JP2012246461A - Adhesive sheet - Google Patents
Adhesive sheet Download PDFInfo
- Publication number
- JP2012246461A JP2012246461A JP2011121800A JP2011121800A JP2012246461A JP 2012246461 A JP2012246461 A JP 2012246461A JP 2011121800 A JP2011121800 A JP 2011121800A JP 2011121800 A JP2011121800 A JP 2011121800A JP 2012246461 A JP2012246461 A JP 2012246461A
- Authority
- JP
- Japan
- Prior art keywords
- group
- adhesive sheet
- general formula
- resin
- alkyl group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 79
- 239000000853 adhesive Substances 0.000 title claims abstract description 78
- 239000004065 semiconductor Substances 0.000 claims abstract description 40
- 239000005011 phenolic resin Substances 0.000 claims abstract description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001187 thermosetting polymer Polymers 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 239000003822 epoxy resin Substances 0.000 claims description 27
- 229920000647 polyepoxide Polymers 0.000 claims description 27
- 150000002989 phenols Chemical class 0.000 claims description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000007822 coupling agent Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 1
- 229920001568 phenolic resin Polymers 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- -1 acrylic ester Chemical class 0.000 description 18
- 239000012790 adhesive layer Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 10
- 125000003700 epoxy group Chemical group 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002966 varnish Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 5
- 229920006243 acrylic copolymer Polymers 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 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 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 229910002026 crystalline silica Inorganic materials 0.000 description 3
- 125000006165 cyclic alkyl group Chemical group 0.000 description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 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 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 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 3
- 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 3
- 239000002245 particle Substances 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- NADHCXOXVRHBHC-UHFFFAOYSA-N 2,3-dimethoxycyclohexa-2,5-diene-1,4-dione Chemical compound COC1=C(OC)C(=O)C=CC1=O NADHCXOXVRHBHC-UHFFFAOYSA-N 0.000 description 2
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- CRGRWBQSZSQVIE-UHFFFAOYSA-N diazomethylbenzene Chemical compound [N-]=[N+]=CC1=CC=CC=C1 CRGRWBQSZSQVIE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000011049 filling Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- UIXPTCZPFCVOQF-UHFFFAOYSA-N ubiquinone-0 Chemical compound COC1=C(OC)C(=O)C(C)=CC1=O UIXPTCZPFCVOQF-UHFFFAOYSA-N 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- DAJPMKAQEUGECW-UHFFFAOYSA-N 1,4-bis(methoxymethyl)benzene Chemical compound COCC1=CC=C(COC)C=C1 DAJPMKAQEUGECW-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- ZEGDFCCYTFPECB-UHFFFAOYSA-N 2,3-dimethoxy-1,4-benzoquinone Natural products C1=CC=C2C(=O)C(OC)=C(OC)C(=O)C2=C1 ZEGDFCCYTFPECB-UHFFFAOYSA-N 0.000 description 1
- AIACLXROWHONEE-UHFFFAOYSA-N 2,3-dimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=C(C)C(=O)C=CC1=O AIACLXROWHONEE-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- SENUUPBBLQWHMF-UHFFFAOYSA-N 2,6-dimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=C(C)C1=O SENUUPBBLQWHMF-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- SOEZXSYRGLWFQV-UHFFFAOYSA-N 2-methyl-4-[1,2,2-tris(4-hydroxy-3-methylphenyl)ethyl]phenol Chemical compound C1=C(O)C(C)=CC(C(C(C=2C=C(C)C(O)=CC=2)C=2C=C(C)C(O)=CC=2)C=2C=C(C)C(O)=CC=2)=C1 SOEZXSYRGLWFQV-UHFFFAOYSA-N 0.000 description 1
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 description 1
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004941 2-phenylimidazoles Chemical class 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- GIPIGLOXWZLRNG-UHFFFAOYSA-N 4-[(4-hydroxy-3-methoxyphenyl)-(4-hydroxy-3-methylphenyl)methyl]-2-methylphenol Chemical compound C1=C(O)C(OC)=CC(C(C=2C=C(C)C(O)=CC=2)C=2C=C(C)C(O)=CC=2)=C1 GIPIGLOXWZLRNG-UHFFFAOYSA-N 0.000 description 1
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 1
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- GVYLCNUFSHDAAW-UHFFFAOYSA-N mirex Chemical compound ClC12C(Cl)(Cl)C3(Cl)C4(Cl)C1(Cl)C1(Cl)C2(Cl)C3(Cl)C4(Cl)C1(Cl)Cl GVYLCNUFSHDAAW-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/151—Die mounting substrate
- H01L2924/156—Material
- H01L2924/157—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
- H01L2924/15738—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950 C and less than 1550 C
- H01L2924/15747—Copper [Cu] as principal constituent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/30—Technical effects
- H01L2924/35—Mechanical effects
- H01L2924/351—Thermal stress
Abstract
Description
本発明は、接着シートに関する。 The present invention relates to an adhesive sheet.
半導体素子をはじめとする各種電子部品を搭載した実装基板として最も重要な特性の一つとして信頼性がある。その中でも、熱疲労に対する接続信頼性は実装基板を用いた機器の信頼性に直接関係するため非常に重要な項目である。この接続信頼性を向上するための１つの課題として、熱膨張係数の異なる各種材料を用いていることから生じる熱応力の緩和が挙げられる。熱応力は、例えば、半導体素子の熱膨張係数が約４ｐｐｍ／℃と小さいのに対して、電子部品を実装する配線板の熱膨張係数が１５ｐｐｍ／℃以上と大きいことから、これらを組み合わせた場合に熱衝撃に対して熱ひずみが発生することに起因する。最近、半導体装置の小型化、薄型化に伴い基板及びウエハの薄型化が進んでおり、上述したような熱応力に起因して素子の反りなどが発生しやくなっている。そのため、より低温、及び低荷重での実装が強く求められている。
一方、近年、携帯電話、携帯オ−ディオ機器用のメモリパッケージチップを多段に積層したスタックドＭＣＰ（Ｍｕｌｔｉ Ｃｈｉｐ Ｐａｃｋａｇｅ）が普及している。このようなパッケージにおいては、チップの接着面に空隙を発生させることなくチップを実装することが、接続信頼性を向上するための課題の一つとなっている。特に、配線などを有する基板上にチップを積層する場合、この基板、リードフレーム、チップ表面の凹凸を十分に埋め込む埋め込み性がパッケージの接続信頼性の確保に重要とされている。
Reliability is one of the most important characteristics as a mounting board on which various electronic components such as semiconductor elements are mounted. Among them, the connection reliability against thermal fatigue is a very important item because it is directly related to the reliability of the equipment using the mounting substrate. One problem for improving the connection reliability is relaxation of thermal stress caused by using various materials having different thermal expansion coefficients. For example, when the thermal stress of a semiconductor element is as small as about 4 ppm / ° C., the thermal expansion coefficient of a wiring board on which an electronic component is mounted is as large as 15 ppm / ° C. or more. This is due to the fact that thermal strain occurs due to thermal shock. Recently, with the miniaturization and thinning of semiconductor devices, thinning of substrates and wafers has progressed, and warping of elements is likely to occur due to the above-described thermal stress. Therefore, mounting at a lower temperature and a lower load is strongly demanded.
On the other hand, in recent years, a stacked MCP (Multi Chip Package) in which memory package chips for mobile phones and portable audio devices are stacked in multiple stages has become widespread. In such a package, mounting a chip without generating a gap on the bonding surface of the chip is one of the problems for improving connection reliability. In particular, when a chip is stacked on a substrate having wiring or the like, embedding ability to sufficiently bury unevenness on the substrate, lead frame, and chip surface is important for ensuring connection reliability of the package.
しかし、低温及び低荷重での圧着実装のみで上記チップ表面の凹凸を十分埋め込むことは難しい。そのため、従来から、接着シート付きチップを基板上に熱圧着して固定し、パッケージ封止工程での熱と圧力で凹凸を埋め込む方法が主流となっている。このような埋め込み性を確保できる接着シートとして、例えば、特許文献１に記載されているようなエポキシ樹脂、フェノール樹脂及びアクリル共重合体を含む接着シートなどが知られている。 However, it is difficult to sufficiently bury the irregularities on the chip surface only by pressure mounting at low temperature and low load. Therefore, conventionally, a method in which a chip with an adhesive sheet is fixed on a substrate by thermocompression bonding and the unevenness is embedded by heat and pressure in a package sealing process has become mainstream. As an adhesive sheet that can ensure such embedding properties, for example, an adhesive sheet including an epoxy resin, a phenol resin, and an acrylic copolymer as described in Patent Document 1 is known.
