JP5286682B2 - Manufacturing method of adhesive sheet for electronic device - Google Patents
Manufacturing method of adhesive sheet for electronic device Download PDFInfo
- Publication number
- JP5286682B2 JP5286682B2 JP2007076062A JP2007076062A JP5286682B2 JP 5286682 B2 JP5286682 B2 JP 5286682B2 JP 2007076062 A JP2007076062 A JP 2007076062A JP 2007076062 A JP2007076062 A JP 2007076062A JP 5286682 B2 JP5286682 B2 JP 5286682B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- layer
- conductive filler
- adhesive layer
- weight
- 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.)
- Expired - Fee Related
Links
- 239000000853 adhesive Substances 0.000 title claims description 113
- 230000001070 adhesive effect Effects 0.000 title claims description 113
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000012790 adhesive layer Substances 0.000 claims description 87
- 239000010410 layer Substances 0.000 claims description 68
- 239000011231 conductive filler Substances 0.000 claims description 64
- 239000000203 mixture Substances 0.000 claims description 53
- 239000007787 solid Substances 0.000 claims description 43
- 230000001681 protective effect Effects 0.000 claims description 42
- 229920000647 polyepoxide Polymers 0.000 claims description 29
- 239000003822 epoxy resin Substances 0.000 claims description 28
- 239000003973 paint Substances 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000008199 coating composition Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 13
- 239000000945 filler Substances 0.000 description 12
- 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 12
- 238000011156 evaluation Methods 0.000 description 11
- -1 silane compound Chemical class 0.000 description 11
- 238000011049 filling Methods 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 7
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 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 7
- 239000002904 solvent Substances 0.000 description 7
- 238000004381 surface treatment Methods 0.000 description 7
- 230000017525 heat dissipation Effects 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 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
- 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 5
- 230000000052 comparative effect Effects 0.000 description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000002313 adhesive film Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
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- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000003351 stiffener Substances 0.000 description 3
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- 238000012546 transfer Methods 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910052582 BN Inorganic materials 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920001646 UPILEX Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-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
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-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
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- ZMPZWXKBGSQATE-UHFFFAOYSA-N 3-(4-aminophenyl)sulfonylaniline Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=CC(N)=C1 ZMPZWXKBGSQATE-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-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
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-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
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-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
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- LMCLQTHHLNHUPN-UHFFFAOYSA-N 4-(4-aminophenyl)sulfonylbenzene-1,2-diamine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C(N)=C1 LMCLQTHHLNHUPN-UHFFFAOYSA-N 0.000 description 1
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 description 1
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- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
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- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- IFXORIIYQORRMJ-UHFFFAOYSA-N tribenzylphosphane Chemical compound C=1C=CC=CC=1CP(CC=1C=CC=CC=1)CC1=CC=CC=C1 IFXORIIYQORRMJ-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- QLAGHGSFXJZWKY-UHFFFAOYSA-N triphenylborane;triphenylphosphane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLAGHGSFXJZWKY-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- IUURMAINMLIZMX-UHFFFAOYSA-N tris(2-nonylphenyl)phosphane Chemical compound CCCCCCCCCC1=CC=CC=C1P(C=1C(=CC=CC=1)CCCCCCCCC)C1=CC=CC=C1CCCCCCCCC IUURMAINMLIZMX-UHFFFAOYSA-N 0.000 description 1
- LFNXCUNDYSYVJY-UHFFFAOYSA-N tris(3-methylphenyl)phosphane Chemical compound CC1=CC=CC(P(C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)=C1 LFNXCUNDYSYVJY-UHFFFAOYSA-N 0.000 description 1
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- AXORVIZLPOGIRG-UHFFFAOYSA-N β-methylphenethylamine Chemical compound NCC(C)C1=CC=CC=C1 AXORVIZLPOGIRG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Description
本発明は、電子機器用接着剤シートの製造方法に関する。より詳しくは、ダイボンディング材、放熱板（ヒートスプレッダー）、補強板（スティフナー）、シールド材の接着剤、銅張り積層板、リードフレームと金属製の支持基板間の絶縁層、カバーレイ、回路間の絶縁層、半導体パッケージとヒートシンクの接着等各種の電子材料を作製するために適した電子機器用接着剤シートの製造方法に関する。 The present invention relates to a process for the preparation of the adhesive sheet for electronic equipment. In more detail, die bonding material, heat sink (heat spreader), reinforcing plate (stiffener), adhesive for shield material, copper-clad laminate, insulation layer between lead frame and metal support substrate, coverlay, between circuits the insulating layer, a method of manufacturing the adhesive sheet for electronic devices that are suitable for making an adhesive such as various electronic materials of the semiconductor package and the heat sink.
近年、電子機器の実装技術の向上に伴い、機器の小型化、薄型化が進んでおり、その結果、電子機器の使用用途は増加の一途をたどっている。電子機器を小型化、薄型化する場合、機器から発生する熱の密度が高まるために、熱の発生を抑えるとともに、使用する半導体集積回路（ＩＣ）パッケージやトランジスタ、ダイオード、電源などの電子部品から発生する熱を効率的に外部に放出させることが重要となってくる。また、パソコン等で使用されるマイクロチッププロセッサ（ＭＰＵ）の動作周波数の上昇とともに、ＭＰＵチップより発生する熱量は非常に大きくなっている。また、プラズマパネルディスプレイ、液晶ディスプレイに代表されるフラットパネルディスプレイ（ＦＰＤ）は、ディスプレイパネルが発熱するため、この熱を外部に放出することが重要となってきている。 In recent years, along with improvements in mounting technology for electronic devices, the size and thickness of devices have been reduced, and as a result, the usage of electronic devices has been increasing. When downsizing and thinning electronic equipment, the density of heat generated from the equipment increases, so the generation of heat is suppressed, and the use of electronic components such as semiconductor integrated circuit (IC) packages, transistors, diodes, and power supplies It is important to efficiently release the generated heat to the outside. Further, as the operating frequency of a microchip processor (MPU) used in a personal computer or the like increases, the amount of heat generated from the MPU chip has become very large. Further, since flat panel displays (FPD) represented by plasma panel displays and liquid crystal displays generate heat in the display panel, it is important to release this heat to the outside.
一般に、上記のような電子部品から発生した熱を外部に放出するには、熱源となる電子部品に、ヒートシンクや金属板、電子機器筐体等のより放熱面積の大きい放熱部品を取り付ける方法が知られている。このとき、電子部品と放熱部品とが接する界面が、熱の移動の上で抵抗となっているため、界面における熱移動を補助する手段として熱伝導グリースや放熱スペーサーなどを界面に挟む方法が知られているが、これらの放熱材料には接着性がないため、部材同士を別途固定する必要があった。 Generally, in order to release the heat generated from the electronic components as described above, it is known to attach a heat radiating component having a larger heat radiating area such as a heat sink, a metal plate, or an electronic device casing to the electronic component serving as a heat source. It has been. At this time, since the interface between the electronic component and the heat dissipation component is a resistance in terms of heat transfer, a method of sandwiching heat conduction grease or a heat dissipation spacer between the interfaces as a means to assist heat transfer at the interface is known. However, since these heat dissipation materials do not have adhesiveness, it is necessary to fix the members separately.
