WO2022123932A1 - Adhesive sheet - Google Patents
Adhesive sheet Download PDFInfo
- Publication number
- WO2022123932A1 WO2022123932A1 PCT/JP2021/039065 JP2021039065W WO2022123932A1 WO 2022123932 A1 WO2022123932 A1 WO 2022123932A1 JP 2021039065 W JP2021039065 W JP 2021039065W WO 2022123932 A1 WO2022123932 A1 WO 2022123932A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive layer
- adhesive sheet
- resin
- Prior art date
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 81
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 81
- 229920005989 resin Polymers 0.000 claims abstract description 135
- 239000011347 resin Substances 0.000 claims abstract description 135
- 238000007789 sealing Methods 0.000 claims abstract description 79
- 239000004065 semiconductor Substances 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 53
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 312
- 239000010410 layer Substances 0.000 claims description 176
- 239000003431 cross linking reagent Substances 0.000 claims description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 38
- 229920000058 polyacrylate Polymers 0.000 claims description 22
- 230000008859 change Effects 0.000 claims description 19
- 239000004593 Epoxy Substances 0.000 claims description 17
- 229920005601 base polymer Polymers 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- XOQUTYDTROZTID-UHFFFAOYSA-N 2-[(4-tert-butylphenyl)-[(4-tert-butylphenyl)-(oxiran-2-yl)methoxy]methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1C(C1OC1)OC(C=1C=CC(=CC=1)C(C)(C)C)C1OC1 XOQUTYDTROZTID-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 2
- 239000012790 adhesive layer Substances 0.000 abstract description 19
- 239000003522 acrylic cement Substances 0.000 abstract description 2
- -1 polyethylene terephthalate Polymers 0.000 description 55
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 53
- 239000000178 monomer Substances 0.000 description 34
- 229920000103 Expandable microsphere Polymers 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000000470 constituent Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 21
- 239000000523 sample Substances 0.000 description 20
- 238000005259 measurement Methods 0.000 description 19
- 229920000139 polyethylene terephthalate Polymers 0.000 description 19
- 239000005020 polyethylene terephthalate Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 11
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 11
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 11
- 239000012948 isocyanate Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 150000002513 isocyanates Chemical class 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 239000004745 nonwoven fabric Substances 0.000 description 8
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 229920006243 acrylic copolymer Polymers 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 238000009864 tensile test Methods 0.000 description 7
- 150000003505 terpenes Chemical class 0.000 description 7
- 235000007586 terpenes Nutrition 0.000 description 7
- 229940095095 2-hydroxyethyl acrylate Drugs 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 239000013032 Hydrocarbon resin Substances 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920006270 hydrocarbon resin Polymers 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000002788 crimping Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
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- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
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- 229920001223 polyethylene glycol Polymers 0.000 description 3
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- 229920002635 polyurethane Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- KANZWHBYRHQMKZ-UHFFFAOYSA-N 2-ethenylpyrazine Chemical compound C=CC1=CN=CC=N1 KANZWHBYRHQMKZ-UHFFFAOYSA-N 0.000 description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229920001342 Bakelite® Polymers 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 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 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- NWAHZAIDMVNENC-UHFFFAOYSA-N octahydro-1h-4,7-methanoinden-5-yl methacrylate Chemical compound C12CCCC2C2CC(OC(=O)C(=C)C)C1C2 NWAHZAIDMVNENC-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000913 palmityl 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])[H] 0.000 description 1
- 125000002958 pentadecyl 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])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- AAYRWMCIKCRHIN-UHFFFAOYSA-N propane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCCS(O)(=O)=O AAYRWMCIKCRHIN-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 150000003349 semicarbazides Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 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 1
- 239000013638 trimer Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
Classifications
-
- 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
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
- H01L21/568—Temporary substrate used as encapsulation process aid
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- 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
-
- 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
-
- 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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
-
- 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
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
Definitions
- the present invention relates to an adhesive sheet.
- the semiconductor chips may be resin-sealed in order to prevent damage to the semiconductor chips, expand metal wiring, and the like.
- the semiconductor chip may be resin-sealed on the pressure-sensitive adhesive sheet from the viewpoint of workability and the like.
- a plurality of semiconductor chips are arranged on an adhesive sheet as a predetermined temporary fixing material, and the semiconductor chips are collectively sealed on the adhesive sheet.
- the pressure-sensitive adhesive sheet is peeled off from the resin encapsulating the semiconductor chip.
- the present invention has been made to solve the above-mentioned conventional problems, and an object thereof is to have an appropriate adhesiveness to a sealing resin for encapsulating a semiconductor chip and a semiconductor chip, and the sealing thereof.
- an adhesive sheet that can be easily peeled off from the stop resin does not easily leave adhesive residue during peeling, and does not easily cause a step between the semiconductor chip and the sealing resin after the adhesive sheet is peeled off. be.
- the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet including a base material and a pressure-sensitive adhesive layer arranged on at least one side of the base material, wherein the pressure-sensitive adhesive layer contains an acrylic pressure-sensitive adhesive, and the pressure-sensitive adhesive sheet is used.
- the amount of subduction under the environment of 23 ° C. using TMA is 5 ⁇ m or less, and the T 2 relaxation time (T 2s ) of the S component by pulse NMR of the pressure-sensitive adhesive layer is 45 ⁇ sec or less.
- the rate of change in the thickness of the pressure-sensitive adhesive layer after dropping 4-tertiary butylphenylglycidyl ether onto the surface of the pressure-sensitive adhesive layer and allowing it to stand for 1 minute is 160% or less.
- the amount of change in the thickness of the pressure-sensitive adhesive layer after dropping 4-tertiary butylphenylglycidyl ether onto the surface of the pressure-sensitive adhesive layer and allowing it to stand for 1 minute is 20 ⁇ m or less.
- the pressure-sensitive adhesive layer comprises a pressure-sensitive adhesive, wherein the pressure-sensitive adhesive has a sp value of 18 (cal / cm 3 ) 1/2 to 20 (cal / cm 3 ) 1/2 . including.
- the acrylic pressure-sensitive adhesive comprises a crosslinked body of the acrylic polymer as a base polymer.
- the acrylic pressure-sensitive adhesive comprises an epoxy-based cross-linking agent.
- the blending amount of the epoxy-based cross-linking agent is 0.6 parts by weight to 15 parts by weight with respect to 100 parts by weight of the acrylic polymer.
- the substrate is a resin sheet composed of a resin having a glass transition temperature (Tg) of 25 ° C. or higher.
- Tg glass transition temperature
- the thickness of the substrate is 20% to 90% with respect to the total thickness of the pressure-sensitive adhesive sheet.
- the amount of subduction of the pressure-sensitive adhesive sheet in an environment of 145 ° C. using TMA is 1 ⁇ m to 35 ⁇ m.
- the amount of nitrogen gas generated when the pressure-sensitive adhesive layer is heat-treated is 0.06% by weight to 1% by weight.
- the pressure-sensitive adhesive sheet is a second base material, a pressure-sensitive adhesive layer arranged on one side of the base material, and a second surface of the base material opposite to the pressure-sensitive adhesive layer. Provided with a pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive sheet is a temporary fixing material used in the resin sealing step of a semiconductor chip. In one embodiment, the pressure-sensitive adhesive sheet is used to cure the sealing resin on the pressure-sensitive adhesive sheet.
- the present invention has an appropriate adhesiveness to the encapsulating resin for encapsulating a semiconductor chip and the semiconductor chip, can be easily peeled from the encapsulating resin, and is unlikely to leave adhesive residue during peeling. Moreover, it is possible to provide an adhesive sheet that does not easily cause a step between the semiconductor chip and the sealing resin after the adhesive sheet is peeled off.
- FIG. 3 is a schematic cross-sectional view of an adhesive sheet according to another embodiment of the present invention.
- FIG. 1 of the pressure-sensitive adhesive sheet is a schematic cross-sectional view of the pressure-sensitive adhesive sheet according to one embodiment of the present invention.
- the pressure-sensitive adhesive sheet 100 includes a base material 10 and a pressure-sensitive adhesive layer (first pressure-sensitive adhesive layer) 20 arranged on at least one side of the base material 10.
- the pressure-sensitive adhesive layer contains an acrylic pressure-sensitive adhesive.
- the pressure-sensitive adhesive sheet of the present invention can be suitably used as a temporary fixing material when sealing a semiconductor chip with a resin. More specifically, in the pressure-sensitive adhesive sheet of the present invention, semiconductor chips are arranged on the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet, the semiconductor chips are covered with a resin (usually an epoxy resin), and the sealing resin is cured. Can be used as a temporary fixing material for the semiconductor chip when the semiconductor chip is resin-sealed. After the semiconductor chip is resin-sealed, the pressure-sensitive adhesive sheet is a sealing resin and a semiconductor during a predetermined post-process (for example, backside grinding of the sealing resin, pattern formation, bump formation, chip formation (cutting)). It can be peeled off from the structure composed of the chip.
- the epoxy equivalent of the sealing resin is, for example, 50 g / eq to 500 g / eq.
- the amount of subduction of the pressure-sensitive adhesive sheet in an environment of 23 ° C. using TMA is 5 ⁇ m or less. Further, the T 2 relaxation time (T 2s ) of the S component by pulse NMR of the pressure-sensitive adhesive layer is 45 ⁇ sec or less. According to the pressure-sensitive adhesive sheet having these characteristics, when the semiconductor chip is resin-sealed on the pressure-sensitive adhesive sheet and then the pressure-sensitive adhesive sheet is peeled off, the generation of a step between the semiconductor chip and the sealing resin is prevented.
- FIG. 2A shows an example of the case where the conventional pressure-sensitive adhesive sheet 100'is used for resin encapsulation of a semiconductor chip.
- the pressure-sensitive adhesive sheet 100' has a pressure-sensitive adhesive layer, and the outer surface of the pressure-sensitive adhesive layer is used as a sticking surface.
- the semiconductor chip is resin-sealed, the semiconductor chip 1 is first attached to the pressure-sensitive adhesive sheet 100'(ai).
- composition 2'containing the monomer which is the precursor of the sealing resin 2 is applied (a-ii) so as to seal the semiconductor chip 1, and then the composition 2'is cured (a). -Iii).
- a composition containing a naphthalene-type bifunctional epoxy resin epoxy equivalent: 144.
- the pressure-sensitive adhesive sheet 100' is peeled off from the structure A containing the semiconductor chip 1 and the sealing resin 2 during a predetermined post-process (a-iv).
- a mixed phase with the sealing resin component is formed. If the mixed phase is formed, when the pressure-sensitive adhesive sheet is peeled off, the mixed phase is destroyed and a part of the sealing resin is peeled off together with the pressure-sensitive adhesive sheet, resulting in a step between the semiconductor chip and the sealing resin. Occurs.
- a part of the semiconductor chip is embedded in the pressure-sensitive adhesive layer due to the force applied to the semiconductor chip.
- the embedding of the pressure-sensitive adhesive layer of the semiconductor chip also causes a step difference between the semiconductor chip and the sealing resin.
- the pressure-sensitive adhesive layer component is transferred to the sealing resin and the semiconductor chip is embedded in the pressure-sensitive adhesive layer (particularly). (Embedding of the semiconductor chip into the pressure-sensitive adhesive layer) can be prevented (FIG. 2 (b)). Further, by setting the T 2 relaxation time (T 2s ) of the S component of the pressure-sensitive adhesive layer by pulse NMR to 45 ⁇ sec or less, the pressure-sensitive adhesive layer component is transferred to the sealing resin and the semiconductor chip is embedded in the pressure-sensitive adhesive layer. (In particular, the transfer of the pressure-sensitive adhesive layer component to the sealing resin) can be prevented (FIG. 2 (b)).
- the amount of subduction of the pressure-sensitive adhesive sheet in an environment of 23 ° C. using TMA is preferably 4 ⁇ m or less, more preferably 3.5 ⁇ m, and further preferably 3 ⁇ m or less. Within such a range, the effect of the present invention becomes remarkable.
- the sinking amount can be set within the above range.
- the "subduction amount of the adhesive sheet in a 23 ° C environment using TMA" is determined after 60 minutes have passed by bringing the probe into contact with the adhesive layer (first adhesive layer) using a thermomechanical analyzer. Means the amount of subduction.
- the measurement conditions are probe: needle insertion, nitrogen gas flow rate: 50.0 ml / min, and indentation load: 0.01 N.
- the standard pressure-sensitive adhesive layer is an acrylic copolymer (2-ethylhexyl acrylate (2EHA), ethyl acrylate (EA), methyl methacrylate (MMA) and 2-hydroxyethyl acrylate (HEA) copolymer, 2EHA constituent unit: EA constituent unit: MMA.
- the amount of subduction of the pressure-sensitive adhesive sheet in an environment of 145 ° C. using TMA is preferably 1 ⁇ m to 35 ⁇ m, more preferably 1 ⁇ m to 34 ⁇ m, and further preferably 2 ⁇ m to 34 ⁇ m. Within such a range, the effect of the present invention becomes remarkable. Further, even when subjected to a high temperature environment (for example, a heat treatment environment at the time of resin encapsulation), embedding of the semiconductor chip in the pressure-sensitive adhesive layer is prevented.
- FIG. 3 is a schematic cross-sectional view of an adhesive sheet according to another embodiment of the present invention.
- the pressure-sensitive adhesive sheet 200 further includes a second pressure-sensitive adhesive layer 30 on the side opposite to the pressure-sensitive adhesive layer 20 of the base material 10. That is, the pressure-sensitive adhesive sheet 200 includes a pressure-sensitive adhesive layer 20, a base material 10, and a second pressure-sensitive adhesive layer 30 in this order.
