CN113214756A - 紫外线固化型粘合片 - Google Patents
紫外线固化型粘合片 Download PDFInfo
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- CN113214756A CN113214756A CN202110073871.6A CN202110073871A CN113214756A CN 113214756 A CN113214756 A CN 113214756A CN 202110073871 A CN202110073871 A CN 202110073871A CN 113214756 A CN113214756 A CN 113214756A
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- Prior art keywords
- ultraviolet
- meth
- adhesive sheet
- acrylate
- adhesive layer
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- 239000000853 adhesive Substances 0.000 title claims abstract description 99
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 99
- 239000012790 adhesive layer Substances 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 238000012360 testing method Methods 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 58
- 239000003999 initiator Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 23
- 229920000178 Acrylic resin Polymers 0.000 claims description 18
- 239000004925 Acrylic resin Substances 0.000 claims description 18
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 11
- 229920000058 polyacrylate Polymers 0.000 claims description 11
- 239000004065 semiconductor Substances 0.000 claims description 8
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical group 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 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 239000004820 Pressure-sensitive adhesive Substances 0.000 abstract description 78
- 238000010186 staining Methods 0.000 abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 76
- 239000000178 monomer Substances 0.000 description 54
- 239000003431 cross linking reagent Substances 0.000 description 38
- -1 polyethylene terephthalate Polymers 0.000 description 37
- 235000012431 wafers Nutrition 0.000 description 30
- 239000000203 mixture Substances 0.000 description 28
- 239000011254 layer-forming composition Substances 0.000 description 25
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 13
- 125000000524 functional group Chemical group 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000004642 Polyimide Substances 0.000 description 8
- 238000011109 contamination Methods 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 229920001721 polyimide Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229920005601 base polymer Polymers 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 229940059574 pentaerithrityl Drugs 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000001035 drying Methods 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