しかしながら、半導体装置は急激に高集積化が進み、スタックドＭＣＰを構成する接着シートは、チップの積層数の増加に伴って繰り返し起こる熱履歴を受けるため、熱劣化を起こすということが大きな問題となっている。長い熱履歴によって、接着シートが脆くなり、接着性が低下し、剥離を起こすといった問題や上述したパッケージ封止工程での熱と圧力で基板等の凹凸を埋め込む方法において、熱履歴のために硬化が進み、凹凸を埋め込むことが難しいといった問題が起こる。さらに近年、低コスト化や半導体素子の高速化のために銅リードフレームのような接着が難しい材料が使用され、接着性を維持するのが困難となっている。以上より、高集積化された半導体装置の信頼性を確保するためには、剥離等を防止するために高接着性であることと、凹凸を完全に埋め込むために長い熱履歴に対しても低弾性であることが求められる。しかしながら、高接着性と低弾性とは相反する特性であり、両立することが非常に困難である。したがって、本発明は、上述の状況に鑑み、高接着性と低弾性を両立し得る接着シート及びそれを用いた半導体装置を提供することを課題とする。 However, semiconductor devices are rapidly becoming highly integrated, and the adhesive sheet constituting the stacked MCP undergoes a thermal history that repeatedly occurs as the number of stacked chips increases. ing. The adhesive sheet becomes brittle due to a long heat history, the adhesiveness is lowered, and peeling occurs, and the method of embedding irregularities such as the substrate with the heat and pressure in the package sealing process described above cures due to the heat history. As a result, problems such as difficulty in embedding irregularities occur. In recent years, materials that are difficult to bond, such as copper lead frames, have been used to reduce costs and increase the speed of semiconductor elements, making it difficult to maintain adhesion. From the above, in order to ensure the reliability of a highly integrated semiconductor device, it is highly adhesive to prevent peeling and the like, and it is low even for a long thermal history to completely fill the unevenness. It is required to be elastic. However, high adhesion and low elasticity are contradictory properties, and it is very difficult to achieve both. Therefore, in view of the above situation, an object of the present invention is to provide an adhesive sheet that can achieve both high adhesiveness and low elasticity and a semiconductor device using the adhesive sheet.
本願発明は、以下の（１）〜（６）に関する。
（１）高分子量成分（Ａ）及び熱硬化性成分（Ｂ）を含有する接着シートであって、前記熱硬化性成分（Ｂ）が、下記一般式（１）で表される構造単位を有するフェノール樹脂もしくは下記一般式（２）又は（３）で表されるフェノール誘導体からなる群から選択される少なくとも一種のフェノール類を含む、接着シート。
（２）さらに硬化促進剤（Ｃ）、カップリング剤（Ｄ）及びフィラー（Ｅ）の少なくとも１種を含む、（１）に記載の接着シート。
（３）前記高分子量成分（Ａ）の配合量が、接着シートの全構成成分の合計質量を基準として、５０〜８０質量％の範囲である、（１）又は（２）に記載の接着シート。
（４）前記熱硬化性成分（Ｂ）がさらにエポキシ樹脂を含む、（１）〜（３）のいずれか１項に記載の接着シート。
（５）前記熱硬化性成分（Ｂ）における前記エポキシ樹脂と前記フェノール類との配合比が、エポキシ当量：ＯＨ当量で１．０：０．５〜１．０：１．２の範囲である、（１）〜（４）のいずれかに記載の接着シート。
（６）（１）〜（５）のいずれかに記載の接着シートを用いて、半導体素子と配線付き基板とを、又は半導体素子同士を接着した構造を有してなる半導体装置。
The present invention relates to the following (1) to (6).
(1) An adhesive sheet containing a high molecular weight component (A) and a thermosetting component (B), wherein the thermosetting component (B) has a structural unit represented by the following general formula (1) An adhesive sheet comprising at least one phenol selected from the group consisting of a phenol resin or a phenol derivative represented by the following general formula (2) or (3).
(2) The adhesive sheet according to (1), further comprising at least one of a curing accelerator (C), a coupling agent (D), and a filler (E).
(3) The adhesive sheet according to (1) or (2), wherein the blending amount of the high molecular weight component (A) is in the range of 50 to 80% by mass based on the total mass of all components of the adhesive sheet. .
(4) The adhesive sheet according to any one of (1) to (3), wherein the thermosetting component (B) further contains an epoxy resin.
(5) The compounding ratio of the epoxy resin and the phenols in the thermosetting component (B) is in the range of 1.0: 0.5 to 1.0: 1.2 in terms of epoxy equivalent: OH equivalent. The adhesive sheet according to any one of (1) to (4).
(6) A semiconductor device having a structure in which a semiconductor element and a substrate with wiring are bonded to each other using the adhesive sheet according to any one of (1) to (5).
本発明によれば、高い接着性と低弾性を両立し、耐熱履歴性を有し、半導体装置の接続信頼性の向上を可能とする接着シート及びそれを用いた半導体装置を提供することができる。より詳細には、本発明による接着シートは、通常、接着性を維持することが困難な銅リードフレームに対して熱履歴をかけた場合であっても優れた接着性を示し、また通常の熱履歴に相当する熱時（170℃）での弾性率も良好である。そのため、本発明による接着シートを用いて構成される半導体装置は、熱時信頼性に優れたものとなる。 According to the present invention, it is possible to provide an adhesive sheet that achieves both high adhesiveness and low elasticity, has heat resistance hysteresis, and can improve the connection reliability of a semiconductor device, and a semiconductor device using the adhesive sheet. . More specifically, the adhesive sheet according to the present invention usually exhibits excellent adhesion even when subjected to a thermal history on a copper lead frame in which adhesion is difficult to maintain, The elastic modulus at heat (170 ° C.) corresponding to the history is also good. Therefore, the semiconductor device configured using the adhesive sheet according to the present invention has excellent thermal reliability.
本発明の接着シートは、高分子量成分（Ａ）及び熱硬化性成分（Ｂ）を含有する接着シートであって、上記熱硬化性成分（Ｂ）が下記一般式（１）で表される構造単位を有するフェノール樹脂と、下記一般式（２）又は（３）で表されるフェノール誘導体とからなる群から選択される少なくとも一種のフェノール類を含むことを特徴とする。
以下、本発明の接着シートを構成する各成分について詳しく説明する。 Hereinafter, each component which comprises the adhesive sheet of this invention is demonstrated in detail.
高分子量成分（Ａ）
本発明における高分子量成分（Ａ）としては、架橋性官能基を有するものであり、例えば架橋性官能基を有するポリイミド樹脂、（メタ）アクリル共重合体、ウレタン樹脂ポリフェニレンエーテル樹脂、ポリエーテルイミド樹脂、フェノキシ樹脂、変性ポリフェニレンエーテル樹脂等が挙げられ、これらのなかでも、架橋性官能基を有する（メタ）アクリル共重合体が好ましい。これら高分子量成分（Ａ）は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。上記架橋性官能基はポリマー鎖中に有していても、ポリマー鎖末端に有していてもよい。架橋性官能基の具体例としては、エポキシ基、アルコール性水酸基、フェノール性水酸基、カルボキシル基等が挙げられ、これらのなかでも、エポキシ基が好ましく、グリシジシル（メタ）アクリレートなどのエポキシ基含有モノマーを用いることによってポリマー鎖に導入することができる。
High molecular weight component (A)
The high molecular weight component (A) in the present invention has a crosslinkable functional group, for example, a polyimide resin having a crosslinkable functional group, a (meth) acrylic copolymer, a urethane resin polyphenylene ether resin, or a polyetherimide resin. , A phenoxy resin, a modified polyphenylene ether resin, and the like. Among these, a (meth) acrylic copolymer having a crosslinkable functional group is preferable. These high molecular weight components (A) may be used alone or in combination of two or more. The crosslinkable functional group may be present in the polymer chain or at the end of the polymer chain. Specific examples of the crosslinkable functional group include an epoxy group, an alcoholic hydroxyl group, a phenolic hydroxyl group, and a carboxyl group. Among these, an epoxy group is preferable, and an epoxy group-containing monomer such as glycidyl (meth) acrylate is used. By being used, it can be introduced into the polymer chain.
本発明において好ましい高分子量成分（Ａ）は、エポキシ基含有（メタ）アクリル共重合体であり、例えば、エポキシ基含有（メタ）アクリル酸エステル共重合体、エポキシ基含有アクリルゴムなどを挙げることができ、エポキシ基含有（メタ）アクリル酸エステル共重合体がより好ましい。アクリルゴムは、アクリル酸エステルを主成分とするものであり、例えば、ブチルアクリレートやエチルアクリレートとアクリロニトリルの共重合体などからなるゴムである。 A preferred high molecular weight component (A) in the present invention is an epoxy group-containing (meth) acrylic copolymer, and examples thereof include an epoxy group-containing (meth) acrylic acid ester copolymer and an epoxy group-containing acrylic rubber. An epoxy group-containing (meth) acrylic acid ester copolymer is more preferable. The acrylic rubber is mainly composed of an acrylic ester, and is a rubber made of, for example, a copolymer of butyl acrylate or ethyl acrylate and acrylonitrile.
