JP5947313B2 - Adhesive sheet and method for producing electronic component using adhesive sheet - Google Patents
Adhesive sheet and method for producing electronic component using adhesive sheet Download PDFInfo
- Publication number
- JP5947313B2 JP5947313B2 JP2013547172A JP2013547172A JP5947313B2 JP 5947313 B2 JP5947313 B2 JP 5947313B2 JP 2013547172 A JP2013547172 A JP 2013547172A JP 2013547172 A JP2013547172 A JP 2013547172A JP 5947313 B2 JP5947313 B2 JP 5947313B2
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- sensitive adhesive
- meth
- adhesive sheet
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims description 52
- 230000001070 adhesive effect Effects 0.000 title claims description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 67
- 229920005989 resin Polymers 0.000 claims description 48
- 239000011347 resin Substances 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 26
- 229920000554 ionomer Polymers 0.000 claims description 24
- 239000004014 plasticizer Substances 0.000 claims description 22
- 229920000728 polyester Polymers 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 21
- 239000004593 Epoxy Substances 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 18
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid group Chemical group C(CCCCC(=O)O)(=O)O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 13
- 239000004800 polyvinyl chloride Substances 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 12
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 150000002513 isocyanates Chemical class 0.000 claims description 11
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 239000012790 adhesive layer Substances 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- -1 aliphatic dicarboxylic acids Chemical class 0.000 description 26
- 230000014759 maintenance of location Effects 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 13
- 150000001805 chlorine compounds Chemical group 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000002216 antistatic agent Substances 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 239000004611 light stabiliser Substances 0.000 description 5
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
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- 238000007639 printing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
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- 239000006229 carbon black Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
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- 239000003063 flame retardant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
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- 239000010703 silicon Substances 0.000 description 3
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- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical group CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- CBZMQWPBAUBAPO-UHFFFAOYSA-N 4-ethenyl-n,n-diethylaniline Chemical group CCN(CC)C1=CC=C(C=C)C=C1 CBZMQWPBAUBAPO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 241001050985 Disco Species 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
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
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- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
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- SDYRIBONPHEWCT-UHFFFAOYSA-N n,n-dimethyl-2-phenylethenamine Chemical compound CN(C)C=CC1=CC=CC=C1 SDYRIBONPHEWCT-UHFFFAOYSA-N 0.000 description 2
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- 230000002950 deficient Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 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
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- TWXDDNPPQUTEOV-FVGYRXGTSA-N methamphetamine hydrochloride Chemical compound Cl.CN[C@@H](C)CC1=CC=CC=C1 TWXDDNPPQUTEOV-FVGYRXGTSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- SJPFBRJHYRBAGV-UHFFFAOYSA-N n-[[3-[[bis(oxiran-2-ylmethyl)amino]methyl]phenyl]methyl]-1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC=1C=C(CN(CC2OC2)CC2OC2)C=CC=1)CC1CO1 SJPFBRJHYRBAGV-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 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
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
- H01L21/67—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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
-
- 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
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
-
- 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]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—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 the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
-
- 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
- C09J2427/00—Presence of halogenated polymer
- C09J2427/006—Presence of halogenated polymer in the substrate
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Dicing (AREA)
- Die Bonding (AREA)
Description
本発明は、粘着シート及び粘着シートを用いた電子部品の製造方法に関する。 The present invention relates to an adhesive sheet and a method for manufacturing an electronic component using the adhesive sheet.
半導体ウエハは、通常、回路を形成した後に粘着シートを貼合してから、素子小片への切断（ダイシング）、洗浄、乾燥、粘着シートの延伸（エキスパンディング）、粘着シートからの素子小片の剥離（ピックアップ）、マウンティングなどの各工程へ配される。これらの工程で使用されるダイシング用及び／又は搬送用粘着シートとして、特許文献１には、基材にポリ塩化ビニルを使用する例が記載されている。 For semiconductor wafers, the adhesive sheet is usually bonded after the circuit is formed, and then cut into element pieces (dicing), washed, dried, stretched (expanded) the adhesive sheet, and peeled off the element pieces from the adhesive sheet. (Pickup), mounting and other processes. As a dicing and / or conveying pressure-sensitive adhesive sheet used in these steps, Patent Document 1 describes an example in which polyvinyl chloride is used as a base material.
また、特許文献２には、粘着剤組成物として、（メタ）アクリル酸エステル共重合体を用いた組成物が開示されている。特許文献３にはアイオノマ樹脂を基材層に用いた粘着シートが開示されている。 Patent Document 2 discloses a composition using a (meth) acrylic acid ester copolymer as the pressure-sensitive adhesive composition. Patent Document 3 discloses an adhesive sheet using an ionomer resin as a base material layer.
従来のポリ塩化ビニルを基材とした粘着シートは、経時的に基材から粘着剤層への可塑剤の移行が生じ、ピックアップ工程におけるチップのピックアップ性に問題が生じていた。
また、粘着シートをウエハやパッケージ基板の被着体のダイシングに使用する場合、粘着シートを被着体の貼り合わせた後に７５℃程度に加温してからダイシングを行う場合と、加温せずにダイシングを行う場合がある。加温は、被着体と粘着シートの密着性が良好でない場合に、被着体と粘着シートの密着性を高めてチップ飛びを防ぐために行うものであるが、加温を行った場合、ダイシング後のチップのピックアップ性が悪化する場合がある。また、加温を行なってもダイシング後のチップのピックアップ性が悪化しないように粘着剤の組成を調整した場合、加温を行わない場合の密着性が悪化する場合がある。このような事情により、加温なしの製造ラインと加温ありの製造ラインで同じ粘着シートを使用することは従来困難であり、加温なし・ありを想定してそれぞれ設計された別々の粘着シートを用いるしかなかった。In the conventional pressure-sensitive adhesive sheet based on polyvinyl chloride, the plasticizer migrates from the base material to the pressure-sensitive adhesive layer over time, which causes a problem in chip pickup performance in the pickup process.
In addition, when the adhesive sheet is used for dicing the adherend of the wafer or package substrate, the adhesive sheet is heated to about 75 ° C. after being attached to the adherend, and then dicing is performed. Dicing may be performed. Heating is performed to improve adhesion between the adherend and the pressure-sensitive adhesive sheet and prevent chip jumping when the adherence between the adherend and the pressure-sensitive adhesive sheet is not good. The pick-up property of later chips may deteriorate. Further, when the composition of the pressure-sensitive adhesive is adjusted so that the pick-up property of the chip after dicing is not deteriorated even if the heating is performed, the adhesiveness when the heating is not performed may be deteriorated. Because of these circumstances, it has been difficult to use the same adhesive sheet in a production line without heating and a production line with heating, and separate adhesive sheets designed with and without heating. There was no choice but to use.
本発明はこのような事情に鑑みてなされたものであり、ピックアップ工程におけるチップのピックアップ性の経時劣化が生じず、且つダイシング前の加温あり及び加温なしの両方の製造ラインで使用可能な粘着シート、及び、この粘着シートを用いた電子部品の製造方法を提供するものである。 The present invention has been made in view of such circumstances, and does not cause deterioration of the pick-up property of the chip in the pick-up process with time, and can be used in both a heating line with and without heating before dicing. An adhesive sheet and an electronic component manufacturing method using the adhesive sheet are provided.
本発明によれば、ポリ塩化ビニルと、ポリエステル系可塑剤とを含む基材フィルム上に粘着剤組成物からなる粘着剤層を有する粘着シートにおいて、前記粘着剤組成物が、（メタ）アクリル酸エステル共重合体１００質量部と、イソシアネート系硬化剤０．１〜７質量部を含み、前記（メタ）アクリル酸エステル共重合体は、メチル（メタ）アクリレート単位を３５〜８５質量％、２−エチルへキシルアクリレート単位を１０〜６０質量％、カルボキシル基を有する単量体単位を０．５〜１０質量％、ヒドロキシル基を有する単量体単位を０．０１〜５質量％含み、前記粘着剤組成物は、エポキシ系硬化剤の含有量が、前記（メタ）アクリル酸エステル共重合体成分１００質量部に対して０〜０．２５質量部である、粘着シートが提供される。 According to this invention, in the adhesive sheet which has an adhesive layer which consists of an adhesive composition on the base film containing a polyvinyl chloride and a polyester plasticizer, the said adhesive composition is (meth) acrylic acid. It contains 100 parts by mass of an ester copolymer and 0.1 to 7 parts by mass of an isocyanate curing agent, and the (meth) acrylic acid ester copolymer has a methyl (meth) acrylate unit of 35 to 85% by mass, 2- 10 to 60% by mass of an ethylhexyl acrylate unit, 0.5 to 10% by mass of a monomer unit having a carboxyl group, and 0.01 to 5% by mass of a monomer unit having a hydroxyl group, the pressure-sensitive adhesive The composition is provided with an adhesive sheet in which the content of the epoxy curing agent is 0 to 0.25 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer component.