- the second pressure-sensitive adhesive layer 30 By providing the second pressure-sensitive adhesive layer 30, when the resin is sealed on the pedestal, the second pressure-sensitive adhesive layer 30 side is attached to the pedestal, and the pressure-sensitive adhesive sheet 200 is arranged with good fixing property. Can be done.
- the second pressure-sensitive adhesive layer comprises thermally expandable microspheres.
- the thermally expandable microspheres can expand at a predetermined temperature.
- the heat-expandable microspheres expand by heating to a predetermined temperature or higher, and the adhesive surface (that is, the surface of the second pressure-sensitive adhesive layer) becomes uneven. Adhesive strength decreases or disappears.
- the necessary adhesiveness is exhibited when the pressure-sensitive adhesive sheet is fixed (for example, fixed to a pedestal), and when the pressure-sensitive adhesive sheet is peeled off (for example, for example). When peeling from the pedestal), the adhesive strength is reduced or disappears by heating, and good peelability is exhibited.
- the pressure-sensitive adhesive force A at 23 ° C. when the pressure-sensitive adhesive layer is attached to polyethylene terephthalate is preferably 0.05 N / 20 mm to 1 N / 20 mm, more preferably 0.1 N / 20 mm to. It is 10N / 20mm, more preferably 0.1N / 20mm to 5N / 20mm, particularly preferably 0.2N / 20mm to 2N / 20mm, and most preferably 0.2N / 20mm to 1N / 20mm. .. Within such a range, an adherend (for example, a semiconductor chip) can be preferably fixed, and a pressure-sensitive adhesive sheet having less adhesive residue at the time of peeling can be obtained.
- an adherend for example, a semiconductor chip
- adheresive strength at 23 ° C. when the adhesive layer is attached to polyethylene terephthalate means that an adhesive sheet (width 20 mm x length 140 mm) is adhered to a polyethylene terephthalate film (thickness 25 ⁇ m).
- the agent layers are bonded (bonding conditions: 1 reciprocation of a 2 kg roller), left at an environmental temperature of 23 ° C. for 30 minutes, and then the sample is subjected to a tensile test (peeling speed: 300 mm / min, peeling angle 180 °). Adhesive strength to be measured.
- the shear adhesive force B at 150 ° C. when the silicon chip is attached to the pressure-sensitive adhesive layer is preferably 500 g or more, more preferably 700 g to 1500 g, and further preferably 800 g to 1200 g. Is.
- the adhesive has a high cohesive force, has a preferable adhesive force even at a high temperature (for example, a heating step for curing the sealing resin), and is arranged on the adhesive sheet. It is possible to prevent the displacement of the adherend (for example, a semiconductor chip).
- the mirror surface of the silicon chip (size: 5 mm x 5 mm) is attached vertically to the adhesive layer so that the tip angle does not hit, and then heated at 130 ° C. for 30 minutes to adhere to the surface of the silicon chip adhesive. Then, the maximum breaking load is read from the load-displacement curve obtained by applying an external force horizontally to the chip at a shear rate of 500 ⁇ m / sec under the measured temperature (150 ° C in the case of shear adhesive force B measurement). This can be measured.
- the measuring device for example, a Dage 4000 manufactured by Nordson is used. Further, the measurement terminal at the time of the above measurement may be located at a height of 250 ⁇ m on the surface of the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive sheet of the present invention has a shear adhesive force at 190 ° C. when the silicon chip is attached to the pressure-sensitive adhesive layer, preferably 300 g to 1000 g, more preferably 350 g to 750 g, and further preferably 400 g to 600 g. Is.
- the pressure-sensitive adhesive sheet includes a second pressure-sensitive adhesive layer containing heat-expandable microspheres
- the second pressure-sensitive adhesive layer side exhibits peelability, that is, the said.
- the adherend on the pressure-sensitive adhesive layer can be preferably fixed.
- the thickness of the pressure-sensitive adhesive sheet of the present invention is preferably 3 ⁇ m to 300 ⁇ m, more preferably 5 ⁇ m to 150 ⁇ m, and further preferably 10 ⁇ m to 100 ⁇ m.
- the adhesive layer is composed of an adhesive containing a base polymer.
- T 2 relaxation time (T 2s ) of the S component by pulse NMR of the pressure-sensitive adhesive layer is 45 ⁇ sec or less.
- the relaxation time means the time until the excited atom (group) returns to the ground state after irradiating the atom with appropriate energy to excite the atom to be measured in the pulse NMR measurement.
- the excited state of an atom (group) can be controlled by the amount and time of energy irradiation. It is also known that there are various energy relaxation mechanisms for excited atoms (groups) to return to the ground state, and the relaxation time is determined according to the relaxation mechanism (for example, for chemists).
- the inventors excited the 1H atom of the acrylic pressure - sensitive adhesive (substantially, the acrylic-based polymer contained in the pressure-sensitive adhesive) under the following conditions, measured the subsequent relaxation behavior, and further analyzed the measured values.
- the S component of the T 2 relaxation time is used as information for knowing the molecular motion related to the degree of cross-linking of the base polymer (typically, an acrylic polymer) contained in the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer. It was found that (T 2s ) is useful, and that the above effect can be obtained by specifying the S component (T 2s ) of the T 2 relaxation time.
- a short T 2s indicates that the molecular motion related to the degree of cross-linking of the base polymer is restricted, that is, the cross-linking progresses and the degree of freedom of motion of the polymer as a whole is reduced. Is shown.
- the gap between the base polymers is small, and the pressure-sensitive adhesive layer component is transferred to the sealing resin and the low molecular weight component contained in the sealing resin is transferred to the pressure-sensitive adhesive layer. Is suppressed.
- the semiconductor chip is resin-sealed on the pressure-sensitive adhesive sheet and then the pressure-sensitive adhesive sheet is peeled off, the generation of a step between the semiconductor chip and the sealing resin is prevented.
- the T 2 relaxation time (T 2s ) of the S component by pulse NMR of the pressure-sensitive adhesive layer is preferably 10 ⁇ sec to 50 ⁇ sec, more preferably 10 ⁇ sec to 45 ⁇ sec, and further preferably 10 ⁇ sec to 40 ⁇ sec. Within such a range, the above effect becomes remarkable.
- T 2 relaxation time (T 2s ) of the S component by pulse NMR a T 2 relaxation curve measured by the solid echo method was obtained using 100 mg of the pressure-sensitive adhesive layer as a measurement sample, and the T 2 relaxation curve was calculated by the following equation (1). You can find it by fitting it to.
- M (t) ⁇ ⁇ exp (-(1 / Wa) (t / T 2s ) Wa ) + ⁇ ⁇ exp (-(1 / Wa) (t / T 2L ) Wa ) ⁇ ⁇ ⁇ (1)
- M (t): Free induction decay ⁇ : Proton ratio (%) of component (S component) with short relaxation time T 2s : T 2 relaxation time (msec) of S component ⁇ : Proton ratio (%) of the component (L component) with a long relaxation time T 2L : T 2 relaxation time (msec) of L component t: Observation time (msec) Wa: Shape coefficient ( 1)
- the measurement conditions in the above measurement are as follows. 90 ° pulse width: 2.1 ⁇ sec ⁇ Repeat time: 1 sec ⁇ Number of integrations: 32 times ⁇ Measurement temperature: 30 ° C
- the rate of change in the thickness of the pressure-sensitive adhesive layer after dropping 4-tertiary butylphenylglycidyl ether onto the surface of the pressure-sensitive adhesive layer and allowing it to stand for 1 minute is preferably 160% or less, more preferably 150% or less. It is more preferably 120% or less, and particularly preferably 100% or less.
- the pressure-sensitive adhesive layer having a thickness change rate in such a range has a high crosslink density and prevents component transfer between the pressure-sensitive adhesive layer and the sealing resin, and as a result, after the semiconductor chip is resin-sealed on the pressure-sensitive adhesive sheet. When the adhesive sheet is peeled off, the generation of a step between the semiconductor chip and the sealing resin is prevented.
- the thickness change rate (and the thickness change amount described later) can be set in the above range by preferably selecting, for example, a base polymer (typically, an acrylic polymer) contained in an acrylic pressure-sensitive adhesive. ..
- a base polymer typically, an acrylic polymer
- an acrylic polymer having a large number of carbon atoms for example, 4 or more, preferably 8 or more
- a pressure-sensitive adhesive layer having a small thickness change rate (and a thickness change amount described later) can be formed.
- the thickness change rate is as follows: 4-tertiary butylphenylglycidyl ether is added dropwise to the surface of the pressure-sensitive adhesive layer in a predetermined amount (0.02 g using a syringe having a diameter of 22 mm) at 23 ° C. and 50% RH for 1 minute. From the thickness (Dt) of the dropping point after leaving and wiping off the 4-tertiary butylphenylglycidyl ether and the thickness (It) of the dropping point before the dropping operation, (Dt-It) / It It is calculated by the formula.
- the amount of change in the thickness of the pressure-sensitive adhesive layer after dropping 4-tertiary butylphenylglycidyl ether onto the surface of the pressure-sensitive adhesive layer and allowing it to stand for 1 minute is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less. It is more preferably 10 ⁇ m or less, and particularly preferably 6 ⁇ m or less.
- the pressure-sensitive adhesive layer having a thickness change in such a range has a high crosslink density and prevents component transfer between the pressure-sensitive adhesive layer and the sealing resin, and as a result, after the semiconductor chip is resin-sealed on the pressure-sensitive adhesive sheet. When the adhesive sheet is peeled off, the generation of a step between the semiconductor chip and the sealing resin is prevented.
- the smaller the thickness change amount, the more preferable, but the lower limit thereof is, for example, 3 ⁇ m (preferably 1 ⁇ m).
- the thickness change amount is obtained from the above Dt and It by the formula of Dt-It.
- the gel fraction of the pressure-sensitive adhesive layer is preferably 75% or more, more preferably 85% or more, and further preferably 90% or more. Within such a range, the molecular motion of the base polymer is preferably restricted by cross-linking, and a pressure-sensitive adhesive layer in which component transfer between the pressure-sensitive adhesive layer and the sealing resin is prevented can be obtained.
- the gel fraction is determined by immersing the crosslinked pressure-sensitive adhesive in ethyl acetate for 7 days and then drying it (dry weight after immersion / dry weight before immersion) ⁇ 100.
- the amount of nitrogen gas generated when the pressure-sensitive adhesive layer is heat-treated is preferably 0.06% by weight to 1.0% by weight, and more preferably 0.06% by weight to 0.9% by weight.
- the acrylic pressure-sensitive adhesive exhibits sufficient cohesive power, and the low-molecular-weight component of the sealing resin is applied to the pressure-sensitive adhesive layer.
- the thickness of the pressure-sensitive adhesive layer is preferably 1 ⁇ m to 50 ⁇ m, more preferably 3 ⁇ m to 30 ⁇ m, and further preferably 5 ⁇ m to 20 ⁇ m. Within such a range, it is possible to obtain an adhesive sheet that is difficult to embed in the resin of the semiconductor chip even by pressurization during the sealing step.
- the elastic modulus of the pressure-sensitive adhesive layer at 25 ° C. by the nanoindentation method is preferably less than 100 MPa, more preferably 0.1 MPa to 50 MPa, and further preferably 0.1 MPa to 10 MPa. Within such a range, an adhesive sheet having an appropriate adhesive strength can be obtained.
- the elastic modulus by the nanoindentation method is the load load-pushing depth obtained by continuously measuring the load on the indenter and the pushing depth when the indenter is pushed into the sample during loading and unloading.
- the elastic modulus obtained from the curve In the present specification, the elastic modulus by the nanoindentation method means the elastic modulus measured as described above under the measurement conditions of load: 1 mN, load / unloading speed: 0.1 mN / s, and holding time: 1s.
- the tensile elastic modulus of the pressure-sensitive adhesive layer at 25 ° C. is preferably less than 100 MPa, more preferably 0.1 MPa to 50 MPa, and further preferably 0.1 MPa to 10 MPa. Within such a range, an adhesive sheet having an appropriate adhesive strength can be obtained.
- the tensile elastic modulus can be measured according to JIS K 7161: 2008.
- the probe tack value of the pressure-sensitive adhesive layer is preferably 50 N / 5 mm ⁇ or more, more preferably 75 N / 5 mm ⁇ or more, and further preferably 100 N / 5 mm ⁇ or more. Within such a range, it is possible to prevent misalignment of the adherend (for example, a semiconductor chip) arranged on the adhesive sheet.
- the measurement conditions for the probe tack value are: probe processing speed: 30 mm / min, test speed: 30 mm / min, adhesion load: 100 gf, adhesion holding time: 1 second, probe area: 5 mm ⁇ SUS.
- the sp value of the base polymer is preferably 10 (cal / cm 3 ) 1/2 to 30 (cal / cm 3 ) 1/2 , and more preferably 15 (cal / cm 3 ) 1/2 to 25 ( It is cal / cm 3 ) 1/2 , and more preferably 18 (cal / cm 3 ) 1/2 to 20 (cal / cm 3 ) 1/2 .
- component transfer between the pressure-sensitive adhesive layer / the sealing resin is preferably prevented.
- the acrylic pressure-sensitive adhesive for example, an acrylic polymer (homopolymer or copolymer) using one or more (meth) acrylic acid alkyl esters as a monomer component is used as a prepolymer, and the prepolymer is used.
- acrylic pressure-sensitive adhesives using a crosslinked polymer as a base polymer.