上記エポキシ基含有（メタ）アクリル共重合体は、グリシジル（メタ）アクリレートを、全モノマー量を基準として、０．５〜６．０質量％含むことが好ましく、０．５〜５．０質量％含むことがより好ましい。グリシジル（メタ）アクリレートの含有量が０.５質量％未満となる場合は接着力が低下する可能性があり、６．０質量％超となる場合はゲル化する可能性がある。グリシジル（メタ）アクリレートと共重合するコモノマーは、エチル（メタ）アクリレートやブチル（メタ）アクリレート又は両者の混合物、アクリロニトリルを用いることができるが、混合比率は、共重合体のガラス転移温度（Ｔｇ）等を考慮して決定すればよい。重合方法は特に制限はなく、パール重合、溶液重合等を使用することができる。なお、本発明では「（メタ）アクリル」とは、「アクリル」、「メタクリル」を意味する。また、グリシジル（メタ）アクリレートは、グリシジルアクリレート、グリシジルメタクリレート及びそれらの混合物を意味する。 The epoxy group-containing (meth) acrylic copolymer preferably contains glycidyl (meth) acrylate in an amount of 0.5 to 6.0% by mass, based on the total monomer amount, and 0.5 to 5.0% by mass. More preferably. When the content of glycidyl (meth) acrylate is less than 0.5% by mass, the adhesive force may be reduced, and when it exceeds 6.0% by mass, gelation may occur. As the comonomer copolymerized with glycidyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, a mixture of both, or acrylonitrile can be used, but the mixing ratio is the glass transition temperature (Tg) of the copolymer. It may be determined in consideration of the above. The polymerization method is not particularly limited, and pearl polymerization, solution polymerization and the like can be used. In the present invention, “(meth) acryl” means “acryl” and “methacryl”. Moreover, glycidyl (meth) acrylate means glycidyl acrylate, glycidyl methacrylate, and mixtures thereof.
高分子量成分（Ａ）のガラス転移温度（以下、「Ｔｇ」と表記する）は、−５０〜５０℃であることが好ましく、−３０〜２０℃であることがより好ましい。前記Ｔｇが−５０℃未満では、シートに成形した後のタック力が上がり取り扱い性が悪化する可能性があり、逆に５０℃を超えると流動性を損なう可能性がある。 The glass transition temperature (hereinafter referred to as “Tg”) of the high molecular weight component (A) is preferably −50 to 50 ° C., and more preferably −30 to 20 ° C. If the Tg is less than −50 ° C., the tack force after being formed into a sheet may be increased and the handleability may be deteriorated. Conversely, if it exceeds 50 ° C., the fluidity may be impaired.
高分子量成分（Ａ）の重量平均分子量（以下、「Ｍｗ」と表記する）は、特に限定されないが、５万〜１２０万であることが好ましく、１０万〜１２０万であることがより好ましく、２０万〜８０万であることが特に好ましい。上記Ｍｗが５万未満では、成膜性が悪くなる傾向があり、逆に１２０万を超えると流動性が落ちてしまう傾向がある。なお、Ｍｗは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定し、標準ポリスチレンによる検量線を用いて換算した値であり、ポンプとして株式会社日立製作所製、製品名：Ｌ−６０００を使用し、カラムとして日立化成工業株式会社製、製品名：ゲルパック（Ｇｅｌｐａｃｋ）ＧＬ−Ｒ４４０、ゲルパックＧＬ−Ｒ４５０及びゲルパックＧＬ−Ｒ４００Ｍ（各１０．７ｍｍ（直径）×３００ｍｍ）をこの順に連結したカラムを使用し、溶離液としてテトラヒドロフラン（以下、「ＴＨＦ」と言う。）を使用し、試料１２０ｍｇを、ＴＨＦ：５ｍｌに溶解させたサンプルについて、流速１．７５ｍＬ／分で測定することができる。 The weight average molecular weight (hereinafter referred to as “Mw”) of the high molecular weight component (A) is not particularly limited, but is preferably 50,000 to 1,200,000, more preferably 100,000 to 1,200,000. Particularly preferred is 200,000 to 800,000. If the Mw is less than 50,000, the film formability tends to be poor, and conversely if it exceeds 1.2 million, the fluidity tends to decrease. Mw is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve. The product name: L-6000 manufactured by Hitachi, Ltd. is used as the pump, and the column As a product manufactured by Hitachi Chemical Co., Ltd., product name: Gelpack GL-R440, Gelpack GL-R450 and Gelpack GL-R400M (each 10.7 mm (diameter) × 300 mm) were used in this order to elute. Tetrahydrofuran (hereinafter referred to as “THF”) is used as a liquid, and a sample in which 120 mg of sample is dissolved in 5 ml of THF can be measured at a flow rate of 1.75 mL / min.
熱硬化性成分（Ｂ）
熱硬化性成分は、熱により架橋反応を起こし得る反応性化合物から構成される成分であり、本発明では、上記熱硬化性成分（Ｂ）として、下記一般式（１）で表される構造単位を有するフェノール樹脂と、下記一般式（２）又は（３）で表されるフェノール誘導体からなる群から選択される少なくとも一種のフェノール成分（以下、「フェノール類（ｂ１）」と表す。）を含有することを特徴とする。
A thermosetting component is a component comprised from the reactive compound which can raise | generate a crosslinking reaction with a heat | fever, and in this invention, as said thermosetting component (B), the structural unit represented by following General formula (1) And at least one phenol component selected from the group consisting of phenol derivatives represented by the following general formula (2) or (3) (hereinafter referred to as “phenols (b1)”). It is characterized by doing.
一般式（１）中のＲ１及びＲ２は、それぞれ独立して、水素原子又はアルキル基であり、例えば、水素原子；メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、オクチル基、２−エチルヘキシル基、ノニル基、デシル基等の鎖状アルキル基；シクロペンチル基、シクロヘキシル基、シクロヘプチル基等の環状アルキル基；等が挙げられる。これらのなかでも、Ｒ１及びＲ２はメチル基が好ましい。
Ｒ３は、アルキル基、アラルキル基、アルケニル基、アリール基、水酸基又はハロゲン原子を示し、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、オクチル基、２−エチルヘキシル基、ノニル基、デシル基、ウンデシル基、ドデシル基等の鎖状アルキル基；シクロペンチル基、シクロヘキシル基、シクロヘプチル基等の環状アルキル基；ベンジル基、フェネチル基等のアラルキル基；ビニル基、アリル基、ブテニル基等のアルケニル基；フェニル基、トリル基、キシリル基等のアリール基；水酸基；塩素、臭素、フッ素、ヨウ素等のハロゲン原子；などが挙げられる。これらのなかでも、水素結合やπ結合などの静電気的相互作用を考慮すると、メチル基やエチル基などのアルキル基が好ましい。
上記一般式（１）で表される構造単位を有するフェノール樹脂の市販品としては、大日本インキ化学工業株式会社製の商品名フェノライトＬＦシリーズがある。
R 1 and R 2 in the general formula (1) are each independently a hydrogen atom or an alkyl group, such as a hydrogen atom; a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, chain alkyl groups such as tert-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, nonyl group and decyl group; cyclic alkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group; . Among these, R 1 and R 2 are preferably methyl groups.
R 3 represents an alkyl group, an aralkyl group, an alkenyl group, an aryl group, a hydroxyl group or a halogen atom, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, or a pentyl group. Chain alkyl groups such as hexyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group; cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group; benzyl group, phenethyl group Aralkyl groups such as vinyl group, allyl group and butenyl group; aryl groups such as phenyl group, tolyl group and xylyl group; hydroxyl groups; halogen atoms such as chlorine, bromine, fluorine and iodine; Among these, in consideration of electrostatic interactions such as hydrogen bonds and π bonds, alkyl groups such as methyl groups and ethyl groups are preferable.
As a commercial product of the phenol resin having the structural unit represented by the general formula (1), there is a trade name Phenolite LF series manufactured by Dainippon Ink & Chemicals, Inc.