このように近年では作業性の観点から、界面における熱移動に加え、電子部品と放熱部品とを固定することのできる材料が求められている。このような要求に対応できる材料として、熱硬化性樹脂および熱伝導性の高いフィラーを含有する接着剤組成物をシート状に加工した材料が挙げられる。例えば、エポキシ樹脂およびその硬化剤、高分子量樹脂、硬化促進剤および球形アルミナを含む、熱伝導率が０．６Ｗ／ｍ・Ｋ以上の熱伝導性接着剤組成物を基材上に塗布し、その硬化度をＤＳＣを用いて測定した場合の全硬化発熱量の１０〜４０％の発熱を終えた状態にした熱伝導性接着フィルムが提案されている（例えば、特許文献１参照）。しかしながら、この熱伝導性接着フィルムの熱伝導率は充分ではなく、接着性も十分とはいえなかった。 Thus, in recent years, from the viewpoint of workability, in addition to heat transfer at the interface, a material capable of fixing the electronic component and the heat dissipation component is required. As a material that can meet such a demand, a material obtained by processing an adhesive composition containing a thermosetting resin and a filler having high thermal conductivity into a sheet shape can be given. For example, a thermal conductive adhesive composition having a thermal conductivity of 0.6 W / m · K or more, including an epoxy resin and its curing agent, a high molecular weight resin, a curing accelerator, and spherical alumina is applied on a substrate. There has been proposed a thermally conductive adhesive film in which the heat generation of 10 to 40% of the total amount of heat generated when the degree of cure is measured using DSC is finished (see, for example, Patent Document 1). However, the heat conductivity of this heat conductive adhesive film is not sufficient, and the adhesiveness is not sufficient.
このような熱伝導性接着フィルムの熱伝導率を向上させる方法としては、含有する熱伝導性フィラーの含有量を増加させる方法がある。しかしながら、熱伝導性フィラーの含有量を増加させると接着性が低下するため、単体で接着性を持たせる場合、その含有量には限界があった。 As a method of improving the heat conductivity of such a heat conductive adhesive film, there is a method of increasing the content of the heat conductive filler contained. However, when the content of the heat conductive filler is increased, the adhesiveness is lowered. Therefore, when the adhesiveness is given alone, the content is limited.
このため、熱伝導性フィラーを含む層の両面に接着性向上を目的として薄い接着剤層を積層する方法が提案されている。例えば、第１層として、エポキシ樹脂、ゴム成分、及び硬化剤成分からなる接着剤組成物を、第２層としてエポキシ樹脂、ゴム成分、及び硬化剤成分からなる接着剤成分に２０〜９０体積％の無機充填材を添加してなる接着剤組成物を、第３層としてエポキシ樹脂、ゴム成分、及び硬化剤からなる接着剤組成物を基材フィルムに塗布し、半硬化状態に熱処理して３層構造とした熱硬化性接着シートが提案されている（例えば、特許文献２参照）。また、無機充填剤を７０〜９５重量％含有するエポキシ樹脂、ゴム成分、硬化剤成分からなる充填剤入りフィルムの両面に、１７０℃における溶融粘度が２Ｐａ．ｓ以下である充填剤を含まないエポキシ樹脂フィルムを貼り合せてなる熱硬化性接着フィルムが提案されている（例えば、特許文献３参照）。しかしながら、中央の層の無機充填剤を増量するとシートが堅くなり、取り扱いが難しくなるという課題があった。
上記のように、従来の熱伝導性接着剤シートは、その熱伝導率を向上させるため熱伝導性フィラーの含有量を増加させると、接着性、取り扱い性が不十分であった。本発明はかかる従来技術の課題に鑑み、熱伝導性と接着性、取り扱い性に優れた電子機器用接着剤シートを提供することを目的とする。 As described above, when the content of the thermally conductive filler is increased in order to improve the thermal conductivity of the conventional thermally conductive adhesive sheet, the adhesiveness and handleability are insufficient. An object of this invention is to provide the adhesive sheet for electronic devices excellent in heat conductivity, adhesiveness, and handleability in view of the subject of this prior art.
上記課題を解決するため、本発明は主として以下の構成を有する。すなわち、少なくとも接着剤層と剥離可能な保護フィルム層を有する電子機器用接着剤シートの製造方法であって、（１）エポキシ樹脂、硬化剤および熱伝導性充填剤を含有し、熱伝導性充填剤を固形分中５０体積％以上含有する接着剤組成物を３０〜６０重量％の固形分濃度で有機溶媒に溶解した塗料を、保護フィルム層に塗布・乾燥することにより、空隙を有する接着剤層（ａ）を形成する工程、（２）前記接着剤層（ａ）に、熱伝導性充填剤の含有量が固形分中０〜２０体積％である接着剤組成物を塗布する工程を有することを特徴とする電子機器用接着剤シートの製造方法である。 In order to solve the above problems, the present invention mainly has the following configuration. That is, a method for producing an adhesive sheet for electronic equipment having at least an adhesive layer and a peelable protective film layer, comprising (1) an epoxy resin, a curing agent and a thermally conductive filler, and thermally conductive filling Adhesive having voids by applying and drying a coating material obtained by dissolving an adhesive composition containing 50% by volume or more of an agent in an organic solvent at a solid content concentration of 30 to 60% by weight on a protective film layer A step of forming a layer (a), and (2) a step of applying an adhesive composition having a heat conductive filler content of 0 to 20% by volume in solid content to the adhesive layer (a). It is a manufacturing method of the adhesive sheet for electronic devices characterized by the above-mentioned.
本発明の製造方法により得られる電子機器用接着剤シートは、熱伝導性、被着体との接着性に優れる。また、屈曲性に優れるため、取り扱い性が大きく向上する。このため、電子機器内の発熱部品とヒートシンクや放熱板等の放熱部品を接着するために好適に用いることができる。また、本発明の製造方法により得られる電子機器用接着剤シートを用いて発熱部品と放熱部品を接着したり、プリント基板を積層することにより、放熱特性に優れた電子機器を得ることができる。 The adhesive sheet for electronic equipment obtained by the production method of the present invention is excellent in thermal conductivity and adhesion to an adherend. Moreover, since it is excellent in flexibility, the handleability is greatly improved. For this reason, it can use suitably in order to adhere | attach heat-emitting components in an electronic device, and heat sink components, such as a heat sink and a heat sink. In addition, an electronic device having excellent heat dissipation characteristics can be obtained by bonding the heat-generating component and the heat-dissipating component using the adhesive sheet for electronic device obtained by the production method of the present invention or by laminating the printed circuit board.
本発明の製造方法により得られる電子機器用接着剤シート（以下、接着剤シートという）は、電子機器内の発熱部品とヒートシンク、放熱板等の放熱部品との接着用シート、リードフレームと金属製の支持基板間の絶縁層、スティフナー、ヒートスプレッダー、ＦＰＣやその補強板、カバーレイや銅張り積層板、多層基板の層間接着剤、およびそれらを用いた基板部品、リードフレーム固定テープ、ＬＯＣ固定テープ、ダイボンディング材、シールド材等に使用でき、それら被着体の形状および材料は特に限定されない。 An adhesive sheet for an electronic device (hereinafter referred to as an adhesive sheet) obtained by the manufacturing method of the present invention is a sheet for bonding an exothermic component in an electronic device to a heat sink such as a heat sink or a heat sink, a lead frame, and a metal Insulating layers between supporting substrates, stiffeners, heat spreaders, FPC and its reinforcing plates, coverlays and copper-clad laminates, interlayer adhesives for multilayer substrates, and board components, lead frame fixing tapes, LOC fixing tapes using them It can be used for die bonding materials, shield materials, etc., and the shape and material of these adherends are not particularly limited.