また、本発明によれば、エチレン単位、メタアクリル酸単位、及び（メタ）アクリル酸アルキルエステル単位を有する共重合体を金属イオンで架橋したアイオノマ樹脂からなる基材フィルム上に粘着剤組成物からなる粘着剤層を有する粘着シートにおいて、前記粘着剤組成物が、（メタ）アクリル酸エステル共重合体１００質量部と、イソシアネート系硬化剤０．１〜７質量部を含み、前記（メタ）アクリル酸エステル共重合体は、メチル（メタ）アクリレート単位を３５〜８５質量％、２−エチルへキシルアクリレート単位を１０〜６０質量％、カルボキシル基を有する単量体単位を０．５〜１０質量％、ヒドロキシル基を有する単量体単位を０．０１〜５質量％含み、前記粘着剤組成物は、エポキシ系硬化剤の含有量が、前記（メタ）アクリル酸エステル共重合体成分１００質量部に対して０〜０．２５質量部である、粘着シートが提供される。 Further, according to the present invention, an adhesive composition is formed on a base film made of an ionomer resin obtained by crosslinking a copolymer having an ethylene unit, a methacrylic acid unit, and a (meth) acrylic acid alkyl ester unit with a metal ion. In the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer, the pressure-sensitive adhesive composition contains 100 parts by weight of a (meth) acrylic acid ester copolymer and 0.1 to 7 parts by weight of an isocyanate curing agent, and the (meth) acrylic. The acid ester copolymer has a methyl (meth) acrylate unit of 35 to 85% by mass, a 2-ethylhexyl acrylate unit of 10 to 60% by mass, and a monomer unit having a carboxyl group of 0.5 to 10% by mass. And 0.01 to 5% by mass of a monomer unit having a hydroxyl group, and the pressure-sensitive adhesive composition has an epoxy-based curing agent content of (meth) a. Is 0-0.25 parts by weight with respect to acrylic acid ester copolymer 100 parts by weight of the component, the adhesive sheet is provided.
本発明者らは、チップのピックアップ性の経時劣化の問題を解決すべく鋭意研究を行ったところ、粘着剤組成物として（メタ）アクリル酸エステル共重合体をベース樹脂とするものを用い、且つ可塑剤としてポリエステル系可塑剤を用いることによって、チップのピックアップ性の経時劣化を防ぐことができることを見出した。
さらに、加温なしの製造ラインと加温ありの製造ラインの両方で使用可能な粘着シートを開発すべく検討を行ったところ、上記組成の（メタ）アクリル酸エステル共重合体をベース樹脂とし、上記含有量のイソシアネート系硬化剤を含有させ、かつエポキシ系硬化剤の含有量を上記範囲内に制限した場合、加温の有無に関わらず、チップ保持性及びピックアップ性の両方が良好となることが分かり、本発明の完成に到った。The inventors of the present invention conducted intensive research to solve the problem of deterioration of pick-up property of the chip over time, and used a pressure-sensitive adhesive composition based on a (meth) acrylate copolymer as a base resin, and It has been found that by using a polyester plasticizer as the plasticizer, deterioration of the chip pick-up property over time can be prevented.
Furthermore, when we studied to develop a pressure-sensitive adhesive sheet that can be used in both the unheated production line and the heated production line, the (meth) acrylic acid ester copolymer of the above composition was used as the base resin, When the isocyanate curing agent of the above content is included and the content of the epoxy curing agent is limited to the above range, both chip retention and pick-up properties are improved regardless of the presence or absence of heating. As a result, the present invention has been completed.
本発明において特に重要なポイントは、特定組成の（メタ）アクリル酸エステル共重合体と特定組成の硬化剤の組み合わせによって初めて、加温の有無に関わらずチップ保持性及びピックアップ性の両方が良好であるという優れた特性を有する粘着シートが得られるという点である。本発明者らは、種々の組成の（メタ）アクリル酸エステル共重合体と種々の組成の硬化剤の組み合わせで実験を行ったが、共重合体と硬化剤のどちらかの組成が上記範囲から外れた場合には、加温なし及び／又は加温ありの際のチップ保持性及び／又はピックアップ性が悪化したため、所望の粘着シートを得ることが出来なかった。特に、エポキシ系硬化剤を全く含有させないか、含有させるとしても上記範囲内に抑えることが重要であることが分かった。エポキシ系硬化剤が上記範囲を超えて含有されている場合、チップ保持性が著しく悪化することが分かったからである。 A particularly important point in the present invention is that only a combination of a (meth) acrylic acid ester copolymer of a specific composition and a curing agent of a specific composition is good for both chip retention and pick-up properties regardless of whether there is heating or not. In other words, a pressure-sensitive adhesive sheet having excellent properties can be obtained. The present inventors conducted experiments with combinations of (meth) acrylic acid ester copolymers of various compositions and curing agents of various compositions, and the composition of either copolymer or curing agent is within the above range. When it came off, since the chip holding property and / or pick-up property when there was no heating and / or heating was deteriorated, a desired pressure-sensitive adhesive sheet could not be obtained. In particular, it has been found that it is important to contain no epoxy curing agent or to keep it within the above range even if it is contained. This is because it has been found that when the epoxy curing agent is contained exceeding the above range, the chip retention is remarkably deteriorated.
以下、本発明の種々の実施形態を例示する。以下の実施形態は互いに組み合わせ可能である。
好ましくは、前記（メタ）アクリル酸エステル共重合体において、前記メチル（メタ）アクリレート単位は、３５〜６２．５質量％、前記２−エチルへキシルアクリレート単位は、２０〜６０質量％である。
好ましくは、前記粘着剤組成物は、前記エポキシ系硬化剤の含有量が、前記（メタ）アクリル酸エステル共重合体成分１００質量部に対して０〜０．１質量部である。
好ましくは、前記カルボキシル基を有する単量体が、アクリル酸である。
好ましくは、前記ヒドロキシル基を有する単量体が、２−ヒドロキシエチルアクリレートである。
好ましくは、前記基材フィルムは、前記ポリ塩化ビニル１００質量部に対して、前記ポリエステル系可塑剤を２５〜４５質量部含む。
好ましくは、前記ポリエステル系可塑剤がアジピン酸系ポリエステルである。
好ましくは、上記粘着シートを被着体とリングフレームに貼り付ける貼付工程と、前記被着体をダイシングしてチップにするダイシング工程と、前記粘着シートから前記チップをピックアップするピックアップ工程と、を含む、電子部品の製造方法が提供される。
好ましくは、前記貼付工程の後であって前記ダイシング工程の前に、前記粘着シートが貼り付けられた前記被着体を、６０〜１００℃に加温する加温工程をさらに備える。Hereinafter, various embodiments of the present invention will be exemplified. The following embodiments can be combined with each other.
Preferably, in the (meth) acrylic acid ester copolymer, the methyl (meth) acrylate unit is 35 to 62.5% by mass, and the 2-ethylhexyl acrylate unit is 20 to 60% by mass.
Preferably, in the pressure-sensitive adhesive composition, the content of the epoxy curing agent is 0 to 0.1 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer component.
Preferably, the monomer having a carboxyl group is acrylic acid.
Preferably, the monomer having a hydroxyl group is 2-hydroxyethyl acrylate.
Preferably, the base film contains 25 to 45 parts by mass of the polyester plasticizer with respect to 100 parts by mass of the polyvinyl chloride.
Preferably, the polyester plasticizer is an adipic acid polyester.
Preferably, the method includes an attaching step for attaching the adhesive sheet to an adherend and a ring frame, a dicing step for dicing the adherend into a chip, and a pickup step for picking up the chip from the adhesive sheet. An electronic component manufacturing method is provided.
Preferably, the method further includes a heating step of heating the adherend to which the pressure-sensitive adhesive sheet has been pasted to 60 to 100 ° C. after the pasting step and before the dicing step.
本明細書において、単量体単位とは単量体に由来する構造単位を意味する。本明細書の部及び％は、特に記載がない限り質量基準とする。本明細書において（メタ）アクリレートとはアクリレート及びメタアクリレートの総称である。同様に（メタ）アクリル酸等の（メタ）を含む化合物も「メタ」を有する化合物と、有しない化合物の総称である。 In the present specification, the monomer unit means a structural unit derived from a monomer. Unless otherwise indicated, parts and% in this specification are based on mass. In this specification, (meth) acrylate is a general term for acrylate and methacrylate. Similarly, a compound containing (meth) such as (meth) acrylic acid is a general term for a compound having “meth” and a compound not having it.
本発明の一実施形態の粘着シートは、ポリ塩化ビニルと、ポリエステル系可塑剤とを含む基材フィルム上に粘着剤組成物からなる粘着剤層を有する粘着シートにおいて、粘着剤組成物が、（メタ）アクリル酸エステル共重合体１００質量部と、イソシアネート系硬化剤０．１〜７質量部を含み、前記（メタ）アクリル酸エステル共重合体は、メチル（メタ）アクリレート単位を３５〜８５質量％、２−エチルへキシルアクリレート単位を１０〜６０質量％、カルボキシル基を有する単量体単位を０．５〜１０質量％、ヒドロキシル基を有する単量体単位を０．０１〜５質量％含み、前記粘着剤組成物は、エポキシ系硬化剤の含有量が、前記（メタ）アクリル酸エステル共重合体成分１００部に対して０〜０．２５質量部である。 The pressure-sensitive adhesive sheet of one embodiment of the present invention is a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive composition on a base film containing polyvinyl chloride and a polyester-based plasticizer. It includes 100 parts by weight of a (meth) acrylic acid ester copolymer and 0.1 to 7 parts by weight of an isocyanate curing agent, and the (meth) acrylic acid ester copolymer has a methyl (meth) acrylate unit of 35 to 85 masses. %, 2-ethylhexyl acrylate unit 10 to 60% by mass, carboxyl group-containing monomer unit 0.5 to 10% by mass, hydroxyl group-containing monomer unit 0.01 to 5% by mass In the pressure-sensitive adhesive composition, the content of the epoxy curing agent is 0 to 0.25 parts by mass with respect to 100 parts of the (meth) acrylic acid ester copolymer component.