- the "base polymer" contained in the acrylic pressure-sensitive adhesive in the pressure-sensitive adhesive layer means a polymer formed by cross-linking a prepolymer (uncrosslinked polymer).
- the base polymer has a crosslinked structure of an acrylic polymer and an epoxy crosslinker.
- (meth) acrylic acid alkyl ester examples include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and butyl (meth) acrylic acid.
- a (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 4 to 20 carbon atoms (more preferably 6 to 20, particularly preferably 8 to 18) is more preferable.
- a (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 4 or more carbon atoms (preferably 8 or more carbon atoms) is used.
- the component transfer between the pressure-sensitive adhesive layer / the sealing resin is preferably prevented.
- the acrylic polymer is another monomer component that can be copolymerized with the (meth) acrylic acid alkyl ester, if necessary, for the purpose of modifying the cohesiveness, heat resistance, crosslinkability and the like. It may contain the unit corresponding to.
- monomer components include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride and icotanic acid anhydride.
- Acid anhydride monomers such as (meth) hydroxyethyl acrylate, (meth) hydroxypropyl acrylate, (meth) hydroxybutyl acrylate, (meth) hydroxyhexyl acrylate, (meth) hydroxyoctyl acrylate, (meth) Hydroxyl group-containing monomers such as hydroxydecyl acrylate, hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methylmethacrylate; styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid.
- Aminoalkyl (meth) acrylate monomers such as aminoethyl, t-butylaminoethyl (meth) acrylate; alkoxyalkyl (meth) acrylate such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate.
- Maleimide-based monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide , N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide and other itaconeimide-based monomers; Succinimide-based monomers such as N- (meth) acryloyl-8-oxyoctamethylene succinimide; vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrro Vinyls such as lidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazin, vinylpyrazine, vinylpyrrole, vinylimidazole,
- Acrylic acid ester-based monomers having such factors: hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol.
- Polyfunctional monomers such as di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate; isoprene, butadiene, Olefin-based monomers such as isobutylene; vinyl ether-based monomers such as vinyl ether and the like can be mentioned. These monomer components may be used alone or in combination of two or more.
- the acrylic polymer has a glass transition temperature (Tg) of ⁇ 5 ° C. to 150 ° C. (preferably 50 ° C. to 150 ° C., more preferably 80 ° C.) when homopolymerized. It further contains a constituent unit a derived from a monomer ( ⁇ 120 ° C.). If such a structural unit a is included, the molecular motion of the acrylic polymer is restricted, and an acrylic polymer in which the T 2 relaxation time (T 2s ) of the S component by pulse NMR is preferably adjusted can be obtained. In addition, an adhesive sheet having excellent low-temperature adhesiveness can be obtained.
- Tg glass transition temperature
- the content of the structural unit a is preferably 0.1% by weight to 20% by weight, more preferably 1% by weight to 10% by weight, particularly, with respect to all the structural units constituting the acrylic polymer. It is preferably 1.5% by weight to 8% by weight, and most preferably 3% by weight to 6% by weight.
- Examples of the monomer having a glass transition temperature (Tg) of -5 ° C to 150 ° C include 2-hydroxyethyl acrylate (Tg: -3 ° C), 2-hydroxyethyl methacrylate (Tg: 77 ° C), and acrylic acid (Tg).
- methyl methacrylate is preferable for improving the visibility of the adherend during processing because it enhances the transparency of the pressure-sensitive adhesive layer, and acrylic acid is strongly adhered to the adherend due to the interaction between molecules.
- Hydroxyethyl acrylate is more preferable for controlling the relaxation time because it exhibits high reactivity with various cross-linking agents.
- the acrylic polymer (prepolymer) further contains a structural unit derived from a hydroxyl group-containing monomer.
- the content of the structural unit derived from the hydroxyl group-containing monomer is preferably 0.1% by weight to 20% by weight, more preferably 0.5% by weight to 10% by weight, based on all the structural units constituting the acrylic polymer. It is% by weight, and particularly preferred is 1% by weight to 7% by weight.
- the acrylic pressure-sensitive adhesive may contain any suitable additive, if necessary.
- the additive include a cross-linking agent, a tackifier, a plasticizer (for example, a trimellitic acid ester-based plasticizer, a pyromellitic acid ester-based plasticizer, etc.), a pigment, a dye, a filler, an antiaging agent, and a conductive material.
- a plasticizer for example, a trimellitic acid ester-based plasticizer, a pyromellitic acid ester-based plasticizer, etc.
- a pigment for example, a trimellitic acid ester-based plasticizer, a pyromellitic acid ester-based plasticizer, etc.
- a pigment for example, a trimellitic acid ester-based plasticizer, a pyromellitic acid ester-based plasticizer, etc.
- a dye for example, a trimellitic acid ester-based plasticizer, a pyromellitic acid ester-based plastic
- cross-linking agent contained in the acrylic pressure-sensitive adhesive examples include an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, a melamine-based cross-linking agent, a peroxide-based cross-linking agent, a urea-based cross-linking agent, and a metal alkoxide-based cross-linking agent.
- examples thereof include a metal chelate-based cross-linking agent, a metal salt-based cross-linking agent, a carbodiimide-based cross-linking agent, an oxazoline-based cross-linking agent, an aziridine-based cross-linking agent, and an amine-based cross-linking agent.
- the amount of the cross-linking agent compounded with respect to the carboxyl group of the acrylic polymer (prepolymer) is preferably 0.08 molar equivalent to 2 molar equivalent, and more preferably 0.1 molar equivalent to 1. It is a molar equivalent. Within such a range, an acrylic pressure-sensitive adhesive having a high crosslink density can be formed, and component transfer between the pressure-sensitive adhesive layer and the sealing resin is preferably prevented.
- the blending amount of the cross-linking agent here means the content of the cross-linking agent before the acrylic polymer is cross-linked.
- isocyanate-based cross-linking agent contained in the acrylic pressure-sensitive adhesive include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate.
- Aromatic isocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; Trimethylol propane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., Commodity) Name "Coronate L”), Trimethylol propane / hexamethylene diisocyanate trimeric adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HL”), isocyanurate form of hexamethylene diisocyanate (manufactured by Japan Polyurethane Industry Co., Ltd., product) Isocyanate adducts such as the name "Coronate HX”); and the like.
- Aromatic isocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane di
- the blending amount of the isocyanate-based cross-linking agent can be set to an arbitrary appropriate amount according to the desired adhesive strength, and is typically 0.1 part by weight to 20 parts by weight with respect to 100 parts by weight of the acrylic polymer. Parts, more preferably 1 part by weight to 10 parts by weight. Within such a range, a pressure-sensitive adhesive sheet having a small amount of residual carboxyl groups of the components in the pressure-sensitive adhesive layer can be obtained.
- the blending amount of the cross-linking agent here means the content of the cross-linking agent before the acrylic polymer is cross-linked.
- an epoxy-based cross-linking agent is preferably used as the cross-linking agent. If an epoxy-based cross-linking agent is used, a pressure-sensitive adhesive sheet capable of preferably reducing the step between the semiconductor chip and the sealing resin can be obtained. In addition, it is possible to form a pressure-sensitive adhesive layer having a high cohesive force, and it is possible to more effectively prevent the displacement of the adherend.
- Examples of the epoxy-based cross-linking agent contained in the acrylic-based pressure-sensitive adhesive include N, N, N', N'-tetraglycidyl-m-xylene diamine, diglycidyl aniline, and 1,3-bis (N, N-).
- the blending amount of the epoxy-based cross-linking agent can be set to an arbitrary appropriate amount according to the desired adhesive strength, and is typically 0.01 parts by weight to 50 parts by weight with respect to 100 parts by weight of the acrylic polymer. It is, more preferably 0.6 parts by weight to 15 parts by weight, still more preferably 2 parts by weight to 13 parts by weight, and particularly preferably 3 parts by weight to 10 parts by weight. Is. Within such a range, a pressure-sensitive adhesive sheet having a small amount of residual carboxyl groups of the components in the pressure-sensitive adhesive layer can be obtained.
- the blending amount of the cross-linking agent here means the content of the cross-linking agent before the acrylic polymer is cross-linked.
- a cross-linking agent containing N atoms is used as the epoxy-based cross-linking agent.
- the use of a cross-linking agent containing N atoms is advantageous in that the cross-linking reaction is promoted by catalytic action and the pressure-sensitive adhesive can be easily gelled.
- any appropriate pressure-sensitive adhesive is used.
- a tackifier resin is used.
- the tackifier resin include rosin-based tackifier resins (eg, unmodified rosin, modified rosin, rosinphenol-based resins, rosin ester-based resins, etc.) and terpene-based tackifier resins (eg, terpene-based resins, terpenes).
- a rosin-based tackifier resin a terpene-based tackifier resin, or a hydrocarbon-based tackifier resin (styrene-based resin, etc.) is preferable.
- the tackifier may be used alone or in combination of two or more.
- the amount of the tackifier added is preferably 5 parts by weight to 100 parts by weight, and more preferably 8 parts by weight to 50 parts by weight with respect to 100 parts by weight of the base polymer.
- a resin having a high softening point or a glass transition temperature (Tg) is used as the tackifier resin.
- Tg glass transition temperature
- a resin having a high softening point or glass transition temperature (Tg) By using a resin having a high softening point or glass transition temperature (Tg), a pressure-sensitive adhesive layer capable of exhibiting high adhesiveness is formed even in a high-temperature environment (for example, in a high-temperature environment such as processing at the time of encapsulating a semiconductor chip). can do.
- the softening point of the tackifier is preferably 100 ° C. to 180 ° C., more preferably 110 ° C. to 180 ° C., and even more preferably 120 ° C. to 180 ° C.
- the glass dislocation temperature (Tg) of the tackifier is preferably 100 ° C. to 180 ° C., more preferably 110 ° C. to 180 ° C., and even more preferably 120 ° C. to 180
- a low-polarity tackifier resin is used as the tackifier resin. If a low-polarity tackifier resin is used, a pressure-sensitive adhesive layer having a low affinity with the sealing material can be formed.
- the low-polarity tackifier resin include an aliphatic hydrocarbon resin, an aliphatic cyclic hydrocarbon resin, an aromatic hydrocarbon resin (for example, a styrene resin, a xylene resin, etc.), and an aliphatic / aromatic resin. Examples thereof include based petroleum resins, aliphatic / alicyclic petroleum resins, and hydrogenated hydrocarbon resins, which are hydrocarbon-based tackifier resins.
- a tackifier having 5 to 9 carbon atoms is preferable. This is because such a pressure-sensitive adhesive has low polarity, is excellent in compatibility with an acrylic polymer, does not undergo phase separation in a wide temperature range, and can form a pressure-sensitive adhesive layer having excellent stability. ..
- the acid value of the tackifier resin is preferably 40 or less, more preferably 20 or less, and further preferably 10 or less. Within such a range, a pressure-sensitive adhesive layer having a low affinity with the sealing material can be formed.
- the hydroxyl value of the tackifier resin is preferably 60 or less, more preferably 40 or less, and further preferably 20 or less. Within such a range, a pressure-sensitive adhesive layer having a low affinity with the sealing material can be formed.
- Base material examples include resin sheets, non-woven fabrics, papers, metal foils, woven fabrics, rubber sheets, foam sheets, and laminates thereof (particularly, laminates including resin sheets).
- the resin constituting the resin sheet include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, and ethylene-.
- Vinyl acetate copolymer (EVA), polyamide (nylon), total aromatic polyamide (aramid), polyimide (PI), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), fluororesin, polyether ether ketone (PEEK) ) Etc.
- EVA Vinyl acetate copolymer
- nylon polyamide
- aramid total aromatic polyamide
- PI polyimide
- PVC polyvinyl chloride
- PPS polyphenylene sulfide
- fluororesin polyether ether ketone
- Etc. Polyether ether ketone
- the non-woven fabric include non-woven fabrics made of natural fibers having heat resistance such as non-woven fabrics containing Manila hemp; synthetic resin non-woven fabrics such as polypropylene resin non-woven fabrics, polyethylene resin non-woven fabrics and ester resin non-woven fabrics.
- the metal foil include copper foil, stainless steel foil, aluminum foil and the like.
- paper include Japanese paper and kraft paper.
- a resin sheet composed of a resin having a glass transition temperature (Tg) of 25 ° C. or higher (preferably 40 ° C. or higher, more preferably 50 ° C. or higher) is preferably used as the base material. If such a resin sheet is also scattered, the shape of the base material is maintained even by heating during the sealing step, and the embedding of the semiconductor chip in the resin is prevented.
- Tg glass transition temperature
- the resin constituting such a resin sheet include polyethylene terephthalate, polyimide, polyethylene naphthalate and the like.
- the thickness of the base material can be set to an arbitrary appropriate thickness depending on the desired strength or flexibility, the purpose of use, and the like.
- the thickness of the substrate is preferably 1000 ⁇ m or less, more preferably 25 ⁇ m to 1000 ⁇ m, further preferably 40 ⁇ m to 500 ⁇ m, particularly preferably 60 ⁇ m to 300 ⁇ m, and most preferably 80 ⁇ m to 250 ⁇ m. In one embodiment, a substrate having a thickness of 25 ⁇ m or more is used. When such a base material is used, the shape of the base material is maintained even by pressurization during the sealing step, and embedding of the semiconductor chip in the pressure-sensitive adhesive layer is prevented.