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- ZVEMLYIXBCTVOF-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-3-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC(C(C)(C)N=C=O)=C1 ZVEMLYIXBCTVOF-UHFFFAOYSA-N 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 2
- VHFGGWSXGDWGOY-UHFFFAOYSA-N 2-isocyanatoethyl 2-methylprop-2-enoate 5-isocyanato-2-methylpent-2-enoic acid Chemical compound N(=C=O)CCC=C(C(=O)O)C.C(C(=C)C)(=O)OCCN=C=O VHFGGWSXGDWGOY-UHFFFAOYSA-N 0.000 description 2
- OZJJSQVLXHKGHV-UHFFFAOYSA-N 2-isocyanoethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC[N+]#[C-] OZJJSQVLXHKGHV-UHFFFAOYSA-N 0.000 description 2
- JEHFRMABGJJCPF-UHFFFAOYSA-N 2-methylprop-2-enoyl isocyanate Chemical compound CC(=C)C(=O)N=C=O JEHFRMABGJJCPF-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
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- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
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- 239000000049 pigment Substances 0.000 description 2
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- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
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- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
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- 239000004094 surface-active agent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
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- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- IAUGBVWVWDTCJV-UHFFFAOYSA-N 1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C=C IAUGBVWVWDTCJV-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- UBPXWZDJZFZKGH-UHFFFAOYSA-N 1-ethenyl-3-methylpyrrolidin-2-one Chemical compound CC1CCN(C=C)C1=O UBPXWZDJZFZKGH-UHFFFAOYSA-N 0.000 description 1
- BMZZOWWYEBTMBX-UHFFFAOYSA-N 1-ethyl-3-methylidenepyrrolidine-2,5-dione Chemical compound CCN1C(=O)CC(=C)C1=O BMZZOWWYEBTMBX-UHFFFAOYSA-N 0.000 description 1
- QSWFISOPXPJUCT-UHFFFAOYSA-N 1-methyl-3-methylidenepyrrolidine-2,5-dione Chemical compound CN1C(=O)CC(=C)C1=O QSWFISOPXPJUCT-UHFFFAOYSA-N 0.000 description 1
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-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
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- 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