一般式（２）中のＲ４ないしＲ７は、それぞれ炭素数１〜４の直鎖状又は分岐状のアルキル基もしくはフェニル基を示し、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基、ｔｅｒｔ−ブチル基等の炭素数１〜４の直鎖状又は分岐状のアルキル基；フェニル基；等が挙げられる。上記Ｒ４ないしＲ７は同一環内又は異なる環内で互いに同一であってもよいし、異なっていてもよい。ａ，ｂ，ｃ及びｄは、それぞれ０〜４の整数を示す。Ｒ８は、炭素数１〜４のアルキレン基、フェニレン基を示し、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基、ｔｅｒｔ−ブチル基等の炭素数１〜４の直鎖状又は分岐状のアルキル基；フェニル基；等が挙げられ、なかでもフェニル基が好ましい。ｅは０〜４の整数を示す。
上記一般式（２）で表されるフェノール誘導体の市販品としては、旭有機材工業株式会社製の商品名：ＡＶライト ＴＥＰ−ＴＰＡ（化学名：α，α，α’，α’−テトラキス（４−ヒドロキシフェニル）−ｐ−キシレン）、ＡＶライト ＴＥＰ−ＤＦ（化学名：１，１，２，２−テトラキス（４−ヒドロキシフェニル）−エタン）、ＡＶライト ＴＥＯＣ−ＤＦ（化学名：１，１，２，２−テトラキス（４−ヒドロキシ−３−メチルフェニル）−エタン）、ＡＶライト ＢＩＰ−ＢＩ２５Ｘ−ＴＰＡ（化学名：α，α−ビス（４−ヒドロキシフェニル）−α’，α’−ビス（４−ヒドロキシ−２，５−ジメチルフェニル）−ｐ−キシレン）等がある。
R 4 to R 7 in the general formula (2) each represent a linear or branched alkyl group having 1 to 4 carbon atoms or a phenyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, Examples thereof include linear or branched alkyl groups having 1 to 4 carbon atoms such as isopropyl group, isobutyl group and tert-butyl group; phenyl group; and the like. R 4 to R 7 may be the same or different in the same ring or in different rings. a, b, c, and d each represent an integer of 0-4. R 8 represents an alkylene group having 1 to 4 carbon atoms or a phenylene group, and examples thereof include 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, and a tert-butyl group. A linear or branched alkyl group; a phenyl group; and the like. Among them, a phenyl group is preferable. e shows the integer of 0-4.
As a commercial item of the phenol derivative represented by the above general formula (2), product name: AV Lite TEP-TPA (chemical name: α, α, α ′, α′-tetrakis (manufactured by Asahi Organic Materials Co., Ltd.) 4-hydroxyphenyl) -p-xylene), AV lite TEP-DF (chemical name: 1,1,2,2-tetrakis (4-hydroxyphenyl) -ethane), AV lite TEOC-DF (chemical name: 1, 1,2,2-tetrakis (4-hydroxy-3-methylphenyl) -ethane), AV light BIP-BI25X-TPA (chemical name: α, α-bis (4-hydroxyphenyl) -α ′, α′- Bis (4-hydroxy-2,5-dimethylphenyl) -p-xylene) and the like.
一般式（３）中のＲ９ないしＲ１１は、それぞれ炭素数１〜４の直鎖状又は分岐状のアルキル基もしくはフェニル基を示し、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基、ｔｅｒｔ−ブチル基等の炭素数１〜４の直鎖状又は分岐状のアルキル基；フェニル基；等が挙げられる。上記Ｒ４ないしＲ７は同一環内又は異なる環内で互いに同一であってもよいし、異なっていてもよい。ｆ，ｇ及びｈは、それぞれ０〜４の整数を示す。Ｒ１２は、水素原子、アルキル基もしくはフェニル基を示し、例えば、水素原子；メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、オクチル基、２−エチルヘキシル基、ノニル基、デシル基、ウンデシル基、ドデシル基等の鎖状アルキル基；シクロペンチル基、シクロヘキシル基、シクロヘプチル基等の環状アルキル基；フェニル基；等が挙げられる。これらのなかでも、水素原子が好ましい。
上記一般式（３）で表されるフェノール誘導体の市販品としては、旭有機材工業株式会社製の商品名：ＡＶライト ＢＩＰ−ＰＨＢＺ（化学名：トリス−（４−ヒドロキシフェニル）メタン）、ＡＶライト ＢＩＯＣ−ＶＡ（化学名：ビス（４−ヒドロキシ−３−メチルフェニル）−４−ヒドロキシ−３−メトキシフェニルメタン等がある。
R 9 to R 11 in the general formula (3) each represent a linear or branched alkyl group or phenyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, Examples thereof include linear or branched alkyl groups having 1 to 4 carbon atoms such as isopropyl group, isobutyl group and tert-butyl group; phenyl group; and the like. R 4 to R 7 may be the same or different in the same ring or in different rings. f, g, and h each represent an integer of 0-4. R 12 represents a hydrogen atom, an alkyl group or a phenyl group, for example, a hydrogen atom; methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group A chain alkyl group such as a group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group and dodecyl group; a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group and a cycloheptyl group; a phenyl group; and the like. Among these, a hydrogen atom is preferable.
As a commercial item of the phenol derivative represented by the above general formula (3), trade name: AV Lite BIP-PHBZ (chemical name: tris- (4-hydroxyphenyl) methane) manufactured by Asahi Organic Materials Co., Ltd., AV Light BIOC-VA (chemical name: bis (4-hydroxy-3-methylphenyl) -4-hydroxy-3-methoxyphenylmethane).
本発明の接着シートによれば、熱硬化性成分（Ｂ）が上記フェノール類（ｂ１）を含むことにより、高い接着性と低弾性を両立し、接続信頼性を確保することができる。理論によって拘束するものではないが、上記フェノール類（ｂ１）は多官能であるため、一官能のフェノール化合物と比較して、反応性が高く、接着性において有利であり、また架橋時にはより多分岐の構造を形成しやすくなり、低弾性と接着性との両立が可能になると推測される。そのため、本発明では、熱硬化性成分（Ｂ）において上記一般式（１）〜（３）の少なくとも１種である上記フェノール類（ｂ１）を含むことが必須となる。上記フェノール類（ｂ１）の中でも、上記一般式（２）で表されるフェノール誘導体は４官能フェノールであり、上記一般式（３）で表されるフェノール誘導体は３官能のフェノールであり、それぞれ放射状の構造を有するため、上記一般式（１）のフェノール樹脂と比較して、分岐の方向が多岐にわたり、規則性が崩れることによって、低弾性化においてより有利であると推測される。そのため、上記フェノール類（ｂ１）の中でも、少なくとも上記一般式（２）又は（３）で表されるフェノール誘導体を使用することがより好ましい。しかし、本発明では、これらの実施形態に限定されることなく、上記フェノール類（ｂ１）の１種を単独で、又は２種以上を組み合わせて使用することができる。 According to the adhesive sheet of the present invention, the thermosetting component (B) contains the phenols (b1), so that both high adhesiveness and low elasticity can be achieved and connection reliability can be ensured. Although not bound by theory, the above phenols (b1) are polyfunctional, and thus have higher reactivity and are advantageous in adhesiveness than monofunctional phenolic compounds, and are more branched at the time of crosslinking. It is presumed that this structure can be easily formed, and both low elasticity and adhesiveness can be achieved. Therefore, in the present invention, it is essential that the thermosetting component (B) contains the phenols (b1) that are at least one of the general formulas (1) to (3). Among the phenols (b1), the phenol derivative represented by the general formula (2) is a tetrafunctional phenol, and the phenol derivative represented by the general formula (3) is a trifunctional phenol, each of which is radial. Therefore, it is presumed that it is more advantageous in lowering elasticity because the branching direction is diversified and the regularity is lost as compared with the phenol resin of the general formula (1). Therefore, it is more preferable to use at least the phenol derivative represented by the general formula (2) or (3) among the phenols (b1). However, in this invention, it is not limited to these embodiment, One type of the said phenols (b1) can be used individually or in combination of 2 or more types.
本発明では、熱硬化性成分（Ｂ）として、上記フェノール類（ｂ１）に加えて、当技術分野で熱硬化性樹脂として周知の化合物（以下、「熱硬化性樹脂（ｂ２）」と表す。）を使用することが好ましい。熱硬化性樹脂（ｂ２）としては、例えば、エポキシ樹脂、シアネート樹脂、ビスマレイミド樹脂、フェノール樹脂（上記フェノール類（ｂ１）を除く）、ユリア樹脂、メラミン樹脂、アルキド樹脂、アクリル樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、シリコーン樹脂、レゾルシノールホルムアルデヒド樹脂、キシレン樹脂、フラン樹脂、ポリウレタン樹脂、ケトン樹脂、トリアリルシアヌレート樹脂、ポリイソシアネート樹脂、トリス（２−ヒドロキシエチル）イソシアヌラートを含有する樹脂、トリアリルトリメリタートを含有する樹脂、シクロペンタジエンから合成された熱硬化性樹脂、芳香族ジシアナミドの三量化による熱硬化性樹脂等が挙げられる。これらのなかでも、高温において優れた接着力を持たせることができる点で、エポキシ樹脂、シアネート樹脂及びビスマレイミド樹脂が好ましく、半導体素子を実装する場合に要求される耐熱性及び耐湿性を有し、１５０℃以上で反応し、高分子量化するエポキシ樹脂を好適に用いることができる。これらの熱硬化性樹脂（ｂ２）は、１種を単独で用いてもよく、２種類以上を組み合わせて用いてもよい。 In the present invention, as the thermosetting component (B), in addition to the phenols (b1), a compound well known as a thermosetting resin in this technical field (hereinafter referred to as “thermosetting resin (b2)”). ) Is preferably used. Examples of the thermosetting resin (b2) include epoxy resins, cyanate resins, bismaleimide resins, phenol resins (excluding the above phenols (b1)), urea resins, melamine resins, alkyd resins, acrylic resins, and unsaturated polyesters. Resin, diallyl phthalate resin, silicone resin, resorcinol formaldehyde resin, xylene resin, furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, polyisocyanate resin, resin containing tris (2-hydroxyethyl) isocyanurate, Examples thereof include a resin containing triallyl trimellitate, a thermosetting resin synthesized from cyclopentadiene, a thermosetting resin by trimerization of aromatic dicyanamide, and the like. Among these, epoxy resin, cyanate resin, and bismaleimide resin are preferable because they can have excellent adhesive force at high temperatures, and have heat resistance and moisture resistance required when mounting semiconductor elements. An epoxy resin that reacts at 150 ° C. or higher and has a high molecular weight can be preferably used. These thermosetting resins (b2) may be used alone or in combination of two or more.
