５μｍ～１０００μｍであり、より好ましくは２０μｍ～３００μｍであり、さらに好ましくは５０μｍ～３００μｍである。 The thickness of the adhesive sheet can be set within any appropriate range. Preferably it is 5 μm to 1000 μm, more preferably 20 μm to 300 μm, even more preferably 50 μm to 300 μm.
Ｂ－２．基材
基材は、任意の適切な樹脂から構成され得る。基材層を構成する樹脂の具体例としては、ポリエステル系樹脂（ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリブチレンナフタレートなど）、エチレン－酢酸ビニル共重合体、エチレン－メタクリル酸メチル共重合体、ポリオレフィン系樹脂（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など）、ポリビニルアルコール、ポリ塩化ビニリデン、ポリ塩化ビニル、塩化ビニル－酢酸ビニル共重合体、ポリ酢酸ビニル、ポリアミド、ポリイミド、セルロース類、フッ素系樹脂、ポリエーテル、ポリスチレン系樹脂（ポリスチレンなど）、ポリカーボネート、ポリエーテルスルホン等が挙げられる。
B-2. Substrate The substrate may be composed of any suitable resin. Specific examples of resins constituting the base layer include polyester resins (polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, etc.), ethylene-vinyl acetate copolymer, and ethylene-methyl methacrylate copolymer. Polyolefin resins (polyethylene, polypropylene, ethylene-propylene copolymer, etc.), polyvinyl alcohol, polyvinylidene chloride, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyamide, polyimide, cellulose, Examples include fluororesin, polyether, polystyrene resin (such as polystyrene), polycarbonate, and polyether sulfone.
基材は、本発明の効果を損なわない範囲で、さらにその他の成分を含んでいてもよい。その他の成分としては、例えば、酸化防止剤、紫外線吸収剤、光安定剤、耐熱安定剤、帯電防止剤等が挙げられる。その他の成分の種類および使用量は、目的に応じて任意の適切な量で用いることができる。 The base material may further contain other components within a range that does not impair the effects of the present invention. Examples of other components include antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, and antistatic agents. The types and amounts of other components can be used in any appropriate amounts depending on the purpose.
基材の厚みは、任意の適切な値に設定され得る。基材の厚みは、好ましくは１０μｍ～２００μｍであり、より好ましくは２０μｍ～１５０μｍである。 The thickness of the base material can be set to any suitable value. The thickness of the base material is preferably 10 μm to 200 μm, more preferably 20 μm to 150 μm.
基材の弾性率は、任意の適切な値に設定され得る。基材の弾性率は、好ましくは５０ＭＰａ～６０００ＭＰａであり、より好ましくは７０ＭＰａ～５０００ＭＰａである。弾性率が上記範囲であることにより、被着体表面の凹凸に適度に追従し得る粘着シートが得られ得る。 The elastic modulus of the base material can be set to any suitable value. The elastic modulus of the base material is preferably 50 MPa to 6000 MPa, more preferably 70 MPa to 5000 MPa. When the elastic modulus is within the above range, a pressure-sensitive adhesive sheet can be obtained that can suitably follow the irregularities on the surface of an adherend.
Ｂ－３．粘着剤層
粘着剤層は上記紫外線硬化型粘着剤組成物を用いて形成され得る。上記紫外線硬化型粘着剤組成物は、紫外線照射前においては、被着体表面の組成および構造に影響されることなく優れた粘着力を発揮し得る。また、紫外線照射時には、粘着剤層の硬化反応のバラつきが抑えられ、軽剥離性が発揮され得る。その結果、被着体表面への糊残りを防止し得る。さらに、上記紫外線硬化型粘着剤組成物を用いて形成された粘着剤層は柔軟であり、被着体の表面に凹凸があるが場合であっても追従性に優れる。そのため、表面の凹凸を有する被着体とも良好な密着性を発揮し得る。
B-3. Adhesive Layer The adhesive layer may be formed using the above-mentioned ultraviolet curable adhesive composition. The above-mentioned ultraviolet curable pressure-sensitive adhesive composition can exhibit excellent adhesive strength without being affected by the composition and structure of the surface of the adherend before irradiation with ultraviolet rays. In addition, upon irradiation with ultraviolet rays, variations in the curing reaction of the adhesive layer can be suppressed, and easy releasability can be exhibited. As a result, it is possible to prevent adhesive from remaining on the surface of the adherend. Furthermore, the adhesive layer formed using the above ultraviolet curable adhesive composition is flexible and has excellent followability even when the surface of the adherend is uneven. Therefore, good adhesion can be exhibited even with adherends having uneven surfaces.
粘着剤層の厚みは、任意の適切な値に設定され得る。粘着剤層の厚みは、好ましくは１μｍ～５０μｍであり、より好ましくは２μｍ～２０μｍであり、さらに好ましくは３μｍ～１０μｍである。 The thickness of the adhesive layer can be set to any appropriate value. The thickness of the adhesive layer is preferably 1 μm to 50 μm, more preferably 2 μm to 20 μm, and even more preferably 3 μm to 10 μm.
粘着剤層は１層であってもよく、２層以上であってもよい。粘着剤層が２層以上である場合、上記紫外線硬化型粘着剤組成物で形成される粘着剤層が少なくとも１層含まれていればよい。粘着剤層が２層以上である場合、粘着シートの被着体と接触する面に上記紫外線硬化型粘着剤組成物で形成された粘着剤層が形成されることが好ましい。上記紫外線硬化型粘着剤組成物を含まない粘着剤層は任意の適切な粘着剤組成物で形成され得る。この粘着剤組成物は紫外線硬化型粘着剤であってもよく、感圧性粘着剤であってもよい。 The adhesive layer may be one layer, or two or more layers. When there are two or more adhesive layers, it is sufficient that at least one adhesive layer formed from the above-mentioned ultraviolet curable adhesive composition is included. When there are two or more adhesive layers, it is preferable that the adhesive layer made of the ultraviolet curable adhesive composition is formed on the surface of the adhesive sheet that comes into contact with the adherend. The adhesive layer that does not contain the ultraviolet curable adhesive composition may be formed of any suitable adhesive composition. This adhesive composition may be an ultraviolet curable adhesive or a pressure sensitive adhesive.
粘着剤層の紫外線照後のポリイミド粘着力とシリコン粘着力との比（ポリイミド粘着力／シリコン粘着力、以下、ＰＩ粘着力／Ｓｉ粘着力ともいう）が好ましくは２以下であり、さらに好ましくは１．９以下であり、さらに好ましくは１．８以下である。ポリイミド粘着力とシリコン粘着力との比が上記範囲であることにより、粘着シート剥離時の被着体への糊残りを防止し得る。本明細書において、紫外線照射後のポリイミド粘着力、および、シリコン粘着力は後述の実施例に記載の方法で測定した粘着力をいう。 The ratio of polyimide adhesive strength to silicone adhesive strength (polyimide adhesive strength/silicon adhesive strength, hereinafter also referred to as PI adhesive strength/Si adhesive strength) after UV irradiation of the adhesive layer is preferably 2 or less, more preferably It is 1.9 or less, more preferably 1.8 or less. When the ratio of the polyimide adhesive strength to the silicone adhesive strength is within the above range, it is possible to prevent adhesive from remaining on the adherend when the adhesive sheet is peeled off. In this specification, the polyimide adhesive strength after ultraviolet irradiation and the silicone adhesive strength refer to the adhesive strength measured by the method described in the Examples below.