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- C09J7/385—Acrylic polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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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
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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Abstract
提供一种对被粘物表面的污染性低的紫外线固化型粘合片。本发明的紫外线固化型粘合片具有基材和粘合剂层。该紫外线固化型粘合片中,在紫外线照射试验后将该紫外线固化型粘合片剥离后的硅晶圆的贴合粘合剂层的面的粒径小于1.5μm的颗粒数少于100个。
Description
技术领域
本发明涉及紫外线固化型粘合片。更详细而言,涉及适合用于半导体晶圆加工的紫外线固化型粘合片。
背景技术
大规模集成电路(LSI)已被用于个人计算机、智能手机、汽车等各种用途中。近年来,LSI的微细化和高功能化正在推进,晶圆的表面结构日益复杂化。另外,作为半导体封装体与集成电路的连接方法,正在使用引线接合。作为引线接合中使用的接合线,使用金(Au)制的线。近年来,从成本角度出发,正在向银(Ag)线或铜(Cu)线变更。这些金属制的线与金相比,向晶圆表面的连接更为困难,需要更高强度的接合处理。另一方面,随着微细化,LSI本身变得脆弱,在连接时难以进行高强度的接合处理(例如超声波)。
半导体晶圆在以大直径状态制造、并在表面形成图案后,对背面进行磨削(背面研磨),通常使晶圆的厚度减薄至40μm~600μm左右。在背面研磨工序中,为了固定半导体晶圆、另外为了保护与磨削面处于相反侧的面,会使用粘合片(背面研磨带)(例如专利文献1)。但是,众所周知粘合片(更详细而言,粘合剂层)会造成晶圆表面的污染(附着微细的颗粒)。在实施引线接合时,这样的污染可能会成为实施不良的原因。
另外,作为晶圆的加工技术,已提出了各种方法。例如提出了在用激光于晶圆上引入切缝后对背面进行磨削而薄型化、并进行单片化的技术(Stealth Dicing BeforeGrinding,SDBG,隐形切割后研磨)(例如,专利文献2)。在背面研磨带和用于SDBG工序的粘合片中,为了在期望的工序后能够容易地剥离而使用紫外线固化型粘合剂。对于具有使用紫外线固化型粘合剂形成的粘合剂层的粘合片而言,也存在在紫外线照射后的剥离工序中微细的颗粒附着于被粘物表面、产生晶圆表面污染的问题。
现有技术文献
专利文献
专利文献1:日本特开2007-084722号公报
专利文献2:日本特开2004-111428号公报
发明内容
发明要解决的问题
本发明是为了解决上述现有课题而作出的,其目的在于,提供对被粘物表面为低污染性的紫外线固化型粘合片。
用于解决问题的方案
在一个实施方式中,本发明的紫外线固化型粘合片具有基材和粘合剂层。该紫外线固化型粘合片中,在紫外线照射试验后将该紫外线固化型粘合片剥离后的硅晶圆的贴合粘合剂层的面的粒径小于1.5μm的颗粒数少于100个。
在一个实施方式中,上述粘合剂层包含光聚合引发剂。
在一个实施方式中,上述光聚合引发剂为2-羟基-1-{4-[4-(2-羟基-2-甲基-丙酰基)-苄基]-苯基}-2-甲基-丙烷-1-酮。
在一个实施方式中,在上述基材与上述粘合剂层之间包含中间层。
在一个实施方式中,上述中间层与上述粘合剂层包含相同的光聚合引发剂。
在一个实施方式中,上述粘合剂层包含向(甲基)丙烯酸系树脂中导入了聚合性碳-碳双键的(甲基)丙烯酸系聚合物。
在一个实施方式中,上述紫外线固化型粘合片用于半导体晶圆加工工序中。
在一个实施方式中,上述紫外线固化型粘合片作为背面研磨片使用。
发明的效果
本发明的紫外线固化型粘合片具有基材和粘合剂层。该紫外线固化型粘合片中,在紫外线照射试验后将该紫外线固化型粘合片剥离后的硅晶圆的贴合粘合剂层的面的粒径小于1.5μm的颗粒数少于100个。通过使用这样的紫外线固化型粘合片,能够防止微细的颗粒污染被粘物表面。因此,能够在对将紫外线固化型粘合片剥离后的被粘物不实施高强度的接合处理的情况下使用成本更低的Ag线或Cu线进行引线接合。因此,能够降低制造中所花费的成本。进而,由于不再需要高强度的接合处理,因此对于薄型化·小型化的LSI也能够良好地进行引线接合。另外,不论被粘物表面的组成(例如金属等无机物、或树脂等有机物)如何,本发明的紫外线固化型粘合片均能够在紫外线照射后发挥优异的轻剥离性。因此,在被粘物表面的组成复杂的情况下,也能够防止被粘物表面上的残胶。
附图说明
图1为本发明的一个实施方式的紫外线固化型粘合片的概要剖视图。
附图标记说明
10 基材
20 粘合剂层
30 中间层
100 粘合片
具体实施方式
A.粘合片
A-1.粘合片的概要
图1为本发明的一个实施方式的紫外线固化型粘合片的概要剖视图。图中例示的紫外线固化型粘合片100具备基材10、和配置在基材10的一个面上的粘合剂层20。在一个实施方式中,紫外线固化型粘合片100在基材10与粘合剂层20之间具备中间层30。典型情况下,粘合剂层20由包含紫外线固化型粘合剂的组合物形成。在实际使用中,在直至使用之前为止,在粘合剂层20上以可剥离的方式临时粘接有分隔件,以适宜地保护粘合剂层20。
在另一实施方式中,粘合剂层为两层构成,紫外线固化型粘合片依次具备第1粘合剂层和第2粘合剂层(未图示)。