以下、本発明の構成を詳述する。本発明の製造方法により得られる接着シートは、少なくとも接着剤層と剥離可能な保護フィルム層を有する電子機器用接着剤シートであって、前記接着層が、エポキシ樹脂、硬化剤および熱伝導性充填剤を含有し、熱伝導性充填剤を固形分中５０体積％以上含有する接着剤組成物を３０〜６０重量％の固形分濃度で有機溶媒に溶解した塗料を、保護フィルム層に塗布・乾燥することにより、空隙を有する接着剤層（ａ）を形成し、次いで、前記接着剤層（ａ）の空隙を、熱伝導性充填剤の含有量が固形分中０〜２０体積％である接着剤組成物により充填して得られることを特徴とする。熱伝導性充填剤を固形分中５０体積％以上含有する接着剤組成物から形成される、空隙を有する接着剤層（ａ）を形成することにより、熱伝導性に優れた接着剤シートを得ることができる。さらに、接着剤層（ａ）の空隙を熱伝導性充填剤の含有量が低い接着剤層により充填することにより、熱伝導性充填剤の含有量が同程度である単一の接着剤層を有する接着剤シートに比べて、接着性と屈曲性が著しく向上する。 Hereinafter, the configuration of the present invention will be described in detail. The adhesive sheet obtained by the production method of the present invention is an adhesive sheet for electronic equipment having at least an adhesive layer and a protective film layer that can be peeled, and the adhesive layer comprises an epoxy resin, a curing agent, and a thermally conductive filling. Applying and drying on the protective film layer a coating material containing an adhesive and containing an adhesive composition containing 50% by volume or more of a thermally conductive filler in an organic solvent at a solid content concentration of 30 to 60% by weight. by, formed adhesive layer having a void a (a), then, the gap of the adhesive layer (a), the content of the thermally conductive filler is 0-20 vol% solids in the adhesive It is obtained by filling with an agent composition. An adhesive sheet having excellent thermal conductivity is obtained by forming an adhesive layer (a) having voids, which is formed from an adhesive composition containing a heat conductive filler in a solid content of 50% by volume or more. be able to. Further, by filling the voids of the adhesive layer (a) with an adhesive layer having a low heat conductive filler content, a single adhesive layer having the same heat conductive filler content can be obtained. Compared with the adhesive sheet which has, adhesiveness and a flexibility are improved remarkably.
以下、接着剤層について説明する。空隙を有する接着剤層（ａ）を形成するための接着剤組成物は、熱伝導性充填剤を固形分中５０体積％以上含有することが必要である。より好ましくは６０体積％以上である。熱伝導性充填剤の含有量が固形分中５０体積％未満であると、十分な熱伝導性が得られない。 Hereinafter, the adhesive layer will be described. The adhesive composition for forming the adhesive layer (a) having voids needs to contain 50% by volume or more of the heat conductive filler in the solid content. More preferably, it is 60 volume% or more. When the content of the heat conductive filler is less than 50% by volume in the solid content, sufficient heat conductivity cannot be obtained.
ここでいう熱伝導性充填剤とは、充填剤単体での熱伝導率が１０（Ｗｍ−１Ｋ−１）以上の充填剤を指す。熱伝導率は、レーザーフラッシュ法により測定できる。例えば、アルバック理工（株）製 熱定数測定装置ＴＣ−７０００を用いて熱拡散率を測定し、別に測定した密度、比熱のパラメータから熱伝導率を算出する。熱伝導性充填剤の具体例としてアルミナ、酸化マグネシウム、窒化アルミニウム、酸化亜鉛、窒化硼素、窒化珪素、銀粉末、銅粉末、アルミニウム粉末、炭化珪素、ダイヤモンド粉末、グラファイト、炭素繊維などが挙げられる。この中でも、熱伝導率の点で窒化アルミニウム、窒化珪素、窒化硼素、アルミナなどが好ましく用いられるがこれに限定されるものではない。これら熱伝導性充填剤を２種以上含有してもよく、更に他の充填剤を含有してもよい。 The term “thermally conductive filler” as used herein refers to a filler having a thermal conductivity of 10 (Wm −1 K −1 ) or more as a single filler. The thermal conductivity can be measured by a laser flash method. For example, the thermal diffusivity is measured using a thermal constant measuring device TC-7000 manufactured by ULVAC-RIKO, and the thermal conductivity is calculated from the separately measured density and specific heat parameters. Specific examples of the thermally conductive filler include alumina, magnesium oxide, aluminum nitride, zinc oxide, boron nitride, silicon nitride, silver powder, copper powder, aluminum powder, silicon carbide, diamond powder, graphite, and carbon fiber. Among these, aluminum nitride, silicon nitride, boron nitride, alumina and the like are preferably used in terms of thermal conductivity, but are not limited thereto. Two or more of these thermally conductive fillers may be contained, and other fillers may be further contained.
熱伝導性充填剤は、充填剤の酸化、加水分解等の変質防止の目的や充填剤と接着剤組成物中のその他の有機成分とのぬれ性向上の目的、および接着剤シートの物性向上のために、表面処理を施してもよい。具体的には、シリカ、リン酸等でのコーティングや、酸化膜付与処理、シランカップリング剤、チタネート系カップリング剤、シラン化合物等での表面処理などが挙げられる。表面処理に使用されるシランカップリング剤の具体例としては、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、２−（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、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリエトキシシラン、ｐ−スチリルトリメトキシシラン、３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、３−アクリロキシプロピルトリメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルメチルジメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリエトキシシラン、３−トリエトキシシリル−Ｎ−（１、３−ジメチル−ブチリデン）プロピルアミン、３−ウレイドプロピルトリエトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−イソシアネートプロピルトリエトキシシランなどが挙げられるがこれらに限定されるものではない。これらシランカップリング剤を２種以上使用してもよい。表面処理に使用するシランカップリング剤の量は、熱伝導性充填剤１００重量部に対して０．３〜１重量部が好ましい。また、接着剤組成物に熱伝導性充填剤以外の充填剤を含有し、これら充填剤を合わせて表面処理する場合は、充填剤の合計１００重量部に対して０．３〜１重量部程度が好ましい。 Thermally conductive fillers are used for the purpose of preventing deterioration of fillers such as oxidation and hydrolysis, improving the wettability of fillers with other organic components in the adhesive composition, and improving the physical properties of adhesive sheets. Therefore, a surface treatment may be performed. Specific examples include coating with silica, phosphoric acid, etc., oxide film application treatment, silane coupling agent, titanate coupling agent, surface treatment with silane compound, and the like. Specific examples of the silane coupling agent used for the surface treatment include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and 3-glycidoxypropyl. Trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p -Styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-a Liloxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxy Silane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyl Although triethoxysilane etc. are mentioned, it is not limited to these. Two or more of these silane coupling agents may be used. The amount of the silane coupling agent used for the surface treatment is preferably 0.3 to 1 part by weight with respect to 100 parts by weight of the heat conductive filler. In addition, when the adhesive composition contains a filler other than the heat conductive filler, and when these fillers are combined and subjected to surface treatment, about 0.3 to 1 part by weight with respect to 100 parts by weight of the filler Is preferred.
熱伝導性充填剤の粒子形状、結晶性は特に制限されず、破砕系、球状、鱗片状等が用いられるが、塗料への分散性の点から、球状が好ましく用いられる。熱伝導性充填剤の平均粒径は接着剤層の厚みに対して１／３以下であることが好ましい。平均粒径が接着剤層の厚みの１／３以下であることにより、接着剤シートの貼りあわせの際にエアーの噛み込み等が少なくなり、接着性がより向上する。本発明において平均粒径とは、粒度分布計で粒度分布を測定し、累積分布をパーセント（％）で表した時の５０％に相当する粒子径（メジアン径）をいう。粒子が球状でない場合には球相当体積を基準とした粒度分布を測定する。粒度分布計としては堀場ＬＡ５００レーザー回折式粒度分布計等が挙げられる。なお、粒度分布は、体積基準で、粒子径表示を５６分割片対数表示（０．１〜２００μｍ）するものとする。熱伝導性充填剤を２種以上含有する場合、例えば、平均粒径が１．７μｍの窒化アルミニウム粉末と平均粒径が０．７μｍのアルミナ粉末のように、粒径の異なる熱伝導性充填剤を組み合わせることで充填性が向上し、熱伝導性がより向上するので好ましい。 The particle shape and crystallinity of the heat conductive filler are not particularly limited, and a crushing system, a spherical shape, a scale shape, and the like are used. From the viewpoint of dispersibility in the paint, a spherical shape is preferably used. The average particle size of the heat conductive filler is preferably 1/3 or less with respect to the thickness of the adhesive layer. When the average particle size is 1/3 or less of the thickness of the adhesive layer, air entrainment or the like is reduced when the adhesive sheet is bonded, and the adhesiveness is further improved. In the present invention, the average particle diameter means a particle diameter (median diameter) corresponding to 50% when the particle size distribution is measured with a particle size distribution meter and the cumulative distribution is expressed in percent (%). When the particles are not spherical, the particle size distribution based on the sphere equivalent volume is measured. Examples of the particle size distribution meter include Horiba LA500 laser diffraction particle size distribution meter. In addition, a particle size distribution shall display a particle diameter display on a volume basis, and a 56 division piece logarithm display (0.1-200 micrometers). When two or more kinds of thermally conductive fillers are contained, for example, thermally conductive fillers having different particle diameters such as aluminum nitride powder having an average particle diameter of 1.7 μm and alumina powder having an average particle diameter of 0.7 μm. Is preferable because the filling property is improved and the thermal conductivity is further improved.