粘着剤層の紫外線照射後の銅粘着力とシリコン粘着力との比（銅（Ｃｕ）粘着力／シリコン粘着力、以下、Ｃｕ粘着力／Ｓｉ粘着力ともいう）が好ましくは１．９以下であり、さらに好ましくは１．８以下であり、さらに好ましくは１．７以下である。銅粘着力とシリコン粘着力との比が上記範囲であることにより、粘着シート剥離時の被着体への糊残りを防止し得る。本明細書において、紫外線照射後の銅粘着力、および、シリコン粘着力は後述の実施例に記載の方法で測定した粘着力をいう。 The ratio of copper adhesive strength to silicon adhesive strength (copper (Cu) adhesive strength/silicon adhesive strength, hereinafter also referred to as Cu adhesive strength/Si adhesive strength) after UV irradiation of the adhesive layer is preferably 1.9 or less. Yes, more preferably 1.8 or less, still more preferably 1.7 or less. By setting the ratio of the copper adhesive strength to the silicon adhesive strength within the above range, it is possible to prevent adhesive from remaining on the adherend when the adhesive sheet is peeled off. In this specification, the copper adhesive force after ultraviolet irradiation and the silicon adhesive force refer to the adhesive force measured by the method described in the Examples below.
紫外線硬化後の粘着剤層は、有機物に対する粘着力とシリコンウエハに対する粘着力との比（例えば、上記ＰＩ粘着力／Ｓｉ粘着力）と、無機物に対する粘着力とシリコンウエハに対する粘着力との比（例えば、上記Ｃｕ粘着力／Ｓｉ粘着力）が同程度であることが好ましい。これらの比が同程度であることにより、被着体表面の組成が複雑な場合であっても、粘着シートを容易に剥離することができる。具体的には、上記ＰＩ粘着力／Ｓｉ粘着力と、Ｃｕ粘着力とＳｉ粘着力との比（（ＰＩ粘着力／Ｓｉ粘着力）／（Ｃｕ粘着力とＳｉ粘着力））は、例えば、０．７５～１．１０であり、１（すなわち、同じ値であること）に近いほど好ましい。 The adhesive layer after UV curing is determined by the ratio of the adhesive force to organic substances and the adhesive force to silicon wafers (for example, the above-mentioned PI adhesive force/Si adhesive force) and the ratio of the adhesive force to inorganic substances and the adhesive force to silicon wafers ( For example, it is preferable that the above-mentioned Cu adhesive strength/Si adhesive strength) be approximately the same. When these ratios are approximately the same, the pressure-sensitive adhesive sheet can be easily peeled off even if the composition of the surface of the adherend is complex. Specifically, the ratio of the above PI adhesive strength/Si adhesive strength to Cu adhesive strength and Si adhesive strength ((PI adhesive strength/Si adhesive strength)/(Cu adhesive strength and Si adhesive strength)) is, for example, The value is from 0.75 to 1.10, and the closer it is to 1 (that is, the same value), the more preferable it is.
粘着剤層の紫外線照射前の弾性率は、好ましくは０．０５ＭＰａ～２．０ＭＰａであり、より好ましくは０．０７５ＭＰａ～１．０ＭＰａであり、さらに好ましくは０．０８ＭＰａ～０．８０ＭＰａであり、特に好ましくは０．１ＭＰａ以上０．７ＭＰａ未満である。このような範囲であれば、被着体を保持するために十分な粘着力を有する粘着シートを得ることができる。本明細書において、粘着剤層の弾性率は以下の方法により測定された弾性率（ヤング率）をいう。
粘着剤層形成組成物を塗布厚みが５μｍとなるようセパレータに塗布し、１３０℃で２分間乾燥した。次いで、塗布乾燥後の粘着剤層のみを端から丸めて棒状の試料を作製し、厚み（断面積）を計測した。得られた試料を、チャック間距離１０ｍｍ、引張速度５０ｍｍ／分、室温の条件で、引張試験機（ＳＨＩＭＡＤＺＵ社製、商品名「ＡＧ－ＩＳ」）で引っ張った際の最初期の傾き（ヤング率）を弾性率とした。
The elastic modulus of the adhesive layer before UV irradiation is preferably 0.05 MPa to 2.0 MPa, more preferably 0.075 MPa to 1.0 MPa, and even more preferably 0.08 MPa to 0.80 MPa, Particularly preferably, it is 0.1 MPa or more and less than 0.7 MPa. Within this range, it is possible to obtain a pressure-sensitive adhesive sheet having sufficient adhesive strength to hold an adherend. In this specification, the elastic modulus of the adhesive layer refers to the elastic modulus (Young's modulus) measured by the following method.
The pressure-sensitive adhesive layer forming composition was applied to the separator to a coating thickness of 5 μm, and dried at 130° C. for 2 minutes. Next, only the adhesive layer after coating and drying was rolled up from the end to prepare a rod-shaped sample, and the thickness (cross-sectional area) was measured. The initial slope (Young's modulus) when the obtained sample was pulled with a tensile tester (manufactured by SHIMADZU, product name "AG-IS") under the conditions of a chuck distance of 10 mm, a pulling speed of 50 mm/min, and room temperature. ) was taken as the elastic modulus.
粘着剤層の紫外線照射後の弾性率は、好ましくは１ＭＰａ以上であり、より好ましくは５ＭＰａ以上であり、さらに好ましくは１０ＭＰａ以上である。このような範囲であれば、所定の工程（例えば、バックグラインド工程）後の剥離性に優れる粘着シートを得ることができる。粘着剤層の紫外線照射後の弾性率は、例えば、１０００ＭＰａ以下であり、好ましくは５００ＭＰａ以下であり、より好ましくは４００ＭＰａ以下である。 The elastic modulus of the adhesive layer after irradiation with ultraviolet rays is preferably 1 MPa or more, more preferably 5 MPa or more, and even more preferably 10 MPa or more. Within this range, a pressure-sensitive adhesive sheet with excellent releasability after a predetermined process (for example, back grinding process) can be obtained. The elastic modulus of the adhesive layer after UV irradiation is, for example, 1000 MPa or less, preferably 500 MPa or less, and more preferably 400 MPa or less.
Ｂ－４．中間層
１つの実施形態においては、粘着シートは基材と粘着剤層との間に中間層を有する。中間層は任意の適切な材料で形成され得る。中間層は、例えば、アクリル系樹脂、ポリエチレン系樹脂、エチレン－ビニルアルコール共重合体、エチレン－酢酸ビニル系樹脂、エチレンメチルメタクリレート樹脂等の樹脂、または、粘着剤で形成され得る。中間層が粘着剤で形成される場合、粘着剤は紫外線硬化型粘着剤であってもよく、感圧性粘着剤であってもよい。
B-4. Intermediate Layer In one embodiment, the adhesive sheet has an intermediate layer between the base material and the adhesive layer. The intermediate layer may be formed of any suitable material. The intermediate layer may be formed of a resin such as an acrylic resin, a polyethylene resin, an ethylene-vinyl alcohol copolymer, an ethylene-vinyl acetate resin, an ethylene methyl methacrylate resin, or an adhesive. When the intermediate layer is formed of an adhesive, the adhesive may be an ultraviolet curable adhesive or a pressure-sensitive adhesive.