上述紫外线固化型粘合片中,在紫外线照射试验后将该紫外线固化型粘合片剥离后的硅晶圆的贴合粘合剂层的面的粒径小于1.5μm的颗粒数少于100个,优选少于95个,进一步优选少于90个。粒径小于1.5μm的微细的颗粒可分布于被粘物(例如硅晶圆)的贴合粘合剂层的整个面上。该微细的颗粒例如在引线接合工序中可能导致接合不良。上述紫外线固化型粘合片的污染性低,能够防止微细的颗粒对剥离后的被粘物的贴合粘合剂层的面的污染。因此,能够将剥离后的被粘物适宜地用于引线接合工序等。在本说明书中,在紫外线照射试验后将该紫外线固化型粘合片剥离后的硅晶圆的贴合粘合剂层的面的粒径小于1.5μm的颗粒数是指:利用后述的实施例中记载的方法测定而得的颗粒数(8英寸晶圆表面的颗粒数)。
粘合片的厚度能够设定为任意的合适的范围。优选为5μm~1000μm,更优选为50μm~300μm,进一步优选为100μm~300μm。
A-2.基材
基材能够由任意的合适的树脂构成。作为构成基材的树脂的具体例,可列举聚酯系树脂(聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸丁二醇酯等)、乙烯-乙酸乙烯酯共聚物、乙烯-甲基丙烯酸甲酯共聚物、聚烯烃系树脂(聚乙烯、聚丙烯、乙烯-丙烯共聚物等)、聚乙烯醇、聚偏氯乙烯、聚氯乙烯、氯乙烯-乙酸乙烯酯共聚物、聚乙酸乙烯酯、聚酰胺、聚酰亚胺、纤维素类、氟系树脂、聚醚、聚苯乙烯系树脂(聚苯乙烯等)、聚碳酸酯、聚醚砜等。
基材可以以不损害本发明的效果的范围进一步包含其他成分。作为其他成分,可列举例如抗氧化剂、紫外线吸收剂、光稳定剂、耐热稳定剂、抗静电剂等。关于其他成分的种类和使用量,可以根据目的以任意的合适的量来使用。
基材的厚度能够设为任意的合适的值。基材的厚度优选为10μm~200μm,更优选为20μm~150μm。
基材的弹性模量能够设为任意的合适的值。基材的弹性模量优选为50MPa~6000MPa,更优选为70MPa~5000MPa。通过使弹性模量为上述范围,能够得到能够适度地追随被粘物表面的凹凸的粘合片。
A-3.粘合剂层
粘合剂层使用任意的合适的粘合剂层形成组合物来形成。粘合剂层形成组合物优选包含光聚合引发剂。通过包含光聚合引发剂,从而在紫外线照射后能够以更小的力将粘合片从被粘物剥离。
A-3-1.粘合剂层形成组合物
粘合剂层能够使用任意的合适的粘合剂层形成组合物来形成。粘合剂层形成组合物优选包含光聚合引发剂。典型情况下,粘合剂层形成组合物包含紫外线固化型粘合剂和光聚合引发剂。
A-3-1-1.紫外线固化型粘合剂
作为紫外线固化型粘合剂,可使用任意的合适的粘合剂。例如,可以为在丙烯酸系粘合剂、橡胶系粘合剂、有机硅系粘合剂、聚乙烯基醚系粘合剂等任意的合适的粘合剂中添加紫外线固化性的单体和/或低聚物而成的粘合剂,也可以为使用在侧链或末端具有碳-碳双键的聚合物作为基础聚合物的粘合剂。优选利用使用了在侧链或末端具有碳-碳双键的聚合物作为基础聚合物的粘合剂。
利用使用了在侧链或末端具有碳-碳双键的聚合物的粘合剂的情况下,作为基础聚合物,使用在侧链或末端具有聚合性碳-碳双键且具有粘合性的聚合物。作为这样的聚合物,可列举例如向(甲基)丙烯酸系树脂、乙烯基烷基醚系树脂、有机硅系树脂、聚酯系树脂、聚酰胺系树脂、氨基甲酸酯系树脂、苯乙烯-二烯嵌段共聚物等树脂中导入了聚合性碳-碳双键的聚合物。优选使用向(甲基)丙烯酸系树脂中导入了聚合性碳-碳双键的(甲基)丙烯酸系聚合物。通过使用该(甲基)丙烯酸系聚合物,从而能够得到粘合剂层的储能模量和拉伸模量容易调整、另外粘合力与剥离性的平衡优异的粘合片。进而,能够降低源自粘合剂的成分造成的被粘物污染。需要说明的是,“(甲基)丙烯*”是指丙烯*和/或甲基丙烯*。
作为(甲基)丙烯酸系树脂,可以使用任意的合适的(甲基)丙烯酸系树脂。作为(甲基)丙烯酸系树脂,可列举例如:将包含一种或两种以上的具有直链烷基或支链烷基的丙烯酸或甲基丙烯酸的酯的单体组合物进行聚合而得到的聚合物。
直链烷基或支链烷基优选碳数为30个以下的烷基,更优选碳数为1个~20个的烷基,进一步优选碳数为4个~18个的烷基。作为烷基,具体而言,可列举甲基、乙基、丙基、异丙基、正丁基、叔丁基、异丁基、戊基、异戊基、己基、庚基、环己基、2-乙基己基、辛基、异辛基、壬基、异壬基、癸基、异癸基、十一烷基、月桂基、十三烷基、十四烷基、硬脂基、十八烷基、十二烷基等。
形成(甲基)丙烯酸系树脂的单体组合物可以包含任意的合适的其他单体。作为其他单体,可列举例如:丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、衣康酸、马来酸、富马酸、巴豆酸等含羧基单体;马来酸酐、衣康酸酐等酸酐单体;(甲基)丙烯酸2-羟乙酯、(甲基)丙烯酸2-羟丙酯、(甲基)丙烯酸4-羟丁酯、(甲基)丙烯酸6-羟己酯、(甲基)丙烯酸8-羟辛酯、(甲基)丙烯酸10-羟癸酯、(甲基)丙烯酸12-羟基月桂酯、丙烯酸(4-羟甲基环己基)甲酯、2-羟乙基乙烯基醚、4-羟丁基乙烯基醚、二乙二醇单乙烯基醚等含羟基单体;苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯酰胺-2-甲基丙磺酸、(甲基)丙烯酰胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯酰氧基萘磺酸等含磺酸基单体;2-羟乙基丙烯酰基磷酸酯等含磷酸基单体等含有官能团的单体。通过包含含有官能团的单体,能得到容易导入聚合性碳-碳双键的(甲基)丙烯酸系树脂。关于含有官能团的单体的含有比例,相对于单体组合物的全部单体100重量份优选为4重量份~30重量份,更优选为6重量份~20重量份。
