CN102971839B - 多层粘合片及电子元件的制造方法 - Google Patents
多层粘合片及电子元件的制造方法 Download PDFInfo
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- CN102971839B CN102971839B CN201180031760.3A CN201180031760A CN102971839B CN 102971839 B CN102971839 B CN 102971839B CN 201180031760 A CN201180031760 A CN 201180031760A CN 102971839 B CN102971839 B CN 102971839B
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- methyl
- acrylate
- adhesive sheet
- copolymer
- layered adhesive
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- 239000000853 adhesive Substances 0.000 title claims abstract description 89
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 229920001577 copolymer Polymers 0.000 claims abstract description 53
- 239000012790 adhesive layer Substances 0.000 claims abstract description 43
- 239000012948 isocyanate Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000004065 semiconductor Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 24
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 16
- -1 vinyl compound Chemical class 0.000 claims description 88
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 74
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 39
- 239000000178 monomer Substances 0.000 claims description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 31
- 238000005520 cutting process Methods 0.000 claims description 26
- 229920002554 vinyl polymer Polymers 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 21
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 18
- 229920001296 polysiloxane Polymers 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 230000005855 radiation Effects 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 claims description 7
- 238000007348 radical reaction Methods 0.000 claims description 7
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 210000004899 c-terminal region Anatomy 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 229960005222 phenazone Drugs 0.000 claims description 3
- 230000002285 radioactive effect Effects 0.000 claims description 3
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- 239000005977 Ethylene Substances 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 235000012431 wafers Nutrition 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 6