＜１．基材フィルム＞
基材フィルムとしては、ポリ塩化ビニルと、ポリ塩化ビニルに対する可塑剤としてのポリエステル系可塑剤とを含む基材フィルム、または、エチレン単位、メタアクリル酸単位、及び（メタ）アクリル酸アルキルエステル単位を有する共重合体を金属イオンで架橋したアイオノマ樹脂からなる基材フィルムを用いる。<1. Base Film>
As the base film, a base film containing polyvinyl chloride and a polyester plasticizer as a plasticizer for polyvinyl chloride, or an ethylene unit, a methacrylic acid unit, and a (meth) acrylic acid alkyl ester unit are used. A base film made of an ionomer resin obtained by crosslinking a copolymer having a metal ion is used.
ポリエステル系可塑剤としては、例えば、アジピン酸、アゼライン酸、セバシン酸、フタル酸、イソフタル酸、テレフタル酸等のような炭素数２〜１０の脂肪族ジカルボン酸および／または芳香族ジカルボン酸等のジカルボン酸と、エチレングリコール、プロピレングリコール、ブチレングリコール、ネオペンチルグリコール、ヘキサンジオール等のような炭素数２〜１０のグリコールとの重縮合によるポリエステルが挙げられる。前記ジカルボン酸としては、アジピン酸、セバチン酸等の脂肪族ジカルボン酸が好ましく、特に汎用性、価格、経時安定性の点でアジピン酸が望ましい。グリコールとしては、直鎖状または側鎖状のいずれも使用でき必要に応じて適宜に選択される。前記グリコールは炭素数２〜６のものが好ましい。ポリエステル系可塑剤の数平均分子量は特に制限されないが、通常、５００〜４０００程度のものを用いる。ポリエステル系可塑剤は、ポリ塩化ビニル１００部に対して２５〜４５部が好ましく、更に、３０〜４０部がより好ましい。 Examples of the polyester plasticizer include dicarboxylic acids such as aliphatic dicarboxylic acids having 2 to 10 carbon atoms such as adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, and / or aromatic dicarboxylic acids. Examples thereof include polyesters obtained by polycondensation of an acid and glycols having 2 to 10 carbon atoms such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexanediol and the like. As the dicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid and sebacic acid are preferable, and adipic acid is particularly preferable in terms of versatility, cost, and stability over time. As the glycol, either a straight chain or a side chain can be used and is appropriately selected as necessary. The glycol preferably has 2 to 6 carbon atoms. The number average molecular weight of the polyester plasticizer is not particularly limited, but usually about 500 to 4000 is used. The polyester plasticizer is preferably 25 to 45 parts, more preferably 30 to 40 parts, relative to 100 parts of polyvinyl chloride.
アイオノマ樹脂とは、カルボキシル基を有するビニル化合物単位を有する多元共重合体樹脂の金属塩の総称である。アイオノマ樹脂とは、例えば、エチレン−メタアクリル酸共重合体、及びエチレン−メタアクリル酸に第３成分としてアクリル酸アルキルエステルやメタアクリル酸アルキルエステル等を重合し、これらをリチウム、ナトリウムイオン、カリウムイオン、及び／又は亜鉛イオン等の金属イオンで架橋したものである。アイオノマ樹脂のカルボキシル基を架橋する金属イオンとしては、ナトリウムイオン、カリウムイオン、亜鉛イオン等が挙げられる。これらの金属イオンのうち、電子部品の不良率への影響が小さい亜鉛イオンを含有するアイオノマ樹脂が好ましい。 The ionomer resin is a general term for metal salts of multi-component copolymer resins having a vinyl compound unit having a carboxyl group. The ionomer resin is, for example, an ethylene-methacrylic acid copolymer, and an ethylene-methacrylic acid polymerized with an acrylic acid alkyl ester, an alkyl methacrylate, etc. as a third component, and these are lithium, sodium ion, potassium Cross-linked with metal ions such as ions and / or zinc ions. Examples of metal ions that crosslink the carboxyl group of the ionomer resin include sodium ions, potassium ions, and zinc ions. Of these metal ions, ionomer resins containing zinc ions that have a small effect on the defective rate of electronic components are preferred.
エチレン単位、メタアクリル酸単位、及び（メタ）アクリル酸アルキルエステル単位を有するアイオノマ樹脂としては、例えば、エチレン−メタアクリル酸−（メタ）アクリル酸プロピルアイオノマ樹脂、エチレン−メタアクリル酸−（メタ）アクリル酸ブチルアイオノマ樹脂、エチレン−メタアクリル酸−（メタ）アクリル酸ヘキシルアイオノマ樹脂、エチレン−メタアクリル酸−（メタ）アクリル酸２−メチルプロピルアイオノマ樹脂、エチレン−メタアクリル酸−（メタ）アクリル酸２−エチルプロピルアイオノマ樹脂、エチレン−メタアクリル酸−（メタ）アクリル酸２−エチルブチルアイオノマ樹脂、エチレン−メタアクリル酸−（メタ）アクリル酸２−メチルヘキシルアイオノマ樹脂、エチレン−メタアクリル酸−（メタ）アクリル酸３−メチルヘキシルアイオノマ樹脂、エチレン−メタアクリル酸−（メタ）アクリル酸２−エチルヘキシルアイオノマ樹脂、及びエチレン−メタアクリル酸−（メタ）アクリル酸１，２−ジメチルブチルアイオノマ樹脂等が挙げられる。これらのアイオノマ樹脂のうち、入手が容易で切削屑の発生が特に少ないエチレン−メタアクリル酸−アクリル酸２−メチルプロピルアイオノマ樹脂が好適に用いられる。 Examples of the ionomer resin having an ethylene unit, a methacrylic acid unit, and a (meth) acrylic acid alkyl ester unit include, for example, ethylene-methacrylic acid- (meth) acrylic acid propyl ionomer resin, ethylene-methacrylic acid- (meta ) Acrylic acid butyl ionomer resin, ethylene-methacrylic acid- (meth) acrylic acid hexyl ionomer resin, ethylene-methacrylic acid- (meth) acrylic acid 2-methylpropyl ionomer resin, ethylene-methacrylic acid- ( (Meth) acrylic acid 2-ethylpropyl ionomer resin, ethylene-methacrylic acid- (meth) acrylic acid 2-ethylbutyl ionomer resin, ethylene-methacrylic acid- (meth) acrylic acid 2-methylhexyl ionomer resin, Ethylene-methacrylic acid- (meth) acrylate 3-methylhexyl ionomer resin of phosphoric acid, ethylene-methacrylic acid- (meth) acrylic acid 2-ethylhexyl ionomer resin, ethylene-methacrylic acid- (meth) acrylic acid 1,2-dimethylbutyl ionomer resin, etc. Is mentioned. Among these ionomer resins, an ethylene-methacrylic acid-acrylic acid 2-methylpropyl ionomer resin that is easily available and generates particularly little cutting waste is preferably used.
また、基材フィルムには、必要に応じて、酸化防止剤、紫外線吸収剤、光安定剤、帯電防止剤、難燃剤、染料や顔料などの着色剤などの各種添加剤を加えることができる。これらの添加剤は、その種類に応じて通常の量で用いられる。 Moreover, various additives, such as antioxidant, a ultraviolet absorber, a light stabilizer, an antistatic agent, a flame retardant, and coloring agents, such as dye and a pigment, can be added to a base film as needed. These additives are used in normal amounts depending on the type.
さらに、これら添加剤について説明すると、酸化防止剤としては従来樹脂あるいは樹脂組成物において酸化防止剤として知られたものであればいずれのものであってもよく、特に限定されない。代表的な酸化防止剤としては、フェノール系（モノフェノール系、ビスフェノール系、高分子型フェノール系）、硫黄系、リン系等、従来一般的に使用されているものが挙げられる。 Further, these additives will be described. The antioxidant is not particularly limited as long as it is known as an antioxidant in conventional resins or resin compositions. Typical antioxidants include those generally used in the past, such as phenolic (monophenolic, bisphenolic, polymeric phenolic), sulfur, and phosphorus.
また、紫外線吸収剤としては、サリチレート系、ベンゾフェノン系、ベンゾトリアゾール系、シアノアクリレート系が挙げられるが、特に紫外線吸収効果の点から、ベンゾフェノン系紫外線吸収剤およびベンゾトリアゾール系紫外線吸収剤が好ましく、特にベンゾトリアゾール系紫外線吸収剤が好適である。 Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based, and benzophenone-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers are particularly preferable from the viewpoint of the ultraviolet absorption effect. A benzotriazole-based ultraviolet absorber is preferred.
光安定剤としては、例えば、ヒンダードアミン系、ヒンダードフェノール系等の光安定剤を使用することができる。光安定剤の添加量は、特に限定されるものではなく、通常使用される量とすればよい。 As the light stabilizer, for example, a light stabilizer such as a hindered amine or hindered phenol can be used. The addition amount of the light stabilizer is not particularly limited, and may be a commonly used amount.
帯電防止剤は特に限定されないが、四級アミン塩単量体等が挙げられる。四級アミン塩単量体としては、例えば、ジメチルアミノエチル（メタ）アクリレート四級塩化物、ジエチルアミノエチル（メタ）アクリレート四級塩化物、メチルエチルアミノエチル（メタ）アクリレート四級塩化物、ｐ−ジメチルアミノスチレン四級塩化物、およびｐ−ジエチルアミノスチレン四級塩化物等が挙げられ、ジメチルアミノエチルメタクリレート四級塩化物が好適に用いられる。 The antistatic agent is not particularly limited, and examples thereof include a quaternary amine salt monomer. Examples of the quaternary amine salt monomer include dimethylaminoethyl (meth) acrylate quaternary chloride, diethylaminoethyl (meth) acrylate quaternary chloride, methylethylaminoethyl (meth) acrylate quaternary chloride, p- Examples thereof include dimethylaminostyrene quaternary chloride and p-diethylaminostyrene quaternary chloride, and dimethylaminoethyl methacrylate quaternary chloride is preferably used.