上記エポキシ樹脂としては、硬化して接着作用を有するものであれば特に制限はない。エポキシ樹脂として、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂等の二官能エポキシ樹脂；フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂；多官能エポキシ樹脂；脂環式エポキシ樹脂など一般に知られているものを適用することができる。これらのなかでも、ビスフェノールＦ型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂等が好ましい。これらは、１種を単独で又は２種以上を組み合わせて用いてもよい。 The epoxy resin is not particularly limited as long as it is cured and has an adhesive action. Examples of the epoxy resin include bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; novolak type epoxy resins such as phenol novolac type epoxy resin and cresol novolac type epoxy resin; An epoxy resin; generally known ones such as an alicyclic epoxy resin can be applied. Among these, bisphenol F type epoxy resin, cresol novolac type epoxy resin and the like are preferable. You may use these individually by 1 type or in combination of 2 or more types.
本発明による樹脂シートにおいて、熱硬化性成分（Ｂ）となる上記フェノール類（ｂ１）と、熱硬化性樹脂（ｂ２）との配合比は、熱硬化性樹脂の硬化が良好に達成できる範囲であれば特に限定されない。本発明の一実施形態において、上記配合比は、１．０：０．５〜１．０：１．２の範囲で適宜調整することが望ましい。例えば、熱硬化性樹脂（ｂ２）としてエポキシ樹脂を使用する場合、上記熱硬化性成分（Ｂ）における上記エポキシ樹脂と上記フェノール類との配合比は、エポキシ当量：ＯＨ当量で１．０：０．５〜１．０：１．２の範囲であることが好ましく、１．０：０．８〜１．０：１．０の範囲であることがより好ましい。上記ＯＨ当量を０．５以上にすることによって、エポキシ樹脂が未硬化となる不具合を低減することができる。また上記ＯＨ当量を１．２以下にすることによって、未反応のフェノール類の量を低減することができ、信頼性を低下させるアウトガスの発生等の抑制することができる。 In the resin sheet according to the present invention, the blending ratio of the phenols (b1) to be the thermosetting component (B) and the thermosetting resin (b2) is within a range where the curing of the thermosetting resin can be satisfactorily achieved. If there is no particular limitation. In one embodiment of the present invention, the blending ratio is desirably adjusted as appropriate in the range of 1.0: 0.5 to 1.0: 1.2. For example, when an epoxy resin is used as the thermosetting resin (b2), the compounding ratio of the epoxy resin and the phenols in the thermosetting component (B) is 1.0: 0 in terms of epoxy equivalent: OH equivalent. 0.5 to 1.0: 1.2 is preferable, and 1.0: 0.8 to 1.0: 1.0 is more preferable. By setting the OH equivalent to 0.5 or more, it is possible to reduce a problem that the epoxy resin is uncured. Moreover, by making the OH equivalent 1.2 or less, it is possible to reduce the amount of unreacted phenols, and to suppress the generation of outgas that lowers the reliability.
また、本発明の接着シートは、硬化促進剤（Ｃ）、カップリング剤（Ｄ）及びフィラー（Ｅ）の少なくとも１種を更に含んでもよい。本発明において、上記高分子量成分（Ａ）及び熱硬化性成分（Ｂ）に加えて、上記成分（Ｃ）〜（Ｅ）の少なくとも１種を含む接着シートは、接着性及び接続信頼性により優れたものとなる。以下、各成分について詳細に説明する。 Moreover, the adhesive sheet of this invention may further contain at least 1 sort (s) of a hardening accelerator (C), a coupling agent (D), and a filler (E). In the present invention, in addition to the high molecular weight component (A) and the thermosetting component (B), the adhesive sheet containing at least one of the components (C) to (E) is superior in adhesiveness and connection reliability. It will be. Hereinafter, each component will be described in detail.
硬化促進剤（Ｃ）
本発明の接着シートは、さらに硬化促進剤（Ｃ）を含有することができる。硬化促進剤（Ｃ）としては、特に制限はなく、例えば、１，８−ジアザビシクロ［５．４．０］ウンデセン−７、１，５−ジアザビシクロ［４．３．０］ノネン−５、５，６−ジブチルアミノ−１，８−ジアザビシクロ［５．４．０］ウンデセン−７等のシクロアミジン化合物及びこれらの化合物に無水マレイン酸、１，４−ベンゾキノン、２，５−トルキノン、１，４−ナフトキノン、２，３−ジメチルベンゾキノン、２，６−ジメチルベンゾキノン、２，３−ジメトキシ−５−メチル−１，４−ベンゾキノン、２，３−ジメトキシ−１，４−ベンゾキノン、フェニル−１，４−ベンゾキノン等のキノン化合物、ジアゾフェニルメタン、フェノール樹脂等のπ結合をもつ化合物を付加してなる分子内分極を有する化合物、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノール等の三級アミン類及びこれらの誘導体、１−シアノエチル−２−フェニルイミダゾール、２−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、２−ヘプタデシルイミダゾール等のイミダゾール類及びこれらの誘導体、トリブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、トリス（４−メチルフェニル）ホスフィン、ジフェニルホスフィン、フェニルホスフィン等の有機ホスフィン類及びこれらのホスフィン類に無水マレイン酸、上記キノン化合物、ジアゾフェニルメタン、フェノール樹脂等のπ結合をもつ化合物を付加してなる分子内分極を有するリン化合物、テトラフェニルホスホニウムテトラフェニルボレート、テトラフェニルホスホニウムエチルトリフェニルボレート、テトラブチルホスホニウムテトラブチルボレート等のテトラ置換ホスホニウム・テトラ置換ボレート、２−エチル−４−メチルイミダゾール・テトラフェニルボレート、Ｎ−メチルモルホリン・テトラフェニルボレート等のテトラフェニルボロン塩及びこれらの誘導体が挙げられる。これらの硬化促進剤は、１種を単独で又は２種以上を組み合わせて用いてもよい。これらのなかでも、硬化促進剤としては、イミダゾール類を含むことが好ましい。
Curing accelerator (C)
The adhesive sheet of the present invention can further contain a curing accelerator (C). The curing accelerator (C) is not particularly limited, and for example, 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonene-5, 5, Cycloamidine compounds such as 6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7 and these compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4- Naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4- Benzyldimethyl, a compound with intramolecular polarization formed by adding a quinone compound such as benzoquinone, a compound having a π bond such as diazophenylmethane or phenol resin Tertiary amines such as amine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 1-cyanoethyl-2-phenylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-phenyl Imidazoles such as -4-methylimidazole and 2-heptadecylimidazole and derivatives thereof, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, and phenylphosphine In addition, phosphorus compounds having intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, the above quinone compound, diazophenylmethane, or a phenol resin to these phosphines, Tetrasubstituted phosphonium / tetrasubstituted borates such as raphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, tetrabutylphosphonium tetrabutylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetra Examples thereof include tetraphenylboron salts such as phenylborate and derivatives thereof. These curing accelerators may be used alone or in combination of two or more. Among these, as a hardening accelerator, it is preferable that imidazoles are included.