- 230000003373 anti-fouling effect Effects 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
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- 150000002148 esters Chemical class 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
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- 239000000839 emulsion Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 2
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 2
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241001050985 Disco Species 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000004520 agglutination Effects 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 2
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- 229920000573 polyethylene Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 2
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- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- SKPQRKCMMUAXSG-UHFFFAOYSA-M CC[N+](C)(C(C)C)OC(C=C)=O.[Cl-] Chemical compound CC[N+](C)(C(C)C)OC(C=C)=O.[Cl-] SKPQRKCMMUAXSG-UHFFFAOYSA-M 0.000 description 1
- RMQNHHVBTGVNIW-UHFFFAOYSA-M CC[N+](CC)(C(C)C)OC(C=C)=O.[Cl-] Chemical compound CC[N+](CC)(C(C)C)OC(C=C)=O.[Cl-] RMQNHHVBTGVNIW-UHFFFAOYSA-M 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
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- 238000011088 calibration curve Methods 0.000 description 1
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- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
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Classifications
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
本发明提供一种多层粘合片,其即使在将丙烯酸酯共聚物用于芯片贴膜的情况下,在拾取时也可容易地将粘合层与芯片贴膜之间予以剥离,由此能够在切割后容易地进行半导体芯片的拾取作业;该多层粘合片具有基材膜、层合于基材膜的一侧表面的粘合层、及层合于粘合层的露出面的芯片贴膜,构成粘合层的粘合剂具有(甲基)丙烯酸酯共聚物(A)、紫外线聚合性化合物(B)、多官能异氰酸酯硬化剂(C)、光聚合引发剂(D)、及硅氧烷聚合物(E)。
Description
技术领域
本发明关于多层粘合片以及使用多层粘合片的电子元件的制造方法。
背景技术
作为IC等电子元件的制造方法,广泛地进行下述方法:在硅、镓-砷等半导体晶圆上形成电路图案后制成电子元件集合体,将电子元件集合体贴附于由基材膜层与粘合层所构成的粘合片上,再将其固定于环形架(ringframe),然后切割分离(dicing)成各个半导体芯片,并根据需要将膜进行扩展(expand),拾取半导体芯片,将半导体芯片用粘合剂固定于引线框架(leadframe)等。
在该制造方法中,提出一种使用多层粘合片(芯片贴膜(dieattachfilm)一体化片)的方法,该多层粘合片通过将芯片贴膜与粘合片层合并一体化,而兼具作为切割用粘合片的功能,以及作为将芯片固定于引线框架等的粘合剂的功能(专利文献1及专利文献2)。通过将芯片贴膜一体化片用于电子元件的制造,可省略粘合剂的涂布步骤,与使用粘合剂的方法相比,具有可控制粘合剂部分的厚度以及抑制溢出的优点。
〔现有技术文献〕
〔专利文献〕
专利文献1:日本特开2006-049509号公报
专利文献2:日本特开2007-246633号公报
发明内容