難燃剤としては特に限定されず、例えば、臭素系難燃剤、水酸化アルミニウム、水酸化マグネシウム、三酸化アンチモン等の無機系難燃剤、メラミンシアヌレート、尿素、メラミン誘導体等を含むトリアジン環含有化合物、芳香族ポリフォスフェート等のリン酸エステル等の有機系難燃剤が挙げられる。 The flame retardant is not particularly limited, for example, brominated flame retardants, inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, antimony trioxide, melamine cyanurate, urea, triazine ring-containing compounds including melamine derivatives, Organic flame retardants, such as phosphate esters, such as aromatic polyphosphate, are mentioned.
着色剤としては、有機系顔料、無機系顔料、染料、カーボンブラック等、公知あるいは周知の着色剤のいずれをも使用することができる。色は任意であり、例えば、白、アイボリー、黒、赤、青、黄、緑等とすることができる。フィルム基材を多層構造とした場合には、全ての層に着色剤を入れてもよく、又は一部の層のみ着色剤を入れてもよい。顔料の例を挙げると、例えば、フタロシアニン系、アゾ系、縮合アゾ系、アゾレーキ系、アンスラキノン系、ペリレン・ペリノン系、インジゴ・チオインジゴ系、イソインドリノン系、アゾメチンアゾ系、ジオキサジン系、キナクリドン系、アニリンブラック系、トリフェニルメタン系、カーボンブラック系等の有機顔料、酸化チタン系、酸化鉄系、水酸化鉄系、酸化クロム系、スピネル型焼成系、クロム酸系、クロムバーミリオン系、紺青系、アルミニウム粉末系、ブロンズ粉末系等が挙げられる。これらの顔料はいずれの形態でもよく、又、これらの顔料は種々公知の方法によって各種の分散処理が施されたものであってもよい。 As the colorant, any of known or well-known colorants such as organic pigments, inorganic pigments, dyes, and carbon black can be used. The color is arbitrary, and can be, for example, white, ivory, black, red, blue, yellow, green, and the like. When the film substrate has a multilayer structure, a colorant may be added to all layers, or a colorant may be added to only a part of the layers. Examples of pigments include, for example, phthalocyanine, azo, condensed azo, azo lake, anthraquinone, perylene / perinone, indigo / thioindigo, isoindolinone, azomethine azo, dioxazine, quinacridone, Organic pigments such as aniline black, triphenylmethane, carbon black, titanium oxide, iron oxide, iron hydroxide, chromium oxide, spinel firing, chromic acid, chromium vermilion, bitumen , Aluminum powder system, bronze powder system and the like. These pigments may be in any form, and these pigments may be subjected to various dispersion treatments by various known methods.
基材フィルムの厚さとしては、特に制限されず適宜決定することができるが、例えば、４０〜２５０μｍであり、好ましくは５０〜２００μｍ、さらに好ましくは６０〜１５０μｍである。 Although it does not restrict | limit especially as thickness of a base film, and it can determine suitably, For example, it is 40-250 micrometers, Preferably it is 50-200 micrometers, More preferably, it is 60-150 micrometers.
基材フィルムの成型方法としては、例えばカレンダー成形法、Ｔダイ押出し法、インフレーション法、及びキャスティング法がある。 Examples of the molding method for the base film include a calendar molding method, a T-die extrusion method, an inflation method, and a casting method.
基材フィルムには、剥離フィルム剥離時における帯電を防止するために、基材フィルムの粘着剤接触面及び／又は非接触に帯電防止処理を施してもよい。帯電防止剤は樹脂中に練り込んでもよい。帯電防止処理には、四級アミン塩単量体等の帯電防止剤を用いることができる。 In order to prevent the base film from being charged when the release film is peeled off, an antistatic treatment may be applied to the pressure-sensitive adhesive contact surface and / or non-contact of the base film. The antistatic agent may be kneaded into the resin. For the antistatic treatment, an antistatic agent such as a quaternary amine salt monomer can be used.
四級アミン塩単量体としては、例えば、ジメチルアミノエチル（メタ）アクリレート四級塩化物、ジエチルアミノエチル（メタ）アクリレート四級塩化物、メチルエチルアミノエチル（メタ）アクリレート四級塩化物、ｐ−ジメチルアミノスチレン四級塩化物、及びｐ−ジエチルアミノスチレン四級塩化物がありジメチルアミノエチルメタクリレート四級塩化物が好ましい。 Examples of the quaternary amine salt monomer include dimethylaminoethyl (meth) acrylate quaternary chloride, diethylaminoethyl (meth) acrylate quaternary chloride, methylethylaminoethyl (meth) acrylate quaternary chloride, p- There are dimethylaminostyrene quaternary chloride and p-diethylaminostyrene quaternary chloride, and dimethylaminoethyl methacrylate quaternary chloride is preferred.
滑り剤及び帯電防止剤の使用方法は特に限定されないが、例えば基材フィルムの片面に粘着剤を塗布し、その裏面に滑り剤及び／又は帯電防止剤を塗布してもよく、滑り剤及び／又は帯電防止剤を基材フィルムの樹脂に練り込んでシート化しても良い。 The method of using the slip agent and the antistatic agent is not particularly limited. For example, the adhesive may be applied to one side of the base film, and the slip agent and / or the antistatic agent may be applied to the back side thereof. Alternatively, an antistatic agent may be kneaded into the resin of the base film to form a sheet.
基材フィルムの片面に粘着剤を積層し、他方の面は平均表面粗さ（Ｒａ）が０．３〜１．５μｍのエンボス面とすることが可能である。エキスパンド装置の機械テーブル側にエンボス面を設置することにより、ダイシング後のエキスパンド工程で基材フィルムを容易に拡張することができる。 An adhesive can be laminated on one side of the base film, and the other side can be an embossed surface with an average surface roughness (Ra) of 0.3 to 1.5 μm. By installing the embossed surface on the machine table side of the expanding device, the base film can be easily expanded in the expanding process after dicing.
ダイシング後のエキスパンド性を向上させるために、基材フィルムの粘着剤非接触面に滑り剤を施したり、基材フィルムに滑り剤を練り込むことができる。 In order to improve the expandability after dicing, a slipping agent can be applied to the adhesive non-contact surface of the base film, or a slipping agent can be kneaded into the base film.
滑り剤は、粘着シートとエキスパンド装置の摩擦係数を低下させる物質であれば特に限定されず、例えばシリコーン樹脂や（変性）シリコーン油等のシリコーン化合物、フッ素樹脂、六方晶ボロンナイトライド、カーボンブラック、及び二硫化モリブデン等が挙げられる。これらの摩擦低減剤は複数の成分を混合してもよい。電子部品の製造はクリーンルームで行われるため、シリコーン化合物又はフッ素樹脂を用いることが好ましい。シリコーン化合物の中でも特にシリコーンマクロモノマ単位を有する共重合体は帯電防止層との相溶性が良く、帯電防止性とエキスパンド性のバランスが図れるため、好適に用いられる。 The slip agent is not particularly limited as long as it is a substance that reduces the friction coefficient of the pressure-sensitive adhesive sheet and the expanding device. For example, silicone compounds such as silicone resins and (modified) silicone oils, fluororesins, hexagonal boron nitride, carbon black, And molybdenum disulfide. These friction reducing agents may mix a plurality of components. Since manufacture of an electronic component is performed in a clean room, it is preferable to use a silicone compound or a fluororesin. Among silicone compounds, a copolymer having a silicone macromonomer unit is particularly preferred because it has good compatibility with the antistatic layer and can achieve a balance between antistatic properties and expandability.
＜２．粘着剤層＞
本実施形態において、粘着剤層を構成する粘着剤組成物は、（メタ）アクリル酸エステル共重合体１００質量部と、イソシアネート系硬化剤０．１〜７質量部を含み、エポキシ系硬化剤の含有量が、前記（メタ）アクリル酸エステル共重合体成分１００質量部に対して０〜０．２５質量部である。<2. Adhesive layer>
In this embodiment, the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer includes 100 parts by weight of a (meth) acrylic acid ester copolymer and 0.1 to 7 parts by weight of an isocyanate-based curing agent. Content is 0-0.25 mass part with respect to 100 mass parts of said (meth) acrylic acid ester copolymer components.
＜２−１．（メタ）アクリル酸エステル共重合体＞
（メタ）アクリル酸エステル共重合体は、メチル（メタ）アクリレート単位を３５〜８５質量％、２−エチルへキシルアクリレート単位を１０〜６０質量％、カルボキシル基を有する単量体単位を０．５〜１０質量％、ヒドロキシル基を有する単量体単位を０．０１〜５質量％を含む共重合体である。<2-1. (Meth) acrylic acid ester copolymer>
The (meth) acrylic acid ester copolymer has a methyl (meth) acrylate unit of 35 to 85% by mass, a 2-ethylhexyl acrylate unit of 10 to 60% by mass, and a monomer unit having a carboxyl group of 0.5. It is a copolymer containing 10 to 10% by mass and 0.01 to 5% by mass of a monomer unit having a hydroxyl group.