カップリング剤（Ｄ）
本発明の接着シートは、異種材料間の界面結合をよくするためにカップリング剤を含有することもできる。カップリング剤としては、シラン系カップリング剤、チタネート系カップリング剤、アルミニウム系カップリング剤が挙げられ、これらのなかでもシラン系カップリング剤が好ましい。
シラン系カップリング剤の具体例としては、ビニルトリクロロシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−メタクリロキシプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、ビニルトリアセトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルメチルジエトキシシラン、γ−アニリノプロピルトリメトキシシラン、γ−アニリノプロピルトリエトキシシラン、γ−（Ｎ，Ｎ−ジメチル）アミノプロピルトリメトキシシラン、γ−（Ｎ，Ｎ−ジエチル）アミノプロピルトリメトキシシラン、γ−（Ｎ，Ｎ−ジブチル）アミノプロピルトリメトキシシラン、γ−（Ｎ−メチル）アニリノプロピルトリメトキシシラン、γ−（Ｎ−エチル）アニリノプロピルトリメトキシシラン、γ−（Ｎ，Ｎ−ジメチル）アミノプロピルトリエトキシシラン、γ−（Ｎ，Ｎ−ジエチル）アミノプロピルトリエトキシシラン、γ−（Ｎ，Ｎ−ジブチル）アミノプロピルトリエトキシシラン、γ−（Ｎ−メチル）アニリノプロピルトリエトキシシラン、γ−（Ｎ−エチル）アニリノプロピルトリエトキシシラン、γ−（Ｎ，Ｎ−ジメチル）アミノプロピルメチルジメトキシシラン、γ−（Ｎ，Ｎ−ジエチル）アミノプロピルメチルジメトキシシラン、γ−（Ｎ，Ｎ−ジブチル）アミノプロピルメチルジメトキシシラン、γ−（Ｎ−メチル）アニリノプロピルメチルジメトキシシラン、γ−（Ｎ−エチル）アニリノプロピルメチルジメトキシシラン、Ｎ−（トリメトキシシリルプロピル）エチレンジアミン、Ｎ−（ジメトキシメチルシリルイソプロピル）エチレンジアミン、メチルトリメトキシシラン、ジメチルジメトキシシラン、メチルトリエトキシシラン、γ−クロロプロピルトリメトキシシラン、ヘキサメチルジシラン、ビニルトリメトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン等が挙げられる。
Coupling agent (D)
The adhesive sheet of the present invention can also contain a coupling agent in order to improve interfacial bonding between different materials. Examples of the coupling agent include silane coupling agents, titanate coupling agents, and aluminum coupling agents, and among these, silane coupling agents are preferable.
Specific examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltri. Methoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxy Silane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ- (N, N-dimethyl) amino Propyltrimethoxysilane, γ- (N, N-diethyl) aminopropyltrimethoxysilane, γ- (N, N-dibutyl) aminopropyltrimethoxysilane, γ- (N-methyl) anilinopropyltrimethoxysilane, γ -(N-ethyl) anilinopropyltrimethoxysilane, γ- (N, N-dimethyl) aminopropyltriethoxysilane, γ- (N, N-diethyl) aminopropyltriethoxysilane, γ- (N, N- Dibutyl) aminopropyltriethoxysilane, γ- (N-methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane , Γ- (N, N-diethyl) aminopropylmethyldimethoxysilane, γ- (N, N-di Butyl) aminopropylmethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxy) Methylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane and the like.
フィラー（Ｅ）
本発明の接着シートは、上記成分の他にフィラー（Ｅ）を含有することもできる。フィラー（Ｅ）としては特に制限はないが、無機フィラーが好ましく、例えば、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウム、酸化カルシウム、酸化マグネシウム、アルミナ、窒化アルミニウム、ほう酸アルミウイスカ、窒化ホウ素、結晶性シリカ及び非晶性シリカを使用できる。これらは１種を単独又は２種類以上を混合して用いてもよいし、特に問題がなければ添加しなくても良い。
Filler (E)
The adhesive sheet of the present invention can contain a filler (E) in addition to the above components. Although there is no restriction | limiting in particular as a filler (E), An inorganic filler is preferable, for example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina, nitriding Aluminum, aluminum borate whiskers, boron nitride, crystalline silica and amorphous silica can be used. These may be used singly or in combination of two or more, and may be omitted if there is no particular problem.
熱伝導性向上の観点からは、アルミナ、窒化アルミニウム、窒化ホウ素、結晶性シリカ又は非晶性シリカを用いることが好ましい。また、溶融粘度の調整やチクソトロピック性の付与の点からは、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウム、酸化カルシウム、酸化マグネシウム、アルミナ、結晶性シリカ又は非晶性シリカを用いることが好ましい。また、ダイシング性の向上の観点からは、アルミナ又はシリカを用いることが好ましい。 From the viewpoint of improving thermal conductivity, it is preferable to use alumina, aluminum nitride, boron nitride, crystalline silica, or amorphous silica. In terms of adjusting melt viscosity and imparting thixotropic properties, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina, crystalline silica Alternatively, it is preferable to use amorphous silica. From the viewpoint of improving dicing properties, it is preferable to use alumina or silica.
フィラー（Ｅ）の平均粒径は、０．００５〜２．０μｍであることが好ましい。平均粒径が０．００５μｍ未満であるか又は２．０μｍを超えると接着シートの接着性が低下する可能性がある。良好な成膜性と高い接着力を得るためには、フィラー（Ｅ）の平均粒径は０．００５〜１．５μｍであることがより好ましく、０．００５〜１．０μｍであることがさらに好ましい。 The average particle size of the filler (E) is preferably 0.005 to 2.0 μm. If the average particle size is less than 0.005 μm or exceeds 2.0 μm, the adhesiveness of the adhesive sheet may be lowered. In order to obtain good film formability and high adhesive strength, the average particle size of the filler (E) is more preferably 0.005 to 1.5 μm, and further preferably 0.005 to 1.0 μm. preferable.
特に限定するものではないが、本発明の好ましい一実施形態として、上記成分（Ａ）〜（Ｅ）の合計量１００質量％を基準として、高分子量成分（Ａ）を５０〜８０質量％、熱硬化性成分（Ｂ）を１５〜５０質量％、硬化促進剤（Ｃ）を０〜０．１５質量％、カップリング剤（Ｄ）を０〜２質量％及びフィラー（Ｅ）を０〜１０質量％から構成される接着シートが挙げられる。 Although it does not specifically limit, as one preferable embodiment of the present invention, the high molecular weight component (A) is 50 to 80% by mass based on 100% by mass of the total amount of the components (A) to (E), and heat The curable component (B) is 15 to 50% by mass, the curing accelerator (C) is 0 to 0.15% by mass, the coupling agent (D) is 0 to 2% by mass, and the filler (E) is 0 to 10% by mass. An adhesive sheet composed of% is cited.
高分子量成分（Ａ）が５０質量％未満では、接着剤層が脆くなる傾向があり、８０質量％を超えると接着剤層の流動性が低下する傾向がある。また、熱硬化性成分（Ｂ）が１５質量％未満では、接着剤層の硬化性が低下する傾向があり、５０質量％を超えると接着剤層が脆くなる傾向がある。 If the high molecular weight component (A) is less than 50% by mass, the adhesive layer tends to be brittle, and if it exceeds 80% by mass, the fluidity of the adhesive layer tends to decrease. Moreover, when the thermosetting component (B) is less than 15% by mass, the curability of the adhesive layer tends to be lowered, and when it exceeds 50% by mass, the adhesive layer tends to be brittle.
本発明の接着シートは、例えば、下記のようにして作製することができる。まず、上述の接着シートを構成する各成分を有機溶媒中で混合、混練してワニスを調製する。ワニスの調製に用いる有機溶媒は、接着シートを構成する成分を均一に溶解、混練又は分散できるものであれば制限はなく、従来公知のものを使用することができる。このような溶剤としては、例えば、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等のアミド系溶媒；アセトン、メチルエチルケトン、シクロヘキサノン等のケトン系溶媒；トルエン、キシレン等の炭化水素系溶媒が挙げられる。乾燥速度が速く、価格が安い点でメチルエチルケトン、シクロヘキサノンを使用することが好ましい。
有機溶媒は、形成される接着剤層中の残存揮発分が全質量基準で０〜１．０質量％となるような範囲で使用することが好ましく、接着剤層の発泡などによる信頼性低下への懸念から全質量基準で０〜０．５質量％となる範囲で使用することが好ましい。
The adhesive sheet of this invention can be produced as follows, for example. First, each component which comprises the above-mentioned adhesive sheet is mixed and knead | mixed in an organic solvent, and a varnish is prepared. The organic solvent used for the preparation of the varnish is not limited as long as it can uniformly dissolve, knead or disperse the components constituting the adhesive sheet, and a conventionally known one can be used. Examples of such solvents include amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; and hydrocarbon solvents such as toluene and xylene. It is preferable to use methyl ethyl ketone and cyclohexanone because the drying speed is fast and the price is low.
The organic solvent is preferably used in such a range that the residual volatile content in the formed adhesive layer is 0 to 1.0% by mass based on the total mass, and the reliability decreases due to foaming of the adhesive layer, etc. It is preferable to use in the range which becomes 0-0.5 mass% on the basis of total mass from concern.
上記の混合、混練は、通常の撹拌機、らいかい機、三本ロール、ボールミル等の分散機を適宜、組み合わせて行うことができる。 The above mixing and kneading can be carried out by appropriately combining dispersers such as a normal stirrer, a raking machine, a triple roll, and a ball mill.