空隙を有する接着剤層（ａ）を形成するための接着剤組成物は、樹脂を含有する。 The adhesive composition for forming the adhesive layer (a) having a gap, you containing resin.
また接着性の点でエポキシ樹脂を含有する。エポキシ樹脂を含有することで、耐熱性、高温での絶縁性、耐薬品性、接着剤層にしたときの強度等の物性バランスを実現することができる。エポキシ樹脂は、１分子中に２個以上のエポキシ基を有するものであれば特に制限されず、例えば、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビフェニル型骨格を有するエポキシ樹脂、ナフタレン骨格含有エポキシ樹脂、ビスフェノール型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、線状脂肪族エポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂、スピロ環含有エポキシ樹脂、およびハロゲン化エポキシ樹脂等が挙げられる。 Also containing epoxy resin in terms of adhesiveness. By containing an epoxy resin, it is possible to achieve a balance of physical properties such as heat resistance, insulation at high temperatures, chemical resistance, and strength when formed into an adhesive layer. The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. For example, a cresol novolac type epoxy resin, a phenol novolac type epoxy resin, an epoxy resin having a biphenyl type skeleton, a naphthalene skeleton containing Examples thereof include epoxy resins, bisphenol type epoxy resins, dicyclopentadiene type epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, and halogenated epoxy resins.
また、エポキシ基と架橋反応する硬化剤を含有する。これにより硬化後の接着力を向上させる。硬化剤の例としては、３，３’，５，５’−テトラメチル−４，４’−ジアミノジフェニルメタン、３，３’，５，５’−テトラエチル−４，４’−ジアミノジフェニルメタン、３，３’−ジメチル−５，５’−ジエチル−４，４’−ジアミノジフェニルメタン、３，３’−ジクロロ−４，４’−ジアミノジフェニルメタン、２，２’，３，３’−テトラクロロ−４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルスルフィド、３，３’−ジアミノベンゾフェノン、３，３’−ジアミノジフェニル
スルホン、４，４’−ジアミノジフェニルスルホン、３，４’−ジアミノジフェニルスルホン、４，４’−ジアミノベンゾフェノン、３，４，４’−トリアミノジフェニルスルホン等の芳香族ポリアミン、三フッ化ホウ素トリエチルアミン錯体等の三フッ化ホウ素のアミン錯体、ジシアンジアミド、フェノールノボラック、クレゾールノボラックなどのノボラック樹脂、ビスフェノールＡなどのビスフェノール化合物等が挙げられる。この中でも、耐熱性に優れることからフェノール系の硬化剤が好ましい。これらを２種以上用いてもよい。
Further, it contains a curing agent that undergoes a crosslinking reaction with the epoxy group . Thus Ru improve the adhesive strength after curing. Examples of curing agents include 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 3, 3′-dimethyl-5,5′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 2,2 ′, 3,3′-tetrachloro-4, 4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, Aromatic polyamines such as 4,4′-diaminobenzophenone and 3,4,4′-triaminodiphenylsulfone, and trifluoride such as boron trifluoride triethylamine complex Amine complexes of U element, dicyandiamide, phenol novolak, novolak resins such as cresol novolak, bisphenol compounds such as bisphenol A and the like. Of these, phenolic curing agents are preferred because of their excellent heat resistance. Two or more of these may be used.
また、エポキシ樹脂と硬化剤の硬化反応促進、硬化速度の調整のために硬化触媒を含有してもよい。硬化触媒の具体例として、２−メチルイミダゾール、２，４−ジメチルイミダゾール、２−エチル−４−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などのイミダゾール化合物、トリエチルアミン、ベンジルジメチルアミン、α−メチルベンジルメチルアミン、２−（ジメチルアミノメチル）フェノール、２，４，６−トリス（ジメチルアミノメチル）フェノール、１，８−ジアザビシクロ（５，４，０）ウンデセン−７などの３級アミン化合物、ジルコニウムテトラメトキシド、ジルコニウムテトラプロポキシド、テトラキス（アセチルアセトナト）ジルコニウム、トリ（アセチルアセトナト）アルミニウムなどの有機金属化合物、トリフェニルホスフィン、トリメチルホスフィン、トリエチルホスフィン、トリ−ｎ−ブチルホスフィン、トリ−ｎ−オクチルホスフィン、トリシクロヘキシルホスフィン、トリベンジルホスフィン、トリ−ｏ−トリルホスフィン、トリ−ｍ−トリルホスフィン、トリ−ｐ−トリルホスフィン、トリス−（ｐ−メトキシフェニル）ホスフィン、ジフェニルシクロヘキシルホスフィン、テトラフェニルホスフォニウムテトラフェニルボレート、トリフェニルホスフィントリフェニルボラン、トリ（ノニルフェニル）ホスフィンなどのホスフィン系化合物が挙げられる。 Moreover, you may contain a curing catalyst for acceleration | stimulation of hardening reaction of an epoxy resin and a hardening | curing agent, and adjustment of a cure rate. Specific examples of the curing catalyst include imidazoles such as 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole. Compound, triethylamine, benzyldimethylamine, α-methylbenzylmethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) Tertiary amine compounds such as undecene-7, organometallic compounds such as zirconium tetramethoxide, zirconium tetrapropoxide, tetrakis (acetylacetonato) zirconium, tri (acetylacetonato) aluminum, triphenylphosphine, Limethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, tribenzylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, Examples thereof include phosphine compounds such as tris- (p-methoxyphenyl) phosphine, diphenylcyclohexylphosphine, tetraphenylphosphonium tetraphenylborate, triphenylphosphine triphenylborane, and tri (nonylphenyl) phosphine.
また、エポキシ樹脂とともに、靭性付与の目的で先に挙げた熱可塑性樹脂を含有してもよい。このとき、熱可塑性樹脂にエポキシ樹脂と反応が可能な官能基を有していてもよい。官能基の具体例として、アミノ基、カルボキシル基、エポキシ基、水酸基、メチロール基、イソシアネート基、ビニル基、シラノール基等が挙げられる。 Moreover, you may contain the thermoplastic resin mentioned previously for the purpose of toughness addition with an epoxy resin. At this time, the thermoplastic resin may have a functional group capable of reacting with the epoxy resin. Specific examples of the functional group include amino group, carboxyl group, epoxy group, hydroxyl group, methylol group, isocyanate group, vinyl group, silanol group and the like.
空隙を有する接着剤層（ａ）を形成する方法は、エポキシ樹脂、硬化剤および熱伝導性充填剤を含有し、熱伝導性充填剤を固形分中５０体積％以上含有する接着剤組成物を、３０〜６０重量％の固形分濃度で有機溶媒に溶解した塗料を、保護フィルム層に塗布・乾燥する方法である。塗料の固形分濃度を３０重量％以上にすることで、溶液粘度が適切な範囲となり、熱伝導性充填剤の沈殿を防ぎ、塗布性が良好となる。また、６０重量％以下にすることで、乾燥時に溶媒成分が揮発し、空隙を有する接着剤層（ａ）を容易に形成することができる。 The method for forming the adhesive layer (a) having voids includes an adhesive composition containing an epoxy resin, a curing agent and a heat conductive filler, and containing the heat conductive filler in a solid content of 50% by volume or more. In this method , a paint dissolved in an organic solvent at a solid content concentration of 30 to 60% by weight is applied to the protective film layer and dried. By setting the solid content concentration of the paint to 30% by weight or more, the solution viscosity becomes an appropriate range, the precipitation of the heat conductive filler is prevented, and the coating property is improved. Moreover, by setting it as 60 weight% or less, a solvent component volatilizes at the time of drying, and the adhesive bond layer (a) which has a space | gap can be formed easily.