通常,在多层粘合片的芯片贴膜中使用丙烯酸树脂、环氧树脂、聚酰胺树脂等一般的粘合剂材料。特别是当使用丙烯酸酯共聚物作为构成芯片贴膜的材料时,能够提高保存稳定性、成膜性。但是,含有丙烯酸酯共聚物的芯片贴膜与粘合片的粘合层的粘结强度过高,拾取半导体芯片时,芯片贴膜难以从粘合层剥离,存在半导体芯片的拾取性差的情形。
本发明是鉴于上述情况而完成的,本发明人发现,通过使构成多层粘合片的粘合层的粘合剂为特定的组成,即使在将丙烯酸酯共聚物用于芯片贴膜的情况下,也容易在拾取时剥离粘合层与芯片贴膜,从而能够容易地进行切割后的半导体芯片的拾取作业,于是完成了本发明。
即,本发明涉及下述多层粘合片及使用多层粘合片的电子元件的制造方法。
(1)、一种多层粘合片,其具有基材膜、层合于基材膜的一侧表面的粘合层、及层合于粘合层的露出面的芯片贴膜;构成粘合层的粘合剂含有(甲基)丙烯酸酯共聚物(A)、紫外线聚合性化合物(B)、多官能异氰酸酯硬化剂(C)、光聚合引发剂(D)、及硅氧烷聚合物(E);(甲基)丙烯酸酯共聚物(A)为(甲基)丙烯酸酯单体的共聚物或(甲基)丙烯酸酯单体与乙烯系化合物单体的共聚物的任一者,(甲基)丙烯酸酯单体与乙烯系化合物单体皆不具羟基;紫外线聚合性化合物(B)是由氨基甲酸酯丙烯酸酯低聚物(B1)与多官能(甲基)丙烯酸酯(B2)所构成,氨基甲酸酯丙烯酸酯低聚物(B1)具有10个以上乙烯基,重均分子量Mw为50000以上,且上述重均分子量Mw与数均分子量Mn的比,即分散度Mw/Mn为5以上;光聚合引发剂(D)具有羟基;硅氧烷聚合物(E)具有羟基;在构成粘合层的粘合剂中,(甲基)丙烯酸酯共聚物(A)为100质量份,紫外线聚合性化合物(B)为5~200质量份,多官能异氰酸酯硬化剂(C)为0.5~20质量份,光聚合引发剂(D)为0.1~20质量份,及硅氧烷聚合物(E)为0.1~20质量份。
(2)、如(1)记载的多层粘合片,其中氨基甲酸酯丙烯酸酯低聚物(B1)是使以二季戊四醇五丙烯酸酯为主成分的含羟基的丙烯酸酯与异佛尔酮二异氰酸酯的三聚体的异氰酸酯基反应而得到的,多官能(甲基)丙烯酸酯(B2)为二季戊四醇六丙烯酸酯。
(3)、如(1)或(2)记载的多层粘合片,其中,构成芯片贴膜的组合物含有丙烯酸酯共聚物。
(4)、一种电子元件的制造方法,其包含:贴附步骤,使用如(1)至(3)中任一项记载的多层粘合片,并将多层粘合片贴附在硅晶圆及环形架进行固定;切割步骤,利用切割刀片切割硅晶圆,制成半导体芯片;拾取步骤,至少照射紫外线或放射线,并从粘合层拾取芯片及芯片贴膜。
根据本发明的多层粘合片,即使在将丙烯酸酯共聚物使用于芯片贴膜的情况下,在拾取时也容易将粘合片与芯片贴膜之间进行剥离,由此能够容易地进行切割后的芯片拾取作业。
另外,本发明的多层粘合片,除芯片的拾取性外,切割造成的芯片飞离少(芯片保持性),且来自粘合层的成分所造成的芯片贴膜的污染少(防污染性),所以适合用于电子元件的制造方法。
具体实施方式
<术语的说明>
单体单元是指来自单体的结构单元。“份”及“%”是以质量为基准。(甲基)丙烯酸酯为丙烯酸酯及甲基丙烯酸酯的总称。(甲基)丙烯酸等冠有(甲基)的化合物等也同样为名称中具有“甲基”的化合物与不具有“甲基”的化合物的总称。
〔多层粘合片〕
多层粘合片具有基材膜、层合于基材膜的一侧表面的粘合层、及层合于粘合层的露出面的芯片贴膜。即,多层粘合片为将基材膜、粘合层、芯片贴膜依此顺序层合得到的多层构造体。在本说明书中,将仅层合基材膜与粘合层并进行一体化的结构称为“粘合片”,将在粘合片上进一步层合芯片贴膜并进行一体化的结构称为“多层粘合片”。
<基材膜>
对基材膜并无特别限定,可使用公知的树脂材料。具体而言,可以列举将聚氯乙烯、聚对苯二甲酸乙二酯、乙烯-醋酸乙烯酯共聚物、乙烯-丙烯酸-丙烯酸酯膜、乙烯-丙烯酸乙酯共聚物、聚乙烯、聚丙烯、丙烯系共聚物、乙烯-丙烯酸共聚物、以及乙烯-(甲基)丙烯酸共聚物或乙烯-(甲基)丙烯酸-(甲基)丙烯酸酯共聚物等用金属离子交联而成的离子键树脂。基材膜可以为上述树脂的混合物、共聚物或其层合物。
其中优选丙烯系共聚物作为基材膜。通过采用丙烯系共聚物,可抑制切割半导体晶圆时所产生的切屑。就丙烯系共聚物而言,例如有丙烯与其他成分的无规共聚物、丙烯与其他成分的嵌段共聚物、丙烯与其他成分的交替共聚物。其他成分可以举出乙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯等α-烯烃;至少2种以上的α-烯烃所构成的共聚物;苯乙烯-二烯共聚物等。其中优选1-丁烯。
就聚合丙烯系共聚物的方法而言,例如,可以举出溶液聚合法、块状聚合法、气相聚合法、逐步聚合法等,但优选至少二个阶段以上的逐步聚合法,即在第一阶段制造丙烯均聚物或丙烯与少量乙烯及/或α-烯烃的无规共聚物后,在第二阶段以后制造α-烯烃的均聚物或丙烯与少量乙烯及/或α-烯烃的无规共聚物。
优选对基材膜进行防静电处理。通过防静电处理,可防止芯片贴膜剥离时产生静电。就防静电处理而言,有以下处理:(1)在构成基材膜的组合物中混合防静电剂的处理,(2)在基材膜的芯片贴膜层合侧表面涂布防静电剂的处理,(3)通过电晕放电进行的带电处理。作为防静电剂,有季铵盐单体等。
就季铵盐单体而言,可列举例如(甲基)丙烯酰氧乙基二甲基氯化铵、(甲基)丙烯酰氧乙基二乙基氯化铵、(甲基)丙烯酰氧乙基甲基乙基氯化铵、对-苯乙烯基二甲基氯化铵、及对-苯乙烯基二乙基氯化铵,并且优选(甲基)丙烯酰氧乙基二甲基氯化铵。