上記で得られたワニスを基材フィルム上に均一に塗工し、ワニスの層を形成する。基材フィルムとして、特に制限はなく、例えば、ポリエステルフィルム、ポリプロピレンフィルム、ポリエチレンテレフタレートフィルム、ポリイミドフィルム、ポリエーテルイミドフィルム、ポリエーテルナフタレートフィルム、メチルペンテンフィルム等が用いられる。これらの基材フィルムに対して、必要に応じてプライマー塗布、ＵＶ処理、コロナ放電処理、研磨処理、エッチング処理等の表面処理を行ってもよい。基材フィルムの厚みは、特に制限はなく、接着剤層の厚みや接着シートの用途によって適宜選択される。 The varnish obtained above is uniformly coated on a base film to form a varnish layer. There is no restriction | limiting in particular as a base film, For example, a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyether naphthalate film, a methylpentene film etc. are used. These substrate films may be subjected to surface treatment such as primer coating, UV treatment, corona discharge treatment, polishing treatment, and etching treatment as necessary. There is no restriction | limiting in particular in the thickness of a base film, It selects suitably by the thickness of an adhesive bond layer, or the use of an adhesive sheet.
上記で得られた、ワニスを塗工した接着剤層を加熱乾燥することにより接着シートを得ることができる。また、接着剤層の乾燥後に基材フィルムを除去して、接着剤層のみから構成される接着シートとしてもよい。加熱乾燥の条件は、使用した有機溶媒が充分に揮散する条件であれば特に制限はないが、通常６０〜２００℃で、０．１〜９０分間加熱して行う。 An adhesive sheet can be obtained by heating and drying the adhesive layer coated with varnish obtained above. Moreover, it is good also as an adhesive sheet comprised only from an adhesive bond layer by removing a base film after drying an adhesive bond layer. The conditions for the heat drying are not particularly limited as long as the organic solvent used is sufficiently volatilized, but it is usually carried out by heating at 60 to 200 ° C. for 0.1 to 90 minutes.
本発明の接着シートは、長い熱履歴でも低弾性を維持し、凹凸の埋め込み性を確保する観点から、１７０℃で５時間硬化後の１７０℃における弾性率が６００ＭＰａ以下であることが好ましく、１００ＭＰａ以下であることがより好ましい。上記弾性率が６００ＭＰａを超えると、埋込性が不十分となる傾向がある。かかる弾性率は、例えば、動的粘弾性測定装置（レオロジ社製、ＤＶＥ）を使用し、接着シートを構成する組成物の硬化物に引張荷重をかけて、周波数１０Ｈｚ、昇温速度３℃／分の条件で室温から２７０℃まで測定する、温度依存性測定モードによって測定できる。 The adhesive sheet of the present invention preferably has an elastic modulus at 170 ° C. of not more than 600 MPa after curing at 170 ° C. for 5 hours from the viewpoint of maintaining low elasticity even with a long heat history and ensuring the embedding property of irregularities. The following is more preferable. When the elastic modulus exceeds 600 MPa, the embedding property tends to be insufficient. For example, the elastic modulus is measured by using a dynamic viscoelasticity measuring device (DVE, manufactured by Rheology Co., Ltd.) and applying a tensile load to the cured product of the composition constituting the adhesive sheet. It can be measured by a temperature-dependent measurement mode in which measurement is performed from room temperature to 270 ° C. under the condition of minutes.
また、接着剤層の厚みは、基板の配線回路や下層のチップの凹凸を充てん可能とするため、３〜２５０μｍであることが好ましい。この厚みが３μｍ未満であると応力緩和効果や接着性が乏しくなる傾向があり、２５０μｍを超えると経済的でなくなる上に、半導体装置の薄型化の要求に応えられない可能性がある。接着剤層の厚みは、接着性確保の点から３〜１００μｍであることが好ましく、半導体装置を薄型化できる点から３〜２５μｍであることがより好ましい。 Further, the thickness of the adhesive layer is preferably 3 to 250 μm in order to be able to fill the wiring circuit of the substrate and the unevenness of the lower chip. If this thickness is less than 3 μm, the stress relaxation effect and adhesiveness tend to be poor, and if it exceeds 250 μm, it is not economical and may not be able to meet the demand for thinning the semiconductor device. The thickness of the adhesive layer is preferably 3 to 100 μm from the viewpoint of securing adhesiveness, and more preferably 3 to 25 μm from the viewpoint of reducing the thickness of the semiconductor device.
本発明の接着シートは、高い接着性を示し、基板又は半導体チップの凹凸を完全に埋め込むために長い熱履歴に対しても低弾性である。従って、半導体装置の製造における半導体チップと基材との間や半導体チップ同士の間を接着するための工程において、接着信頼性に優れる接着シートとして使用することができる。 The adhesive sheet of the present invention exhibits high adhesiveness and has low elasticity even with a long thermal history in order to completely embed the irregularities of the substrate or semiconductor chip. Therefore, it can be used as an adhesive sheet having excellent adhesion reliability in a process for adhering between a semiconductor chip and a base material or between semiconductor chips in the manufacture of a semiconductor device.
基板又は半導体チップの凹凸を接着シートにより充填するときの荷重は適宜選択される。基板又は半導体チップの凹凸を接着シートにより充填する際に、基板の配線、半導体チップの凹凸を加熱することが好ましい。加熱方法としては、凹凸を有する基板又は半導体チップを予め加熱した熱板に接触させる方法が挙げられる。 The load when filling the unevenness of the substrate or the semiconductor chip with the adhesive sheet is appropriately selected. When filling the unevenness of the substrate or the semiconductor chip with the adhesive sheet, it is preferable to heat the unevenness of the wiring of the substrate and the semiconductor chip. Examples of the heating method include a method in which a substrate having unevenness or a semiconductor chip is brought into contact with a preheated hot plate.
本発明の接着シートは、ＩＣ、ＬＳＩ等の半導体素子間、あるいは、半導体素子と、４２アロイリードフレーム、銅リードフレーム等のリードフレーム、ポリイミド、エポキシ樹脂、ポリイミド系樹脂、マレイミド系樹脂等のプラスチックフィルム、ガラス不織布等基材にポリイミド、エポキシ樹脂、ポリイミド系樹脂、マレイミド系樹脂等のプラスチックを含浸・硬化させたもの、アルミナ等のセラミックス等の絶縁性支持基板などの支持部材の接合に用いることができる。すなわち、前記したような半導体素子間、あるいは半導体素子と支持部材との間に本発明の接着フィルムを挟み、加熱圧着して両者を接着させる。
本発明の半導体装置は、上記本発明の接着シートを用いて製造されたものであれば特にその構造に制限はなく、例えば、本発明の接着シートを用いて、半導体素子同士又は半導体素子と支持部材とを接着した構造を有してなる半導体装置が挙げられる。
The adhesive sheet of the present invention can be used between semiconductor elements such as IC and LSI or between semiconductor elements and lead frames such as 42 alloy lead frames and copper lead frames, and plastics such as polyimide, epoxy resin, polyimide resin, and maleimide resin. Use for bonding support members such as insulating support substrates such as films, glass nonwoven fabrics, etc. impregnated and cured with plastics such as polyimide, epoxy resin, polyimide resin, maleimide resin, ceramics such as alumina Can do. That is, the adhesive film of the present invention is sandwiched between semiconductor elements as described above or between a semiconductor element and a support member, and both are bonded by thermocompression bonding.
If the semiconductor device of this invention is manufactured using the adhesive sheet of the said invention, there will be no restriction | limiting in the structure in particular, For example, using the adhesive sheet of this invention, it is semiconductor elements or a semiconductor element and support. Examples include a semiconductor device having a structure in which a member is bonded.
以下、本発明を実施例により詳細に説明するが、本発明はこれらに制限されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not restrict | limited to these.
実施例１〜３、比較例１
［接着シートの作製］
表１に示す質量部で熱硬化性成分（Ｂ）を配合した後に、シクロヘキサノンを加えて撹拌し、次いで表１に示す高分子量成分（Ａ）、硬化促進剤（Ｃ）及びカップリング剤（Ｄ）をそれぞれ加え、各成分が均一になるまで撹拌することによって、接着剤組成物のワニスを得た。
次いで上記ワニスを、基材フィルムである厚み３８μｍの離型処理したポリエチレンテレフタレートフィルム上に塗布し、１１５℃で５分間加熱乾燥して、接着剤層（厚み２５μｍ）が基材フィルム上に形成された接着シートを作製した。
Examples 1-3, Comparative Example 1
[Preparation of adhesive sheet]
After blending the thermosetting component (B) in parts by mass shown in Table 1, cyclohexanone is added and stirred, and then the high molecular weight component (A), curing accelerator (C) and coupling agent (D) shown in Table 1 ) Was added, and each component was stirred until uniform, thereby obtaining a varnish of the adhesive composition.
Next, the varnish was applied on a polyethylene terephthalate film having a thickness of 38 μm, which was a base film, and dried by heating at 115 ° C. for 5 minutes to form an adhesive layer (thickness 25 μm) on the base film. An adhesive sheet was prepared.