１つの実施形態においては、中間層は（メタ）アクリル系ポリマーを含む中間層形成組成物から形成される。好ましくは、（メタ）アクリル系ポリマーは、アルキル（メタ）アクリレート由来の構成成分を含む。アルキル（メタ）アクリレートとしては、例えば、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、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、イソペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、テトラデシル（メタ）アクリレート、ペンタデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ヘプタデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、ノナデシル（メタ）アクリレート、エイコシル（メタ）アクリレート等の（メタ）アクリル酸Ｃ１－Ｃ２０アルキルエステルが挙げられる。 In one embodiment, the intermediate layer is formed from an intermediate layer forming composition that includes a (meth)acrylic polymer. Preferably, the (meth)acrylic polymer contains components derived from alkyl (meth)acrylates. Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s- Butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, Nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl ( Examples include (meth)acrylic acid C1-C20 alkyl esters such as meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, and eicosyl (meth)acrylate.
（メタ）アクリル系ポリマーは、凝集力、耐熱性、架橋性等の改質を目的として、必要に応じて、上記アルキル（メタ）アクリレートと共重合可能な他のモノマーに対応する構成単位を含んでいてもよい。このようなモノマーとして、例えば、アクリル酸、メタクリル酸等のカルボキシル基含有モノマー；無水マレイン酸、無水イコタン酸等の酸無水物モノマー；（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル等のヒドロキシル基含有モノマー；スチレンスルホン酸、アリルスルホン酸、等のスルホン酸基含有モノマー；（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、アクリロイルモルフォリン等の窒素含有モノマー；（メタ）アクリル酸アミノエチル等の（メタ）アクリル酸アミノアルキル系モノマー；（メタ）アクリル酸メトキシエチル等の（メタ）アクリル酸アルコキシアルキル系モノマー；Ｎ－シクロヘキシルマレイミド、Ｎ－イソプロピルマレイミド等のマレイミド系モノマー；Ｎ－メチルイタコンイミド、Ｎ－エチルイタコンイミド等のイタコンイミド系モノマー；スクシンイミド系モノマー；酢酸ビニル、プロピオン酸ビニル、Ｎ－ビニルピロリドン、メチルビニルピロリドン等のビニル系モノマー；アクリロニトリル、メタクリロニトリル等のシアノアクリレートモノマー；（メタ）アクリル酸グリシジル等のエポキシ基含有アクリル系モノマー；（メタ）アクリル酸ポリエチレングリコール、（メタ）アクリル酸ポリプロピレングリコール等のグリコール系アクリルエステルモノマー；（メタ）アクリル酸テトラヒドロフルフリル、フッ素（メタ）アクリレート、シリコーン（メタ）アクリレート等の複素環、ハロゲン原子、ケイ素原子等を有するアクリル酸エステル系モノマー；イソプレン、ブタジエン、イソブチレン等のオレフィン系モノマー；ビニルエーテル等のビニルエーテル系モノマー等が挙げられる。これらの単量体成分は、単独で用いてもよく、２種以上を組み合わせて用いてもよい。上記他のモノマー由来の構成単位の含有割合は、アクリル系ポリマー１００重量部中、好ましくは１重量部～３０重量部であり、より好ましくは３重量部～２５重量部である。 The (meth)acrylic polymer may contain structural units corresponding to other monomers that can be copolymerized with the alkyl (meth)acrylate, as necessary, for the purpose of modifying cohesive strength, heat resistance, crosslinking properties, etc. It's okay to stay. Examples of such monomers include carboxyl group-containing monomers such as acrylic acid and methacrylic acid; acid anhydride monomers such as maleic anhydride and icotanoic anhydride; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc. Hydroxyl group-containing monomers; Sulfonic acid group-containing monomers such as styrene sulfonic acid and allyl sulfonic acid; Nitrogen-containing monomers such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, and acryloylmorpholine; (meth)acrylic Aminoalkyl (meth)acrylate monomers such as aminoethyl (meth)acrylate; Alkoxyalkyl (meth)acrylate monomers such as methoxyethyl (meth)acrylate; Maleimide monomers such as N-cyclohexylmaleimide and N-isopropylmaleimide; - Itaconimide monomers such as methyl itaconimide and N-ethyl itaconimide; Succinimide monomers; Vinyl monomers such as vinyl acetate, vinyl propionate, N-vinylpyrrolidone, and methylvinylpyrrolidone; Cyanoacrylates such as acrylonitrile and methacrylonitrile Monomers: Epoxy group-containing acrylic monomers such as glycidyl (meth)acrylate; glycol-based acrylic ester monomers such as polyethylene glycol (meth)acrylate and polypropylene glycol (meth)acrylate; tetrahydrofurfuryl (meth)acrylate, fluorine Examples include acrylic acid ester monomers having a heterocycle, halogen atom, silicon atom, etc., such as (meth)acrylate and silicone (meth)acrylate; olefin monomers, such as isoprene, butadiene, and isobutylene; and vinyl ether monomers, such as vinyl ether. . These monomer components may be used alone or in combination of two or more. The content of the structural units derived from the other monomers is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, based on 100 parts by weight of the acrylic polymer.
中間層形成組成物は、活性エネルギー線反応性化合物（モノマーまたはオリゴマー）をさらに含んでいてもよい。活性エネルギー線反応性化合物としては、例えば、アクリロイル基、メタクリロイル基、ビニル基、アリル基、アセチレン基等の重合性炭素－炭素多重結合を有する官能基を有する光反応性のモノマーまたはオリゴマーが挙げられる。官能基を２以上有する多官能アクリレートのような多官能モノマーを用いれば、上記アルキル（メタ）アクリレートとの結合により、高分子量のＵＶ重合（メタ）アクリル系ポリマーを得ることができる。該光反応性のモノマーの具体例としては、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールモノヒドロキシペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（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－ヘキサンジオールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート等の（メタ）アクリル酸と多価アルコールとのエステル化物；多官能ウレタン（メタ）アクリレート；エポキシ（メタ）アクリレート；オリゴエステル（メタ）アクリレート等が挙げられる。また、メタクリロイソシアネート、２－メタクリロイルオキシエチルイソシアネート（２－イソシアナトエチルメタクリレート）、ｍ－イソプロペニル－α，α－ジメチルベンジルイソシアネート等のモノマーを用いてもよい。光反応性のオリゴマーの具体例としては、上記モノマーの２～５量体等が挙げられる。 The intermediate layer forming composition may further contain an active energy ray-reactive compound (monomer or oligomer). Examples of active energy ray-reactive compounds include photoreactive monomers or oligomers having functional groups having polymerizable carbon-carbon multiple bonds such as acryloyl groups, methacryloyl groups, vinyl groups, allyl groups, and acetylene groups. . If a polyfunctional monomer such as a polyfunctional acrylate having two or more functional groups is used, a high molecular weight UV-polymerized (meth)acrylic polymer can be obtained by bonding with the alkyl (meth)acrylate. Specific examples of the photoreactive monomer include trimethylolpropane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol monomer. Hydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, etc. Examples include esterified products of meth)acrylic acid and polyhydric alcohols; polyfunctional urethane (meth)acrylates; epoxy (meth)acrylates; oligoester (meth)acrylates. Furthermore, monomers such as methacryloisocyanate, 2-methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate), and m-isopropenyl-α,α-dimethylbenzyl isocyanate may be used. Specific examples of photoreactive oligomers include dimers to pentamers of the above monomers.