- the thickness of the substrate is 20% to 90% (preferably 20% to 89%, more preferably 20% to 88%) with respect to the total thickness of the pressure-sensitive adhesive sheet. Within such a range, the semiconductor chip is prevented from being embedded in the pressure-sensitive adhesive layer.
- the base material may be surface-treated.
- the surface treatment include corona treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage impact exposure, ionizing radiation treatment, coating treatment with an undercoat agent, and the like.
- the organic coating material examples include the materials described in Plastic Hard Coat Material II (CMC Publishing, (2004)).
- Urethane-based polymers are preferably used, and polyacrylic urethane, polyester urethane or precursors thereof are more preferably used. This is because it is easy to apply and apply to the base material, and various types can be industrially selected and obtained at low cost.
- the urethane-based polymer is, for example, a polymer composed of a reaction mixture of an isocyanato monomer and an alcoholic hydroxyl group-containing monomer (for example, a hydroxyl group-containing acrylic compound or a hydroxyl group-containing ester compound).
- the organic coating material may contain a chain extender such as polyamine, an antiaging agent, an oxidation stabilizer and the like as arbitrary additives.
- the thickness of the organic coating layer is not particularly limited, but is preferably about 0.1 ⁇ m to 10 ⁇ m, preferably about 0.1 ⁇ m to 5 ⁇ m, and more preferably about 0.5 ⁇ m to 5 ⁇ m.
- the second adhesive layer can be an adhesive layer composed of any suitable adhesive.
- the second pressure-sensitive adhesive layer further comprises thermally expandable microspheres.
- the pressure-sensitive adhesive contained in the second pressure-sensitive adhesive layer may be a curable pressure-sensitive adhesive (for example, an active energy ray-curable pressure-sensitive adhesive) or a pressure-sensitive pressure-sensitive adhesive.
- a curable pressure-sensitive adhesive for example, an active energy ray-curable pressure-sensitive adhesive
- a pressure-sensitive pressure-sensitive adhesive examples include an acrylic pressure-sensitive adhesive and a rubber-based pressure-sensitive adhesive.
- JP-A-2018-909050 can be referred to. The entire description of the publication is incorporated herein by reference.
- any suitable heat-expandable microsphere can be used as long as it is a microsphere that can be expanded or foamed by heating.
- a microsphere in which a substance that easily expands by heating is contained in an elastic shell can be used.
- Such a heat-expandable microsphere can be produced by any suitable method, for example, a core selvation method, an interfacial polymerization method, or the like.
- Substances that easily expand by heating include, for example, propane, propylene, butene, normal butane, isobutane, isopentan, neopentane, normalpentane, normal hexane, isohexane, heptane, octane, petroleum ether, methane halides, and tetraalkylsilanes.
- Low boiling point liquids such as; azodicarboxylic amides gasified by thermal decomposition; and the like.
- nitrile monomers such as acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethoxyacrylonitrile, and fumaronitrile; acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.
- Carboxylic acid monomers such as citraconic acid; vinylidene chloride; vinyl acetate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, (Meta) acrylic acid esters such as isobornyl (meth) acrylates, cyclohexyl (meth) acrylates, benzyl (meth) acrylates and ⁇ -carboxyethyl acrylates; styrene monomers such as styrene, ⁇ -methylstyrene and chlorostyrene; acrylamides and substituted acrylamides.
- Acrylic acid esters such as isobornyl (meth) acrylates, cyclohexyl (meth) acrylates, benzyl (meth) acrylates and ⁇ -carboxye
- Acrylate monomers such as methacrylicamide and substituted methacrylicamide; and the like.
- the polymer composed of these monomers may be a homopolymer or a copolymer.
- the copolymer include vinylidene chloride-methyl methacrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile-methacrylonitrile copolymer, methyl methacrylate-acrylonitrile copolymer, and acrylonitrile-methacrylonitrile-itaconic acid. Examples include polymers.
- an inorganic foaming agent or an organic foaming agent may be used as the heat-expandable microspheres.
- the inorganic foaming agent include ammonium carbonate, ammonium hydrogencarbonate, sodium hydrogencarbonate, ammonium nitrite, sodium boron hydroxide, various azides and the like.
- the organic foaming agent include salt fluoride alkane-based compounds such as trichloromonofluoromethane and dichloromonofluoromethane; azo compounds such as azobisisobutyronitrile, azodicarboxylicamide, and barium azodicarboxylate.
- Hydrazide compounds such as paratoluenesulfonyl hydrazide, diphenylsulfone-3,3'-disulfonylhydrazide, 4,4'-oxybis (benzenesulfonylhydrazide), allylbis (sulfonylhydrazide); p-toluylenesulfonyl semicarbazide, 4, Semicarbazide compounds such as 4'-oxybis (benzenesulfonyl semicarbazide); triazole compounds such as 5-morpholyl-1,2,3,4-thiatriazole; N, N'-dinitrosopentamethylenetetramine, N, N' Examples thereof include N-nitroso compounds such as -dimethyl-N, N'-dinitrosoterephthalamide; and the like.
- the particle size of the heat-expandable microspheres before heating is preferably 0.5 ⁇ m to 80 ⁇ m, more preferably 5 ⁇ m to 45 ⁇ m, still more preferably 10 ⁇ m to 20 ⁇ m, and particularly preferably 10 ⁇ m to 15 ⁇ m. .. Therefore, the particle size of the heat-expandable microspheres before heating is preferably 6 ⁇ m to 45 ⁇ m, more preferably 15 ⁇ m to 35 ⁇ m in terms of average particle size.
- the above particle size and average particle size are values obtained by the particle size distribution measurement method in the laser scattering method.
- the heat-expandable microspheres preferably have an appropriate strength that does not burst until the coefficient of thermal expansion is preferably 5 times or more, more preferably 7 times or more, and even more preferably 10 times or more.
- the adhesive strength can be efficiently reduced by the heat treatment.
- the content ratio of the heat-expandable microspheres in the pressure-sensitive adhesive layer can be appropriately set according to the desired decrease in adhesive strength and the like.
- the content of the heat-expandable microspheres is, for example, 1 part by weight to 150 parts by weight, preferably 10 parts by weight to 130 parts by weight, based on 100 parts by weight of the base polymer forming the second pressure-sensitive adhesive layer. More preferably, it is 25 parts by weight to 100 parts by weight.
- the arithmetic surface roughness Ra of the pressure-sensitive adhesive layer before the heat-expandable microspheres expand is preferably 500 nm or less, more preferably. Is 400 nm or less, more preferably 300 nm or less. Within such a range, an adhesive sheet having excellent adhesion to the adherend can be obtained.
- the pressure-sensitive adhesive layer having excellent surface smoothness can be obtained by, for example, setting the thickness of the pressure-sensitive adhesive layer within the above range, or by applying the pressure-sensitive adhesive layer to a peeling liner and transferring the pressure-sensitive adhesive layer when another pressure-sensitive adhesive layer is provided. ,Obtainable.
- the other pressure-sensitive adhesive layer may contain heat-expandable microspheres. Even when another pressure-sensitive adhesive layer contains heat-expandable microspheres, the arithmetic surface roughness Ra of the pressure-sensitive adhesive layer is preferably in the above range.
- the pressure-sensitive adhesive layer contains thermally expandable microspheres
- the pressure-sensitive adhesive layer is composed of a base polymer having a dynamic storage elastic modulus in the range of 5 kPa to 1 MPa (more preferably 10 kPa to 0.8 MPa) at 80 ° C. It is preferable to include a pressure-sensitive adhesive. With such a pressure-sensitive adhesive layer, it is possible to form a pressure-sensitive adhesive sheet which has an appropriate adhesiveness before heating and whose adhesive strength tends to decrease by heating.
- the dynamic storage elastic modulus can be measured by using a dynamic viscoelasticity measuring device (for example, trade name "ARES” manufactured by Leometrics Co., Ltd.) under measurement conditions of a frequency of 1 Hz and a heating rate of 10 ° C./min. ..
- a dynamic viscoelasticity measuring device for example, trade name "ARES” manufactured by Leometrics Co., Ltd.
- the adhesive sheet of the present invention can be produced by any suitable method.
- the pressure-sensitive adhesive sheet of the present invention is formed, for example, by directly applying a composition containing an acrylic pressure-sensitive adhesive onto a substrate, or by applying a composition containing an acrylic-based pressure-sensitive adhesive onto any suitable substrate. Examples thereof include a method of transferring the applied coating layer to a base material.
- the composition containing the acrylic pressure-sensitive adhesive may contain any suitable solvent.
- a composition containing the heat-expandable microspheres, a pressure-sensitive adhesive, and an arbitrary suitable solvent is applied to a substrate to form the pressure-sensitive adhesive layer.
- the heat-expandable microspheres are embedded in the pressure-sensitive adhesive using a laminator or the like to form a pressure-sensitive adhesive layer containing the heat-expandable microspheres. It may be formed.
- each layer can be formed by drying after application.
- the coating method include a coating method using a multi-coater, a die coater, a gravure coater, an applicator, and the like.
- the drying method include natural drying and heat drying. The heating temperature for heat-drying can be set to any suitable temperature depending on the characteristics of the substance to be dried.
- T 2 relaxation time (T 2s ) of S component by pulse NMR of the pressure-sensitive adhesive layer Using the trade name "TD-NMR the minispec mq20" manufactured by Bruker, a T 2 relaxation curve measured by the solid echo method was obtained using a pressure-sensitive adhesive layer of 100 mg as a measurement sample, and the T 2 relaxation curve was obtained by the following formula (1). ), And the T 2 relaxation time (T 2s ) of the S component by pulse NMR of the pressure-sensitive adhesive layer. Asked.
- M (t) ⁇ ⁇ exp (-(1 / Wa) (t / T 2s ) Wa ) + ⁇ ⁇ exp (-(1 / Wa) (t / T 2L ) Wa ) ⁇ ⁇ ⁇ (1)
- ⁇ Proton ratio (%) of component (S component) with short relaxation time
- T 2s T 2 relaxation time (msec) of S component
- ⁇ Proton ratio (%) of the component (L component) with a long relaxation time
- T 2L T 2 relaxation time (msec) of L component
- t Observation time (msec)
- Adhesive strength (against PET) 2 kg of SUS304 plate via double-sided adhesive tape (manufactured by Nitto Denko, trade name "No. 531") on the entire surface of the adhesive sheet (width 20 mm x length 140 mm) opposite to the adhesive layer. It was attached using a hand roller.
- a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumirror S-10", thickness: 25 ⁇ m, width: 30 mm) was attached to the entire surface of the pressure-sensitive adhesive layer (temperature: 23 ° C., humidity: 65%). 2kg roller 1 round trip).
- the evaluation sample obtained as described above was subjected to a tensile test.
- the trade name "Shimadzu Autograph AG-120kN” manufactured by Shimadzu Corporation was used as the tensile tester. After setting the evaluation sample in the tensile tester, the sample was left at an environmental temperature of 23 ° C. for 30 minutes, and then the tensile test was started. The conditions for the tensile test were a peeling angle of 180 ° and a peeling speed (pulling speed): 300 mm / min. The load when the adhesive sheet was peeled off from the PET film was measured, and the maximum load at that time was taken as the adhesive force of the adhesive sheet.
- Adhesive strength (anti-sealing resin)
- a mold (mold size: 35 mm x 90 mm rectangle, thickness: 564 ⁇ m) is bonded onto the first pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (width 50 mm ⁇ length 140 mm), and a granular epoxy resin system is used in the mold.
- the sealing material G730 manufactured by Sumitomo Bakelite Co., Ltd.
- cover it with a silicone-treated release liner cover it with a silicone-treated release liner, and apply the "hydraulic molding machine NS-VPF" manufactured by Meijo Press Co., Ltd.
- the sealing resin was cured in an oven under a heating environment of 150 ° C. ⁇ 7 hours. After the curing of the sealing resin was completed, the sample was allowed to stand at 23 ° C. and 50% RH for 2 hours, and then the portion where the sealing resin and the first adhesive layer were in contact was cut into a width of 20 mm and a length of 88 mm. ..
- the evaluation sample obtained as described above was subjected to a tensile test.
- the trade name "Shimadzu Autograph AG-120kN” manufactured by Shimadzu Corporation was used as the tensile tester. After setting the evaluation sample in the tensile tester, the sample was left at an environmental temperature of 23 ° C. for 30 minutes, and then the tensile test was started. The conditions for the tensile test were a peeling angle of 180 ° and a peeling speed (pulling speed): 300 mm / min. The load when the adhesive sheet was peeled off from the sealing resin was measured, and the average load at that time was taken as the adhesive force of the adhesive sheet.
- Step between the semiconductor chip and the sealing resin The sealing step is carried out on the surface of the adhesive of the adhesive tape under the conditions described below, and the height of the step at the interface between the semiconductor chip (Si chip) and the sealing resin (6) Stand-off) was measured.
- Carrier SUS carrier 220mm ⁇ Chip: Si mirror chip 7 mm x 7 mm x 400 ⁇ m thickness Bonding device: FC3000W (manufactured by Toray Industries, Ltd.) Bonding conditions: Crimping time: 6 seconds Crimping pressure: 10N Crimping temperature: 23 ° C Sealing equipment: MS-150HP (manufactured by Apic Yamada) Encapsulating resin: G730 (manufactured by Sumitomo Bakelite) Preheat conditions: 130 ° C x 30 seconds Time from preheat to the start of sealing: 1 hour Sealing temperature: 145 ° C Vacuum time: 5 seconds Sealing time: 600 seconds Clamping force: 3.6 MPa Sealing thickness: 600 ⁇ m The sealing work was carried out according to the following procedure.