<粘合剂>
粘合层是由粘合剂构成,粘合剂具有:(甲基)丙烯酸酯共聚物(A)、紫外线聚合性化合物(B)、多官能异氰酸酯硬化剂(C)、光聚合引发剂(D)及硅氧烷聚合物(E)。
〔(甲基)丙烯酸酯共聚物(A)〕
(甲基)丙烯酸酯共聚物为仅由(甲基)丙烯酸酯单体构成的共聚物,或(甲基)丙烯酸酯单体与乙烯系化合物单体的共聚物,这些单体不具有羟基。
就(甲基)丙烯酸酯单体而言,可列举例如(甲基)丙烯酸丁酯、(甲基)丙烯酸2-丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸肉豆蔻酯、(甲基)丙烯酸鲸蜡酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸二环戊酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸丁氧基甲酯及(甲基)丙烯酸乙氧基正丙酯。
作为乙烯系化合物单体,可举出具有由羧基、环氧基、酰胺基、氨基、羟甲基、磺酸基、氨基磺酸基或(亚)磷酸酯基所组成的官能基组中的一种以上的含有官能基的单体。
就含有羧基的乙烯系化合物单体而言,可列举(甲基)丙烯酸、巴豆酸、马来酸、马来酸酐、衣康酸、富马酸、丙烯酰胺N-乙醇酸、及桂皮酸等。
就具有环氧基的乙烯系化合物单体而言,可列举烯丙基缩水甘油基醚及(甲基)丙烯酸缩水甘油基醚。
就具有酰胺基的乙烯系化合物单体而言,可列举(甲基)丙烯酰胺。
就具有氨基的乙烯系化合物单体而言,可列举(甲基)丙烯酸N,N-二甲基氨基乙酯。
就具有羟甲基的乙烯系化合物单体而言,可列举N-羟甲基丙烯酰胺。
就(甲基)丙烯酸酯共聚物的制造方法而言,有乳液聚合、溶液聚合。其中,考虑到放射线照射后,粘合片容易从芯片贴膜剥离,并且可维持半导体芯片的高拾取性,优选乳液聚合。
〔紫外线聚合性化合物(B)〕
紫外线聚合性化合物(B)为氨基甲酸酯丙烯酸酯低聚物(B1)与多官能(甲基)丙烯酸酯(B2)的混合物。氨基甲酸酯丙烯酸酯低聚物(B1)与多官能(甲基)丙烯酸酯(B2)的添加比(B1:B2)优选为50:50以上至95:5以下,更优选为65:35以上至85:15以下。
〔氨基甲酸酯丙烯酸酯低聚物(B1)〕
氨基甲酸酯丙烯酸酯低聚物(B1)具有10个以上的乙烯基,重均分子量Mw为50000以上,且上述重均分子量Mw与数均分子量Mn的比,即分散度Mw/Mn为5以上。
就氨基甲酸酯丙烯酸酯低聚物(B1)而言,有以下物质:(1)使含有羟基及多个(甲基)丙烯酸酯基的(甲基)丙烯酸酯化合物与具有多个异氰酸酯基的化合物(例如二异氰酸酯化合物)反应而制造的物质;(2)在具有多个羟基末端的多元醇低聚物中,添加过剩的具有多个异氰酸酯基的化合物(例如二异氰酸酯化合物)并使其反应,制成具有多个异氰酸酯基末端的低聚物,然后使该低聚物与含有羟基及多个(甲基)丙烯酸酯基的(甲基)丙烯酸酯化合物反应而得到的物质。
若氨基甲酸酯丙烯酸酯低聚物(B1)的乙烯基数目为10个以上,则在放射线照射后容易使粘合片与芯片贴膜之间剥离。因此,可良好地维持半导体芯片的拾取性。
另外,若氨基甲酸酯丙烯酸酯低聚物(B1)的重均分子量Mw为50000以上,且重均分子量Mw与数均分子量Mn的比,即分散度Mw/Mn为5以上,则可降低粘合片与芯片贴膜之间的粘结强度,并在放射线照射后容易将芯片贴膜从粘合片剥离。
就可构成氨基甲酸酯丙烯酸酯低聚物(B1)的含有羟基及多个(甲基)丙烯酸酯基的(甲基)丙烯酸酯化合物而言,可列举例如羟基丙基化三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、二季戊四醇羟基五丙烯酸酯、双(季戊四醇)四丙烯酸酯、四羟甲基甲烷三丙烯酸酯、缩水甘油二丙烯酸酯,或将上述化合物的丙烯酸酯基的一部分或全部变为甲基丙烯酸酯基而得到的化合物。
就可构成氨基甲酸酯丙烯酸酯低聚物(B1)的具有多个异氰酸酯基的化合物而言,有芳香族异氰酸酯、脂环族异氰酸酯及脂肪族异氰酸酯。这些异氰酸酯中,优选具有多个异氰酸酯基的脂环族异氰酸酯及脂肪族异氰酸酯。就异氰酸酯成分的形态而言,有单体、二聚体及三聚体,其中优选三聚体。
就芳香族二异氰酸酯而言,例如有甲苯二异氰酸酯、4,4-二苯基甲烷二异氰酸酯、二甲苯二异氰酸酯。
就脂环族二异氰酸酯而言,例如有异佛尔酮二异氰酸酯、亚甲基双(4-环己基异氰酸酯)。
就脂肪族二异氰酸酯而言,例如有1,6-己二异氰酸酯、三甲基六亚甲基二异氰酸酯。
就可构成氨基甲酸酯丙烯酸酯低聚物(B1)的具有多个羟基末端的多元醇低聚物的多元醇成分而言,例如有聚(环氧丙烷)二醇、聚(环氧丙烷)三醇、共聚(环氧乙烷-环氧丙烷)二醇、聚(四氢呋喃)二醇、乙氧基化双酚A、乙氧基化双酚S螺环二醇、己内酯改性二醇及碳酸酯二醇。
〔多官能(甲基)丙烯酸酯(B2)〕
就多官能(甲基)丙烯酸酯(B2)而言,例如有三羟甲基丙烷三丙烯酸酯、羟丙基化三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇乙氧基四丙烯酸酯、二季戊四醇羟基五丙烯酸酯、二季戊四醇六丙烯酸酯、双(季戊四醇)四丙烯酸酯、四羟甲基甲烷三丙烯酸酯、缩水甘油二丙烯酸酯,或上述化合物的丙烯酸酯基的一部分或全部变为甲基丙烯酸酯基的化合物。