上記活性エネルギー線反応性化合物として、エポキシ化ブタジエン、グリシジルメタクリレート、アクリルアミド、ビニルシロキサン等のモノマー；または該モノマーから構成されるオリゴマーを用いてもよい。 As the active energy ray-reactive compound, monomers such as epoxidized butadiene, glycidyl methacrylate, acrylamide, and vinyl siloxane; or oligomers composed of these monomers may be used.
活性エネルギー線反応性化合物として、オニウム塩等の有機塩類と、分子内に複数の複素環を有する化合物との混合物を用いてもよい。該混合物は、活性エネルギー線（例えば、紫外線、電子線）の照射により有機塩が開裂してイオンを生成し、これが開始種となって複素環の開環反応を引き起こして３次元網目構造を形成し得る。上記有機塩類としては、例えば、ヨードニウム塩、フォスフォニウム塩、アンチモニウム塩、スルホニウム塩、ボレート塩等が挙げられる。上記分子内に複数の複素環を有する化合物における複素環としては、オキシラン、オキセタン、オキソラン、チイラン、アジリジン等が挙げられる。 As the active energy ray-reactive compound, a mixture of an organic salt such as an onium salt and a compound having a plurality of heterocycles in the molecule may be used. In this mixture, the organic salt is cleaved by irradiation with active energy rays (e.g., ultraviolet rays, electron beams) to generate ions, which act as starting species to cause a ring-opening reaction of heterocycles to form a three-dimensional network structure. It is possible. Examples of the organic salts include iodonium salts, phosphonium salts, antimonium salts, sulfonium salts, borate salts, and the like. Examples of the heterocycle in the above-mentioned compound having a plurality of heterocycles in the molecule include oxirane, oxetane, oxolane, thiirane, and aziridine.
中間層形成用組成物が活性エネルギー線反応性化合物を含む場合、活性エネルギー線反応性化合物の含有割合は、ベースポリマー１００重量部に対して、好ましくは０．１重量部～１００重量部であり、より好ましくは０．１重量部～５０重量部であり、さらに好ましくは０．１重量部～１０重量部である。 When the composition for forming an intermediate layer contains an active energy ray-reactive compound, the content of the active energy ray-reactive compound is preferably 0.1 parts by weight to 100 parts by weight based on 100 parts by weight of the base polymer. , more preferably 0.1 parts by weight to 50 parts by weight, still more preferably 0.1 parts by weight to 10 parts by weight.
中間層形成用組成物は、光重合開始剤を含んでいてもよい。１つの実施形態においては、中間層はフェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルを光重合開始剤として含む。好ましくは、中間層は上記粘着剤層と同一のフェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルを含む。中間層と粘着剤層とが同一のフェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルを含むことにより、被着体の組成および構造体によらず、紫外線照射後には被着体への糊残りを防止し得る。 The intermediate layer forming composition may contain a photopolymerization initiator. In one embodiment, the intermediate layer includes an alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate as a photoinitiator. Preferably, the intermediate layer contains the same alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate as the adhesive layer. Since the intermediate layer and the adhesive layer contain the same alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, the adherend will not be affected by ultraviolet irradiation regardless of the composition and structure of the adherend. It can prevent adhesive residue.
フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキル以外の光重合開始剤としては、任意の適切な光重合開始剤が用いられ得る。例えば、ＢＡＳＦ社製の商品名「イルガキュア１８４」、「イルガキュア６５１」、「イルガキュア３６９」、「イルガキュア３７９ｅｘ」、「イルガキュア８１９」、「イルガキュアＯＸＥ２」、「イルガキュア１２７」；Ｌａｍｂｅｒｔｉ社製の商品名「エサキュアｏｎｅ」、「エサキュア１００１ｍ」；旭電化工業社製の商品名「アデカオプトマーＮ－１４１４」、「アデカオプトマーＮ－１６０６」、「アデカオプトマーＮ－１７１７」等が挙げられる。光重合開始剤の含有割合は、中間層形成用組成物中のポリマー構成成分１００重量部に対して、好ましくは０．１重量部～２０重量部であり、より好ましくは１重量部～１０重量部である。 As the photopolymerization initiator other than alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, any suitable photopolymerization initiator may be used. For example, BASF's product names "Irgacure 184", "Irgacure 651", "Irgacure 369", "Irgacure 379ex", "Irgacure 819", "Irgacure OXE2", "Irgacure 127"; Lamberti's product name " Examples include "Esacure one" and "Esacure 1001m"; trade names "ADEKA OPTOMER N-1414", "ADEKA OPTOMER N-1606", and "ADEKA OPTOMER N-1717" manufactured by Asahi Denka Kogyo Co., Ltd. The content of the photopolymerization initiator is preferably 0.1 parts by weight to 20 parts by weight, more preferably 1 parts by weight to 10 parts by weight, based on 100 parts by weight of the polymer components in the intermediate layer forming composition. Department.
１つの実施形態においては、上記中間層形成用組成物は、架橋剤をさらに含む。架橋剤としては、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、メラミン系架橋剤、過酸化物系架橋剤、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、カルボジイミド系架橋剤、アミン系架橋剤等が挙げられる。 In one embodiment, the composition for forming an intermediate layer further includes a crosslinking agent. Examples of crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, melamine crosslinking agents, peroxide crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, Examples include metal chelate crosslinking agents, metal salt crosslinking agents, carbodiimide crosslinking agents, and amine crosslinking agents.
中間層形成用組成物が架橋剤を含む場合、架橋剤の含有割合は、中間層形成用組成物中のポリマー構成成分１００重量部に対して、好ましくは０．５重量部～１０重量部であり、より好ましくは１重量部～８重量部である。 When the composition for forming an intermediate layer contains a crosslinking agent, the content of the crosslinking agent is preferably 0.5 parts by weight to 10 parts by weight with respect to 100 parts by weight of the polymer component in the composition for forming an intermediate layer. The amount is more preferably 1 part by weight to 8 parts by weight.
中間層形成用組成物は、必要に応じて、任意の適切な添加剤をさらに含み得る。添加剤としては、例えば、活性エネルギー線重合促進剤、ラジカル捕捉剤、粘着付与剤、可塑剤（例えば、トリメリット酸エステル系可塑剤、ピロメリット酸エステル系可塑剤等）、顔料、染料、充填剤、老化防止剤、導電材、帯電防止剤、紫外線吸収剤、光安定剤、剥離調整剤、軟化剤、界面活性剤、難燃剤、酸化防止剤等が挙げられる。 The composition for forming an intermediate layer may further contain any appropriate additives, if necessary. Examples of additives include active energy ray polymerization accelerators, radical scavengers, tackifiers, plasticizers (e.g., trimellitic acid ester plasticizers, pyromellitic acid ester plasticizers, etc.), pigments, dyes, and fillers. agents, anti-aging agents, conductive materials, antistatic agents, ultraviolet absorbers, light stabilizers, release modifiers, softeners, surfactants, flame retardants, antioxidants and the like.