- the laminate was heated on a hot plate, and the adhesive attached to the SUS carrier was foamed and peeled off to form SUS.
- the carrier was separated.
- the adhesive tape was peeled off from the laminated body after separating the SUS carrier to obtain a sealing resin and a sealing body of Si chips.
- the step at the interface between the Si chip and the sealing resin on the surface that was in contact with the adhesive of the sealing resin and the sealing body of the Si chip was measured using a laser confocal microscope (OLS-4000 OLYMPUS). The height of the step at the interface between the sealing resin and the Si chip was measured.
- epoxy-based cross-linking agent Mitsubishi Gas Chemicals, Inc.
- the composition for forming the pressure-sensitive adhesive layer is applied to one side of a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumilar S10", thickness 38 ⁇ m) as a base material, and the base material and the first pressure-sensitive adhesive layer (manufactured by Toray Industries, Inc., thickness 38 ⁇ m) are coated.
- Acrylic copolymer C (2-ethylhexyl acrylate, ethyl acrylate, methyl methacrylate and 2-hydroxyethyl acrylate) on the surface of the pressure-sensitive adhesive sheet (1) opposite to the first pressure-sensitive adhesive layer of the polyethylene terephthalate film.
- the composition for forming the pressure-sensitive adhesive layer is applied to one side of a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumilar S10", thickness 38 ⁇ m) as a base material, and the base material and the first pressure-sensitive adhesive layer (manufactured by Toray Industries, Inc., thickness 38 ⁇ m) are coated.
- An adhesive sheet (2) composed of a thickness of 10 ⁇ m) was obtained.
- a second pressure-sensitive adhesive layer was formed on the surface of the pressure-sensitive adhesive sheet (2) opposite to the first pressure-sensitive adhesive layer of the polyethylene terephthalate film in the same manner as in Example 1 to obtain a double-sided pressure-sensitive adhesive sheet.
- epoxy-based cross-linking agent manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C
- tackifier manufactured by Yasuhara Chemical Co., Ltd., trade name
- the composition for forming the pressure-sensitive adhesive layer is applied to one side of a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumilar S10", thickness 38 ⁇ m) as a base material, and the base material and the first pressure-sensitive adhesive layer (manufactured by Toray Industries, Inc., thickness 38 ⁇ m) are coated.
- An adhesive sheet (3) composed of a thickness of 10 ⁇ m) was obtained.
- a second pressure-sensitive adhesive layer was formed on the surface of the pressure-sensitive adhesive sheet (3) opposite to the first pressure-sensitive adhesive layer of the polyethylene terephthalate film in the same manner as in Example 1 to obtain a double-sided pressure-sensitive adhesive sheet.
- Example 4 A double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 2 except that a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name “Lumilar S10”, thickness 100 ⁇ m) was used as a base material.
- a polyethylene terephthalate film manufactured by Toray Industries, Inc., trade name “Lumilar S10”, thickness 100 ⁇ m
- the composition for forming the pressure-sensitive adhesive layer is applied to one side of a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumilar S10", thickness 38 ⁇ m) as a base material, and the base material and the pressure-sensitive adhesive layer (thickness 10 ⁇ m) are coated.
- An adhesive sheet (4) composed of the above was obtained.
- a second pressure-sensitive adhesive layer was formed on the surface of the pressure-sensitive adhesive sheet (4) opposite to the first pressure-sensitive adhesive layer of the polyethylene terephthalate film in the same manner as in Example 1 to obtain a double-sided pressure-sensitive adhesive sheet.
- a composition for forming a pressure-sensitive adhesive layer was prepared by mixing 1.5 parts by weight of an agent (manufactured by Toso Co., Ltd., trade name "Coronate L”) and 100 parts by weight of toluene.
- the composition for forming the pressure-sensitive adhesive layer is applied to one side of a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumilar S10", thickness 38 ⁇ m) as a base material, and the base material and the pressure-sensitive adhesive layer (thickness 10 ⁇ m) are coated.
- An adhesive sheet (5) composed of the above was obtained.
- a second pressure-sensitive adhesive layer was formed on the surface of the pressure-sensitive adhesive sheet (5) opposite to the first pressure-sensitive adhesive layer of the polyethylene terephthalate film in the same manner as in Example 1 to obtain a double-sided pressure-sensitive adhesive sheet.
- Base material Adhesive layer 30 Second adhesive layer 100, 200 Adhesive sheet
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Abstract
Description
1つの実施形態においては、上記粘着剤層表面に、4-ターシャリーブチルフェニルグリシジルエーテルを滴下し、1分間静置した後の該粘着剤層の厚み変化率が、160%以下である。
1つの実施形態においては、上記粘着剤層表面に、4-ターシャリーブチルフェニルグリシジルエーテルを滴下し、1分間静置した後の該粘着剤層の厚み変化量が、20μm以下である。
1つの実施形態においては、上記粘着剤層が粘着剤を含み、該粘着剤が、sp値が18(cal/cm3)1/2~20(cal/cm3)1/2であるベースポリマーを含む。
1つの実施形態においては、上記アクリル系粘着剤が、ベースポリマーとして、アクリル系ポリマーの架橋体を含む。
1つの実施形態においては、上記アクリル系粘着剤が、エポキシ系架橋剤を含む。
1つの実施形態においては、上記エポキシ系架橋剤の配合量が、アクリル系ポリマー100重量部に対して、0.6重量部~15重量部である。
1つの実施形態においては、上記基材が、ガラス転移温度(Tg)が25℃以上の樹脂から構成される樹脂シートである。
1つの実施形態においては、上記基材の厚みが、粘着シートの総厚に対して、20%~90%、である。
1つの実施形態においては、上記粘着シートのTMAを用いた145℃環境下における沈み込み量が、1μm~35μmである。
1つの実施形態においては、上記粘着剤層を加熱処理した際の窒素ガスの発生量が、0.06重量%~1重量%である。
1つの実施形態においては、上記粘着シートは、上記基材と、該基材の片側に配置された上記粘着剤層と、該基材の該粘着剤層とは反対側に配置された第2の粘着剤層とを備える。
1つの実施形態においては、上記粘着シートは、半導体チップの樹脂封止工程で用いられる仮固定材である。
1つの実施形態においては、上記粘着シートは、上記粘着シート上で、封止樹脂を硬化する際に用いられる。 The pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet including a base material and a pressure-sensitive adhesive layer arranged on at least one side of the base material, wherein the pressure-sensitive adhesive layer contains an acrylic pressure-sensitive adhesive, and the pressure-sensitive adhesive sheet is used. The amount of subduction under the environment of 23 ° C. using TMA is 5 μm or less, and the T 2 relaxation time (T 2s ) of the S component by pulse NMR of the pressure-sensitive adhesive layer is 45 μsec or less.
In one embodiment, the rate of change in the thickness of the pressure-sensitive adhesive layer after dropping 4-tertiary butylphenylglycidyl ether onto the surface of the pressure-sensitive adhesive layer and allowing it to stand for 1 minute is 160% or less.
In one embodiment, the amount of change in the thickness of the pressure-sensitive adhesive layer after dropping 4-tertiary butylphenylglycidyl ether onto the surface of the pressure-sensitive adhesive layer and allowing it to stand for 1 minute is 20 μm or less.
In one embodiment, the pressure-sensitive adhesive layer comprises a pressure-sensitive adhesive, wherein the pressure-sensitive adhesive has a sp value of 18 (cal / cm 3 ) 1/2 to 20 (cal / cm 3 ) 1/2 . including.
In one embodiment, the acrylic pressure-sensitive adhesive comprises a crosslinked body of the acrylic polymer as a base polymer.
In one embodiment, the acrylic pressure-sensitive adhesive comprises an epoxy-based cross-linking agent.
In one embodiment, the blending amount of the epoxy-based cross-linking agent is 0.6 parts by weight to 15 parts by weight with respect to 100 parts by weight of the acrylic polymer.
In one embodiment, the substrate is a resin sheet composed of a resin having a glass transition temperature (Tg) of 25 ° C. or higher.
In one embodiment, the thickness of the substrate is 20% to 90% with respect to the total thickness of the pressure-sensitive adhesive sheet.
In one embodiment, the amount of subduction of the pressure-sensitive adhesive sheet in an environment of 145 ° C. using TMA is 1 μm to 35 μm.
In one embodiment, the amount of nitrogen gas generated when the pressure-sensitive adhesive layer is heat-treated is 0.06% by weight to 1% by weight.
In one embodiment, the pressure-sensitive adhesive sheet is a second base material, a pressure-sensitive adhesive layer arranged on one side of the base material, and a second surface of the base material opposite to the pressure-sensitive adhesive layer. Provided with a pressure-sensitive adhesive layer.
In one embodiment, the pressure-sensitive adhesive sheet is a temporary fixing material used in the resin sealing step of a semiconductor chip.
In one embodiment, the pressure-sensitive adhesive sheet is used to cure the sealing resin on the pressure-sensitive adhesive sheet.
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。粘着シート100は、基材10と、基材10の少なくとも片側に配置された粘着剤層(第1の粘着剤層)20とを備える。粘着剤層は、アクリル系粘着剤を含む。 A. Schematic FIG. 1 of the pressure-sensitive adhesive sheet is a schematic cross-sectional view of the pressure-sensitive adhesive sheet according to one embodiment of the present invention. The pressure-sensitive
上記粘着剤層は、ベースポリマーを含む粘着剤から構成される。上記のとおり、粘着剤層のパルスNMRによるS成分のT2緩和時間(T2s)が45μsec以下である。緩和時間とはパルスNMR測定において、測定対象となる原子を励起するのに適切なエネルギーを照射した後、励起された原子(群)が基底状態に戻るまでの時間を意味する。原子(群)をどのような励起状態にするかは、エネルギー照射の量や時間により制御することができる。また、励起された原子(群)が基底状態に戻るには、様々なエネルギー緩和機構があることが知られており、その緩和機構に応じて緩和時間が決まってくる(例えば、化学者のための最新NMR概説、化学同人 (1997))。発明者らは、下記条件でアクリル系粘着剤(実質的には、粘着剤に含まれるアクリル系ポリマー)の1H原子を励起してその後の緩和挙動を計測し、さらに、計測値を解析したところ、その中に、粘着剤層を構成する粘着剤に含まれるベースポリマー(代表的には、アクリル系ポリマー)の架橋の程度に関係する分子運動を知る情報として、T2緩和時間のS成分(T2s)が有用であることを見いだし、当該T2緩和時間のS成分(T2s)を特定することにより、上記の効果が得られることを見いだした。T2sが短いことは、ベースポリマーの架橋の程度に関係する分子運動が制限された状態であることを示し、すなわち、架橋が進んでポリマー全体としても運動の自由度が低下した状態であることを示す。このような状態のアクリル系粘着剤においては、ベースポリマー間の隙間が小さく、粘着剤層成分の封止樹脂への移行、および、封止樹脂に含まれる低分子量成分の粘着剤層への移行が抑制される。その結果、半導体チップを粘着シート上で樹脂封止した後、粘着シートを剥離した際に、半導体チップと封止樹脂との段差の発生が防止される。 B. Adhesive layer The adhesive layer is composed of an adhesive containing a base polymer. As described above, the T 2 relaxation time (T 2s ) of the S component by pulse NMR of the pressure-sensitive adhesive layer is 45 μsec or less. The relaxation time means the time until the excited atom (group) returns to the ground state after irradiating the atom with appropriate energy to excite the atom to be measured in the pulse NMR measurement. The excited state of an atom (group) can be controlled by the amount and time of energy irradiation. It is also known that there are various energy relaxation mechanisms for excited atoms (groups) to return to the ground state, and the relaxation time is determined according to the relaxation mechanism (for example, for chemists). Overview of the latest NMR of the above, Chemistry (1997)). The inventors excited the 1H atom of the acrylic pressure - sensitive adhesive (substantially, the acrylic-based polymer contained in the pressure-sensitive adhesive) under the following conditions, measured the subsequent relaxation behavior, and further analyzed the measured values. However, the S component of the T 2 relaxation time is used as information for knowing the molecular motion related to the degree of cross-linking of the base polymer (typically, an acrylic polymer) contained in the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer. It was found that (T 2s ) is useful, and that the above effect can be obtained by specifying the S component (T 2s ) of the T 2 relaxation time. A short T 2s indicates that the molecular motion related to the degree of cross-linking of the base polymer is restricted, that is, the cross-linking progresses and the degree of freedom of motion of the polymer as a whole is reduced. Is shown. In the acrylic pressure-sensitive adhesive in such a state, the gap between the base polymers is small, and the pressure-sensitive adhesive layer component is transferred to the sealing resin and the low molecular weight component contained in the sealing resin is transferred to the pressure-sensitive adhesive layer. Is suppressed. As a result, when the semiconductor chip is resin-sealed on the pressure-sensitive adhesive sheet and then the pressure-sensitive adhesive sheet is peeled off, the generation of a step between the semiconductor chip and the sealing resin is prevented.
M(t)=α・exp(-(1/Wa)(t/T2s)Wa)
+β・exp(-(1/Wa)(t/T2L)Wa) ・・・(1)
M(t):自由誘導減衰
α:緩和時間が短い成分(S成分)のプロトン比率(%)
T2s:S成分のT2緩和時間(msec)
β:緩和時間が長い成分(L成分)のプロトン比率(%)
T2L:L成分のT2緩和時間(msec)
t:観測時間(msec)
Wa:形状係数(=1)
上記測定における測定条件は、以下のとおりである。
・90°パルス幅:2.1μsec
・繰り返し時間 :1sec
・積算回数 :32回
・測定温度 :30℃ For the T 2 relaxation time (T 2s ) of the S component by pulse NMR, a T 2 relaxation curve measured by the solid echo method was obtained using 100 mg of the pressure-sensitive adhesive layer as a measurement sample, and the T 2 relaxation curve was calculated by the following equation (1). You can find it by fitting it to.