作为其他单体,可以使用多官能单体。通过使用多官能单体,能够提高粘合剂的内聚力、耐热性、粘接性等。另外,粘合剂层中的低分子量成分减少,因此能够得到不易污染被粘物的粘合片。作为多官能性单体,可列举例如己二醇(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、环氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯等。关于多官能单体的含有比例,相对于上述单体组合物的全部单体100重量份优选为1重量份~100重量份,更优选为5重量份~50重量份。
(甲基)丙烯酸系树脂的重均分子量优选为30万以上,更优选为50万以上,进一步优选为80万~300万。若为这样的范围,则能够防止低分子量成分的渗出、得到低污染性的粘合片。(甲基)丙烯酸系树脂的分子量分布(重均分子量/数均分子量)优选为1~20,更优选为3~10。通过使用分子量分布窄的(甲基)丙烯酸系树脂,能够防止低分子量成分的渗出、得到低污染性的粘合片。需要说明的是,重均分子量和数均分子量可以通过凝胶渗透色谱测定(溶剂:四氢呋喃,聚苯乙烯换算)来求出。
在侧链或末端具有聚合性碳-碳双键的聚合物可以通过任意的合适的方法来得到。例如,能通过使利用任意的合适的聚合方法得到的树脂与具有聚合性碳-碳双键的化合物反应(例如缩合反应、加成反应)来得到。具体而言,在使用(甲基)丙烯酸系树脂的情况下,使包含来自具有任意的合适的官能团的单体的构成单元的(甲基)丙烯酸系树脂(共聚物)在任意的合适的溶剂中聚合,之后使该丙烯酸系树脂的官能团和具有能够与该官能团反应的聚合性碳-碳双键的化合物反应,由此能够得到上述聚合物。具有进行反应的聚合性碳-碳双键的化合物的量相对于上述树脂100重量份优选为4重量份~30重量份,更优选为4重量份~20重量份。作为溶剂,可以使用任意的合适的溶剂,可列举例如乙酸乙酯、甲乙酮、甲苯等各种有机溶剂。
在如上述那样使树脂与具有聚合性碳-碳双键的化合物反应的情况下,优选树脂和具有聚合性碳-碳双键的化合物分别具有能够彼此反应的官能团。作为官能团的组合,可列举例如羧基/环氧基、羧基/氮丙啶基、羟基/异氰酸酯基等。在这些官能团的组合中,从容易追踪反应的角度出发,优选羟基与异氰酸酯基的组合。
作为上述具有聚合性碳-碳双键的化合物,可列举例如甲基丙烯酸2-异氰基乙酯、甲基丙烯酰基异氰酸酯、2-甲基丙烯酰氧基乙基异氰酸酯(甲基丙烯酸2-异氰酸根合乙酯)、间异丙烯基-α,α-二甲基苄基异氰酸酯等。
A-3-1-2.光聚合引发剂
作为光聚合引发剂,可以使用任意的合适的光聚合引发剂。优选使用例如2-羟基-1-{4-[4-(2-羟基-2-甲基-丙酰基)-苄基]-苯基}-2-甲基-丙烷-1-酮。通过使用这些光聚合引发剂,能够得到污染性更低的紫外线固化型粘合片。光聚合引发剂既可以仅使用一种,也可以将两种以上组合使用。
能够以任意的合适的量来使用光聚合引发剂。光聚合引发剂的含量相对于上述紫外线固化型粘合剂100重量份优选为0.1重量份~10重量份,更优选为0.5重量份~7重量份。
A-3-1-3.交联剂
粘合剂层形成组合物优选还包含交联剂。作为交联剂,可列举例如异氰酸酯系交联剂、环氧系交联剂、噁唑啉系交联剂、氮丙啶系交联剂、三聚氰胺系交联剂、过氧化物系交联剂、脲系交联剂、金属醇盐系交联剂、金属螯合物系交联剂、金属盐系交联剂、碳二亚胺系交联剂、胺系交联剂等。
在一个实施方式中,优选使用异氰酸酯系交联剂。异氰酸酯系交联剂从能够与多种官能团反应的角度出发是优选的。作为上述异氰酸酯系交联剂的具体例,可列举:亚丁基二异氰酸酯、六亚甲基二异氰酸酯等低级脂肪族多异氰酸酯类;亚环戊基二异氰酸酯、亚环己基二异氰酸酯、异佛尔酮二异氰酸酯等脂环族异氰酸酯类;2,4-甲苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯等芳香族异氰酸酯类;三羟甲基丙烷/甲苯二异氰酸酯三聚体加成物(具体而言,东曹公司制造、商品名“Coronate L”)、三羟甲基丙烷/六亚甲基二异氰酸酯三聚体加成物(具体而言,日本聚氨酯工业公司制造、商品名“Coronate HL”)、六亚甲基二异氰酸酯的异氰脲酸酯体(具体而言,日本聚氨酯工业公司制造、商品名“Coronate HX”)等异氰酸酯加成物;等。优选使用具有3个以上异氰酸酯基的交联剂。
交联剂的含量可调整为任意的合适的量。例如,相对于紫外线固化型粘合剂100重量份,优选为0.005重量份~20重量份,更优选为0.02重量份~10重量份。
A-3-1-4.其他成分
紫外线固化型粘合剂组合物可以还包含任意的合适的添加剂。作为添加剂,可列举例如活性能量射线聚合促进剂、自由基捕捉剂、增粘剂、增塑剂(例如偏苯三酸酯系增塑剂、均苯四酸酯系增塑剂)、颜料、染料、填充剂、防老剂、导电材料、抗静电剂、紫外线吸收剂、光稳定剂、剥离调整剂、软化剂、表面活性剂、阻燃剂、抗氧化剂等。其他添加剂可以以任意的合适的量来使用。
粘合剂层的厚度能够设为任意的合适的值。粘合剂层的厚度优选为1μm~50μm,更优选为2μm~20μm,进一步优选为3μm~10μm。
粘合剂层的紫外线照后的聚酰亚胺粘合力与硅粘合力之比(聚酰亚胺粘合力/硅粘合力)优选为2以下,进一步优选为1.9以下,进一步优选为1.8以下。通过使聚酰亚胺粘合力与硅粘合力之比为上述范围,能够防止粘合片剥离时的被粘物上的残胶。在本说明书中,紫外线照射后的聚酰亚胺粘合力和硅粘合力是指:用后述的实施例中记载的方法测定而得的粘合力。
粘合剂层的紫外线照射前的弹性模量优选为0.05MPa~2.0MPa,更优选为0.075MPa~1.0MPa,进一步优选为0.08MPa~0.80MPa,特别优选为0.1MPa以上且小于0.7MPa。若为这样的范围,则能够得到具有对于保持被粘物而言充分的粘合力的粘合片。在本说明书中,粘合剂层的弹性模量是指:利用以下的方法测定得到的弹性模量(杨氏模量)。