上記（メタ）アクリル系ポリマーの重量平均分子量は、好ましくは３０万～１５００万であり、より好ましくは５０万～１５０万である。重量平均分子量は、ＧＰＣ（溶媒：ＴＨＦ）により測定され得る。 The weight average molecular weight of the (meth)acrylic polymer is preferably 300,000 to 15,000,000, more preferably 500,000 to 1,500,000. The weight average molecular weight can be measured by GPC (solvent: THF).
上記（メタ）アクリル系ポリマーのガラス転移温度は、好ましくは－５０℃～３０℃であり、より好ましくは－４０℃～２０℃である。このような範囲であれば、耐熱性に優れ、加熱工程で好適に使用され得る粘着シートを得ることができる。 The glass transition temperature of the (meth)acrylic polymer is preferably -50°C to 30°C, more preferably -40°C to 20°C. Within this range, it is possible to obtain a pressure-sensitive adhesive sheet that has excellent heat resistance and can be suitably used in a heating process.
中間層の厚みは、例えば、１０μｍ～５００μｍである。このような厚みを有する中間層を形成することにより、凹凸面を良好に埋め込み得る粘着シートを得ることができる。中間層の厚みは、好ましくは２０μｍ～３００μｍであり、より好ましくは２０μｍ～２００μｍであり、さらに好ましくは２０μｍ～１５０μｍであり、特に好ましくは２０μｍ～１００μｍである。 The thickness of the intermediate layer is, for example, 10 μm to 500 μm. By forming an intermediate layer having such a thickness, it is possible to obtain a pressure-sensitive adhesive sheet that can satisfactorily embed an uneven surface. The thickness of the intermediate layer is preferably 20 μm to 300 μm, more preferably 20 μm to 200 μm, even more preferably 20 μm to 150 μm, particularly preferably 20 μm to 100 μm.
中間層がフェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸アルキルを含む場合、中間層を形成する樹脂としては、上記Ａ－１項で例示した紫外線硬化型粘着剤を用いてもよい。中間層が紫外線硬化型粘着剤から形成される場合、用いられる紫外線硬化型粘着剤は粘着剤層と同一であってもよく、異なっていてもよい。 When the intermediate layer contains alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, the resin forming the intermediate layer may be an ultraviolet curable adhesive exemplified in Section A-1 above. When the intermediate layer is formed from an ultraviolet curable adhesive, the ultraviolet curable adhesive used may be the same as or different from the adhesive layer.
中間層の弾性率は、好ましくは０．０５ＭＰａ～１０ＭＰａであり、より好ましくは０．０７５ＭＰａ～５ＭＰａであり、さらに好ましくは０．１０ＭＰａ～０．５０ＭＰａである。このような範囲であれば、被着体表面の凹凸を良好に埋め込み得る粘着シートが得られ得る。また、粘着シートの被着体保持力が向上し得る。 The elastic modulus of the intermediate layer is preferably 0.05 MPa to 10 MPa, more preferably 0.075 MPa to 5 MPa, and even more preferably 0.10 MPa to 0.50 MPa. Within this range, a pressure-sensitive adhesive sheet can be obtained that can satisfactorily fill in irregularities on the surface of an adherend. Moreover, the adhesive sheet's ability to hold onto an adherend can be improved.
Ｃ．粘着シートの製造方法
粘着シートは、任意の適切な方法により製造され得る。粘着シートは、例えば、基材上に、上記紫外線硬化型粘着剤組成物を塗工して得られ得る。塗工方法としては、バーコーター塗工、エアナイフ塗工、グラビア塗工、グラビアリバース塗工、リバースロール塗工、リップ塗工、ダイ塗工、ディップ塗工、オフセット印刷、フレキソ印刷、スクリーン印刷など種々の方法を採用することができる。また、別途、セパレータに粘着剤層を形成した後、それを基材に貼り合せる方法等を採用してもよい。
C. Method for Manufacturing Adhesive Sheet A pressure-sensitive adhesive sheet can be manufactured by any appropriate method. The pressure-sensitive adhesive sheet can be obtained, for example, by coating the above-mentioned ultraviolet curable pressure-sensitive adhesive composition on a base material. Coating methods include bar coater coating, air knife coating, gravure coating, gravure reverse coating, reverse roll coating, lip coating, die coating, dip coating, offset printing, flexo printing, screen printing, etc. Various methods can be adopted. Alternatively, a method may be adopted in which a pressure-sensitive adhesive layer is separately formed on a separator and then bonded to a base material.
粘着シートが中間層を含む場合、粘着シートは、例えば、基材上に、中間層を形成した後、粘着剤層を形成することにより作製され得る。中間層は任意の適切な方法により形成され得る。具体的には、上記粘着剤層と同様の方法により形成することができる。 When the pressure-sensitive adhesive sheet includes an intermediate layer, the pressure-sensitive adhesive sheet can be produced by, for example, forming the intermediate layer on a base material and then forming a pressure-sensitive adhesive layer. The intermediate layer may be formed by any suitable method. Specifically, it can be formed by the same method as the adhesive layer described above.
Ｄ．粘着シートの用途
本発明の粘着シートは、紫外線照射前においては、被着体表面の組成（例えば、金属等の無機物、または、樹脂等の有機物）に影響されることなく、優れた粘着力を発揮し得る。さらに、凹凸への追従性にも優れるため、被着体表面の構造（例えば、凹凸）が複雑な場合であっても優れた粘着力を発揮し得る。また、この粘着シートは紫外線照射後においては、被着体表面の組成および構造に影響されることなく、粘着力が低下し、軽剥離性を奏し得る。そのため、被着体表面への糊残りを防止し得る。したがって、これらの特性が要求される用途に好適に用いることができる。
D. Applications of the adhesive sheet The adhesive sheet of the present invention exhibits excellent adhesive strength without being affected by the composition of the surface of the adherend (for example, inorganic substances such as metals, or organic substances such as resins) before irradiation with ultraviolet rays. It can be demonstrated. Furthermore, since it has excellent followability to irregularities, it can exhibit excellent adhesive strength even when the structure (for example, irregularities) of the surface of the adherend is complex. Furthermore, after irradiation with ultraviolet rays, this pressure-sensitive adhesive sheet exhibits low adhesive strength and easy releasability without being affected by the composition and structure of the surface of the adherend. Therefore, it is possible to prevent adhesive from remaining on the surface of the adherend. Therefore, it can be suitably used in applications requiring these characteristics.
１つの実施形態においては、本発明の粘着シートは、半導体ウエハの加工工程に好適に用いることができる。上記粘着シートは被着体表面の組成および構造に影響されることなく優れた粘着力を発揮し得ることから、金属配線およびはんだバンプ等により表面が複雑な構成である半導体ウエハの加工にも好適に用いることができる。また、ＳＤＢＧプロセスのように、より強力な粘着力を要求される工程においてもバックグラインドテープとして好適に用いることができる。上記粘着シートは紫外線照射後には優れた軽剥離性を発揮し得る。そのため、バックグラインド工程後には容易に被着体から剥離することができ、被着体への糊残りも防止され得る。 In one embodiment, the adhesive sheet of the present invention can be suitably used in semiconductor wafer processing steps. The above-mentioned adhesive sheet can exhibit excellent adhesive strength without being affected by the composition and structure of the surface of the adherend, so it is suitable for processing semiconductor wafers whose surfaces have complex structures such as metal wiring and solder bumps. It can be used for. Furthermore, it can be suitably used as a backgrind tape in processes that require stronger adhesive strength, such as the SDBG process. The pressure-sensitive adhesive sheet can exhibit excellent easy releasability after being irradiated with ultraviolet rays. Therefore, it can be easily peeled off from the adherend after the back grinding process, and adhesive residue on the adherend can be prevented.