M (t) = α · exp (-(1 / Wa) (t / T 2s ) Wa )
+ Β ・ exp (-(1 / Wa) (t / T 2L ) Wa ) ・ ・ ・ (1)
M (t): Free induction decay α: Proton ratio (%) of component (S component) with short relaxation time
T 2s : T 2 relaxation time (msec) of S component
β: Proton ratio (%) of the component (L component) with a long relaxation time
T 2L : T 2 relaxation time (msec) of L component
t: Observation time (msec)
Wa: Shape coefficient (= 1)
The measurement conditions in the above measurement are as follows.
90 ° pulse width: 2.1 μsec
・ Repeat time: 1 sec
・ Number of integrations: 32 times ・ Measurement temperature: 30 ° C
・キャリアーガス:O2(300mL/min)、Ar(300mL/min)
・標準試料:ピリジン/トルエン溶液
・検出器:減圧化学発光検出器
・レンジ:高濃度 The amount of nitrogen gas generated when the pressure-sensitive adhesive layer is heat-treated is preferably 0.06% by weight to 1.0% by weight, and more preferably 0.06% by weight to 0.9% by weight. When the amount of nitrogen gas generated when the pressure-sensitive adhesive layer is heat-treated is within such a range, the acrylic pressure-sensitive adhesive exhibits sufficient cohesive power, and the low-molecular-weight component of the sealing resin is applied to the pressure-sensitive adhesive layer. By suppressing the migration, a mixed layer of the pressure-sensitive adhesive layer component and the sealing resin component is not formed, and a step is less likely to occur at the interface between the semiconductor chip and the sealing resin. For the amount of nitrogen gas when the pressure-sensitive adhesive layer was heat-treated, 2 mg of the pressure-sensitive adhesive layer was collected, placed in a ceramic board, and weighed with a microbalance. The amount of nitrogen gas generated is determined using a TN (trace total nitrogen analysis) device. The conditions for measurement can be as follows.
-Carrier gas: O 2 (300 mL / min), Ar (300 mL / min)
・ Standard sample: Pyridine / toluene solution ・ Detector: Vacuum chemiluminescence detector ・ Range: High concentration
上記アクリル系粘着剤としては、例えば、(メタ)アクリル酸アルキルエステルの1種または2種以上を単量体成分として用いたアクリル系ポリマー(ホモポリマーまたはコポリマー)をプレポリマーとし、該プレポリマーの架橋体をベースポリマーとするアクリル系粘着剤等が挙げられる。なお、本明細書において、粘着剤層中のアクリル系粘着剤に含まれる「ベースポリマー」とは、プレポリマー(未架橋ポリマー)を架橋させて形成されたポリマーを意味する。1つの実施形態においては、上記ベースポリマーは、アクリル系ポリマーとエポキシ架橋剤による架橋体構造を有する。 (Acrylic adhesive)
As the acrylic pressure-sensitive adhesive, for example, an acrylic polymer (homopolymer or copolymer) using one or more (meth) acrylic acid alkyl esters as a monomer component is used as a prepolymer, and the prepolymer is used. Examples thereof include acrylic pressure-sensitive adhesives using a crosslinked polymer as a base polymer. In the present specification, the "base polymer" contained in the acrylic pressure-sensitive adhesive in the pressure-sensitive adhesive layer means a polymer formed by cross-linking a prepolymer (uncrosslinked polymer). In one embodiment, the base polymer has a crosslinked structure of an acrylic polymer and an epoxy crosslinker.
上記基材としては、例えば、樹脂シート、不織布、紙、金属箔、織布、ゴムシート、発泡シート、これらの積層体(特に、樹脂シートを含む積層体)等が挙げられる。樹脂シートを構成する樹脂としては、例えば、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリブチレンテレフタレート(PBT)、ポリエチレン(PE)、ポリプロピレン(PP)、エチレン-プロピレン共重合体、エチレン-酢酸ビニル共重合体(EVA)、ポリアミド(ナイロン)、全芳香族ポリアミド(アラミド)、ポリイミド(PI)、ポリ塩化ビニル(PVC)、ポリフェニレンサルファイド(PPS)、フッ素系樹脂、ポリエーテルエーテルケトン(PEEK)等が挙げられる。不織布としては、マニラ麻を含む不織布等の耐熱性を有する天然繊維による不織布;ポリプロピレン樹脂不織布、ポリエチレン樹脂不織布、エステル系樹脂不織布等の合成樹脂不織布等が挙げられる。金属箔としては、銅箔、ステンレス箔、アルミニウム箔等が挙げられる。紙としては、和紙、クラフト紙等が挙げられる。 C. Base material Examples of the base material include resin sheets, non-woven fabrics, papers, metal foils, woven fabrics, rubber sheets, foam sheets, and laminates thereof (particularly, laminates including resin sheets). Examples of the resin constituting the resin sheet include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, and ethylene-. Vinyl acetate copolymer (EVA), polyamide (nylon), total aromatic polyamide (aramid), polyimide (PI), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), fluororesin, polyether ether ketone (PEEK) ) Etc. can be mentioned. Examples of the non-woven fabric include non-woven fabrics made of natural fibers having heat resistance such as non-woven fabrics containing Manila hemp; synthetic resin non-woven fabrics such as polypropylene resin non-woven fabrics, polyethylene resin non-woven fabrics and ester resin non-woven fabrics. Examples of the metal foil include copper foil, stainless steel foil, aluminum foil and the like. Examples of paper include Japanese paper and kraft paper.
上記第2の粘着剤層は、任意の適切な粘着剤から構成される粘着剤層であり得る。1つの実施形態においては、上記のとおり、第2の粘着剤層は、熱膨張性微小球をさらに含む。 D. Second Adhesive Layer The second adhesive layer can be an adhesive layer composed of any suitable adhesive. In one embodiment, as described above, the second pressure-sensitive adhesive layer further comprises thermally expandable microspheres.
本発明の粘着シートは、任意の適切な方法により製造することができる。本発明の粘着シートは、例えば、基材上に直接、アクリル系粘着剤を含む組成物を塗工する方法、または任意の適切な基体上にアクリル系粘着剤を含む組成物を塗工し形成された塗工層を基材に転写する方法等が挙げられる。アクリル系粘着剤を含む組成物は、任意の適切な溶媒を含み得る。 E. Method for Producing Adhesive Sheet The adhesive sheet of the present invention can be produced by any suitable method. The pressure-sensitive adhesive sheet of the present invention is formed, for example, by directly applying a composition containing an acrylic pressure-sensitive adhesive onto a substrate, or by applying a composition containing an acrylic-based pressure-sensitive adhesive onto any suitable substrate. Examples thereof include a method of transferring the applied coating layer to a base material. The composition containing the acrylic pressure-sensitive adhesive may contain any suitable solvent.
Bruker社製の商品名「TD-NMR the minispec mq20」を用い、粘着剤層100mgを測定サンプルとして、ソリッドエコー法により測定されたT2緩和曲線を得、当該T2緩和曲線を下記式(1)にフィッテイングして、粘着剤層のパルスNMRによるS成分のT2緩和時間(T2s)
を求めた。
M(t)=α・exp(-(1/Wa)(t/T2s)Wa)
+β・exp(-(1/Wa)(t/T2L)Wa) ・・・(1)
M(t):自由誘導減衰
α:緩和時間が短い成分(S成分)のプロトン比率(%)
T2s:S成分のT2緩和時間(msec)
β:緩和時間が長い成分(L成分)のプロトン比率(%)
T2L:L成分のT2緩和時間(msec)
t:観測時間(msec)
Wa:形状係数(=1)
上記測定における測定条件は、以下のとおりとした。
・90°パルス幅:2.1μsec
・繰り返し時間 :1sec
・積算回数 :32回
・測定温度 :30℃
(2)TMAを用いた23℃環境下における沈み込み量
TMA Q400(TA-instrument社製)を用いて、プローブ:針入 窒素ガス流量:50.0ml/min 押し込み荷重:0.01N 測定雰囲気温度:23.0℃ 押し込み負荷時間:60minの条件で、第1の粘着剤層の沈み込み量を計測した。測定はN=5で実施し、これら測定値の中の最大値と最小値を除くN=3の平均値をサンプルの沈み込み量とした。
(3)4-ターシャリーブチルフェニルグリシジルエーテル滴下による厚み変化
粘着剤層の表面に4-ターシャリーブチルフェニルグリシジルエーテルを所定量(22mm径のシリンジを用いて、0.02g)滴下し、23℃50%RHの環境下で1分間放置し、4-ターシャリーブチルフェニルグリシジルエーテルを拭き取った後の、当該滴下箇所の厚み(Dt)と、上記滴下操作前の当該箇所の厚み(It)とから、厚み変化率((Dt-It)/It)および厚み変化量(Dt-It)を求めた。
(4)粘着力(対PET)
粘着シート(幅20mm×長さ140mm)の粘着剤層とは反対側の面の全面に、両面接着テープ(日東電工社製、商品名「No.531」)を介して、SUS304板を、2kgハンドローラーを用いて貼着した。
次いで、粘着剤層の表面全面に、ポリエチレンテレフタレートフィルム(東レ社製、商品名「ルミラーS-10」、厚さ:25μm、幅:30mm)を貼着した(温度:23℃、湿度:65%、2kgローラー1往復)。
上記のようにして得られた評価用試料を、引っ張り試験に供した。引っ張り試験機としては、島津製作社製の商品名「島津オートグラフAG-120kN」を用いた。引っ張り試験機に評価用試料をセットした後、23℃の環境温度下で30分間放置した後に、引っ張り試験を開始した。引っ張り試験の条件は、剥離角度:180°、剥離速度(引っ張り速度):300mm/minとした。上記PETフィルムから粘着シートを剥離した時の荷重を測定し、その際の最大荷重を粘着シートの粘着力とした。
(5)粘着力(対封止樹脂)
粘着シート(幅50mm×長さ140mm)の第1の粘着剤層上に、型枠(型サイズ:35mm×90mmの長方形、厚み:564μm)を貼り合せ、型枠内に顆粒状のエポキシ樹脂系封止材(住友ベークライト社製、G730)を、硬化後の樹脂厚みが0.3mmとなるようにまぶした後に、シリコーン処理剥離ライナーを被せ、名庄プレス社製の「油圧成形機NS-VPF-50」を用いて、温度145℃、成形時間600秒、加圧条件0.3MPa(300mm□のステージサイズ)、真空時間600秒、真空度-0.1MPaの条件で、封止樹脂を粘着層上で加熱成形した。
その後、封止樹脂を150℃×7時間の加熱環境下のオーブン内でキュアさせた。封止樹脂のキュア完了後、サンプルを23℃50%RH下で2時間静置した後、封止樹脂と第1の粘着剤層が接触している部分を幅20mm×長さ88mmにカットした。
上記のようにして得られた評価用試料を、引っ張り試験に供した。引っ張り試験機としては、島津製作社製の商品名「島津オートグラフAG-120kN」を用いた。引っ張り試験機に評価用試料をセットした後、23℃の環境温度下で30分間放置した後に、引っ張り試験を開始した。引っ張り試験の条件は、剥離角度:180°、剥離速度(引っ張り速度):300mm/minとした。上記封止樹脂から粘着シートを剥離した時の荷重を測定し、その際の平均荷重を粘着シートの粘着力とした。
(6)半導体チップと封止樹脂との段差
下記に記載する条件で粘着テープの該粘着剤表面上で封止工程を実施し、半導体チップ(Siチップ)と封止樹脂界面の段差高さ(スタンドオフ)を計測した。
キャリア:SUS製キャリア 220mmΦ
チップ:Siミラーチップ 7mm×7mm×400μm厚み
ボンディング装置:FC3000W(東レエンジニアリング社製)
ボンディング条件:下記の通り
圧着時間:6秒
圧着圧力:10N
圧着温度:23℃
封止設備:MS-150HP(アピックヤマダ製)
封止樹脂:G730(住友ベークライト製)
プレヒート条件:130℃×30秒
プレヒート~封止開始までの時間:1時間
封止温度:145℃
バキューム時間:5秒
封止時間:600秒
クランピングフォース:3.6MPa
封止厚み:600μm
封止作業は、以下の手順で実施した。
1)SUSキャリアに粘着シートを貼付した。
貼付条件:23℃雰囲気下
貼付シリンダー圧力:0.1MPa
貼付速度:0.5m/min
SUS貼付面は、第2の粘着剤層外面とした。
粘着シートが片面テープ(第2の粘着剤層を備えない)場合は、PETフィルム厚み38μmのシリコーン剥離ライナー(MRF38 三菱化学製)とPETフィルム厚み75μmのシリコーン剥離ライナー(PET-75-SCA0 フジコー製)を用いて作製した基材レスの熱膨張微小球を含有する粘着剤層48μmでSUSキャリアと片面テープを固定して評価を実施した。
2)SUSキャリアに貼付した粘着シートの該粘着剤層上に、Siミラーチップをボンディング装置を使用してチップを1個配置した。
3)Siミラーチップを貼り付けた状態のSUSキャリアを所定の時間でプレヒートを実施した。
4)プレヒート後23℃50%RH環境下で1時間静置したのち、所定の封止設備、樹脂、条件にて封止を実施した。封止樹脂は、手でSUSキャリア上に満遍なく散布して、封止作業を実施した。
5)封止作業で得られた積層体をオーブンを用いて150℃×4時間加熱硬化を行った。
6)加熱硬化を行った積層体を23℃50%RH環境下で5日間放置した後、この積層体をホットプレート上で加熱し、SUSキャリアと貼付している粘着剤を発泡剥離させ、SUSキャリアを分離した。
7)SUSキャリアを分離した後の積層体から、粘着テープを剥離し封止樹脂とSiチップの封止体を得た。
8)この封止樹脂とSiチップの封止体の粘着剤と接していた表面のSiチップと封止樹脂の界面の段差をレーザー共焦点顕微鏡(OLS-4000 OLYMPUS製)を用いて計測し、封止樹脂とSiチップの界面の段差高さを測定した。 (1) T 2 relaxation time (T 2s ) of S component by pulse NMR of the pressure-sensitive adhesive layer
Using the trade name "TD-NMR the minispec mq20" manufactured by Bruker, a T 2 relaxation curve measured by the solid echo method was obtained using a pressure-sensitive adhesive layer of 100 mg as a measurement sample, and the T 2 relaxation curve was obtained by the following formula (1). ), And the T 2 relaxation time (T 2s ) of the S component by pulse NMR of the pressure-sensitive adhesive layer.