相对于(甲基)丙烯酸酯共聚物(A)100质量份,紫外线聚合性化合物(B)的混合量优选为5质量份以上至200质量份以下。若紫外线聚合性化合物(B)的混合量过少,则在放射线照射后芯片贴膜难以从粘合片剥离,并且容易产生有关半导体芯片拾取性的问题。若紫外线聚合性化合物(B)的混合量过多,则在切割时因粘合剂的渗出而容易发生拾取不良的问题,同时反应残余物带来微量的残余粘合剂而将芯片贴膜污染,由此导致在将芯片贴膜所附着的半导体芯片粘结到引线框架上后,在进行升温时容易发生粘结不良。
〔多官能异氰酸酯硬化剂(C)〕
多官能异氰酸酯硬化剂(C)具有2个以上异氰酸酯基,例如有芳香族多异氰酸酯、脂肪族多异氰酸酯、脂环族多异氰酸酯。
就芳香族多异氰酸酯而言,例如有1,3-苯二异氰酸酯、4,4’-二苯基二异氰酸酯、1,4-苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4’-甲苯胺二异氰酸酯、2,4,6-三异氰酸酯基甲苯、1,3,5-三异氰酸酯基苯、联茴香胺二异氰酸酯、4,4’-二苯基醚二异氰酸酯、4,4’,4”-三苯基甲烷三异氰酸酯、ω,ω’-二异氰酸酯基-1,3-二甲基苯、ω,ω’-二异氰酸酯基-1,4-二甲基苯、ω,ω’-二异氰酸酯基-1,4-二乙基苯、1,4-四甲基二甲苯二异氰酸酯及1,3-四甲基二甲苯二异氰酸酯。
就脂肪族多异氰酸酯而言,例如有三亚甲基二异氰酸酯、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯、五亚甲基二异氰酸酯、1,2-丙二异氰酸酯、2,3-丁二异氰酸酯、1,3-丁二异氰酸酯、十二甲撑二异氰酸酯及2,4,4-三甲基六亚甲基二异氰酸酯。
就脂环族多异氰酸酯而言,例如有3-异氰酸酯基甲基-3,5,5-三甲基环己基异氰酸酯、1,3-环戊烷二异氰酸酯、1,3-环己烷二异氰酸酯、1,4-环己烷二异氰酸酯、甲基-2,4-环己烷二异氰酸酯、甲基-2,6-环己烷二异氰酸酯、4,4’-亚甲基双(环己基异氰酸酯)、1,4-双(异氰酸酯基甲基)环己烷及1,4-双(异氰酸酯基甲基)环己烷。
上述多异氰酸酯中,优选1,3-苯二异氰酸酯、4,4’-二苯二异氰酸酯、1,4-苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4’-甲苯胺二异氰酸酯、六亚甲基二异氰酸酯。
关于多官能异氰酸酯硬化剂(C)的混合比,优选相对于(甲基)丙烯酸酯共聚物(A)100质量份为以0.5质量份以上至20质量份以下,更优选下限为1.0质量份以上,上限为10质量份以下。多官能异氰酸酯硬化剂(C)为0.5质量份以上时,由于粘结强度不会过高,所以可抑制拾取不良的发生。多官能异氰酸酯硬化剂(C)为20质量份以下时,由于粘结强度不会过低,所以在切割时可维持半导体芯片的保持性。
〔光聚合引发剂(D)〕
光聚合引发剂(D)具有至少1个羟基。作为具有1个羟基的光聚合引发剂,可列举:2-羟基-甲基-1-苯基-丙烷-1-酮(Ciba日本公司制,制品名Darocur1173)、1-羟基-环己基-苯基-酮(Ciba日本公司制,制品名Irgacure184)等;作为具有2个以上羟基的光聚合引发剂,可列举:1-〔4-(羟基乙氧基)-苯基〕-2-羟基-2-甲基-1-丙烷-1-酮(Ciba日本公司制,制品名Irgacure2959)、2-羟基-1-{4-〔4-(2-羟基-2-甲基-丙酰基)-苯甲基〕-苯基}-2-甲基-丙烷-1-酮((Ciba日本公司制,制品名Irgacure127)等。具有羟基的光聚合引发剂(D)的羟基数优选为2个以上。通过具有2个以上羟基,在放射线照射后开裂的光聚合引发剂被(甲基)丙烯酸酯单体(A)的丙烯酰基的反应体系摄入,所以能够抑制向芯片贴膜的移动。需要说明的是,对于羟基数的上限,并无特别限定。
关于光聚合引发剂(D)的混合量,优选相对于(甲基)丙烯酸酯聚合物(A)100质量份为0.1质量份以上至20质量份以下。若该混合量过少,则在放射线照射后,不容易将芯片贴膜从粘合片剥离,而有发生半导体芯片的拾取性降低的倾向。若该比例过多,则无法抑制因渗出而对粘合层表面所造成的污染,并且将芯片贴膜所附着的半导体芯片安装在引线框架上后,在进行升温时容易发生粘结不良的倾向。
〔硅氧烷聚合物(E)〕
优选混合到粘合剂中的硅氧烷聚合物(E)具有单体单元,该单体单元来源于在聚二甲基硅氧烷键的末端具有乙烯基的单体(以下,称为“聚硅氧烷大分子单体”)。具体而言,有聚硅氧烷大分子单体的均聚物、聚硅氧烷大分子单体与其他乙烯系化合物聚合而得到的乙烯系聚合物。聚硅氧烷大分子单体优选聚二甲基硅氧烷键的末端是(甲基)丙烯酰基或苯乙烯基等乙烯系基团的化合物。
就构成硅氧烷聚合物(E)的聚硅氧烷大分子单体以外的乙烯系化合物而言,可使用(甲基)丙烯酸类单体。若使用此种硅氧烷聚合物,则在将粘合片与芯片贴膜层合时,可防止硅氧烷聚合物向芯片贴膜移动,并且能够防止在拾取半导体芯片时产生所谓胶粒的微量的残余粘合剂。就(甲基)丙烯酸类单体而言,有(甲基)丙烯酸烷基酯、(甲基)丙烯酸羟烷基酯、改性羟基(甲基)丙烯酸酯、及(甲基)丙烯酸。
就(甲基)丙烯酸烷基酯而言,例如有(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸异冰片酯、及(甲基)丙烯酸羟烷基酯。
就(甲基)丙烯酸羟烷基酯而言,例如有(甲基)丙烯酸羟乙基酯、(甲基)丙烯酸羟丙基酯、(甲基)丙烯酸羟丁基酯。