以下、実施例によって本発明を具体的に説明するが、本発明はこれら実施例によって限定されるものではない。実施例における試験および評価方法は以下のとおりである。また、特に明記しない限り、「部」および「％」は重量基準である。 EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. Tests and evaluation methods in Examples are as follows. Furthermore, unless otherwise specified, "parts" and "%" are based on weight.
＜製造例１＞粘着剤ベースポリマー溶液の調製
アクリル酸－２－エチルヘキシル１００重量部と、アクリロイルモロフォリン酸２５．５重量部と、アクリル酸－２－ヒドロキシルエチル１８．５重量部と、重合開始剤（過酸化ベンゾイル（ＢＰＯ））０．２重量部と、溶媒（トルエン）とを混合してモノマー組成物を調製した。該モノマー組成物を、１Ｌ丸底セパラブルフラスコに、セパラブルカバー、分液ロート、温度計、窒素導入管、リービッヒ冷却器、バキュームシール、撹拌棒、撹拌羽が装備された重合用実験装置に投入し、撹拌しながら、常温で６時間、窒素置換した。その後、窒素を流入下、撹拌しながら、６０℃下で８時間保持して重合し、樹脂溶液を得た。
得られた樹脂溶液を室温まで冷却し、その後、該樹脂溶液に、重合性炭素－炭素二重結合を有する化合物として、２－イソシアネートエチルメタクリレート（昭和電工社製、商品名「カレンズＭＯＩ」）２２．４重量部を加えた。さらに、ジラウリン酸ジブチルスズＩＶ（和光純薬工業社製）０．１１重量部を添加し、空気雰囲気下、５０℃で２４時間撹拌し、ポリマー溶液を得た。
<Production Example 1> Preparation of adhesive
The obtained resin solution was cooled to room temperature, and then 2-isocyanate ethyl methacrylate (manufactured by Showa Denko K.K., trade name "Karens MOI") 22 was added to the resin solution as a compound having a polymerizable carbon-carbon double bond. .4 parts by weight were added. Further, 0.11 parts by weight of dibutyltin dilaurate IV (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at 50° C. for 24 hours in an air atmosphere to obtain a polymer solution.
＜製造例２＞中間層ベースポリマーの調製
ブチルアクリレート５０重量部と、エチルアクリレート５０重量部と、アクリル酸５重量部と、アゾビスイソブチロニトリル０．１重量部とを、トルエン中、窒素雰囲気下、６０℃で６時間重合し、重量平均分子量６５万のアクリル系樹脂を得た。
<Production Example 2> Preparation of intermediate layer base polymer 50 parts by weight of butyl acrylate, 50 parts by weight of ethyl acrylate, 5 parts by weight of acrylic acid, and 0.1 part by weight of azobisisobutyronitrile were added in toluene with nitrogen Polymerization was carried out in an atmosphere at 60° C. for 6 hours to obtain an acrylic resin having a weight average molecular weight of 650,000.
［実施例１］
（粘着剤層形成組成物の調製）
製造例１で得られたポリマー溶液１００重量部に、架橋剤（東ソー社製、商品名：コロネートＬ）２重量部、および、フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸エチル（光重合開始剤、ＩＧＭ Ｒｅｓｉｎｓ社製、商品名：Ｏｍｎｉｒａｄ ＴＰＯ－Ｌ）３重量部を配合・撹拌し、紫外線硬化型粘着剤組成物を得た。
（中間層形成組成物の調製）
製造例２で得られたアクリル系樹脂１００重量部に、架橋剤（東ソー社製、商品名：コロネートＬ）１重量部、フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸エチル（光重合開始剤、ＩＧＭ Ｒｅｓｉｎｓ社製、商品名：Ｏｍｎｉｒａｄ ＴＰＯ－Ｌ）３重量部、を配合・撹拌し、中間層形成組成物を得た。
（粘着シートの作製）
基材として、ポリエチレンテレフタレートフィルム（東レ社製、製品名：ルミラーＳ１０＃１００、厚み：１００μｍ）の一方の面にコロナ処理を施したものを用いた。基材のコロナ処理面に、中間層形成組成物を塗布、乾燥し、厚み９５μｍの中間層を形成した。次いで、形成された中間層に粘着剤層形成組成物を乾燥後の厚みが５μｍとなるよう塗布、乾燥し、粘着シート１を得た。
[Example 1]
(Preparation of adhesive layer forming composition)
To 100 parts by weight of the polymer solution obtained in Production Example 1, 2 parts by weight of a crosslinking agent (manufactured by Tosoh Corporation, trade name: Coronate L) and ethyl phenyl (2,4,6-trimethylbenzoyl)phosphinate (photopolymerized) 3 parts by weight of an initiator (manufactured by IGM Resins, trade name: Omnirad TPO-L) was blended and stirred to obtain an ultraviolet curable adhesive composition.
(Preparation of intermediate layer forming composition)
To 100 parts by weight of the acrylic resin obtained in Production Example 2, 1 part by weight of a crosslinking agent (manufactured by Tosoh Corporation, trade name: Coronate L), ethyl phenyl (2,4,6-trimethylbenzoyl)phosphinate (photopolymerization initiation 3 parts by weight of Omnirad TPO-L, manufactured by IGM Resins, Inc., were blended and stirred to obtain an intermediate layer forming composition.
(Preparation of adhesive sheet)
As a base material, a polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name:
（比較例１～６）
粘着剤層形成組成物における光重合開始剤の種類、含有量、および、架橋剤の含有量、ならびに、中間層形成組成物における光重合開始剤の含有量を表１に記載のように変更した以外は実施例１と同様にして、粘着シートＣ１～Ｃ６を作製した。
(Comparative Examples 1 to 6)
The type and content of the photopolymerization initiator in the adhesive layer forming composition, the content of the crosslinking agent, and the content of the photopolymerization initiator in the intermediate layer forming composition were changed as shown in Table 1. Adhesive sheets C1 to C6 were produced in the same manner as in Example 1 except for this.