メチル（メタ）アクリレート単位は、３５〜８５質量％である。この範囲を下回るとピックアップ性が低下し、この範囲を上回るとチップ保持性が低下してしまう。また、より好ましくは３５〜６２．５質量％である。この範囲内であれば、チップ保持性とピックアップ性の両方に関して優れた性能を示すことができる。具体的には例えば３５質量％、４０質量％、４５質量％、４７．５質量％、５０質量％、５２．５質量％、５５質量％、５７．５質量％、６０質量％、６２．５質量％、６５質量％、７０質量％、７５質量％、８０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The methyl (meth) acrylate unit is 35 to 85% by mass. If it falls below this range, the pick-up property deteriorates, and if it exceeds this range, the chip retainability deteriorates. Moreover, More preferably, it is 35-62.5 mass%. Within this range, excellent performance can be exhibited in terms of both chip retention and pickup properties. Specifically, for example, 35 mass%, 40 mass%, 45 mass%, 47.5 mass%, 50 mass%, 52.5 mass%, 55 mass%, 57.5 mass%, 60 mass%, 62.5 They are mass%, 65 mass%, 70 mass%, 75 mass%, and 80 mass%, and may be in the range between any two of the numerical values exemplified here.
２−エチルへキシルアクリレート単位は、１０〜６０質量％％である。この範囲を下回るとチップ保持性が低下し、この範囲を上回るとピックアップ性が低下してしまう。また、より好ましくは２０〜６０質量％％である。この範囲内であれば、チップ保持性とピックアップ性の両方に関して優れた性能を示すことができる。具体的には例えば、１０質量％、２０質量％、３０質量％、３５質量％、４０質量％、４５質量％、５０質量％、６０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The 2-ethylhexyl acrylate unit is 10 to 60% by mass. If it falls below this range, the chip retainability deteriorates, and if it exceeds this range, the pick-up property falls. More preferably, it is 20 to 60% by mass. Within this range, excellent performance can be exhibited in terms of both chip retention and pickup properties. Specifically, for example, 10% by mass, 20% by mass, 30% by mass, 35% by mass, 40% by mass, 45% by mass, 50% by mass, 60% by mass, and any two of the numerical values exemplified here It may be within the range between.
カルボキシル基を有する単量体としては、例えば（メタ）アクリル酸、クロトン酸、マレイン酸、無水マレイン酸、イタコン酸、フマール酸、アクリルアミドＮ−グリコール酸、及びケイ皮酸がある。カルボキシル基を有する単量体単位は、０．５質量％〜１０質量％である。この範囲を下回るとチップ保持性が低下し、この範囲を上回るとピックアップ性が低下してしまう。また、より好ましくは２質量％〜１０質量％である。この範囲内であれば、チップ保持性とピックアップ性の両方に関して優れた性能を示すことができる。具体的には例えば０．５質量％、１質量％、２質量％、３質量％、４質量％、５質量％、６質量％、７質量％、８質量％、９質量％、１０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 Examples of the monomer having a carboxyl group include (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide N-glycolic acid, and cinnamic acid. The monomer unit which has a carboxyl group is 0.5 mass%-10 mass%. If it falls below this range, the chip retainability deteriorates, and if it exceeds this range, the pick-up property falls. Moreover, More preferably, it is 2 mass%-10 mass%. Within this range, excellent performance can be exhibited in terms of both chip retention and pickup properties. Specifically, for example, 0.5 mass%, 1 mass%, 2 mass%, 3 mass%, 4 mass%, 5 mass%, 6 mass%, 7 mass%, 8 mass%, 9 mass%, 10 mass% It may be within the range between any two of the numerical values exemplified here.
ヒドロキシル基を有する単量体としては、例えば２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、及び２−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシビニルエーテルがある。ヒドロキシル基を有する単量体単位は、０．０１〜５質量％である。この範囲を下回るとピックアップ性が低下し、この範囲を上回るとチップ保持性が低下してしまう。また、より好ましくは０．１〜２質量％％である。この範囲内であれば、チップ保持性とピックアップ性の両方に関して優れた性能を示すことができる。具体的には例えば、０．０１質量％、０．０５質量％、０．１質量％、０．２５質量％、０．５質量％、０．７５質量％、１質量％、２質量％、３質量％、４質量％、５質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxyvinyl ether. The monomer unit having a hydroxyl group is 0.01 to 5% by mass. If it falls below this range, the pick-up property deteriorates, and if it exceeds this range, the chip retainability deteriorates. More preferably, it is 0.1 to 2% by mass. Within this range, excellent performance can be exhibited in terms of both chip retention and pickup properties. Specifically, for example, 0.01% by mass, 0.05% by mass, 0.1% by mass, 0.25% by mass, 0.5% by mass, 0.75% by mass, 1% by mass, 2% by mass, 3% by mass, 4% by mass, and 5% by mass, and may be within a range between any two of the numerical values exemplified here.
（メタ）アクリル酸エステル重合体の製造方法としては、乳化重合、溶液重合等がある。 Examples of the method for producing the (meth) acrylic acid ester polymer include emulsion polymerization and solution polymerization.
＜２−２．イソシアネート系硬化剤＞
イソシアネート系硬化剤は、（メタ）アクリル酸エステル共重合体１００質量部に対して、０．１〜７質量部である。この範囲を下回るとピックアップ性が低下し、この範囲を上回るとチップ保持性が低下する。また、より好ましくは０．５質量部〜２質量部である。この範囲内であれば、チップ保持性とピックアップ性の両方に関して優れた性能を示すことができる。具体的には例えば、０．１質量部、０．５質量部、１質量部、１．５質量部、２質量部、３質量部、４質量部、５質量部、６質量部、７質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。<2-2. Isocyanate-based curing agent>
An isocyanate type hardening | curing agent is 0.1-7 mass parts with respect to 100 mass parts of (meth) acrylic acid ester copolymers. If it falls below this range, the pick-up property decreases, and if it exceeds this range, the chip retainability deteriorates. Moreover, More preferably, it is 0.5 mass part-2 mass parts. Within this range, excellent performance can be exhibited in terms of both chip retention and pickup properties. Specifically, for example, 0.1 part by weight, 0.5 part by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, and 7 parts by weight. It may be within a range between any two of the numerical values exemplified here.
イソシアネート系硬化剤としては複数のイソシアネート基を有する化合物が使用される。複数のイソシアネート基を有する化合物としては、例えば芳香族系イソシアネート、脂環族系イソシアネート、及び脂肪族系イソシアネートがある。 As the isocyanate curing agent, a compound having a plurality of isocyanate groups is used. Examples of the compound having a plurality of isocyanate groups include aromatic isocyanates, alicyclic isocyanates, and aliphatic isocyanates.
芳香族系イソシアネートとしては、例えば、トリレンジイソシアネート、４，４−ジフェニルメタンジイソシアネート、キシリレンジイソシアネートがある。 Examples of the aromatic isocyanate include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, and xylylene diisocyanate.
脂環族系イソシアネートとしては、例えばイソホロンジイソシアネート、メチレンビス（４−シクロヘキシルイソシアネート）がある。 Examples of the alicyclic isocyanate include isophorone diisocyanate and methylene bis (4-cyclohexyl isocyanate).
脂肪族イソシアネートとしては、例えばヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネートがある。 Examples of the aliphatic isocyanate include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.
これらのイソシアネート化合物は二量体や三量体であってもよく、またポリオール化合物とを反応させて得られるアダクト体であってもよい。 These isocyanate compounds may be dimers or trimers, or may be adducts obtained by reacting with a polyol compound.
＜２−３．エポキシ系硬化剤＞
エポキシ系硬化剤は、（メタ）アクリル酸エステル共重合体１００質量部に対して、０〜０．２５質量部である。この範囲を上回るとチップ保持性が低下する。また、より好ましくは０〜０．１質量部である。この範囲内であれば、チップ保持性とピックアップ性の両方に関して優れた性能を示すことができる。さらに好ましくは０質量部である。０質量部であれば生産性の向上とコストの削減を行うことができる。具体的には例えば、０質量部、０．０５質量部、０．１質量部、０．１５質量部、０．２質量部、０．２５質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。<2-3. Epoxy curing agent>
An epoxy-type hardening | curing agent is 0-0.25 mass part with respect to 100 mass parts of (meth) acrylic acid ester copolymers. If this range is exceeded, the chip retention will be reduced. Moreover, More preferably, it is 0-0.1 mass part. Within this range, excellent performance can be exhibited in terms of both chip retention and pickup properties. More preferably, it is 0 mass part. If it is 0 mass part, productivity can be improved and cost can be reduced. Specifically, for example, 0 part by mass, 0.05 part by mass, 0.1 part by mass, 0.15 part by mass, 0.2 part by mass, 0.25 part by mass, and any of the numerical values exemplified here It may be within a range between the two.
エポキシ系硬化剤としては、例えばビスフェノールＡ型エポキシ化合物、ビスフェノールＦ型エポキシ化合物、Ｎ，Ｎ−ジグリシジルアニリン、Ｎ，Ｎ−ジグリシジルトルイジン、ｍ−Ｎ，Ｎ−ジグリシジルアミノフェニルグリシジルエーテル、ｐ−Ｎ，Ｎ−ジグリシジルアミノフェニルグリシジルエーテル、トリグリシジルイソシアヌレート、Ｎ，Ｎ，Ｎ’ ，Ｎ’−テトラグリシジルジアミノジフェニルメタン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシリレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’，Ｎ’’−ペンタグリシジルジエチレントリアミンがある。 Examples of the epoxy curing agent include bisphenol A type epoxy compound, bisphenol F type epoxy compound, N, N-diglycidylaniline, N, N-diglycidyltoluidine, m-N, N-diglycidylaminophenylglycidyl ether, p -N, N-diglycidylaminophenylglycidyl ether, triglycidyl isocyanurate, N, N, N ', N'-tetraglycidyldiaminodiphenylmethane, N, N, N', N'-tetraglycidyl-m-xylylenediamine N, N, N ′, N ′, N ″ -pentaglycidyldiethylenetriamine.