就改性羟基(甲基)丙烯酸酯而言,例如有经环氧乙烷改性的羟基(甲基)丙烯酸酯、经内酯改性的羟基(甲基)丙烯酸酯。
关于硅氧烷聚合物(E)的混合量,优选相对于(甲基)丙烯酸酯聚合物(A)100质量份为0.1质量份以上至20质量份以下。若该混合量过少,则于放射线照射后,不容易将芯片贴膜从粘合片剥离,有发生半导体芯片的拾取性降低的倾向。另一方面,若该混合量过多,则无法抑制初始粘着力的降低,有切割时损坏半导体芯片的保持性的倾向。
硅氧烷聚合物(E)中聚硅氧烷大分子单体单元的比例,优选在硅氧烷聚合物100质量份中为15质量份以上至50质量份以下。若该比例变少,则在放射线照射后,不容易将芯片贴膜从粘合片剥离,有发生半导体芯片的拾取性降低的倾向。若该比例变多,则无法抑制因渗出而对粘合层表面所造成的污染,并且存在将芯片贴膜所附着的半导体芯片粘结于引线框架上后,在进行升温时容易发生粘结不良的倾向。
粘合剂中,在不影响到其他材料的范围内,可添加软化剂、防老化剂、填充剂、紫外线吸收剂、及光稳定剂等添加剂。
粘合层的厚度优选为3μm以上至100μm以下,特别优选为5μm以上至20μm以下。
<芯片贴膜>
用于多层粘合片的芯片贴膜是将粘合剂成型为膜状而得到的。就构成芯片贴膜的具体组合物而言,有丙烯酸酯共聚物、聚酰胺、聚乙烯、聚砜、环氧树脂、聚酰亚胺、聚酰胺酸、硅树脂、酚醛树脂、橡胶、氟树胶及氟树脂的单体或这些物质的混合物、共聚物及层合体。从与芯片的粘结可靠性方面考虑,构成芯片贴膜的组合物优选含有丙烯酸酯共聚物。可以在该组合物中添加光聚合引发剂、防静电剂、交联剂、交联促进剂、填充剂等。
<多层粘合片的制造方法>
可以通过将粘合剂涂布到基材膜上制成粘合片后,将芯片贴膜贴附于粘合片的粘合剂涂布面来制造多层粘合片。另外,还可以通过将粘合剂涂布在由聚对苯二甲酸乙二酯等所构成的分离膜上,随意干燥后,层合在基材膜上,制成粘合片,然后在除去分离膜后的露出面上贴附芯片贴膜,从而制造多层粘合片。
芯片贴膜与粘合片之间的粘结强度,若过大则有发生拾取不良的倾向,若过小则有芯片保持性降低的倾向,因此优选为0.05~1.5N/20mm。通过使构成粘合片的粘合层的粘合剂为上述特定的组成,即使在芯片贴膜中使用丙烯酸酯共聚物的情况下,也能够保持适当的粘结强度。
〔电子元件的制造方法〕
使用上述多层粘合片制造电子元件的方法包含下列步骤。
(1)将多层粘合片贴附于硅晶圆及环形架而固定的贴附步骤;
(2)用切割刀片将硅晶圆与芯片贴膜一起切割,形成半导体芯片的切割步骤;
(3)至少照射紫外线或放射线,将芯片贴膜所附着的半导体芯片从粘合层拾取的拾取步骤。
如上所述,多层粘合片在半导体芯片的芯片保持性、拾取性及防污染性方面优良,所以,能够降低上述切割步骤(2)中芯片飞离的发生,还能够在上述拾取步骤(3)中容易地将芯片贴膜所附着的半导体芯片从粘合片剥离,进行拾取,并且,由于拾取后芯片贴膜不会被污染,所以对引线框架等具有高粘着力。
实施例
使用以下记载的基材膜、粘合层及芯片贴膜,制造实施例及比较例的各种多层粘合片。
<基材膜>
在全部实施例及比较例中,基材膜使用SunAllomer公司制的丙烯系共聚物(产品号:X500F)。该膜的MFR(熔融流动速率)值为7.5g/10分钟,密度为0.89g/cm3,厚度为80μm。
<粘合层>
粘合层是使用含有以下记载的(甲基)丙烯酸酯共聚物(A)、紫外线聚合性化合物(B)、多官能异氰酸酯硬化剂(C)、光聚合引发剂(D)、及硅氧烷聚合物(E)的粘合剂来形成。
<粘合剂>
〔(甲基)丙烯酸酯共聚物(A)〕
A-1:日本Zeon公司制丙烯酸橡胶AR53L;为丙烯酸乙酯40%、丙烯酸丁酯23%、丙烯酸甲氧基乙酯37%的共聚物,其是通过乳液聚合而得到。任一化合物皆不含羟基。
A-2:本公司的聚合物,为丙烯酸乙酯40%、丙烯酸丁酯22%、丙烯酸甲氧基乙酯37%、丙烯酸1%的共聚物,其是通过乳液聚合而得到。任一项化合物皆不含羟基。
A-3:综研化学公司制SKDyne1435;为丙烯酸丁酯67%、丙烯酸甲酯28%、丙烯酸2-羟乙基酯5%的共聚物,其是通过溶液聚合而得到。丙烯酸2-羟乙基酯含有羟基。
〔紫外线聚合性化合物(B)〕
B-1:根上工业公司制UN-905;B-1是由氨基甲酸酯丙烯酸酯低聚物(B1)与多官能(甲基)丙烯酸酯(B2)构成。氨基甲酸酯丙烯酸酯低聚物(B1)为使以二季戊四醇五丙烯酸酯为主成分的含羟基丙烯酸酯与异佛尔酮二异氰酸酯的三聚体的异氰酸酯基反应而得到的。多官能(甲基)丙烯酸酯(B2)以二季戊四醇六丙烯酸酯为主成分。两种成分的混合比为:氨基甲酸酯丙烯酸酯低聚物(B1)占75%,多官能(甲基)丙烯酸酯(B2)占25%。氨基甲酸酯丙烯酸酯低聚物(B1)的重均分子量为100000,分散度为10.7,乙烯基的数目为15个。
B-2:根上工业公司制UN-3320HS;B-2是由氨基甲酸酯丙烯酸酯低聚物(B1)与多官能(甲基)丙烯酸酯(B2)构成。氨基甲酸酯丙烯酸酯低聚物(B1)是使二季戊四醇五丙烯酸酯为主成分的含羟基丙烯酸酯与异佛尔酮二异氰酸酯的三聚体的异氰酸酯基反应而得到的。多官能(甲基)丙烯酸酯(B2)以二季戊四醇六丙烯酸酯为主成分。两成分的混合比为:氨基甲酸酯丙烯酸酯低聚物(B1)占45%,多官能(甲基)丙烯酸酯(B2)占55%。氨基甲酸酯丙烯酸酯低聚物(B1)的重均分子量为11000,分散度为1.2,乙烯基的数目为15个。