実施例および比較例で得られた粘着シートを用いて以下の評価を行った。結果を表２に示す。
（１）粘着力
被着体としてＳｉミラーウエハ（信越化学製）、非感光性ポリイミドがコーティングされたウエハ（ＫＳＴワールド製）、銅板（神戸製鋼社製、商品名：ＫＬＨ－１９４－Ｈ）を用いて、シリコン粘着力（Ｓｉ粘着力）、ポリイミド粘着力（ＰＩ粘着力）、銅粘着力（Ｃｕ粘着力）をそれぞれ測定した。被着体はトルエン、メタノール、トルエンの順で洗浄・乾燥して前処理し、次いで各実施例または比較例の粘着シートを貼り付け、常温で３０分間保管した。その後、ＵＶ照射前のもの、および、ＵＶ照射（１０００ｍＪ／ｃｍ２）を高圧水銀灯（７０ｍＷ／ｃｍ２、日東精機社製、製品名：ＵＭ－８１０）で約１２秒間照射）した後（ＵＶ照射後）のものについて、それぞれ以下の条件で粘着力（Ｎ／２０ｍｍ）を測定した。また、粘着剤層の黄変の有無、および、糊残りの有無を目視で確認した。
＜粘着力測定条件＞
引張速度：３００ｍｍ／分
剥離角度：１８０°
温度：２３℃
湿度：５０％ＲＨ
テープ幅：２０ｍｍ
The following evaluations were performed using the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples. The results are shown in Table 2.
(1) Adhesive strength Si mirror wafer (manufactured by Shin-Etsu Chemical), wafer coated with non-photosensitive polyimide (manufactured by KST World), and copper plate (manufactured by Kobe Steel, product name: KLH-194-H) were used as adherends. Silicon adhesive strength (Si adhesive strength), polyimide adhesive strength (PI adhesive strength), and copper adhesive strength (Cu adhesive strength) were each measured using the adhesive. The adherend was pretreated by washing and drying in the order of toluene, methanol, and toluene, and then the adhesive sheet of each example or comparative example was attached and stored at room temperature for 30 minutes. After that, those before UV irradiation and after UV irradiation (1000 mJ/cm 2 ) was irradiated with a high-pressure mercury lamp (70 mW/cm 2 , manufactured by Nitto Seiki Co., Ltd., product name: UM-810) for about 12 seconds (UV irradiation) The adhesive strength (N/20 mm) of each of the following items was measured under the following conditions. In addition, the presence or absence of yellowing of the adhesive layer and the presence or absence of adhesive residue were visually confirmed.
<Adhesive force measurement conditions>
Tensile speed: 300mm/min Peeling angle: 180°
Temperature: 23℃
Humidity: 50%RH
Tape width: 20mm
（２）弾性率
各実施例および比較例で用いた粘着剤層形成組成物を塗布厚みが５μｍとなるようセパレータに塗布し、１３０℃×２分間乾燥した。次いで、塗布乾燥後の粘着剤層のみを端から丸めて棒状の試料を作製し、厚み（断面積）を計測した。得られた試料を、チャック間距離１０ｍｍ、引張速度５０ｍｍ／分、室温の条件で、引張試験機（ＳＨＩＭＡＤＺＵ社製、商品名「ＡＧ－ＩＳ」）で引っ張った際の最初期の傾き（ヤング率）を弾性率とした。
(2) Elastic modulus The adhesive layer forming composition used in each Example and Comparative Example was applied to a separator to a coating thickness of 5 μm, and dried at 130° C. for 2 minutes. Next, only the adhesive layer after coating and drying was rolled up from the end to prepare a rod-shaped sample, and the thickness (cross-sectional area) was measured. The initial slope (Young's modulus) when the obtained sample was pulled with a tensile tester (manufactured by SHIMADZU, product name "AG-IS") under the conditions of a chuck distance of 10 mm, a pulling speed of 50 mm/min, and room temperature. ) was taken as the elastic modulus.
（３）バンプウエハ評価
ダミーバンプウエハ（均一に高さ４５μｍ、径２５μｍ、ピッチ５５μｍ）が形成された３００ｍｍφウエハに、各実施例および比較例で得られた粘着シートを以下の条件で貼り付けたものを試料とした。この試料を用いて、以下の方法により、剥離力、埋まり性、および、糊残りの有無を評価した。
貼り付け条件
装置：日東精機社製、商品名：ＤＲ－３０００ＩＩＩ
圧力：０．５ＭＰａ
貼付速度：１０ｍｍ／秒
温度：室温
＜バンプウエハ剥離力＞
各実施例および比較例で得られた粘着シートに、テープ流れ方向（ＭＤ方向）にスリット（２０ｍｍ幅）を入れたものを試料として用いた。この試料を、上記の条件でダミーバンプウエハが形成されたウエハに貼り付けた。貼り付け後、常温で３０分間保管した。次いで、ＵＶ照射（１０００ｍＪ／ｃｍ２）を高圧水銀灯（７０ｍＷ／ｃｍ２、日東精機社製、製品名：ＵＭ－８１０）で１２秒間行った。次いで、粘着テープを、室温で、引張速度３００ｍｍ／分、剥離角度１８０°で剥離し、剥離力（Ｎ／ｍｍ）を測定した。
＜埋まり性および糊残り＞
粘着シートを貼り合わせたバンプウエハを、該ウエハのＶノッチが０時方向となるよう静置した。次いで、ウエハの０時方向、３時方向、６時方向、９時方向、および、中央部を光学顕微鏡（倍率２５０倍）で各部分を観察し、以下の基準で評価した。次いで、ＵＶ照射（１０００ｍＪ／ｃｍ２）を高圧水銀灯（７０ｍＷ／ｃｍ２、日東精機社製、製品名：ＵＭ－８１０）で１２秒間行った。その後、粘着シートを剥離し、剥離後のバンプウエハ表面を光学顕微鏡（倍率２５０倍）で観察し、以下の基準で評価した。
埋まり性評価基準
３：全ての部分においてバンプ間に粘着剤層が気泡なく埋め込まれている
２：一部ではバンプ間では気泡が見られるが、概ね粘着剤層が気泡なく埋め込まれている
１：全ての部分においてバンプ間で気泡が見られる
糊残り評価基準
３：糊残りなし
２：微小な糊残り
１：重度の糊残り
０：剥離不可
(3) Bump wafer evaluation
The adhesive sheets obtained in each example and comparative example were attached to a 300 mmφ wafer on which a dummy bump wafer (uniformly formed with a height of 45 μm, a diameter of 25 μm, and a pitch of 55 μm) was used as a sample under the following conditions. Using this sample, peeling force, embedding property, and presence or absence of adhesive residue were evaluated by the following methods.
Pasting conditions
Equipment: Nitto Seiki Co., Ltd., product name: DR-3000III
Pressure: 0.5MPa
Pasting speed: 10mm/sec
Temperature: room temperature
<Bump wafer peeling force>
Adhesive sheets obtained in each of the Examples and Comparative Examples with slits (20 mm width) in the tape flow direction (MD direction) were used as samples. This sample was attached to a wafer on which a dummy bump wafer was formed under the above conditions. After pasting, it was stored at room temperature for 30 minutes. Next, UV irradiation (1000 mJ/cm2) with a high pressure mercury lamp (70mW/cm2(manufactured by Nitto Seiki Co., Ltd., product name: UM-810) for 12 seconds. Next, the adhesive tape was peeled off at room temperature at a pulling speed of 300 mm/min and a peeling angle of 180°, and the peeling force (N/mm) was measured.
<Fillability and adhesive residue>
The bump wafer bonded with the adhesive sheet was left standing so that the V notch of the wafer was in the 0 o'clock direction. Next, each part of the wafer was observed at 0 o'clock direction, 3 o'clock direction, 6 o'clock direction, 9 o'clock direction, and the central part using an optical microscope (magnification: 250 times), and evaluated according to the following criteria. Next, UV irradiation (1000 mJ/cm2) with a high pressure mercury lamp (70mW/cm2(manufactured by Nitto Seiki Co., Ltd., product name: UM-810) for 12 seconds. Thereafter, the adhesive sheet was peeled off, and the surface of the bump wafer after peeling was observed with an optical microscope (magnification: 250 times), and evaluated based on the following criteria.