上記接着シートの作製で使用した各種成分の詳細は以下のとおりである。
高分子量成分（Ａ）
グリシジルメタクリレート２．４質量％、メタクリル酸メチル４３．５質量％、アクリル酸エチル１８．３質量％及びアクリル酸ブチル３５．８質量％のエポキシ基含有アクリル系ランダム共重合体：重量平均分子量 ８０万、Ｔｇ −１３℃
Details of various components used in the production of the adhesive sheet are as follows.
High molecular weight component (A)
Epoxy group-containing acrylic random copolymer of glycidyl methacrylate 2.4% by mass, methyl methacrylate 43.5% by mass, ethyl acrylate 18.3% by mass and butyl acrylate 35.8% by mass: weight average molecular weight 800,000 , Tg-13 ° C
熱硬化性成分（Ｂ）
クレゾールノボラック型エポキシ樹脂：東都化成株式会社製、商品名「ＹＤＣＮ−７００−１０」、エポキシ当量：２１０
フェノール樹脂１：三井化学株式会社製、商品名「ミレックスＸＬＣ−ＬＬ」、水酸基当量１７５、フェノール・p−キシリレングリコールジメチルエーテル共重合樹脂
フェノール樹脂２：大日本インキ化学工業株式会社製、商品名「フェノライトＬＦ−４８７１」、水酸基当量１１８、ビスフェノールＡノボラック樹脂
フェノール誘導体１：旭有機材工業株式会社製、商品名「ＢＩＰ−ＰＨＢＺ」、水酸基当量２９２、構造式は下記式（４）で示される。
Cresol novolac type epoxy resin: manufactured by Toto Kasei Co., Ltd., trade name “YDCN-700-10”, epoxy equivalent: 210
Phenol resin 1: manufactured by Mitsui Chemicals, Inc., trade name “Mirex XLC-LL”, hydroxyl group equivalent 175, phenol / p-xylylene glycol dimethyl ether copolymer resin Phenol resin 2: manufactured by Dainippon Ink & Chemicals, Inc. "Phenolite LF-4871", hydroxyl group equivalent 118, bisphenol A novolac resin Phenol derivative 1: Asahi Organic Materials Co., Ltd., trade name "BIP-PHBZ", hydroxyl group equivalent 292, structural formula is represented by the following formula (4) .
硬化促進剤（Ｃ）
１−シアノエチル−２−フェニルイミダゾールキュアゾール：四国化成工業株式会社製、商品名「２ＰＺ−ＣＮ」
Curing accelerator (C)
1-cyanoethyl-2-phenylimidazolecazole: manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name “2PZ-CN”
カップリング剤（Ｄ）
γ―メルカプトプロピルトリメトキシシラン：日本ユニカー株式会社製、商品名「ＮＵＣ Ａ−１８９」
γ―ウレイドプロピルトリエトキシシラン：日本ユニカー株式会社製、商品名「ＮＵＣ Ａ−１１６０」
Coupling agent (D)
γ-mercaptopropyltrimethoxysilane: manufactured by Nippon Unicar Co., Ltd., trade name “NUC A-189”
γ-Ureidopropyltriethoxysilane: Nippon Unicar Co., Ltd., trade name “NUC A-1160”
［接着シートの評価］
実施例１〜３及び比較例１で作製した接着シートの特性を、以下のようにして評価した。
（１）接着強度の測定
接着剤層のダイシェア強度（接着強度）を下記の方法により測定した。まず、接着シートの接着剤層を厚み４００μｍの半導体ウエハに７０℃で貼り付けた。次に、それらを５ｍｍ角にダイシングして接着剤層付き半導体チップを得た。個片化した接着剤層付き半導体チップの接着剤層側を銅リードフレーム（古河電気工業株式会社製、商品名「ＴＥＣ−６４Ｔ」）表面上に、１２０℃、１ｋｇｆ／ｃｍ２、１秒間の条件で熱圧着してサンプルを得た。得られたサンプルの接着剤層を１３０℃で０．５時間硬化させ、６．７ＭＰａの圧力下、１８１℃で３０秒の加熱、加圧処理を行ったあと、１７０℃で５時間硬化した。８５℃、８５％のＲＨの恒温恒湿槽に４８時間投入した後、万能ボンドテスター（Ｄａｇｅ社製、シリーズ４０００）を用いて、２６０℃でダイシェア強度を測定し、接着強度とした。結果を表１に示す。
[Evaluation of adhesive sheet]
The characteristics of the adhesive sheets prepared in Examples 1 to 3 and Comparative Example 1 were evaluated as follows.
(1) Measurement of adhesive strength The die shear strength (adhesive strength) of the adhesive layer was measured by the following method. First, the adhesive layer of the adhesive sheet was attached to a semiconductor wafer having a thickness of 400 μm at 70 ° C. Next, they were diced to 5 mm square to obtain a semiconductor chip with an adhesive layer. The adhesive layer side of the separated semiconductor chip with an adhesive layer is placed on the surface of a copper lead frame (trade name “TEC-64T” manufactured by Furukawa Electric Co., Ltd.) at 120 ° C., 1 kgf / cm 2 , for 1 second. A sample was obtained by thermocompression bonding under conditions. The obtained adhesive layer of the sample was cured at 130 ° C. for 0.5 hour, subjected to heating and pressure treatment at 181 ° C. for 30 seconds under a pressure of 6.7 MPa, and then cured at 170 ° C. for 5 hours. After putting it in a constant temperature and humidity chamber of 85 ° C. and 85% RH for 48 hours, the die shear strength was measured at 260 ° C. using a universal bond tester (Dage, Series 4000) to obtain the adhesive strength. The results are shown in Table 1.
（２）１７０℃での動的粘弾性の測定
動的粘弾性測定装置ＤＶＥ レオスペクトラ（レオロジ株式会社製）を用いて以下の手順にて測定した。実施例１〜３及び比較例１で作製した接着シートから基材フィルムを剥離した後、接着剤層を長さ２０．０ｍｍ、幅４．０ｍｍに切断して試験片（膜厚：25μｍ）を作製し、１７０℃で５時間硬化させて硬化物を得た。その硬化物を昇温速度３℃／分で、室温から２７０℃までの粘弾性測定を行い、１７０℃の弾性率を読み取った。なお、測定中の空気流量は３５Ｌ／分とした。
(2) Measurement of dynamic viscoelasticity at 170 ° C. Measurement was performed in the following procedure using a dynamic viscoelasticity measuring device DVE Leospectra (manufactured by Rheology Co., Ltd.). After peeling the substrate film from the adhesive sheets prepared in Examples 1 to 3 and Comparative Example 1, the adhesive layer was cut to a length of 20.0 mm and a width of 4.0 mm to obtain a test piece (film thickness: 25 μm). It was prepared and cured at 170 ° C. for 5 hours to obtain a cured product. The cured product was measured for viscoelasticity from room temperature to 270 ° C. at a heating rate of 3 ° C./min, and the elastic modulus at 170 ° C. was read. The air flow rate during measurement was 35 L / min.
半導体パッケージの製造において、弾性率が１００ＭＰａ以下、接着強度が１．５ＭＰａ以上の接着シートが実現できれば、一般的な現行のＰＫＧの集積数に耐え得ると考えられる。表１に示されるように、実施例１〜３は共に、接着強度が１．５ＭＰａ以上であるため、分岐した多官能のフェノール樹脂を用いることにより、高接着性を有することが明らかである。
さらに、実施例１、２は、分岐したフェノールの中でも、放射状となったフェノール樹脂を用いているが、直鎖状フェノール樹脂を使用した実施例３、直鎖状でも分岐していないフェノール樹脂を用いた比較例１と比較しても低弾性であり、高い接着性と低弾性との両立において良好な結果が得られた。今後、集積数が増加した場合には、より低弾性率で高接着性の接着シートが求められると考えられる。上述の実施例から明らかなように、本発明によれば、現行のＰＫＧの集積数に耐え得る弾性率及び接着性とを実現し、半導体装置の接続信頼性を向上することができるだけでなく、さらなるニーズにも十分に対応可能であると推測される。
In the manufacture of semiconductor packages, if an adhesive sheet having an elastic modulus of 100 MPa or less and an adhesive strength of 1.5 MPa or more can be realized, it can be considered that it can withstand a general current number of PKGs. As shown in Table 1, since Examples 1 to 3 all have an adhesive strength of 1.5 MPa or more, it is clear that the use of a branched polyfunctional phenol resin has high adhesion.
Furthermore, although Examples 1 and 2 use the phenol resin which became radial also among the branched phenol, Example 3 which uses a linear phenol resin, and the phenol resin which is not branched even in a linear form. Even when compared with Comparative Example 1 used, the elasticity was low, and good results were obtained in achieving both high adhesion and low elasticity. In the future, when the number of integration increases, it is considered that an adhesive sheet having a lower elastic modulus and higher adhesion is required. As is clear from the above-described embodiments, according to the present invention, not only can the elastic modulus and adhesiveness that can withstand the current number of PKGs be integrated, and the connection reliability of the semiconductor device can be improved, It is speculated that it is possible to respond to further needs.
Claims (6)
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