Asked.
M (t) = α · exp (-(1 / Wa) (t / T 2s ) Wa )
+ Β ・ exp (-(1 / Wa) (t / T 2L ) Wa ) ・ ・ ・ (1)
M (t): Free induction decay α: Proton ratio (%) of component (S component) with short relaxation time
T 2s : T 2 relaxation time (msec) of S component
β: Proton ratio (%) of the component (L component) with a long relaxation time
T 2L : T 2 relaxation time (msec) of L component
t: Observation time (msec)
Wa: Shape coefficient (= 1)
The measurement conditions in the above measurement were as follows.
90 ° pulse width: 2.1 μsec
・ Repeat time: 1 sec
・ Number of integrations: 32 times ・ Measurement temperature: 30 ° C
(2) Subduction amount in a 23 ° C environment using TMA Using TMA Q400 (manufactured by TA-instrument), probe: needle-inserted nitrogen gas flow rate: 50.0 ml / min Push-in load: 0.01N Measurement atmosphere temperature The sinking amount of the first pressure-sensitive adhesive layer was measured under the condition of: 23.0 ° C. pushing load time: 60 min. The measurement was carried out at N = 5, and the average value of N = 3 excluding the maximum and minimum values among these measured values was taken as the subduction amount of the sample.
(3) Change in thickness due to dropping 4-tertiary butyl phenyl glycidyl ether A predetermined amount (0.02 g using a 22 mm diameter syringe) of 4-tertiary butyl phenyl glycidyl ether was dropped on the surface of the pressure-sensitive adhesive layer, and the temperature was 23 ° C. From the thickness (Dt) of the dropping point after leaving for 1 minute in an environment of 50% RH and wiping off the 4-tertiary butylphenylglycidyl ether, and the thickness (It) of the dropping point before the dropping operation. , Thickness change rate ((Dt-It) / It) and thickness change amount (Dt-It) were determined.
(4) Adhesive strength (against PET)
2 kg of SUS304 plate via double-sided adhesive tape (manufactured by Nitto Denko, trade name "No. 531") on the entire surface of the adhesive sheet (
Next, a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumirror S-10", thickness: 25 μm, width: 30 mm) was attached to the entire surface of the pressure-sensitive adhesive layer (temperature: 23 ° C., humidity: 65%). 2kg roller 1 round trip).
The evaluation sample obtained as described above was subjected to a tensile test. As the tensile tester, the trade name "Shimadzu Autograph AG-120kN" manufactured by Shimadzu Corporation was used. After setting the evaluation sample in the tensile tester, the sample was left at an environmental temperature of 23 ° C. for 30 minutes, and then the tensile test was started. The conditions for the tensile test were a peeling angle of 180 ° and a peeling speed (pulling speed): 300 mm / min. The load when the adhesive sheet was peeled off from the PET film was measured, and the maximum load at that time was taken as the adhesive force of the adhesive sheet.
(5) Adhesive strength (anti-sealing resin)
A mold (mold size: 35 mm x 90 mm rectangle, thickness: 564 μm) is bonded onto the first pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (width 50 mm × length 140 mm), and a granular epoxy resin system is used in the mold. After sprinkling the sealing material (G730 manufactured by Sumitomo Bakelite Co., Ltd.) so that the resin thickness after curing becomes 0.3 mm, cover it with a silicone-treated release liner, and apply the "hydraulic molding machine NS-VPF" manufactured by Meijo Press Co., Ltd. -50 "is used to adhere the sealing resin under the conditions of temperature 145 ° C., molding time 600 seconds, pressurization condition 0.3 MPa (stage size of 300 mm □), vacuum time 600 seconds, and vacuum degree -0.1 MPa. Heat molded on the layer.
Then, the sealing resin was cured in an oven under a heating environment of 150 ° C. × 7 hours. After the curing of the sealing resin was completed, the sample was allowed to stand at 23 ° C. and 50% RH for 2 hours, and then the portion where the sealing resin and the first adhesive layer were in contact was cut into a width of 20 mm and a length of 88 mm. ..
The evaluation sample obtained as described above was subjected to a tensile test. As the tensile tester, the trade name "Shimadzu Autograph AG-120kN" manufactured by Shimadzu Corporation was used. After setting the evaluation sample in the tensile tester, the sample was left at an environmental temperature of 23 ° C. for 30 minutes, and then the tensile test was started. The conditions for the tensile test were a peeling angle of 180 ° and a peeling speed (pulling speed): 300 mm / min. The load when the adhesive sheet was peeled off from the sealing resin was measured, and the average load at that time was taken as the adhesive force of the adhesive sheet.
(6) Step between the semiconductor chip and the sealing resin The sealing step is carried out on the surface of the adhesive of the adhesive tape under the conditions described below, and the height of the step at the interface between the semiconductor chip (Si chip) and the sealing resin (6) Stand-off) was measured.
Carrier: SUS carrier 220mmΦ
Chip: Si mirror chip 7 mm x 7 mm x 400 μm thickness Bonding device: FC3000W (manufactured by Toray Industries, Ltd.)
Bonding conditions: Crimping time: 6 seconds Crimping pressure: 10N
Crimping temperature: 23 ° C
Sealing equipment: MS-150HP (manufactured by Apic Yamada)
Encapsulating resin: G730 (manufactured by Sumitomo Bakelite)
Preheat conditions: 130 ° C x 30 seconds Time from preheat to the start of sealing: 1 hour Sealing temperature: 145 ° C
Vacuum time: 5 seconds Sealing time: 600 seconds Clamping force: 3.6 MPa
Sealing thickness: 600 μm
The sealing work was carried out according to the following procedure.
1) An adhesive sheet was attached to the SUS carrier.
Pasting conditions: Under an atmosphere of 23 ° C
Sticking cylinder pressure: 0.1MPa
Sticking speed: 0.5m / min
The SUS affixed surface was the outer surface of the second pressure-sensitive adhesive layer.
If the adhesive sheet is a single-sided tape (without a second adhesive layer), a silicone release liner with a PET film thickness of 38 μm (MRF38 Mitsubishi Chemical) and a silicone release liner with a PET film thickness of 75 μm (PET-75-SCA0 made by Fujiko). ) Was used to fix the SUS carrier and the single-sided tape with the pressure-sensitive adhesive layer 48 μm containing the heat-expanding microspheres without the base material, and the evaluation was carried out.
2) One Si mirror chip was placed on the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet attached to the SUS carrier using a bonding device.
3) The SUS carrier with the Si mirror chip attached was preheated for a predetermined time.
4) After preheating, the mixture was allowed to stand for 1 hour in a 23 ° C. and 50% RH environment, and then sealed under the specified sealing equipment, resin, and conditions. The sealing resin was sprayed evenly on the SUS carrier by hand to carry out the sealing operation.
5) The laminate obtained by the sealing operation was heat-cured at 150 ° C. for 4 hours using an oven.
6) After the heat-cured laminate was left to stand in a 23 ° C. and 50% RH environment for 5 days, the laminate was heated on a hot plate, and the adhesive attached to the SUS carrier was foamed and peeled off to form SUS. The carrier was separated.
7) The adhesive tape was peeled off from the laminated body after separating the SUS carrier to obtain a sealing resin and a sealing body of Si chips.
8) The step at the interface between the Si chip and the sealing resin on the surface that was in contact with the adhesive of the sealing resin and the sealing body of the Si chip was measured using a laser confocal microscope (OLS-4000 OLYMPUS). The height of the step at the interface between the sealing resin and the Si chip was measured.
アクリル系コポリマーA(アクリル酸2エチルヘキシルとアクリル酸とのコポリマー、アクリル酸2エチルヘキシル構成単位:アクリル酸構成単位=95:5(重量比))100重量部と、エポキシ系架橋剤(三菱ガス化学社製、商品名「テトラッドC」)5重量部と、トルエン100重量部とを混合し、粘着剤層形成用組成物を調製した。
該粘着剤層形成用組成物を、基材としてのポリエチレンテレフタレートフィルム(東レ社製、商品名「ルミラーS10」、厚み38μm)の片面に塗工して、基材と第1の粘着剤層(厚み10μm)とから構成される粘着シート(1)を得た。
この粘着シート(1)のポリエチレンテレフタレートフィルムの第1の粘着剤層とは反対側の面にアクリル系コポリマーC(アクリル酸2エチルヘキシルとアクリル酸エチルとメタクリル酸メチルとアクリル酸2ヒドロキシエチルとのコポリマー、アクリル酸2エチルヘキシル構成単位:アクリル酸エチル構成単位:メタクリル酸メチル構成単位:アクリル酸構成単位=30:70:5:4(重量比))100重量部と、熱膨張性微小球(松本油脂製薬社製、商品名「マツモトマイクロスフェア― F-190D」)30重量部、イソシアネート系架橋剤(東ソー社製、商品名「コロネートL」)1.4重量部と、粘着付与剤(ヤスハラケミカル社製、商品名「マイティーエースG125」)10重量部と、トルエン100重量部とを混合し調整した粘着剤層形成用組成物を塗布し、第2の粘着剤層(厚み45μm)を形成し両面粘着シートを得た。 [Example 1]
Acrylic copolymer A (copolymer of 2 ethylhexyl acrylate and acrylic acid, 2 ethylhexyl acrylate constituent unit: acrylic acid constituent unit = 95: 5 (weight ratio)) 100 parts by weight and epoxy-based cross-linking agent (Mitsubishi Gas Chemicals, Inc.) , Trade name "Tetrad C") 5 parts by weight and 100 parts by weight of toluene were mixed to prepare a composition for forming an adhesive layer.
The composition for forming the pressure-sensitive adhesive layer is applied to one side of a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumilar S10", thickness 38 μm) as a base material, and the base material and the first pressure-sensitive adhesive layer (manufactured by Toray Industries, Inc., thickness 38 μm) are coated. An adhesive sheet (1) composed of a thickness of 10 μm) was obtained.
Acrylic copolymer C (2-ethylhexyl acrylate, ethyl acrylate, methyl methacrylate and 2-hydroxyethyl acrylate) on the surface of the pressure-sensitive adhesive sheet (1) opposite to the first pressure-sensitive adhesive layer of the polyethylene terephthalate film. , 2 ethylhexyl acrylate constituent unit: ethyl acrylate constituent unit: methyl methacrylate constituent unit: acrylic acid constituent unit = 30: 70: 5: 4 (weight ratio)) 100 parts by weight and heat-expandable microspheres (Matsumoto oil and fat) 30 parts by weight of Pharmaceutical Co., Ltd., trade name "Matsumoto Microsphere-F-190D"), 1.4 parts by weight of isocyanate-based cross-linking agent (manufactured by Toso Co., Ltd., trade name "Coronate L"), and adhesive (Yasuhara Chemical Co., Ltd.) , Trade name "Mighty Ace G125") 10 parts by weight and 100 parts by weight of toluene are mixed and adjusted to apply a pressure-sensitive adhesive layer forming composition to form a second pressure-sensitive adhesive layer (thickness 45 μm). I got a sheet.
アクリル系コポリマーA(アクリル酸2エチルヘキシルとアクリル酸とのコポリマー、アクリル酸2エチルヘキシル構成単位:アクリル酸構成単位=95:5(重量比))100重量部と、エポキシ系架橋剤(三菱ガス化学社製、商品名「テトラッドC」)5重量部と、粘着付与剤(ヤスハラケミカル社製、商品名「マイティーエースG125」)10重量部と、トルエン100重量部とを混合し、粘着剤層形成用組成物を調製した。
該粘着剤層形成用組成物を、基材としてのポリエチレンテレフタレートフィルム(東レ社製、商品名「ルミラーS10」、厚み38μm)の片面に塗工して、基材と第1の粘着剤層(厚み10μm)とから構成される粘着シート(2)を得た。
この粘着シート(2)のポリエチレンテレフタレートフィルムの第1の粘着剤層とは反対側の面に、実施例1と同様にして第2の粘着剤層を形成し、両面粘着シートを得た。 [Example 2]
Acrylic copolymer A (copolymer of 2 ethylhexyl acrylate and acrylic acid, 2 ethylhexyl acrylate constituent unit: acrylic acid constituent unit = 95: 5 (weight ratio)) 100 parts by weight and epoxy-based cross-linking agent (Mitsubishi Gas Chemicals, Inc.) 5 parts by weight of a pressure-sensitive adhesive (manufactured by Yasuhara Chemical Co., Ltd., trade name "Mighty Ace G125") and 100 parts by weight of toluene are mixed to form a pressure-sensitive adhesive layer. The thing was prepared.