Fillability evaluation criteria
3: The adhesive layer is embedded between bumps in all parts without air bubbles.
2: Air bubbles can be seen between the bumps in some areas, but the adhesive layer is generally embedded without air bubbles.
1: Air bubbles are seen between bumps in all parts
Glue residue evaluation criteria
3: No glue residue
2: Minute glue residue
1: Severe adhesive residue
0: Cannot be peeled off
表２から明らかなように、実施例１の粘着シートは、被着体表面が有機物である（ＰＩ粘着力）か、無機物であるか（Ｃｕ粘着力）に関わらず、シリコンウエハに対する粘着力と同等の粘着力を有していた。また、紫外線照射後には優れた剥離性を有し、被着体への糊残りも防止されていた。さらに、被着体表面が凹凸を有する場合であっても、凹凸に対する埋め性と糊残り防止とを両立し得るものであった。他方、比較例においては、埋まり性に優れるものでは糊残りが、糊残りの防止性に優れるものでは埋まり性に改善の余地があり、これらを両立することが困難なものであった。 As is clear from Table 2, the adhesive sheet of Example 1 has excellent adhesive strength to silicon wafers regardless of whether the adherend surface is organic (PI adhesive strength) or inorganic (Cu adhesive strength). They had the same adhesive strength. Furthermore, it had excellent removability after irradiation with ultraviolet rays, and adhesive residue on adherends was also prevented. Furthermore, even when the surface of the adherend has irregularities, it was possible to achieve both filling of the irregularities and prevention of adhesive residue. On the other hand, in Comparative Examples, there was room for improvement in the filling property with excellent embedding properties, and adhesive residue with excellent embedding properties, and it was difficult to achieve both of these.
１０ 基材
２０ 粘着剤層
１００ 粘着シート
10
Claims (9)
該紫外線硬化型粘着剤組成物を用いて形成した粘着剤層の、紫外線照射後のポリイミド粘着力とシリコン粘着力の比（ＰＩ粘着力／Ｓｉ粘着力）と紫外線照射後の銅粘着力とシリコン粘着力との比（Ｃｕ粘着力／Ｓｉ粘着力）との比（（ＰＩ粘着力／Ｓｉ粘着力）／（Ｃｕ粘着力／Ｓｉ粘着力））が、０．７５～１．１０である、紫外線硬化型粘着剤組成物。 An ultraviolet curable adhesive composition comprising an ultraviolet curable adhesive and an alkyl phenyl(2,4,6-trimethylbenzoyl)phosphinate ,
The ratio of polyimide adhesive strength to silicon adhesive strength (PI adhesive strength/Si adhesive strength) after UV irradiation and the copper adhesive strength and silicon after UV irradiation of the adhesive layer formed using the UV curable adhesive composition. The ratio of the adhesive strength to the adhesive strength (Cu adhesive strength/Si adhesive strength) ((PI adhesive strength/Si adhesive strength)/(Cu adhesive strength/Si adhesive strength)) is 0.75 to 1.10. UV-curable adhesive composition .
該粘着剤層が請求項１または２に記載の紫外線硬化型粘着剤組成物から形成される、粘着シート。 An adhesive sheet comprising a base material and an adhesive layer,
A pressure-sensitive adhesive sheet, wherein the pressure-sensitive adhesive layer is formed from the ultraviolet curable pressure-sensitive adhesive composition according to claim 1 or 2.
The pressure-sensitive adhesive sheet according to claim 8, which is used as a backgrind sheet.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020007711A JP7386088B2 (en) | 2020-01-21 | 2020-01-21 | Adhesive composition and adhesive sheet using the adhesive composition |
| TW110101088A TW202132515A (en) | 2020-01-21 | 2021-01-12 | Adhesive composition and adhesive sheet using said adhesive composition having excellent adhesion to an adherend before ultraviolet irradiation and excellent peelability after ultraviolet irradiation |
| KR1020210005061A KR20210094468A (en) | 2020-01-21 | 2021-01-14 | Adhesive composition and adhesive sheet using said adhesive composition |
| CN202110074380.3A CN113214765A (en) | 2020-01-21 | 2021-01-20 | Adhesive composition and adhesive sheet using the same |
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| JP2020007711A JP7386088B2 (en) | 2020-01-21 | 2020-01-21 | Adhesive composition and adhesive sheet using the adhesive composition |
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| JP2021113298A JP2021113298A (en) | 2021-08-05 |
| JP7386088B2 true JP7386088B2 (en) | 2023-11-24 |
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| JP (1) | JP7386088B2 (en) |
| KR (1) | KR20210094468A (en) |
| CN (1) | CN113214765A (en) |
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| JP7426260B2 (en) | 2020-03-06 | 2024-02-01 | 日東電工株式会社 | Adhesive tape |
| JP7173392B1 (en) | 2022-05-12 | 2022-11-16 | 大日本印刷株式会社 | Adhesive tape for semiconductor processing |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090017323A1 (en) | 2007-07-13 | 2009-01-15 | 3M Innovative Properties Company | Layered body and method for manufacturing thin substrate using the layered body |
| JP2017183309A (en) | 2016-03-28 | 2017-10-05 | リンテック株式会社 | Semiconductor-processing sheet |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62153376A (en) | 1985-12-27 | 1987-07-08 | F S K Kk | Pressure-sensitive adhesive sheet |
| JP3491911B2 (en) | 1992-07-29 | 2004-02-03 | リンテック株式会社 | Adhesive sheet for semiconductor wafer processing |
| JP2004111428A (en) | 2002-09-13 | 2004-04-08 | Tokyo Seimitsu Co Ltd | Chip manufacturing method |
| JP2004204090A (en) * | 2002-12-26 | 2004-07-22 | C I Kasei Co Ltd | Film with pressure sensitive adhesive layer and its manufacturing method |
| JP6261115B2 (en) * | 2013-09-19 | 2018-01-17 | 日東電工株式会社 | Adhesive sheet |
| KR20180126761A (en) * | 2017-05-18 | 2018-11-28 | 동우 화인켐 주식회사 | Adhesive Composition and Adhesive Sheet Using the Same |
| JP2019156967A (en) * | 2018-03-13 | 2019-09-19 | 日東電工株式会社 | Semiconductor protective adhesive tape |
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2020
- 2020-01-21 JP JP2020007711A patent/JP7386088B2/en active Active
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- 2021-01-12 TW TW110101088A patent/TW202132515A/en unknown
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090017323A1 (en) | 2007-07-13 | 2009-01-15 | 3M Innovative Properties Company | Layered body and method for manufacturing thin substrate using the layered body |
| JP2017183309A (en) | 2016-03-28 | 2017-10-05 | リンテック株式会社 | Semiconductor-processing sheet |
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| Publication number | Publication date |
|---|---|
| JP2021113298A (en) | 2021-08-05 |
| KR20210094468A (en) | 2021-07-29 |
| CN113214765A (en) | 2021-08-06 |
| TW202132515A (en) | 2021-09-01 |
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