有機溶剤は、樹脂成分を溶解させることができれば特に制限されない。具体例としてクロロベンゼン、ベンジルアルコール、ジメチルホルムアミド、ジメチルアセトアミド、メチルイソブチルケトン、メチルエチルケトン、アセトン、トルエン、Ｎ−メチルピロリドンなどが挙げられる。 The organic solvent is not particularly limited as long as the resin component can be dissolved. Specific examples include chlorobenzene, benzyl alcohol, dimethylformamide, dimethylacetamide, methyl isobutyl ketone, methyl ethyl ketone, acetone, toluene, N-methylpyrrolidone and the like.
塗料を塗布する保護フィルム層は、工程により自由に選択される。一例として、離型処理を施したＰＥＴフィルムや、前記のＰＥＴフィルム上に、熱伝導性充填剤の含有量が固形分中０〜２０体積％である接着剤組成物から形成された厚み１〜１０μｍの接着剤層を有するもの等が挙げられるが、これらに限定されるものではない。 The protective film layer to which the paint is applied is freely selected depending on the process. As an example, a PET film that has been subjected to a release treatment, or a thickness 1 to 1 formed from an adhesive composition having a thermal conductive filler content of 0 to 20% by volume in the solid content on the PET film. Although what has an adhesive bond layer of 10 micrometers is mentioned, It is not limited to these.
本発明における接着剤層は、前記のように形成した空隙を有する接着剤層（ａ）の空隙を、熱伝導性充填剤の含有量が固形分中０〜２０体積％である接着剤組成物により充填して得られる。これにより、接着剤シートの接着性と屈曲性が著しく向上する。このとき、熱伝導性充填剤の含有量が固形分中２０体積％以下であることが重要である。熱伝導性充填剤の含有量が２０体積％を超えると、空隙を有する接着剤層（ａ）の空隙を十分に充填することができず、接着性と屈曲性の向上効果を十分に得ることができない。さらに、耐熱性が低下する。なお、ここで用いる接着剤組成物は、熱伝導性充填剤を含有しなくてもかまわない。 The adhesive layer in the present invention is an adhesive composition in which the voids of the adhesive layer (a) having voids formed as described above are the content of the heat conductive filler in the solid content of 0 to 20% by volume. Obtained by filling. Thereby, the adhesiveness and flexibility of the adhesive sheet are remarkably improved. At this time, it is important that the content of the heat conductive filler is 20% by volume or less in the solid content. When the content of the thermally conductive filler exceeds 20% by volume, the voids of the adhesive layer (a) having voids cannot be sufficiently filled, and sufficient effects of improving adhesiveness and flexibility are obtained. I can't. Furthermore, the heat resistance is reduced. In addition, the adhesive composition used here does not need to contain a heat conductive filler.
熱伝導性充填剤の含有量が固形分中０〜２０体積％である接着剤組成物は、樹脂、硬化剤、硬化促進剤を含有することが好ましい。また、熱伝導性充填剤以外の充填剤を含有してもよい。これらの例としては、熱伝導性充填剤を固形分中５０体積％以上含有する接着剤組成物として例示したものを挙げることができる。 The adhesive composition in which the content of the heat conductive filler is 0 to 20% by volume in the solid content preferably contains a resin, a curing agent, and a curing accelerator. Moreover, you may contain fillers other than a heat conductive filler. Examples thereof include those exemplified as an adhesive composition containing a heat conductive filler in a solid content of 50% by volume or more.
空隙を有する接着剤層（ａ）の空隙を充填する方法は、空隙を有する接着剤層（ａ）に、熱伝導性充填剤の含有量が固形分中０〜２０体積％である接着剤組成物を塗布・乾燥する方法である。 The method of filling the voids of the adhesive layer (a) having voids is such that the adhesive layer (a) having voids contains 0 to 20% by volume of the heat conductive filler in the solid content. This is a method of applying and drying an object.
このとき、熱伝導性充填剤の含有量が固形分中０〜２０体積％である接着剤組成物を、固形分濃度が５〜３０重量％となるように有機溶媒に溶解した塗料とし、空隙を有する接着剤層（ａ）に塗布することが、空隙の充填性の点で好ましい。 At this time, the adhesive composition in which the content of the heat conductive filler is 0 to 20% by volume in the solid content is a paint dissolved in an organic solvent so that the solid content concentration is 5 to 30% by weight. It is preferable to apply to the adhesive layer (a) having a void filling property.
本発明において、接着力をより向上させるため、接着剤層の最表面は、熱伝導性充填剤の含有量が固形分中０〜２０体積％の層であることが好ましい。その厚みは１〜１０μｍが好ましく、熱伝導性と接着性をより高いレベルで両立させるためには、２〜５μｍがより好ましい。接着剤層の最表面を熱伝導性充填剤の含有量が固形分中０〜２０体積％の層とするためには、熱伝導性充填剤の含有量が固形分中０〜２０体積％である接着剤組成物からなる接着剤層（ｂ）の上に、熱伝導性充填剤を固形分中５０体積％以上含有する接着剤組成物により空隙を有する接着剤層（ａ）を形成し、さらに、熱伝導性充填剤の含有量が固形分中０〜２０体積％である接着剤組成物を適切な厚みに塗布・乾燥する方法や、保護フィルム層上に熱伝導性充填剤を固形分中５０体積％以上含有する接着剤組成物により空隙を有する接着剤層（ａ）を形成し、これを保護フィルム層から剥離して、熱伝導性充填剤の含有量が固形分中０〜２０体積％である接着剤組成物に含浸・乾燥する方法などが挙げられるが、これらに限定されるものではない。また、空隙を有する接着剤層（ａ）を複数層設けてもかまわない。 In this invention, in order to improve adhesive force more, it is preferable that the outermost surface of an adhesive bond layer is a layer whose content of a heat conductive filler is 0-20 volume% in solid content. The thickness is preferably 1 to 10 μm, and more preferably 2 to 5 μm in order to achieve both higher thermal conductivity and adhesiveness. In order to make the outermost surface of the adhesive layer a layer having a heat conductive filler content of 0 to 20% by volume in the solid content, the content of the heat conductive filler is 0 to 20% by volume in the solid content. On the adhesive layer (b) made of an adhesive composition, an adhesive layer (a) having voids is formed by an adhesive composition containing a heat conductive filler in a solid content of 50% by volume or more, Furthermore, a method of applying and drying an adhesive composition having a heat conductive filler content of 0 to 20% by volume in the solid content to an appropriate thickness, and a heat conductive filler on the protective film layer. An adhesive layer (a) having voids is formed by an adhesive composition containing 50% by volume or more of the medium, and this is peeled off from the protective film layer , so that the content of the heat conductive filler is 0 to 20 in the solid content. Examples include, but are not limited to, methods of impregnating and drying the adhesive composition in volume%. No. Further, a plurality of adhesive layers (a) having voids may be provided.
本発明の製造方法により得られる接着剤シートは、接着剤層と、剥離可能な保護フィルム層とを有する構成のものをいう。例えば、保護フィルム層／接着剤層の２層構成、あるいは、保護フィルム層／接着剤層／保護フィルム層の３層構成がこれに該当する。また、接着剤層と保護フィルム層以外に別の層を有していてもよい。例えば、接着剤層の内部に炭素繊維のクロス等の熱伝導性材料を積層した複合構造、接着剤層の内部にポリイミド等の絶縁性フィルムが積層された複合構造等がこれにあたる。 The adhesive sheet obtained by the production method of the present invention refers to a structure having an adhesive layer and a peelable protective film layer. For example, a two-layer structure of a protective film layer / adhesive layer or a three-layer structure of a protective film layer / adhesive layer / protective film layer corresponds to this. Moreover, you may have another layer other than an adhesive bond layer and a protective film layer. For example, a composite structure in which a heat conductive material such as a carbon fiber cloth is laminated inside the adhesive layer, or a composite structure in which an insulating film such as polyimide is laminated inside the adhesive layer.