これらの化合物は単独で用いてもよく、二種以上を組み合わせて用いてもよい。 These compounds may be used alone or in combination of two or more.
粘着剤組成物には、粘着強度を調整するために粘着付与樹脂を添加してもよい。粘着付与樹脂は特に限定されず、例えばロジン樹脂、ロジンエステル樹脂、テルペン樹脂、テルペンフェノール樹脂、フェノール樹脂、キシレン樹脂、クマロン樹脂、クマロンインデン樹脂、スチレン樹脂、脂肪族石油樹脂、芳香族石油樹脂、脂肪族芳香族共重合石油樹脂、脂環族炭化水素樹脂、及びこれらの変性品、誘導体、水素添加品等が挙げられる。 A tackifier resin may be added to the pressure-sensitive adhesive composition in order to adjust the pressure-sensitive adhesive strength. The tackifying resin is not particularly limited. For example, rosin resin, rosin ester resin, terpene resin, terpene phenol resin, phenol resin, xylene resin, coumarone resin, coumarone indene resin, styrene resin, aliphatic petroleum resin, aromatic petroleum resin , Aliphatic aromatic copolymer petroleum resins, alicyclic hydrocarbon resins, and modified products, derivatives, hydrogenated products, and the like thereof.
粘着付与樹脂の配合量は特に限定されず、（メタ）アクリル酸エステル共重合体１００質量部に対して２００質量部以下、好ましくは３０質量部以下とすることが好ましい。 The compounding quantity of tackifying resin is not specifically limited, It is 200 mass parts or less with respect to 100 mass parts of (meth) acrylic acid ester copolymers, Preferably it is preferable to set it as 30 mass parts or less.
＜２−４．添加剤等＞
粘着剤組成物には、例えば、硬化剤、重合開始剤、軟化剤、老化防止剤、充填剤、紫外線吸収剤、及び光安定剤、光重合性化合物、光開始剤等の各種添加剤を添加してもよい。<2-4. Additives>
Various additives such as a curing agent, a polymerization initiator, a softening agent, an anti-aging agent, a filler, an ultraviolet absorber, a light stabilizer, a photopolymerizable compound, and a photoinitiator are added to the pressure-sensitive adhesive composition. May be.
＜３．粘着シートの製造＞
基材フィルム上に粘着剤層を形成して粘着シートとする方法としては、例えばグラビアコーター、コンマコーター、バーコーター、ナイフコーター又はロールコーターといったコーターで基材フィルム上に粘着剤を直接塗布する方法や、剥離フィルムに粘着剤を塗布／乾燥後に基材フィルムに貼り合わせる方法がある。凸板印刷、凹板印刷、平板印刷、フレキソ印刷、オフセット印刷、又はスクリーン印刷等で基材フィルム上に粘着剤組成物を印刷してよい。<3. Manufacture of adhesive sheet>
As a method of forming a pressure-sensitive adhesive layer on a base film and forming a pressure-sensitive adhesive sheet, for example, a method of directly applying a pressure-sensitive adhesive on a base film with a coater such as a gravure coater, comma coater, bar coater, knife coater or roll coater Alternatively, there is a method in which a pressure-sensitive adhesive is applied to a release film and bonded to a base film after drying. The pressure-sensitive adhesive composition may be printed on the substrate film by convex plate printing, concave plate printing, flat plate printing, flexographic printing, offset printing, screen printing, or the like.
粘着剤層の厚さは１〜１００μｍが好ましく、５〜４０μｍがより好ましい。粘着剤層が薄いと粘着力が低下し、ダイシング時のチップ保持性、及びリングフレームからの剥がれが生じる場合がある。粘着剤層が厚いと粘着力が高く、ピックアップ不良が発生する場合がある。 1-100 micrometers is preferable and, as for the thickness of an adhesive layer, 5-40 micrometers is more preferable. If the pressure-sensitive adhesive layer is thin, the adhesive strength is reduced, and chip retention during dicing and peeling from the ring frame may occur. If the pressure-sensitive adhesive layer is thick, the adhesive strength is high, and pickup failure may occur.
＜４．電子部品の製造＞
以下、上記の粘着シートを用いて電子部品を製造する方法を説明する。この方法は、以下に説明するように、貼付工程、ダイシング工程、及びピックアップ工程を含んでいる。また、前記貼付工程の後であって前記ダイシング工程の前に加温工程を任意的に備える。
以下、各工程について説明する。<4. Manufacture of electronic components>
Hereinafter, a method for manufacturing an electronic component using the above-described pressure-sensitive adhesive sheet will be described. This method includes a sticking step, a dicing step, and a pickup step, as will be described below. Further, a heating step is optionally provided after the pasting step and before the dicing step.
Hereinafter, each step will be described.
（１）貼付工程
最初に、貼付工程では、粘着シートを被着体とリングフレームに貼り付ける。被着体としては、半導体ウエハや、パッケージ基板が挙げられる。(1) Sticking process First, in a sticking process, an adhesive sheet is stuck on an adherend and a ring frame. Examples of the adherend include a semiconductor wafer and a package substrate.
（２）加温工程
次に、被着体と粘着シートの間の密着性が良好でない場合には、両者の密着性を向上させるために、加温工程を行う。加温工程は、前記被着体を、６０〜１００℃に加温することによって行うことができる。(2) Heating process Next, when the adhesiveness between a to-be-adhered body and an adhesive sheet is not favorable, in order to improve both adhesiveness, a heating process is performed. The heating step can be performed by heating the adherend to 60 to 100 ° C.
（３）ダイシング工程
次に、ダイシング工程では、被着体が粘着シートに貼り付けられた状態で、被着体のダイシングを行ってチップにする。ダイシングによって形成される個々のチップが電子部品となる。ダイシングは、ダイシングブレードを用いて行うことができる。粘着シートは、紫外線及び／又は放射線照射前のチップ保持性に優れているため、ダイシング時に、チップが剥離してしまうこと（チップ飛び）を抑制できる。(3) Dicing Step Next, in the dicing step, the adherend is diced into a chip with the adherend attached to the adhesive sheet. Each chip formed by dicing becomes an electronic component. Dicing can be performed using a dicing blade. Since the pressure-sensitive adhesive sheet is excellent in chip retention before irradiation with ultraviolet rays and / or radiation, it is possible to prevent the chips from peeling off (chip jumping) during dicing.
（４）ピックアップ工程
次に、ピックアップ工程では、ダイシング工程後に、粘着シートから前記チップをピックアップする。この工程は、具体的には、例えば、以下の方法で行うことができる。粘着シートの基材フィルム側から紫外線及び／又は放射線（不図示）を照射し、次いで、粘着シートを放射状に拡大してチップ間隔を広げた後、チップをニードル等（不図示）で突き上げる。そして、真空コレット又はエアピンセット等（不図示）でチップを吸着し、チップをピックアップする。紫外線及び／又は放射線の光源は、公知のものが使用できる。紫外線源として、低圧水銀灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプがある。放射線は電子線、α線、β線、γ線が好適に用いられる。(4) Pickup Step Next, in the pickup step, the chip is picked up from the adhesive sheet after the dicing step. Specifically, this step can be performed, for example, by the following method. Ultraviolet rays and / or radiation (not shown) are irradiated from the base film side of the pressure-sensitive adhesive sheet, and then the pressure-sensitive adhesive sheet is radially expanded to widen the chip interval, and then the chip is pushed up with a needle or the like (not shown). Then, the chip is picked up by a vacuum collet or air tweezers (not shown) and picked up. A well-known thing can be used for the light source of an ultraviolet-ray and / or a radiation. There are low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, and metal halide lamps as ultraviolet light sources. As the radiation, electron beams, α rays, β rays, and γ rays are preferably used.
紫外線及び／又は放射線を照射することにより、粘着剤組成物内のビニル基を三次元網状化させて、粘着剤組成物の粘着力を低下させることができる。これにより、紫外線及び／又は放射線を照射する前においては、粘着剤組成物が初期の高い粘着力を有するため、優れたチップ保持性を示すことができ、紫外線及び／又は放射線を照射した後は、粘着剤組成物の粘着力が低下するため、チップのピックアップ性を向上させることができる。 By irradiating with ultraviolet rays and / or radiation, the vinyl group in the pressure-sensitive adhesive composition can be three-dimensionally reticulated to reduce the pressure-sensitive adhesive strength of the pressure-sensitive adhesive composition. Thereby, before irradiating with ultraviolet rays and / or radiation, since the pressure-sensitive adhesive composition has an initial high adhesive force, it can exhibit excellent chip retention, and after being irradiated with ultraviolet rays and / or radiation. Since the adhesive strength of the pressure-sensitive adhesive composition is reduced, the pick-up property of the chip can be improved.
ピックアップ工程でピックアップしたチップは、リードフレームや回路基板上にマウントすることができる。 The chip picked up in the pick-up process can be mounted on a lead frame or a circuit board.
実施例・比較例に係る粘着剤組成物及び粘着シートを次の処方で製造した。主な配合と、各実験例の結果を表１〜表４に示す。 The pressure-sensitive adhesive compositions and pressure-sensitive adhesive sheets according to Examples and Comparative Examples were produced with the following formulation. Tables 1 to 4 show main formulations and results of each experimental example.