将粘合剂层形成组合物以涂布厚度达到5μm的方式涂布于分隔件,在130℃干燥2分钟。接着,仅将涂布干燥后的粘合剂层从端部卷起而制作棒状的试样,计测厚度(截面积)。将在卡盘间距离为10mm、拉伸速度为50mm/分钟、室温的条件下用拉伸试验机(SHIMADZU公司制造、商品名“AG-IS”)对得到的试样进行拉伸时的最初的斜率(杨氏模量)作为弹性模量。
粘合剂层的紫外线照射后的弹性模量优选为1MPa以上,更优选为5MPa以上,进一步优选为10MPa以上。若为这样的范围,则能够得到规定工序(例如背面研磨工序)后的剥离性优异的粘合片。粘合剂层的紫外线照射后的弹性模量为例如1000MPa以下,优选为500MPa以下,更优选为400MPa以下。
粘合剂层可以为1层,也可以为2层以上。在粘合剂层为2层以上时,只要包含至少1层使用包含上述光聚合引发剂的粘合剂层形成组合物形成的粘合剂层即可。在粘合剂层为2层以上的情况下,优选在粘合片的与被粘物接触的面上形成粘合剂层,且所述粘合剂层是使用包含光聚合引发剂的粘合剂组合物形成的。不是由上述粘合剂层形成组合物形成的粘合剂层能够用任意的合适的粘合剂组合物来形成。该粘合剂组合物可以为紫外线固化型粘合剂,也可以为压敏性粘合剂。
A-4.中间层
在一个实施方式中,紫外线固化型粘合片在基材与粘合剂层之间具有中间层。中间层能够用任意的合适的材料来形成。中间层例如能够用丙烯酸系树脂、聚乙烯系树脂、乙烯-乙烯醇共聚物、乙烯乙酸乙烯酯系树脂、和乙烯-甲基丙烯酸甲酯树脂等树脂或者粘合剂来形成。在用粘合剂形成中间层的情况下,粘合剂可以为紫外线固化型粘合剂,也可以为压敏性粘合剂。
在一个实施方式中,中间层由包含(甲基)丙烯酸系聚合物的中间层形成组合物形成。优选(甲基)丙烯酸系聚合物包含来自(甲基)丙烯酸烷基酯的构成成分。作为(甲基)丙烯酸烷基酯,可列举例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸异戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸异壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等(甲基)丙烯酸C1-C20烷基酯。
以改善内聚力、耐热性、交联性等为目的,(甲基)丙烯酸系聚合物可以根据需要包含对应于能够与上述(甲基)丙烯酸烷基酯共聚的其他单体的构成单元。作为这样的单体,可列举例如:丙烯酸、甲基丙烯酸等含羧基单体;马来酸酐、衣康酸酐等酸酐单体;(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯等含羟基单体;苯乙烯磺酸、烯丙基磺酸等含磺酸基单体;(甲基)丙烯酰胺、N,N-二甲基(甲基)丙烯酰胺、丙烯酰基吗啉等含氮单体;(甲基)丙烯酸氨基乙酯等(甲基)丙烯酸氨基烷基酯系单体;(甲基)丙烯酸甲氧基乙酯等(甲基)丙烯酸烷氧基烷基酯系单体;N-环己基马来酰亚胺、N-异丙基马来酰亚胺等马来酰亚胺系单体;N-甲基衣康酰亚胺、N-乙基衣康酰亚胺等衣康酰亚胺系单体;琥珀酰亚胺系单体;乙酸乙烯酯、丙酸乙烯酯、N-乙烯基吡咯烷酮、甲基乙烯基吡咯烷酮等乙烯基系单体;丙烯腈、甲基丙烯腈等氰基丙烯酸酯单体;(甲基)丙烯酸缩水甘油酯等含环氧基丙烯酸系单体;(甲基)丙烯酸聚乙二醇酯、(甲基)丙烯酸聚丙二醇酯等二醇系丙烯酸酯单体;(甲基)丙烯酸四氢糠酯、氟代(甲基)丙烯酸酯、有机硅(甲基)丙烯酸酯等具有杂环、卤原子、硅原子等的丙烯酸酯系单体;异戊二烯、丁二烯、异丁烯等烯烃系单体;乙烯基醚等乙烯基醚系单体等。这些单体成分既可以单独使用,也可以将两种以上组合使用。关于来自上述其他单体的构成单元的含有比例,在丙烯酸系聚合物100重量份中优选为1重量份~30重量份,更优选为3重量份~25重量份。
中间层形成组合物可以还包含活性能量射线反应性化合物(单体或低聚物)。作为活性能量射线反应性化合物,可列举例如含有丙烯酰基、甲基丙烯酰基、乙烯基、烯丙基、乙炔基等具有聚合性碳-碳多重键的官能团的光反应性的单体或低聚物。若使用具有2个以上官能团的多官能丙烯酸酯之类的多官能单体,则能够通过与上述(甲基)丙烯酸烷基酯键合而得到高分子量的UV聚合(甲基)丙烯酸系聚合物。作为该光反应性的单体的具体例,可列举三羟甲基丙烷三(甲基)丙烯酸酯、四羟甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇单羟基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯等(甲基)丙烯酸与多元醇的酯化物;多官能氨基甲酸酯(甲基)丙烯酸酯;环氧(甲基)丙烯酸酯;低聚酯(甲基)丙烯酸酯等。另外,还可以使用甲基丙烯酰基异氰酸酯、2-甲基丙烯酰氧基乙基异氰酸酯(甲基丙烯酸2-异氰酸根合乙酯)、间异丙烯基-α,α-二甲基苄基异氰酸酯等单体。作为光反应性的低聚物的具体例,可列举上述单体的二聚体~五聚体等。
作为上述活性能量射线反应性化合物,可以使用:环氧化丁二烯、甲基丙烯酸缩水甘油酯、丙烯酰胺、乙烯基硅氧烷等单体;或由该单体构成的低聚物。
作为活性能量射线反应性化合物,可以使用鎓盐等有机盐类与在分子内具有多个杂环的化合物的混合物。该混合物能够通过照射活性能量射线(例如紫外线、电子束)而发生有机盐裂解、生成离子并以其为起始种引发杂环的开环反应、从而形成三维网状结构。作为上述有机盐类,可列举例如碘鎓盐、鏻盐、锑鎓盐、锍盐、硼酸盐等。作为上述在分子内具有多个杂环的化合物中的杂环,可列举环氧乙烷、氧杂环丁烷、四氢呋喃、环硫乙烷、氮丙啶等。