接着剤層の厚みは、弾性率および線膨張係数との関係で適宜選択できるが、１０〜５００μｍが好ましく、より好ましくは２０〜２００μｍである。接着剤層は接着部材の表面に凹凸に追従できるのであれば、なるべく薄い方が熱伝導の点で好ましい。 Although the thickness of an adhesive bond layer can be suitably selected in relation to an elastic modulus and a linear expansion coefficient, it is preferably 10 to 500 μm, more preferably 20 to 200 μm. If the adhesive layer can follow the unevenness on the surface of the adhesive member, it is preferable that the adhesive layer is as thin as possible in terms of heat conduction.
保護フィルム層は、接着剤層の形態および機能を損なうことなく剥離できれば特に限定されない。例えば、ポリエステル、ポリオレフィン、ポリフェニレンスルフィド、ポリ塩化ビニル、ポリテトラフルオロエチレン、ポリフッ化ビニリデン、ポリフッ化ビニル、ポリビニルブチラール、ポリ酢酸ビニル、ポリビニルアルコール、ポリカーボネート、ポリアミド、ポリイミド、ポリメチルメタクリレート等のプラスチックフィルム、これらにシリコーンあるいはフッ素化合物等の離型剤のコーティング処理を施したフィルムおよびこれらのフィルムをラミネートした紙、離型性のある樹脂を含浸あるいはコーティングした紙等が挙げられる。保護フィルム層は、加工時に視認性が良いように、例えば、顔料による着色が施されていてもよい。これにより、先に剥離する側の保護フィルム層が簡便に認識できるため、誤使用を避けることができる。 A protective film layer will not be specifically limited if it can peel, without impairing the form and function of an adhesive bond layer. For example, plastic films such as polyester, polyolefin, polyphenylene sulfide, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, polycarbonate, polyamide, polyimide, polymethyl methacrylate, Examples thereof include films obtained by coating a release agent such as silicone or a fluorine compound, papers laminated with these films, and papers impregnated or coated with a releasable resin. The protective film layer may be colored with a pigment, for example, so that the visibility is good during processing. Thereby, since the protective film layer of the side which peels previously can be recognized easily, misuse can be avoided.
接着剤層の両面に保護フィルム層を有する場合、それぞれの保護フィルム層の接着剤層に対する剥離力をＦ１、Ｆ２（Ｆ１＞Ｆ２）としたとき、Ｆ１−Ｆ２は好ましくは５Ｎｍ−１以上、さらに好ましくは１５Ｎｍ−１以上である。Ｆ１−Ｆ２を５Ｎｍ−１以上とすることで、目的の保護フィルム層を安定して剥離することができるため作業性が良い。また、剥離力Ｆ１、Ｆ２はいずれも好ましくは１〜２００Ｎｍ−１、さらに好ましくは３〜１００Ｎｍ−１である。この範囲であれば、保護フィルム層の脱落や、接着剤層の損傷等のトラブルを防ぐことができる。 When the protective film layers are provided on both surfaces of the adhesive layer, when the peeling force of each protective film layer to the adhesive layer is F 1 and F 2 (F 1 > F 2 ), F 1 -F 2 is preferably It is 5 Nm −1 or more, more preferably 15 Nm −1 or more. By setting F 1 -F 2 to 5 Nm −1 or more, the target protective film layer can be stably peeled off, so that workability is good. Further, the peeling forces F 1 and F 2 are preferably 1 to 200 Nm −1 , more preferably 3 to 100 Nm −1 . If it is this range, troubles, such as omission of a protective film layer and damage to an adhesive bond layer, can be prevented.
本発明の製造方法により得られる接着剤シートは、ダイボンディング材、放熱板（ヒートスプレッダー）、補強板（スティフナー）、シールド材の接着剤、銅張り積層板、リードフレームと金属製の支持基板間の絶縁層、カバーレイ、回路間の絶縁層、半導体パッケージとヒートシンクの接着等に好適に用いられる。特に、発熱が多く、放熱性が必要とされる部位に特に好ましく用いられる。 The adhesive sheet obtained by the production method of the present invention includes a die bonding material, a heat radiating plate (heat spreader), a reinforcing plate (stiffener), a shielding material adhesive, a copper-clad laminate, a lead frame and a metal support substrate. It is suitably used for bonding an insulating layer, a coverlay, an insulating layer between circuits, a semiconductor package and a heat sink. In particular, it is particularly preferably used for a portion that generates a large amount of heat and requires heat dissipation.
以下に実施例を挙げて本発明を説明するが、本発明はこれらの実施例に限定されるものではない。まず、各実施例で行った評価方法について述べる。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. First, an evaluation method performed in each example will be described.
（１）接着力：接着剤シートの一方の保護フィルム層を剥がし、０．３５ｍｍ厚のＳＵＳ３０４上に１３０℃、１ＭＰａの条件でラミネートした。その後、先のＳＵＳ上にラミネートした接着剤層のもう一方の保護フィルム層を剥がし、ポリイミドフィルム（厚み７５μｍ：宇部興産（株）製“ユーピレックス”（登録商標）７５Ｓ）を１３０℃、１ＭＰａ、０．３ｍ／分の条件でさらにラミネートした後、０．５ＭＰａ加圧下、１７０℃、２時間の加熱処理を行い、評価用サンプルを作製した。ポリイミドフィルムを５ｍｍ幅にスリットした後、５ｍｍ幅のポリイミドフィルムを９０°方向に５０ｍｍ／分の速度で剥離し、その際の接着力を測定した。ここで、接着力としては、加工性、ハンドリング性、半導体装置の信頼性の観点より、８．０Ｎ／ｃｍ以上であれば良好と判断した。 (1) Adhesive strength: One protective film layer of the adhesive sheet was peeled off and laminated on SUS304 having a thickness of 0.35 mm under conditions of 130 ° C. and 1 MPa. Then, the other protective film layer of the adhesive layer laminated on the previous SUS was peeled off, and a polyimide film (thickness 75 μm: “Upilex” (registered trademark) 75S manufactured by Ube Industries, Ltd.) was applied at 130 ° C., 1 MPa, 0 After further laminating under conditions of 3 m / min, a heat treatment was performed at 170 ° C. for 2 hours under a 0.5 MPa pressure to prepare a sample for evaluation. After slitting the polyimide film to a width of 5 mm, the polyimide film having a width of 5 mm was peeled at a rate of 50 mm / min in the 90 ° direction, and the adhesive force at that time was measured. Here, the adhesive strength was determined to be good if it was 8.0 N / cm or more from the viewpoint of workability, handling properties, and reliability of the semiconductor device.
（２）熱伝導率：アルバック理工（株）製 熱定数測定装置ＴＣ−７０００により、測定温度１００℃、照射光：ルビーレーザー光、真空雰囲気中にて熱拡散率を測定した。また、アルキメデス法により接着剤組成物の密度を測定し、ＤＳＣ法により比熱を測定し、これらのパラメータから熱伝導率を算出した。 (2) Thermal conductivity: Thermal diffusivity was measured with a thermal constant measuring device TC-7000 manufactured by ULVAC-RIKO Co., Ltd. in a measurement temperature of 100 ° C., irradiation light: ruby laser light, in a vacuum atmosphere. Moreover, the density of the adhesive composition was measured by the Archimedes method, the specific heat was measured by the DSC method, and the thermal conductivity was calculated from these parameters.