B-3:本公司聚合物A;B-3是由氨基甲酸酯丙烯酸酯低聚物(B1)与多官能(甲基)丙烯酸酯(B2)构成。氨基甲酸酯丙烯酸酯低聚物(B1)为使以二季戊四醇五丙烯酸酯为主成分的含羟基丙烯酸酯与六亚甲基二异氰酸酯的三聚体的异氰酸酯基反应而得到的。多官能(甲基)丙烯酸酯(B2)以二季戊四醇六丙烯酸酯为主成分。两成分的混合比为:氨基甲酸酯丙烯酸酯低聚物(B1)占45%,多官能(甲基)丙烯酸酯(B2)占55%。氨基甲酸酯丙烯酸酯低聚物(B1)的重均分子量为70000,分散度为1.2,乙烯基的数目为15个。
B-4:本公司聚合物B;B-4是由氨基甲酸酯丙烯酸酯低聚物(B1)与多官能(甲基)丙烯酸酯(B2)构成。氨基甲酸酯丙烯酸酯低聚物(B1)为使二季戊四醇五丙烯酸酯为主成分的含羟基丙烯酸酯与六亚甲基二异氰酸酯的三聚体的异氰酸酯基反应而得到的。多官能(甲基)丙烯酸酯(B2)以二季戊四醇六丙烯酸酯为主成分。两成分的混合比为:氨基甲酸酯丙烯酸酯低聚物(B1)占45%,多官能(甲基)丙烯酸酯(B2)占55%。氨基甲酸酯丙烯酸酯低聚物(B1)的重均分子量为30000,分散度为7.5,乙烯基的数目为15个。
B-5:本公司聚合物C;B-5是由氨基甲酸酯丙烯酸酯低聚物(B1)与多官能(甲基)丙烯酸酯(B2)构成。氨基甲酸酯丙烯酸酯低聚物(B1)为使以季戊四醇三丙烯酸酯为主成分的含羟基丙烯酸酯与六亚甲基二异氰酸酯的三聚体的异氰酸酯基反应而得到的。多官能(甲基)丙烯酸酯(B2)以季戊四醇四丙烯酸酯为主成分。两成分的混合比为:氨基甲酸酯丙烯酸酯低聚物(B1)占45%,多官能(甲基)丙烯酸酯(B2)为55%。氨基甲酸酯丙烯酸酯低聚物(B1)的重均分子量为70000,分散度为8.2,乙烯基的数目为6个。
〔多官能异氰酸酯硬化剂(C)〕
C-1:日本聚氨基甲酸酯公司制CoronateL-45E;2,4-甲苯基二异氰酸酯的三羟甲基丙烷加成物。
〔光聚合引发剂(D)〕
D-1:Ciba日本公司制,制品名Irgacure127;2-羟基-1-{4-〔4-(2-羟基-2-甲基-丙酰基)-苯甲基〕-苯基}-2-甲基-丙烷-1-酮。具有羟基。
D-2:Ciba日本公司制,制品名Irgacure184;1-羟基-环己基-苯基-酮。具有羟基。
D-3:Ciba日本公司制,制品名Irgacure651;苄基二甲基缩酮。无羟基。
〔硅氧烷聚合物(E)〕
E-1:综研化学公司制UTMM-LS2;在聚硅氧烷分子链的末端含有具有(甲基)丙烯酰基的硅氧烷低聚物类单元,并且是聚合了由甲基丙烯酸甲酯等所构成的丙烯酸系乙烯系单元而得到的聚硅氧烷接枝共聚物。具有羟基。
E-2:硅油,市售品。无羟基。
紫外线聚合性化合物(B)所含的氨基甲酸酯丙烯酸酯低聚物(B1)的分子量按照以下记载的GPC测定条件进行测定。
装置名:HLC-8120GPC(东曹公司制)
柱子:将一根TSKGuardHZ-L及3根HZM-N串联
温度:40℃
检测:示差折射率
溶剂:四氢呋喃
浓度:0.2质量/体积%
检量线:使用标准聚苯乙烯(PS)(Varian公司制)做成,分子量以PS换算值表示。
<芯片贴膜>
芯片贴膜使用以下任一种。
1:以丙烯酸酯共聚物为主体,厚度30μm。
2:以环氧系粘合剂为主体,厚度30μm。
<多层粘合片的制造>
将粘合剂涂布于由聚对苯二甲酸乙二酯制成的分离膜上,使干燥后的粘合层厚度为10μm。将该粘合层与基材膜层合,在40℃进行熟化7日,得到附有分离膜的粘合片。然后除去分离膜,在露出的粘合层上层合裁切成直径8.2英寸的圆形芯片贴膜,得到多层粘合片。
<多层粘合片的评价>
使用得到的多层粘合片,依照以下的步骤(1)~(3),将硅晶圆固定、切割,拾取半导体芯片,然后针对芯片保持性、拾取性及防污染性进行评价。
(1)贴附步骤:将形成虚拟电路图案的直径8英寸×厚度0.1mm的硅晶圆及环形架贴附并固定于多层粘合片的粘合层。
(2)切割步骤:使用切割刀片,将硅晶圆与多层粘合片的芯片贴膜一起裁切成9mm×9mm尺寸的半导体芯片。利用下述装置及条件进行切割步骤。
切割装置:DISCO公司制DAD341
切割刀片:DISCO公司制NBC-ZH2050-27HEEE
切割刀片形状:外径55.56mm,刃宽35μm,内径19.05mm
切割刀片转速:40000rpm
切割刀片推送速度:50mm/秒
对粘合片的切入量:15μm
切削水温度:25℃
切削水量:1.0L/分钟
(3)拾取步骤:照射紫外线,使粘合层的粘着力降低后,将芯片贴膜所附着的半导体芯片从粘合层剥离,并进行拾取。通过以下的装置及条件进行拾取步骤。
拾取装置:CannonMachinery公司制CAP-300II
针销(needlepin)形状:250μmR
针销突起高度:0.5mm
扩展量:8mm
<芯片保持性>
芯片保持性是以切断步骤后,被保持在粘合片的半导体芯片的残存率来评价。
◎(优):小于5%的芯片飞离
○(良):5%以上且小于10%的芯片飞离
×(不合格):10%以上芯片飞离
<拾取性>
拾取性是以拾取步骤中,可拾取的芯片的比率来评价。
◎(优):95%以上的芯片可拾取
○(良):80%以上且小于95%的芯片可拾取
×(不合格):小于80%的芯片可拾取
<防污染性>
如下评价防污染性:将粘合片的粘合层与芯片贴膜贴合,保管1周后,利用高压水银灯以500mJ/cm2照射紫外线,照射后再保管1周后或保管4周后,将芯片贴膜从粘合片剥离,对芯片贴膜进行GC-MS分析,确认来自粘合剂成分的峰,并进行评价。