表１〜表４中の組成についての数値は、質量部を表す。可塑剤についての数値は、ポリ塩化ビニル樹脂を１００部としたときの可塑剤の質量部を表す。架橋剤についての数値は、（メタ）アクリル酸エステル共重合体を１００部としたときの架橋剤の質量部を表す。可塑剤、樹脂フィルム及び硬化剤の詳細は、以下の通りである。
・アジピン酸系ポリエステル：大日本インキ化学工業株式会社製、商品名ポリサイザーＷ２３１０、数平均分子量２３００
・テレフタル酸系ポリエステル：市販品（ポリエチレンテレフタラート）
・樹脂フィルムＡ：アイオノマ樹脂製フィルム、エチレン−メタアクリル酸−アクリル酸２−メチルプロピル共重合体のＺｎ塩を主体。ＭＦＲ ２．８ｇ／１０ｍｉｎ（ＪＩＳ Ｋ７２１０法、２１０℃）、三井・デュポンポリケミカル株式会社製、市販品。表３では、これを「アイオノマＡ」と表す。
・樹脂フィルムＢ：アイオノマ樹脂製フィルム、エチレン−メタアクリル酸共重合体Ｚｎ塩を主体、ＭＦＲ ２．８ｇ／１０ｍｉｎ（ＪＩＳ Ｋ７２１０法、２１０℃）、三井・デュポンポリケミカル株式会社製。
・イソシアネート系硬化剤：２，４−トリレンジイソシアネートのトリメチロールプロパンアダクト体、市販品。表４では、これを「アイオノマＢ」と表す。
・エポキシ系硬化剤：ＴＥＴＲＡＤ−Ｘ、三菱ガス化学品The numerical value about the composition in Table 1-Table 4 represents a mass part. The numerical value about a plasticizer represents the mass part of a plasticizer when a polyvinyl chloride resin is 100 parts. The numerical value about a crosslinking agent represents the mass part of a crosslinking agent when a (meth) acrylic acid ester copolymer is 100 parts. Details of the plasticizer, the resin film, and the curing agent are as follows.
Adipic acid polyester: manufactured by Dainippon Ink & Chemicals, Inc., trade name: Polycizer W2310, number average molecular weight 2300
・ Terephthalic acid polyester: Commercial product (polyethylene terephthalate)
Resin film A: Mainly composed of ionomer resin film, Zn salt of ethylene-methacrylic acid-acrylic acid 2-methylpropyl copolymer. MFR 2.8 g / 10 min (JIS K7210 method, 210 ° C.), manufactured by Mitsui DuPont Polychemical Co., Ltd., a commercial product. In Table 3, this is represented as “Ionoma A”.
Resin film B: Film made of ionomer resin, ethylene-methacrylic acid copolymer Zn salt, MFR 2.8 g / 10 min (JIS K7210 method, 210 ° C.), manufactured by Mitsui DuPont Polychemical Co., Ltd.
Isocyanate-based curing agent: Trimethylolpropane adduct of 2,4-tolylene diisocyanate, commercially available product. In Table 4, this is represented as “Ionoma B”.
・ Epoxy curing agent: TETRAD-X, Mitsubishi Gas Chemicals
表１及び表２における「基材フィルム」は、ポリ塩化ビニル（ＰＶＣ）と、表１及び表２に示す可塑剤を含有するフィルムである。
アジピン酸系ポリエステル、テレフタル酸系ポリエステルは、何れもポリエステル系可塑剤の例である。
メチルアクリレート、メチルメタクリレート、ブチルアクリレートは、何れも（メタ）アクリレート単位の例である。
アクリル酸は、カルボキシル基を有する単量体単位の例である。
２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレートは、ヒドロキシル基を有する単量体単位の例である。The “base film” in Tables 1 and 2 is a film containing polyvinyl chloride (PVC) and the plasticizer shown in Tables 1 and 2.
Adipic acid-based polyester and terephthalic acid-based polyester are both examples of polyester-based plasticizers.
Methyl acrylate, methyl methacrylate, and butyl acrylate are all examples of (meth) acrylate units.
Acrylic acid is an example of a monomer unit having a carboxyl group.
2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are examples of monomer units having a hydroxyl group.
まず、ポリ塩化ビニル樹脂と、表１〜表４に示す可塑剤と、その他安定剤、顔料、充填剤を配合した。この樹脂混和物をバンバリーミキサーで混練したのち、カレンダー加工にて７０μｍの厚さに形成して、基材フィルムを得た。 First, a polyvinyl chloride resin, a plasticizer shown in Tables 1 to 4 and other stabilizers, pigments, and fillers were blended. This resin mixture was kneaded with a Banbury mixer and then formed into a thickness of 70 μm by calendering to obtain a base film.
次に、表１〜表４に示す組成の粘着剤組成物をＰＥＴ製剥離フィルム上に乾燥後の粘着剤層の厚みが１５μｍとなるように塗工し、基材フィルムに積層し粘着シートを得た。得られた粘着シートについて以下の評価を行った。 Next, the pressure-sensitive adhesive composition having the composition shown in Tables 1 to 4 was applied onto a PET release film so that the thickness of the pressure-sensitive adhesive layer after drying was 15 μm, and the pressure-sensitive adhesive sheet was laminated on the base film. Obtained. The following evaluation was performed about the obtained adhesive sheet.
（１）経時による粘着力上昇の評価
シリコンウエハ鏡面に粘着シートを貼り合わせ、２ｋｇロ−ラの１往復で圧着し２０分放置後に、１８０°ピ−ル、引張り速度３００ｍｍ／分の条件で粘着力を測定した。シリコンウエハには、７２５μｍ厚のウエハ（６インチ）を用いた。
また、上記条件で圧着した後に７日放置した試験体を作成し、この試験体についても同様の方法で粘着力を測定した。２０分放置の試験体の粘着力（Ｘ）および７日放置の試験体の粘着力（Ｙ）から次の式に従って上昇率を求めた。
上昇率＝（１００×（Ｙ−Ｘ））／Ｘ(1) Evaluation of increase in adhesive strength over time Adhesive sheet is attached to a mirror surface of a silicon wafer, and then pressed with one reciprocation of a 2 kg roller, left for 20 minutes, and then adhered under conditions of 180 ° peel and pulling speed of 300 mm / min. The force was measured. As the silicon wafer, a 725 μm thick wafer (6 inches) was used.
In addition, a test specimen that was allowed to stand for 7 days after pressure bonding under the above conditions was prepared, and the adhesive strength of this test specimen was also measured in the same manner. The rate of increase was determined from the adhesive strength (X) of the specimen left for 20 minutes and the adhesive strength (Y) of the specimen left for 7 days according to the following formula.
Rate of increase = (100 × (Y−X)) / X
算出された上昇率から以下の基準により、経時による粘着力上昇を評価した。
◎（優）：上昇率が５％未満。
○（良） ：上昇率が５％以上１０％未満。
×（不可）：上昇率が１０％以上。From the calculated rate of increase, the increase in adhesive strength over time was evaluated according to the following criteria.
◎ (excellent): Increase rate is less than 5%.
○ (Good): Increase rate is 5% or more and less than 10%.
X (impossible): The increase rate is 10% or more.
（２）チップ保持性及びピックアップ性の評価
得られた粘着シートをダミーの回路パターンを形成した直径８インチ×厚さ０．１ｍｍのシリコンウエハとリングフレームに貼り合わせた。その後、加温する場合は７５℃で３０分間、オーブンで加温した。その後、ダイシング、ピックアップの各工程を行った。(2) Evaluation of chip holding property and pick-up property The obtained adhesive sheet was bonded to a ring frame and a silicon wafer having a diameter of 8 inches and a thickness of 0.1 mm on which a dummy circuit pattern was formed. Then, when heating, it heated in oven at 75 degreeC for 30 minutes. Thereafter, dicing and pick-up processes were performed.
ダイシング工程の条件は以下の通りとした。
ダイシング装置：ＤＩＳＣＯ社製ＤＡＤ３４１
ダイシングブレード：ＤＩＳＣＯ社製ＮＢＣ−ＺＨ２０５Ｏ−２７ＨＥＥＥ
ダイシングブレード形状：外径５５．５６ｍｍ、刃幅３５μｍ、内径１９．０５ｍｍ
ダイシングブレード回転数：４０、０００ｒｐｍ
ダイシングブレード送り速度：５０ｍｍ／秒
ダイシングサイズ：１．５ｍｍ角
粘着シートへの切り込み量：１５μｍ
切削水温度：２５℃
切削水量：１．０リットル／分The conditions for the dicing process were as follows.
Dicing machine: DAD341 manufactured by DISCO
Dicing blade: NBC-ZH205O-27HEEE made by DISCO
Dicing blade shape: outer diameter 55.56 mm, blade width 35 μm, inner diameter 19.05 mm
Dicing blade rotation speed: 40,000 rpm
Dicing blade feed rate: 50 mm / sec. Dicing size: 1.5 mm square. Cutting depth into adhesive sheet: 15 μm
Cutting water temperature: 25 ° C
Cutting water volume: 1.0 l / min
ピックアップ工程の条件は以下の通りとした。
ピックアップ装置：キヤノンマシナリー社製ＣＡＰ−３００ＩＩ
エキスパンド量：８ｍｍ
ニードルピン形状：７０μｍＲ
ニードルピン数：１本
ニードルピン突き上げ高さ：１．５ｍｍThe conditions for the pick-up process were as follows.
Pickup device: CAP-300II manufactured by Canon Machinery
Expanding amount: 8mm
Needle pin shape: 70μmR
Number of needle pins: 1 Needle pin push-up height: 1.5 mm
ダイシング工程およびピックアップ工程において、以下の評価を行った。 The following evaluation was performed in the dicing process and the pickup process.