（３）耐熱性：３０ｍｍ角に型抜きした接着剤シートの一方の保護フィルムを剥がし、３０ｍｍ角の０．３５ｍｍ厚ＳＵＳ３０４の上に置いた。１３０℃、１ＭＰａ、０．３ｍ／分の条件でロールラミネートした後、続いて接着剤シートのもう一方の保護フィルムを剥がし、ポリイミドフィルム（厚み７５μｍ：宇部興産（株）製“ユーピレックス”（登録商標）７５Ｓ）を１３０℃、１ＭＰａ、０．３ｍ／分の条件でさらにラミネートした後、０．５ＭＰａ加圧下、１７０℃、２時間の加熱処理を行い、耐熱性評価用サンプルを作製した。サンプル２０個を３０℃／７０％ＲＨの条件下、１６８時間吸湿させた後、すみやかに温度設定のされた赤外線リフロー炉を３回通過させた。その後サンプル内部に膨れが発生したか否かを超音波探傷機により観察した。赤外線リフロー炉の最高温度は２６０℃、保持時間は１０秒である。評価用サンプル２０個片中で膨れが発生したサンプル数を計数した。 (3) Heat resistance: One protective film of the adhesive sheet which had been die-cut to 30 mm square was peeled off and placed on a 30 mm square 0.35 mm thick SUS304. After roll lamination under conditions of 130 ° C., 1 MPa, 0.3 m / min, the other protective film of the adhesive sheet was peeled off, and then a polyimide film (thickness 75 μm: “UPILEX” manufactured by Ube Industries, Ltd. (registered trademark) 75S) was further laminated under the conditions of 130 ° C., 1 MPa, 0.3 m / min, and then subjected to heat treatment at 170 ° C. for 2 hours under 0.5 MPa pressure to produce a sample for heat resistance evaluation. Twenty samples were subjected to moisture absorption for 168 hours under the conditions of 30 ° C./70% RH, and then immediately passed through an infrared reflow furnace whose temperature was set three times. Thereafter, it was observed with an ultrasonic flaw detector whether or not swelling occurred inside the sample. The maximum temperature of the infrared reflow furnace is 260 ° C., and the holding time is 10 seconds. The number of samples in which swelling occurred in 20 evaluation samples was counted.
（４）取り扱い性：接着剤シートを保護フィルム層が付いた状態で直径３インチ（７．６２センチメートル）のプラスチック製のコアに巻き付け、接着剤シートの割れの有無を目視にて評価した。 (4) Handling property: The adhesive sheet was wound around a plastic core having a diameter of 3 inches (7.62 cm) with a protective film layer attached, and the presence or absence of cracking of the adhesive sheet was visually evaluated.
実施例１
１−ｉ：空隙を有する接着剤層（ａ）の形成
熱伝導性充填剤として窒化アルミニウム粉末（Ｈグレード、平均粒径Ｄ５０＝１μｍ（株）トクヤマ製）と球状アルミナ（ＡＯ５０２、平均粒径Ｄ５０＝０．７μｍ、（株）アドマテックス製）を８：２の重量比で混合し、熱伝導性充填剤１００重量部をシランカップリング剤（ＫＢＭ４０３、信越化学工業（株）製）０．５重量部で乾式処理を行った。この表面処理を行った熱伝導性充填剤１９０重量部、樹脂成分として、ビスフェノール型エポキシ（“エピコート”（登録商標）８２８、エポキシ当量１９０、ジャパンエポキシレジン（株）製）１３重量部、フェノールノボラック樹脂（ＰＳＭ４３２６、水酸基当量１０５、群栄化学工業（株）製）５重量部、熱可塑性樹脂（ＳＧＰ−３、ナガセケムテックス（株）製、ブチルアクリレートを主成分とするエポキシ基含有アクリルゴム）１８重量部、エポキシ樹脂硬化触媒（トリフェニルホスフィン）０．１重量部に希釈溶媒としてメチルイソブチルケトン（ＭＩＢＫ）１８０重量部を添加し、４０℃の条件下でミキサーで均一となるまで攪拌し塗料とした。このときの固形分濃度は５６重量％、塗料中の熱伝導性充填剤の含有量は全固形分中６６体積％であった。
Example 1
1-i: Formation of adhesive layer (a) having voids Aluminum nitride powder (H grade, average particle size D 50 = 1 μm, manufactured by Tokuyama Corporation) and spherical alumina (AO502, average particle size) as a thermally conductive filler D 50 = 0.7 μm, manufactured by Admatechs Co., Ltd.) at a weight ratio of 8: 2, and 100 parts by weight of the heat conductive filler was added to the silane coupling agent (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) 0 Dry processing was performed with 5 parts by weight. 190 parts by weight of the thermally conductive filler subjected to this surface treatment, 13 parts by weight of bisphenol type epoxy (“Epicoat” (registered trademark) 828, epoxy equivalent 190, manufactured by Japan Epoxy Resins Co., Ltd.) as a resin component, phenol novolac Resin (PSM4326, hydroxyl group equivalent 105, manufactured by Gunei Chemical Industry Co., Ltd.) 5 parts by weight, thermoplastic resin (SGP-3, manufactured by Nagase ChemteX Corporation, epoxy group-containing acrylic rubber based on butyl acrylate) 18 parts by weight, 0.1 parts by weight of epoxy resin curing catalyst (triphenylphosphine), 180 parts by weight of methyl isobutyl ketone (MIBK) as a diluent solvent are added, and the mixture is stirred with a mixer at 40 ° C. until uniform. It was. At this time, the solid content concentration was 56% by weight, and the content of the heat conductive filler in the paint was 66% by volume in the total solid content.
次にこの塗料を、保護フィルム層としてシリコーン離型剤付きの厚さ３８μｍのポリエチレンテレフタレートフィルム（藤森工業（株）製“フィルムバイナ”（登録商標）ＧＴ）に、バーコータで約３０μｍの乾燥厚さとなるように塗布し、１２０℃で５分間乾燥し、接着剤層（ａ）を形成した。この接着剤層の断面を観察すると、空隙が存在することが確認された。 Next, this paint was applied to a 38 μm thick polyethylene terephthalate film (“Film Vina” (registered trademark) GT manufactured by Fujimori Kogyo Co., Ltd.) with a silicone release agent as a protective film layer , and a dry thickness of about 30 μm with a bar coater. Then, it was coated at 120 ° C. for 5 minutes to form an adhesive layer (a). When the cross section of this adhesive layer was observed, it was confirmed that voids existed.
１−ii：１−ｉで作製したシートの空隙の充填
接着剤組成物として“エピコート”（登録商標）８２８を１３重量部、ＰＳＭ４３２６を５重量部、ＳＧＰ−３を１８重量部、トリフェニルホスフィンを０．１重量部配合し、更に希釈溶媒としてＭＩＢＫを２６５重量部添加し、４０℃の条件下でミキサーで均一となるまで攪拌し塗料とした。このときの固形分濃度は１２重量％であった。
1-ii: Filling the gaps in the sheet prepared in 1-i As an adhesive composition, 13 parts by weight of “Epicoat” (registered trademark) 828, 5 parts by weight of PSM4326, 18 parts by weight of SGP-3, triphenylphosphine 0.1 part by weight was added, and 265 parts by weight of MIBK was further added as a diluent solvent, and the mixture was stirred with a mixer at 40 ° C. until uniform, to obtain a paint. The solid concentration at this time was 12% by weight.
次にこの塗料を前記ｉで作製したシートの表面にバーコータで塗布し、１２０℃で５分間乾燥し、接着剤層を形成した。このときの塗布厚みは、乾燥時に最表面に２μｍの該接着剤組成物の層が形成されるよう調整した。 Next, this paint was applied to the surface of the sheet prepared in i above with a bar coater and dried at 120 ° C. for 5 minutes to form an adhesive layer. The coating thickness at this time was adjusted so that a 2 μm layer of the adhesive composition was formed on the outermost surface during drying.