中间层形成用组合物包含活性能量射线反应性化合物的情况下,活性能量射线反应性化合物的含有比例相对于基础聚合物100重量份优选为0.1重量份~100重量份,更优选为0.1重量份~50重量份,进一步优选为0.1重量份~10重量份。
中间层形成用组合物可以包含光聚合引发剂。优选中间层包含与上述粘合剂层相同的光聚合引发剂。通过使中间层和粘合剂层包含相同的光聚合引发剂,从而能够得到污染性更低的紫外线固化型粘合片。
在包含除粘合剂层形成组合物所用的光聚合引发剂以外的光聚合引发剂的情况下,作为光聚合引发剂,能够使用任意的合适的光聚合引发剂。可列举例如:BASF公司制造的商品名“Irgacure 184”、“Irgacure 651”、“Irgacure369”、“Irgacure 379ex”、“Irgacure 819”、“Irgacure OXE2”、“Irgacure 127”;Lamberti公司制造的商品名“Esacure one”、“Esacure 1001m”;旭电化工业公司制造的商品名“Adeka Optomer N-1414”、“Adeka Optomer N-1606”、“Adeka Optomer N-1717”等。关于光聚合引发剂的含有比例,相对于中间层形成用组合物中的聚合物构成成分100重量份优选为0.1重量份~20重量份,更优选为2重量份~10重量份。
在一个实施方式中,上述中间层形成用组合物还包含交联剂。作为交联剂,可列举例如异氰酸酯系交联剂、环氧系交联剂、噁唑啉系交联剂、氮丙啶系交联剂、三聚氰胺系交联剂、过氧化物系交联剂、脲系交联剂、金属醇盐系交联剂、金属螯合物系交联剂、金属盐系交联剂、碳二亚胺系交联剂、胺系交联剂等。
中间层形成用组合物包含交联剂的情况下,交联剂的含有比例相对于中间层形成用组合物中的聚合物构成成分100重量份优选为0.5重量份~10重量份,更优选为1重量份~8重量份。
中间层形成用组合物可根据需要还包含任意的合适的添加剂。作为添加剂,可列举例如活性能量射线聚合促进剂、自由基捕捉剂、增粘剂、增塑剂(例如偏苯三酸酯系增塑剂、均苯四酸酯系增塑剂等)、颜料、染料、填充剂、防老剂、导电材料、抗静电剂、紫外线吸收剂、光稳定剂、剥离调整剂、软化剂、表面活性剂、阻燃剂、抗氧化剂等。
上述(甲基)丙烯酸系聚合物的重均分子量优选为30万~1500万,更优选为50万~150万。重均分子量可利用GPC(溶剂:THF)来测定。
上述(甲基)丙烯酸系聚合物的玻璃化转变温度优选为-50℃~30℃,更优选为-40℃~20℃。若为这样的范围,则能够得到耐热性优异、可适宜地用于加热工序的粘合片。
中间层的厚度为10μm~1000μm。通过形成具有这样的厚度的中间层,能够得到能够良好地填埋凹凸面的粘合片。中间层的厚度优选为20μm~300μm,更优选为20μm~200μm,进一步优选为20μm~150μm,特别优选为20μm~100μm。
在一个实施方式中,中间层可以使用上述A-2-1-1项中例示的紫外线固化型粘合剂。在中间层由紫外线固化型粘合剂形成的情况下,所使用的紫外线固化型粘合剂可以与粘合剂层相同,也可以不同。
中间层的弹性模量优选为0.05MPa~10MPa,更优选为0.075MPa~5MPa,进一步优选为0.10MPa~0.50MPa。若为这样的范围,则能够得到能良好地填埋被粘物表面的凹凸的粘合片。另外,能够提高粘合片的被粘物保持力。
C.紫外线固化型粘合片的制造方法
紫外线固化型粘合片能够通过任意的合适的方法来制造。紫外线固化型粘合片例如能够通过在基材上涂覆上述紫外线固化型粘合剂组合物来得到。作为涂覆方法,可采用棒涂机涂覆、气刀涂覆、凹版涂覆、凹版反向涂覆、反向辊涂覆、唇式涂覆、模涂、浸渍涂覆、胶版印刷、柔版印刷、丝网印刷等各种方法。另外,也可以采用另行在分隔件上形成粘合剂层后将其贴合在基材上的方法等。
紫外线固化型粘合片包含中间层的情况下,粘合片例如可通过在基材上形成中间层、之后形成粘合剂层来制作。中间层可通过任意的合适的方法来形成。具体而言,可通过与上述粘合剂层相同的方法来形成。
D.紫外线固化型粘合片的用途
本发明的紫外线固化型粘合片为对被粘物表面的污染性低的紫外线固化型粘合片。因此,能够适合用于被粘物上的污染、特别是微细的颗粒所致的被粘物表面上的污染会成为问题的用途。
在一个实施方式中,本发明的紫外线固化型粘合片可适合用于半导体晶圆的加工工序。上述紫外线固化型粘合片对被粘物表面的污染性低。因此,能够适合用于后续工序中要求防止被粘物表面的污染的工序、例如包括引线接合工序在内的半导体晶圆的加工工序。
在一个实施方式中,上述紫外线固化型粘合片可以适宜地作为背面研磨带使用。上述紫外线固化型粘合片在紫外线照射后能够发挥优异的轻剥离性。另外,在紫外线照射后,不论被粘物表面的组成(例如金属等无机物或树脂等有机物)如何,均能够发挥优异的轻剥离。因此,即使在被粘物表面的组成复杂的情况下,也能够防止被粘物表面上的残胶。因此,在背面研磨工序后能够容易地从被粘物剥离,还能够防止被粘物上的残胶。
实施例
以下,通过实施例具体地说明本发明,但本发明不受这些实施例的限定。实施例中的试验和评价方法如下所述。另外,只要没有特别声明,则“份”和“%”为重量基准。
<制造例1>粘合剂基础聚合物溶液的制备
将丙烯酸-2-乙基己酯100重量份、丙烯酰基吗啉25.5重量份、丙烯酸-2-羟乙酯18.5重量份、聚合引发剂(过氧化苯甲酰(BPO))0.2重量份、和溶剂(甲苯)混合,由此制备单体组合物。将该单体组合物投入在1L圆底可拆式烧瓶上装备可拆式盖、分液漏斗、温度计、氮气导入管、李比希冷凝器、真空密封件、搅拌棒、搅拌叶片而成的聚合用实验装置中,一边搅拌,一边在常温下进行6小时氮气置换。之后,在通入氮气的情况下,一边搅拌一边在60℃下保持8小时而进行聚合,得到树脂溶液。