The composition for forming the pressure-sensitive adhesive layer is applied to one side of a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumilar S10", thickness 38 μm) as a base material, and the base material and the first pressure-sensitive adhesive layer (manufactured by Toray Industries, Inc., thickness 38 μm) are coated. An adhesive sheet (2) composed of a thickness of 10 μm) was obtained.
A second pressure-sensitive adhesive layer was formed on the surface of the pressure-sensitive adhesive sheet (2) opposite to the first pressure-sensitive adhesive layer of the polyethylene terephthalate film in the same manner as in Example 1 to obtain a double-sided pressure-sensitive adhesive sheet.
アクリル系コポリマーB(アクリル酸エチルとアクリル酸ブチルとアクリル酸とアクリル酸2ヒドロキシエチルのコポリマー、アクリル酸エチル構成単位:アクリル酸ブチル構成単位:アクリル酸:アクリル酸ヒドロキシエチル構成単位構成単位=50:50:5:0.1(重量比))100重量部と、エポキシ系架橋剤(三菱ガス化学社製、商品名「テトラッドC」)5重量部と、粘着付与剤(ヤスハラケミカル社製、商品名「マイティーエースG125」)10重量部と、トルエン100重量部とを混合し、粘着剤層形成用組成物を調製した。
該粘着剤層形成用組成物を、基材としてのポリエチレンテレフタレートフィルム(東レ社製、商品名「ルミラーS10」、厚み38μm)の片面に塗工して、基材と第1の粘着剤層(厚み10μm)とから構成される粘着シート(3)を得た。
この粘着シート(3)のポリエチレンテレフタレートフィルムの第1の粘着剤層とは反対側の面に、実施例1と同様にして第2の粘着剤層を形成し、両面粘着シートを得た。 [Example 3]
Acrylic Copolymer B (Acrylic acid, butyl acrylate, acrylic acid, and dihydroxyethyl acrylate copolymer, ethyl acrylate constituent unit: butyl acrylate constituent unit: acrylate: hydroxyethyl acrylate constituent unit constituent unit = 50: 50: 5: 0.1 (weight ratio)) 100 parts by weight, epoxy-based cross-linking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Tetrad C") 5 parts by weight, and tackifier (manufactured by Yasuhara Chemical Co., Ltd., trade name) "Mighty Ace G125") 10 parts by weight and 100 parts by weight of toluene were mixed to prepare a composition for forming a pressure-sensitive adhesive layer.
The composition for forming the pressure-sensitive adhesive layer is applied to one side of a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumilar S10", thickness 38 μm) as a base material, and the base material and the first pressure-sensitive adhesive layer (manufactured by Toray Industries, Inc., thickness 38 μm) are coated. An adhesive sheet (3) composed of a thickness of 10 μm) was obtained.
A second pressure-sensitive adhesive layer was formed on the surface of the pressure-sensitive adhesive sheet (3) opposite to the first pressure-sensitive adhesive layer of the polyethylene terephthalate film in the same manner as in Example 1 to obtain a double-sided pressure-sensitive adhesive sheet.
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、商品名「ルミラーS10」、厚み100μm)を用いたこと以外は実施例2と同様にして、両面粘着シートを得た。 [Example 4]
A double-sided pressure-sensitive adhesive sheet was obtained in the same manner as in Example 2 except that a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name “Lumilar S10”,
アクリル系コポリマーC(アクリル酸2エチルヘキシルとアクリル酸エチルとメタクリル酸メチルとアクリル酸2ヒドロキシエチルとのコポリマー、アクリル酸2エチルヘキシル構成単位:アクリル酸エチル構成単位:メタクリル酸メチル構成単位:アクリル酸2ヒドロキシエチル構成単位=30:70:5:4(重量比))100重量部と、イソシアネート系架橋剤(東ソー社製、商品名「コロネートL」)1.5重量部と、粘着付与剤(ヤスハラケミカル社製、商品名「マイティーエースG125」)5重量部を、トルエン100重量部とを混合し、粘着剤層形成用組成物を調製した。
該粘着剤層形成用組成物を、基材としてのポリエチレンテレフタレートフィルム(東レ社製、商品名「ルミラーS10」、厚み38μm)の片面に塗工して、基材と粘着剤層(厚み10μm)とから構成される粘着シート(4)を得た。
この粘着シート(4)のポリエチレンテレフタレートフィルムの第1の粘着剤層とは反対側の面に、実施例1と同様にして第2の粘着剤層を形成し、両面粘着シートを得た。 [Comparative Example 1]
Acrylic copolymer C (copolymer of 2ethylhexyl acrylate, ethyl acrylate, methyl methacrylate and 2hydroxyethyl acrylate, 2-ethylhexyl acrylate constituent unit: ethyl acrylate constituent unit: methyl methacrylate constituent unit: 2 hydroxyacrylate Ethyl constituent unit = 30:70: 5: 4 (weight ratio)) 100 parts by weight, isocyanate-based cross-linking agent (manufactured by Toso Co., Ltd., trade name "Coronate L") 1.5 parts by weight, and tackifier (Yasuhara Chemical Co., Ltd.) , Trade name "Mighty Ace G125") 5 parts by weight was mixed with 100 parts by weight of toluene to prepare a composition for forming an adhesive layer.
The composition for forming the pressure-sensitive adhesive layer is applied to one side of a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumilar S10", thickness 38 μm) as a base material, and the base material and the pressure-sensitive adhesive layer (
A second pressure-sensitive adhesive layer was formed on the surface of the pressure-sensitive adhesive sheet (4) opposite to the first pressure-sensitive adhesive layer of the polyethylene terephthalate film in the same manner as in Example 1 to obtain a double-sided pressure-sensitive adhesive sheet.
アクリル系コポリマーD(アクリル酸2エチルヘキシルとアクリル酸2ヒドロキシエチルとのコポリマー、アクリル酸2エチルヘキシル構成単位:アクリル酸2ヒドロキシエチル構成単位=100:4(重量比))100重量部と、イソシアネート系架橋剤(東ソー社製、商品名「コロネートL」)1.5重量部と、トルエン100重量部とを混合し、粘着剤層形成用組成物を調製した。
該粘着剤層形成用組成物を、基材としてのポリエチレンテレフタレートフィルム(東レ社製、商品名「ルミラーS10」、厚み38μm)の片面に塗工して、基材と粘着剤層(厚み10μm)とから構成される粘着シート(5)を得た。
この粘着シート(5)のポリエチレンテレフタレートフィルムの第1の粘着剤層とは反対側の面に、実施例1と同様にして第2の粘着剤層を形成し、両面粘着シートを得た。 [Comparative Example 2]
Acrylic copolymer D (copolymer of 2ethylhexyl acrylate and 2hydroxyethyl acrylate, 2ethylhexyl acrylate constituent unit: 2 hydroxyethyl acrylate constituent unit = 100: 4 (weight ratio)) 100 parts by weight and isocyanate-based cross-linking A composition for forming a pressure-sensitive adhesive layer was prepared by mixing 1.5 parts by weight of an agent (manufactured by Toso Co., Ltd., trade name "Coronate L") and 100 parts by weight of toluene.
The composition for forming the pressure-sensitive adhesive layer is applied to one side of a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumilar S10", thickness 38 μm) as a base material, and the base material and the pressure-sensitive adhesive layer (
A second pressure-sensitive adhesive layer was formed on the surface of the pressure-sensitive adhesive sheet (5) opposite to the first pressure-sensitive adhesive layer of the polyethylene terephthalate film in the same manner as in Example 1 to obtain a double-sided pressure-sensitive adhesive sheet.
20 粘着剤層
30 第2の粘着剤層
100、200 粘着シート
10
Claims (14)
- 基材と、該基材の少なくとも片側に配置された粘着剤層とを備える粘着シートであって、
該粘着剤層が、アクリル系粘着剤を含み、
該粘着シートのTMAを用いた23℃環境下における沈み込み量が、5μm以下であり、
該粘着剤層のパルスNMRによるS成分のT2緩和時間(T2s)が45μsec以下である、
粘着シート。 A pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer arranged on at least one side of the base material.
The pressure-sensitive adhesive layer contains an acrylic pressure-sensitive adhesive.
The amount of subduction of the adhesive sheet in an environment of 23 ° C. using TMA is 5 μm or less.
The T 2 relaxation time (T 2s ) of the S component by pulse NMR of the pressure-sensitive adhesive layer is 45 μsec or less.
Adhesive sheet. - 前記粘着剤層表面に、4-ターシャリーブチルフェニルグリシジルエーテルを滴下し、1分間静置した後の該粘着剤層の厚み変化率が、160%以下である、請求項1に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, wherein the thickness change rate of the pressure-sensitive adhesive layer after dropping 4-tertiary butylphenylglycidyl ether onto the surface of the pressure-sensitive adhesive layer and allowing it to stand for 1 minute is 160% or less. ..
- 前記粘着剤層表面に、4-ターシャリーブチルフェニルグリシジルエーテルを滴下し、1分間静置した後の該粘着剤層の厚み変化量が、20μm以下である、請求項1または2に記載の粘着シート。 The pressure-sensitive adhesive according to claim 1 or 2, wherein the amount of change in the thickness of the pressure-sensitive adhesive layer after dropping 4-tertiary butylphenylglycidyl ether onto the surface of the pressure-sensitive adhesive layer and allowing it to stand for 1 minute is 20 μm or less. Sheet.
- 前記粘着剤層が粘着剤を含み、
該粘着剤が、sp値が18(cal/cm3)1/2~20(cal/cm3)1/2であるベースポリマーを含む、
請求項1から3のいずれかに記載の粘着シート。 The pressure-sensitive adhesive layer contains a pressure-sensitive adhesive.
The pressure-sensitive adhesive comprises a base polymer having an sp value of 18 (cal / cm 3 ) 1/2 to 20 (cal / cm 3 ) 1/2 .
The adhesive sheet according to any one of claims 1 to 3. - 前記アクリル系粘着剤が、ベースポリマーとして、アクリル系ポリマーの架橋体を含む、請求項1から4のいずれかに記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the acrylic pressure-sensitive adhesive contains a crosslinked body of the acrylic-based polymer as a base polymer.
- 前記アクリル系粘着剤が、エポキシ系架橋剤を含む、請求項1から5のいずれかに記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 5, wherein the acrylic pressure-sensitive adhesive contains an epoxy-based cross-linking agent.
- 前記エポキシ系架橋剤の配合量が、アクリル系ポリマー100重量部に対して、0.6重量部~15重量部である、請求項6に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 6, wherein the blending amount of the epoxy-based cross-linking agent is 0.6 parts by weight to 15 parts by weight with respect to 100 parts by weight of the acrylic polymer.
- 前記基材が、ガラス転移温度(Tg)が25℃以上の樹脂から構成される樹脂シートである、請求項1から7のいずれかに記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 7, wherein the base material is a resin sheet composed of a resin having a glass transition temperature (Tg) of 25 ° C. or higher.
- 前記基材の厚みが、粘着シートの総厚に対して、20%~90%、である、請求項1から8のいずれかに記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 8, wherein the thickness of the base material is 20% to 90% with respect to the total thickness of the pressure-sensitive adhesive sheet.
- 前記粘着シートのTMAを用いた145℃環境下における沈み込み量が、1μm~35μmである、請求項1から9のいずれかに記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 9, wherein the amount of the pressure-sensitive adhesive sheet submerged in an environment of 145 ° C. using TMA is 1 μm to 35 μm.
- 前記粘着剤層を加熱処理した際の窒素ガスの発生量が、0.06重量%~1.0重量%である、請求項1から10のいずれかに記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 10, wherein the amount of nitrogen gas generated when the pressure-sensitive adhesive layer is heat-treated is 0.06% by weight to 1.0% by weight.
- 前記基材と、該基材の片側に配置された前記粘着剤層と、該基材の該粘着剤層とは反対側に配置された第2の粘着剤層とを備える、請求項1から11のいずれかに記載の粘着シート。 The first aspect of the present invention comprises the base material, the pressure-sensitive adhesive layer arranged on one side of the base material, and the second pressure-sensitive adhesive layer arranged on the side opposite to the pressure-sensitive adhesive layer of the base material. The adhesive sheet according to any one of 11.
- 半導体チップの樹脂封止工程で用いられる仮固定材である、請求項1から12のいずれかに記載の粘着シート。 The adhesive sheet according to any one of claims 1 to 12, which is a temporary fixing material used in the resin sealing process of a semiconductor chip.
- 前記粘着シート上で、封止樹脂を硬化する際に用いられる、請求項13に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 13, which is used when the sealing resin is cured on the pressure-sensitive adhesive sheet.
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CN202180069545.6A CN116368199A (en) | 2020-12-07 | 2021-10-22 | Pressure-sensitive adhesive sheet |
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WO2023286620A1 (en) * | 2021-07-13 | 2023-01-19 | 日東電工株式会社 | Pressure-sensitive adhesive sheet |
WO2023286619A1 (en) * | 2021-07-13 | 2023-01-19 | 日東電工株式会社 | Adhesive sheet |
WO2023286621A1 (en) * | 2021-07-13 | 2023-01-19 | 日東電工株式会社 | Pressure-sensitive adhesive sheet |
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