（２−１）チップ保持性
チップ保持性は、ダイシング工程後において、半導体チップが粘着シートに保持されている半導体チップの残存率に基づき、以下の基準により評価した。
◎（優） ：チップ飛びが５％未満
○（良） ：チップ飛びが５％以上１０％未満
×（不可）：チップ飛びが１０％以上(2-1) Chip Retention The chip retention was evaluated according to the following criteria based on the remaining rate of the semiconductor chips held on the adhesive sheet after the dicing step.
◎ (Excellent): Chip skipping is less than 5% ○ (Good): Chip skipping is 5% or more and less than 10% × (Not possible): Chip skipping is 10% or more
（２−２）ピックアップ性
ピックアップ性は、ピックアップ工程において、半導体チップがピックアップできた率に基づき、以下の基準により評価した。
◎（優）：チップのピックアップ成功率が９５％以上
○（良）：チップのピックアップ成功率が８０％以上９５％未満
×（不可）：チップのピックアップ成功率が８０％未満(2-2) Pickup property Pickup property was evaluated according to the following criteria based on the rate at which a semiconductor chip could be picked up in the pickup process.
◎ (Excellent): Chip pickup success rate is 95% or more ○ (Good): Chip pickup success rate is 80% or more and less than 95% × (Not possible): Chip pickup success rate is less than 80%
表１、表２から明らかなように、全ての実施例（実施例１〜実施例１４）において、経時による粘着力上昇が小さく、且つ加温の有無に関わらずチップ保持性とピックアップ性の両方において優れた結果が得られた。
実施例１〜実施例３を比較すると、エポキシ系硬化剤の含有量を０．１質量部以下にすると、チップ保持性が特に良好になることが分かった。
実施例１〜実施例１４を比較すると、アジピン酸系ポリエステルを用いた場合には、経時による粘着力上昇が特に小さくなることが分かった。
比較例１では、エポキシ系硬化剤の含有量が多すぎたため、加温なしの場合にチップ保持性が良好でなかった。
比較例２〜比較例７では、（メタ）アクリル酸エステル共重合体を構成する単量体単位の種類は実施例と同じであるが、その割合が適切でなかったため、良好な結果が得られなかった。
比較例８〜比較例１２では、（メタ）アクリル酸エステル共重合体を構成する単量体単位の種類が実施例と異なっており、良好な結果が得られなかった。
比較例１３では、ポリエステル系ではない可塑剤が使用されたため、経時による粘着力上昇が大きかった。As is clear from Tables 1 and 2, in all Examples (Examples 1 to 14), the increase in adhesive strength with time is small, and both the chip holding property and the pick-up property regardless of the presence or absence of heating. Excellent results were obtained.
When Examples 1 to 3 were compared, it was found that when the content of the epoxy curing agent was 0.1 parts by mass or less, the chip retention was particularly good.
When Example 1 to Example 14 were compared, it was found that when an adipic acid-based polyester was used, the increase in adhesive strength with time was particularly small.
In Comparative Example 1, since the content of the epoxy curing agent was too much, the chip retention was not good when there was no heating.
In Comparative Examples 2 to 7, the types of monomer units constituting the (meth) acrylic acid ester copolymer are the same as those in the Examples, but the ratio was not appropriate, so good results were obtained. There wasn't.
In Comparative Example 8 to Comparative Example 12, the types of monomer units constituting the (meth) acrylic acid ester copolymer were different from those in Examples, and good results were not obtained.
In Comparative Example 13, since a non-polyester plasticizer was used, the increase in adhesive strength with time was large.
表３〜表４から明らかなように、全ての実施例（実施例１５〜実施例２９）において、加温の有無に関わらずチップ保持性とピックアップ性の両方において優れた結果が得られた。
実施例１５〜実施例１７を比較すると、エポキシ系硬化剤の含有量を０．１質量部以下にすると、チップ保持性が特に良好になることが分かった。
比較例１４では、エポキシ系硬化剤の含有量が多すぎたため、加温なしの場合にチップ保持性が良好でなかった。
比較例１５〜２０では、（メタ）アクリル酸エステル共重合体を構成する単量体単位の種類は実施例と同じであるが、その割合が適切でなかったため、良好な結果が得られなかった。
比較例２１〜２５では、（メタ）アクリル酸エステル共重合体を構成する単量体単位の種類が実施例と異なっており、良好な結果が得られなかった。
比較例２６では、アイオノマ樹脂がエチレン-メタアクリル酸共重合体Ｚｎ塩の２元系であるため、良好な結果が得られなかった。As is apparent from Tables 3 to 4, in all Examples (Examples 15 to 29), excellent results were obtained in both the chip holding property and the pickup property regardless of the presence or absence of heating.
When Example 15 to Example 17 were compared, it was found that when the content of the epoxy curing agent was 0.1 parts by mass or less, the chip retention was particularly good.
In Comparative Example 14, since the content of the epoxy curing agent was too much, the chip retention was not good when there was no heating.
In Comparative Examples 15 to 20, the type of the monomer unit constituting the (meth) acrylic acid ester copolymer is the same as that of the example, but the ratio was not appropriate, and thus good results were not obtained. .
In Comparative Examples 21 to 25, the types of monomer units constituting the (meth) acrylic acid ester copolymer were different from those in Examples, and good results were not obtained.
In Comparative Example 26, since the ionomer resin was a binary system of ethylene-methacrylic acid copolymer Zn salt, good results were not obtained.
Claims (10)
前記粘着剤組成物が、（メタ）アクリル酸エステル共重合体１００質量部と、イソシアネート系硬化剤０．１〜７質量部を含み、
前記（メタ）アクリル酸エステル共重合体は、メチル（メタ）アクリレート単位を３５〜８５質量％、２−エチルへキシルアクリレート単位を１０〜６０質量％、カルボキシル基を有する単量体単位を０．５〜１０質量％、ヒドロキシル基を有する単量体単位を０．０１〜５質量％含み、
前記粘着剤組成物は、エポキシ系硬化剤の含有量が、前記（メタ）アクリル酸エステル共重合体成分１００質量部に対して０〜０．２５質量部である、粘着シート。In a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive composition on a base film containing polyvinyl chloride and a polyester plasticizer,
The pressure-sensitive adhesive composition contains 100 parts by weight of a (meth) acrylic acid ester copolymer and 0.1 to 7 parts by weight of an isocyanate curing agent,
The (meth) acrylic acid ester copolymer has a methyl (meth) acrylate unit of 35 to 85% by mass, a 2-ethylhexyl acrylate unit of 10 to 60% by mass, and a monomer unit having a carboxyl group of 0.0. 5 to 10% by mass, containing 0.01 to 5% by mass of a monomer unit having a hydroxyl group,
The pressure-sensitive adhesive composition is a pressure-sensitive adhesive sheet in which the content of the epoxy curing agent is 0 to 0.25 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer component.
前記粘着剤組成物が、（メタ）アクリル酸エステル共重合体１００質量部と、イソシアネート系硬化剤０．１〜７質量部を含み、
前記（メタ）アクリル酸エステル共重合体は、メチル（メタ）アクリレート単位を３５〜８５質量％、２−エチルへキシルアクリレート単位を１０〜６０質量％、カルボキシル基を有する単量体単位を０．５〜１０質量％、ヒドロキシル基を有する単量体単位を０．０１〜５質量％含み、
前記粘着剤組成物は、エポキシ系硬化剤の含有量が、前記（メタ）アクリル酸エステル共重合体成分１００質量部に対して０〜０．２５質量部である、粘着シート。An adhesive sheet having an adhesive layer made of an adhesive composition on a base film made of an ionomer resin obtained by crosslinking a copolymer having an ethylene unit, a methacrylic acid unit, and a (meth) acrylic acid alkyl ester unit with a metal ion In
The pressure-sensitive adhesive composition contains 100 parts by weight of a (meth) acrylic acid ester copolymer and 0.1 to 7 parts by weight of an isocyanate curing agent,
The (meth) acrylic acid ester copolymer has a methyl (meth) acrylate unit of 35 to 85% by mass, a 2-ethylhexyl acrylate unit of 10 to 60% by mass, and a monomer unit having a carboxyl group of 0.0. 5 to 10% by mass, containing 0.01 to 5% by mass of a monomer unit having a hydroxyl group,
The pressure-sensitive adhesive composition is a pressure-sensitive adhesive sheet in which the content of the epoxy curing agent is 0 to 0.25 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer component.
前記被着体をダイシングしてチップにするダイシング工程と、
前記粘着シートから前記チップをピックアップするピックアップ工程と、
を含む、電子部品の製造方法。An attaching step of attaching the pressure-sensitive adhesive sheet according to any one of claims 1 to 8 to an adherend and a ring frame;
A dicing step of dicing the adherend into a chip;
A pickup step of picking up the chip from the adhesive sheet;
A method for manufacturing an electronic component, comprising:
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| JP6624825B2 (en) * | 2014-09-25 | 2019-12-25 | 日東電工株式会社 | Heat release type adhesive sheet |
| CN108243615B (en) * | 2016-02-29 | 2021-03-09 | 琳得科株式会社 | Semiconductor processing sheet |
| JP6343725B2 (en) * | 2016-02-29 | 2018-06-13 | リンテック株式会社 | Base film for semiconductor processing sheet and semiconductor processing sheet |
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| JP2001089731A (en) * | 1999-09-20 | 2001-04-03 | Lintec Corp | Pressure-sensitive adhesive composition and adhesive optical function member made thereof |
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