将得到的树脂溶液冷却到室温,之后,向该树脂溶液中加入作为具有聚合性碳-碳双键的化合物的甲基丙烯酸2-异氰基乙酯(昭和电工公司制造、商品名“Karenz MOI”)22.4重量份。进而,添加二月桂酸二丁基锡IV(和光纯药工业公司制造)0.11重量份,在空气氛围下在50℃搅拌24小时,得到聚合物溶液。
<制造例2>中间层基础聚合物的制备
将丙烯酸丁酯50重量份、丙烯酸乙酯50重量份、丙烯酸5重量份、和偶氮双异丁腈0.1重量份在甲苯中在氮气气氛、60℃下聚合6小时,得到重均分子量为65万的丙烯酸系树脂。
[实施例1]
(粘合剂层形成组合物的制备)
向制造例1中得到的聚合物溶液100重量份中配混交联剂(东曹公司制造、商品名:Coronate L)2重量份和光聚合引发剂1(IGM Resins公司制造、商品名:Omnirad 127、2-羟基-1-{4-[4-(2-羟基-2-甲基-丙酰基)-苄基]-苯基}-2-甲基-丙烷-1-酮)3重量份并进行搅拌,得到紫外线固化型粘合剂组合物。
(中间层形成组合物的制备)
向制造例2中得到的丙烯酸系树脂100重量份中配混交联剂(东曹公司制造、商品名:Coronate L)1重量份、光聚合引发剂1(IGM Resins公司制造、商品名:Omnirad 127、2-羟基-1-{4-[4-(2-羟基-2-甲基-丙酰基)-苄基]-苯基}-2-甲基-丙烷-1-酮)3重量份并进行搅拌,得到中间层形成组合物。
(粘合片的制作)
作为基材,使用对聚对苯二甲酸乙二醇酯薄膜(东丽公司制造、制品名:LumirrorS10#100、厚:100μm)的一个面实施了电晕处理而成的薄膜。在基材的电晕处理面上涂布中间层形成组合物并干燥,形成厚95μm的中间层。接着,在形成的中间层上以干燥后的厚度达到5μm的方式涂布粘合剂层形成组合物并干燥,得到粘合片1。
(比较例1)
在粘合剂层形成组合物和中间层形成组合物中,使用光聚合引发剂2(IGM Resins公司制造、商品名:Omnirad 369、2-苄基-2-二甲基氨基-1-(4-吗啉代苯基)-丁酮-1)1重量份代替光聚合引发剂1,除此以外与实施例1同样地进行,得到粘合片C1。
(比较例2)
在粘合剂层形成组合物和中间层形成组合物中,使用光聚合引发剂3(IGM Resins公司制造、商品名:Omnirad TPO、2,4,6-三甲基苯甲酰基-二苯基氧化膦)3重量份代替光聚合引发剂1,除此以外与实施例1同样地进行,得到粘合片C2。
使用实施例和比较例中得到的粘合片进行以下的评价。将结果示于表1。
(1)粘合力
使用Si镜面晶圆(信越化学制造)、涂布有非感光性聚酰亚胺的晶圆(KST WORLD制造)、铜板(神戸制钢公司制造、商品名:KLH-194-H)作为被粘物,分别测定硅粘合力(Si粘合力)、聚酰亚胺粘合力(PI粘合力)、铜粘合力(Cu粘合力)。将被粘物依次用甲苯、甲醇、甲苯进行洗涤·干燥而进行预处理,接着贴合各实施例或比较例的粘合片,在常温下保管30分钟。之后,用高压汞灯(70mW/cm2、日东精机公司制造、制品名:UM-810)照射约12秒钟而进行UV照射(1000mJ/cm2)后(UV照射后),分别在以下的条件下测定粘合力。另外,目视确认粘合剂层有无黄变。
<粘合力测定条件>
拉伸速度:300mm/分钟
剥离角度:180°
温度:23℃
湿度:50%RH
带宽:20mm
(2)颗粒数测定
在洁净台内,于未使用的硅镜面晶圆(8英寸)上贴合实施例或比较例中得到的粘合片。之后保管30分钟,用高压汞灯(70mW/cm2、日东精机公司制造、制品名:UM-810)进行约12秒钟的UV照射(1000mJ/cm2)。接着,将粘合片从硅镜面晶圆剥离,在以下的条件下测定硅晶圆表面的颗粒数。
<测定条件>
测定装置:晶圆检查装置Surfscan SP1(KLA-Tencor公司制造)
光源:氩离子激光(波长:488nm)
激光照射角度:Normal(激光垂直照射)
处理量:低
边缘切割:55mm
测定粒形区间:0.28μm以上~小于0.39μm、0.39μm以上~小于1.5μm、1.5μm以上~小于2.5μm、2.5μm以上~小于10μm
将在0.28μm以上~小于0.39μm和0.39μm以上~小于1.5μm的区间测定出的颗粒的合计作为颗粒个数。
[表1]
由表1可明确,实施例1的粘合片的粒径小于1.5μm的颗粒的个数少于100个,防止了晶圆表面的源自粘合剂组合物的污染。另外,在紫外线照射后,对硅、聚酰亚胺和铜发挥了同样的轻剥离性,防止了被粘物上的残胶。另一方面,在使用比较例1和比较例2的粘合片的情况下,剥离后的晶圆表面残存有较多颗粒。其中,剥离了比较例2的粘合片的晶圆表面的颗粒数非常多,难以测定个数(超限)。
Claims (8)
1.一种紫外线固化型粘合片,其具有基材和粘合剂层,
在紫外线照射试验后,剥离该紫外线固化型粘合片后的硅晶圆的贴合粘合剂层的面的粒径小于1.5μm的颗粒数少于100个。
2.根据权利要求1所述的紫外线固化型粘合片,其中,所述粘合剂层包含光聚合引发剂。
3.根据权利要求2所述的紫外线固化型粘合片,其中,所述光聚合引发剂为2-羟基-1-{4-[4-(2-羟基-2-甲基-丙酰基)-苄基]-苯基}-2-甲基-丙烷-1-酮。
4.根据权利要求1所述的紫外线固化型粘合片,其中,在所述基材与所述粘合剂层之间包含中间层。
5.根据权利要求4所述的紫外线固化型粘合片,其中,所述中间层和所述粘合剂层包含相同的光聚合引发剂。
6.根据权利要求1所述的紫外线固化型粘合片,其中,所述粘合剂层包含向(甲基)丙烯酸系树脂中导入了聚合性碳-碳双键的(甲基)丙烯酸系聚合物。
7.根据权利要求1所述的粘合片,其用于半导体晶圆加工工序中。
8.根据权利要求7所述的粘合片,其作为背面研磨片使用。
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