◎(优):照射紫外线,保管1周后及保管4周后,针对任何从粘合片剥离的芯片贴膜均未见有来自粘合剂成分的峰。
○(良):在照射紫外线并保管1周后,针对从粘合片剥离的芯片贴膜未观察到来自粘合剂成分的峰,但是,在照射紫外线并保管4周后,针对从粘合片剥离的芯片贴膜可观察到来自粘合剂成分的峰。
×(不合格):照射紫外线,保管1周后及保管4周后,针对任何从粘合片剥离的芯片贴膜,均观察到来自粘合剂成分的吸收峰。
构成粘合层的粘合剂的组成、所用芯片贴膜的种类、评价结果,如表1所示。在表1中,表示构成粘合层的粘合剂的组成的数值为质量份。
〔表1〕
如表1所示,通过使构成粘合片的粘合层的粘合剂为特定组成,即使在将丙烯酸酯共聚物用于芯片贴膜的情况下,也可得到在拾取时容易将粘合层与芯片贴膜之间进行剥离,且半导体芯片的拾取性及芯片贴膜的防污染性优良的多层粘合片。
Claims (14)
1.一种多层粘合片,其具有基材膜、层合于基材膜的一侧表面的粘合层、以及层合于粘合层的露出面的芯片贴膜;
构成粘合层的粘合剂含有(甲基)丙烯酸酯共聚物(A)、紫外线聚合性化合物(B)、多官能异氰酸酯硬化剂(C)、光聚合引发剂(D)、及硅氧烷聚合物(E);
(甲基)丙烯酸酯共聚物(A)为(甲基)丙烯酸酯单体的共聚物或(甲基)丙烯酸酯单体与乙烯系化合物单体的共聚物的任一者,(甲基)丙烯酸酯单体与乙烯系化合物单体皆不具有羟基;
紫外线聚合性化合物(B)由氨基甲酸酯丙烯酸酯低聚物(B1)与多官能(甲基)丙烯酸酯(B2)所构成,氨基甲酸酯丙烯酸酯低聚物(B1)具有10个以上乙烯基,重均分子量Mw为50000以上,且所述重均分子量Mw与数均分子量Mn的比,即分散度Mw/Mn为5以上;
光聚合引发剂(D)具有羟基;
硅氧烷聚合物(E)具有羟基;
在构成粘合层的粘合剂中,(甲基)丙烯酸酯共聚物(A)为100质量份,紫外线聚合性化合物(B)为5~200质量份,多官能异氰酸酯硬化剂(C)为0.5~20质量份,光聚合引发剂(D)为0.1~20质量份,及硅氧烷聚合物(E)为0.1~20质量份。
2.如权利要求1所述的多层粘合片,其中,氨基甲酸酯丙烯酸酯低聚物与多官能(甲基)丙烯酸酯的质量比为50:50以上至95:5以下。
3.如权利要求1或2所述的多层粘合片,其中,氨基甲酸酯丙烯酸酯低聚物(B1)是(1)使含有羟基及多个(甲基)丙烯酸酯基的(甲基)丙烯酸酯化合物与具有多个异氰酸酯基的化合物反应而制造的物质;或者是(2)在具有多个羟基末端的多元醇低聚物中,添加过剩的具有多个异氰酸酯基的化合物,并使其反应,制成具有多个异氰酸酯基末端的低聚物,并进一步与含有羟基及多个(甲基)丙烯酸酯基的(甲基)丙烯酸酯化合物反应而得到的物质。
4.如权利要求1或2所述的多层粘合片,其中,氨基甲酸酯丙烯酸酯低聚物(B1)是使以二季戊四醇五丙烯酸酯作为主成分的含羟基的丙烯酸酯与异佛尔酮二异氰酸酯的三聚体的异氰酸酯基反应而得到的,多官能(甲基)丙烯酸酯(B2)为二季戊四醇六丙烯酸酯。
5.如权利要求1或2所述的多层粘合片,其中,(甲基)丙烯酸酯共聚物(A)是(甲基)丙烯酸丁酯、(甲基)丙烯酸乙酯及(甲基)丙烯酸甲氧基乙酯的共聚物;或者(甲基)丙烯酸酯共聚物(A)是(甲基)丙烯酸丁酯、(甲基)丙烯酸乙酯及(甲基)丙烯酸甲氧基乙酯与(甲基)丙烯酸的共聚物。
6.如权利要求1或2所述的多层粘合片,其中,多官能异氰酸酯硬化剂(C)具有2个以上异氰酸酯基。
7.如权利要求1或2所述的多层粘合片,其中,多官能异氰酸酯硬化剂(C)是芳香族多异氰酸酯。
8.如权利要求1或2所述的多层粘合片,其中,光聚合引发剂(D)具有至少1个羟基。
9.如权利要求1或2所述的多层粘合片,其中,光聚合引发剂(D)选自2-羟基-1-{4-〔4-(2-羟基-2-甲基-丙酰基)-苯甲基〕-苯基}-2-甲基-丙烷-1-酮和1-羟基-环己基-苯基-酮。
10.如权利要求1或2所述的多层粘合片,其中,硅氧烷聚合物(E)具有单体单元,所述单体单元来源于在聚二甲基硅氧烷键的末端具有乙烯基的单体。
11.如权利要求1或2所述的多层粘合片,其中,硅氧烷聚合物(E)有聚硅氧烷大分子单体的均聚物、聚硅氧烷大分子单体与其他乙烯系化合物聚合而得到的乙烯系聚合物。
12.如权利要求1或2所述的多层粘合片,其中,硅氧烷聚合物(E)在聚硅氧烷分子链的末端含有具有(甲基)丙烯酰基的硅氧烷低聚物类单元,并且是聚合了由甲基丙烯酸甲酯所构成的丙烯酸系乙烯系单元而得到的聚硅氧烷接枝共聚物。
13.如权利要求1或2所述的多层粘合片,其中,构成芯片贴膜的组合物具有丙烯酸酯共聚物。
14.一种电子元件的制造方法,包含:
贴附步骤,使用权利要求1至13中任一项所述的多层粘合片,并将多层粘合片贴附在硅晶圆及环形架进行固定;
切割步骤,用切割刀片切割硅晶圆,制成半导体芯片;
拾取步骤,至少照射紫外线或放射线,并从粘合层拾取芯片及芯片贴膜。
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PCT/JP2011/065149 WO2012008316A1 (ja) | 2010-07-14 | 2011-07-01 | 多層粘着シート及び電子部品の製造方法 |
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