その後、保護フィルム層を塗布面に貼り合わせた。さらに、空隙を有する接着剤層を形成する際に使用した保護フィルム層を剥がし、上記と同様の方法で接着剤層の形成、保護フィルムの貼り合わせを行い、本発明の製造方法により得られる接着剤シートを得た。 Then, the protective film layer was bonded together to the application surface. Furthermore, the protective film layer used when forming the adhesive layer having voids is peeled off, the adhesive layer is formed and the protective film is bonded in the same manner as described above, and the adhesive obtained by the production method of the present invention An agent sheet was obtained.
得られた接着剤シートの接着剤層の断面を観察すると、空隙は該接着剤組成物で充填され、接着剤層（ａ）の両面に２μｍの該接着剤組成物の層が形成されていた。接着剤シートの評価結果を表１に示す。 When the cross section of the adhesive layer of the obtained adhesive sheet was observed, the voids were filled with the adhesive composition, and 2 μm of the adhesive composition layer was formed on both sides of the adhesive layer (a). . The evaluation results of the adhesive sheet are shown in Table 1.
実施例２
２−ｉ：接着剤層の形成
１−iiで調整した塗料溶液と同一の塗料を調合し、保護フィルム層としてシリコーン離型剤付きの厚さ３８μｍのポリエチレンテレフタレートフィルム（藤森工業（株）製“フィルムバイナ”（登録商標）ＧＴ）に、バーコータで約２μｍの乾燥厚さとなるように塗布し、１２０℃で５分間乾燥し、接着剤層を形成した。
Example 2
2-i: Formation of an adhesive layer The same paint as the coating solution prepared in 1-ii was prepared, and a 38 μm thick polyethylene terephthalate film with a silicone release agent as a protective film layer (manufactured by Fujimori Kogyo Co., Ltd. “ Film binder “(registered trademark) GT) was applied with a bar coater to a dry thickness of about 2 μm, and dried at 120 ° C. for 5 minutes to form an adhesive layer.
２−ii：空隙を有する接着剤層（ａ）の形成
実施例１の１−ｉで調整した塗料溶液と同一の組成の塗料を調合し、保護フィルム層として２−ｉで作製した２μｍの接着剤層がついたフィルムの接着剤側にバーコータで約３０μｍの乾燥厚さとなるように塗布し、１２０℃で５分間乾燥し、接着剤層（ａ）を形成した。
2-ii: Formation of an adhesive layer (a) having voids A paint having the same composition as the paint solution prepared in 1-i of Example 1 was prepared, and a 2 μm adhesion produced in 2-i as a protective film layer The adhesive layer (a) was formed on the adhesive side of the film with the adhesive layer by applying a dry thickness of about 30 μm with a bar coater and drying at 120 ° C. for 5 minutes.
このシート接着剤層の断面を観察すると、保護フィルム層上に２μｍの接着剤層、空隙が存在する接着剤層（ａ）が順に存在していることが確認された。 When the cross section of this sheet adhesive layer was observed, it was confirmed that a 2 μm adhesive layer and an adhesive layer (a) having voids were sequentially present on the protective film layer .
２−iii：２−iiで作製したシートの空隙の充填
１−iiで調整した塗料と同一の組成の塗料を調合し、２−iiで作製したシートの表面にバーコータで塗布し、１２０℃で５分間乾燥し、接着剤層を形成した。このときの塗布厚みは乾燥時に最表面に２μｍの該接着剤組成物の層が形成されるよう調整した。得られた接着剤層の断面を観察すると、空隙は該接着剤組成物で充填され、接着剤層（ａ）の両面に２μｍの該接着剤組成物の層が形成されていた。接着剤シートの評価結果を表１に示す。
2-iii: Filling the gaps in the sheet prepared in 2-ii A paint having the same composition as the paint prepared in 1-ii was prepared and applied to the surface of the sheet prepared in 2-ii with a bar coater at 120 ° C. It was dried for 5 minutes to form an adhesive layer. The coating thickness at this time was adjusted so that a 2 μm layer of the adhesive composition was formed on the outermost surface during drying. When the cross section of the obtained adhesive layer was observed, the voids were filled with the adhesive composition, and 2 μm of the adhesive composition layer was formed on both sides of the adhesive layer (a). The evaluation results of the adhesive sheet are shown in Table 1.
実施例３
空隙を有する接着剤層（ａ）を実施例１の１−ｉと同様に作製した。
Example 3
An adhesive layer (a) having voids was prepared in the same manner as 1-i in Example 1.
次いで、接着剤組成物としてＡＯ５０２：１００重量部をＫＢＭ４０３：０．５重量部でシラン処理した熱伝導性充填剤を１７重量部、“エピコート”（登録商標）８２８を１３重量部、ＰＳＭ４３２６を５重量部、ＳＧＰ−３を１８重量部、トリフェニルホスフィンを０．１重量部配合し、更に希釈溶媒としてＭＩＢＫを１６０重量部添加し、４０℃の条件下でミキサーで均一となるまで攪拌し塗料とした。このときの固形分濃度は１７重量％、塗料中の熱伝導性充填剤の含有量は全固形分中１４体積％であった。 Next, 17 parts by weight of thermally conductive filler obtained by silanizing AO502: 100 parts by weight with KBM403: 0.5 parts by weight as an adhesive composition, 13 parts by weight of “Epicoat” (registered trademark) 828, and 5 parts of PSM4326 Part by weight, 18 parts by weight of SGP-3, 0.1 part by weight of triphenylphosphine, and 160 parts by weight of MIBK as a diluent solvent are added, and the mixture is stirred with a mixer at 40 ° C. until uniform. It was. The solid content concentration at this time was 17% by weight, and the content of the heat conductive filler in the paint was 14% by volume in the total solid content.
次に、この塗料を、空隙を有する接着剤層（ａ）の表面にバーコータで塗布し、１２０℃で５分間乾燥し、接着剤層を形成した。このときの塗布厚みは、乾燥時に最表面に５μｍの該接着剤組成物の層が形成されるよう調整した。 Next, this paint was applied to the surface of the adhesive layer (a) having voids with a bar coater and dried at 120 ° C. for 5 minutes to form an adhesive layer. The coating thickness at this time was adjusted so that a 5 μm layer of the adhesive composition was formed on the outermost surface during drying.
その後、保護フィルムを塗布面に貼り合わせ、空隙を有する接着剤層を形成する際に使用した保護フィルム層を剥がし、上記と同様の方法で接着剤層の形成、保護フィルムの貼り合わせを行った。 Thereafter, the protective film was bonded to the coated surface, the protective film layer used when forming the adhesive layer having voids was peeled off, and the adhesive layer was formed and the protective film was bonded in the same manner as described above. .
得られた接着剤層の断面を観察すると、空隙は該接着剤組成物で充填され、接着剤層（ａ）の両面に５μｍの該接着剤組成物の層が形成されていた。接着剤シートの評価結果を表１に示す。 When the cross section of the obtained adhesive layer was observed, the voids were filled with the adhesive composition, and 5 μm of the adhesive composition layer was formed on both sides of the adhesive layer (a). The evaluation results of the adhesive sheet are shown in Table 1.
実施例４
最表面に形成される接着剤の層をそれぞれ０．５μｍとした以外は実施例１同様に接着剤シートを作製した。評価結果を表１に示す。
Example 4
An adhesive sheet was prepared in the same manner as in Example 1 except that the adhesive layer formed on the outermost surface was 0.5 μm. The evaluation results are shown in Table 1.
実施例５
最表面に形成される接着剤の層をそれぞれ１０μｍとした以外は実施例１に同様に接着剤シートを作製した。評価結果を表１に示す。
Example 5
An adhesive sheet was prepared in the same manner as in Example 1 except that the thickness of the adhesive layer formed on the outermost surface was 10 μm. The evaluation results are shown in Table 1.
比較例１
実施例１の１−ｉで作製した塗料のうち、希釈溶媒の量を５０重量部に変更して調合を行った。このとき、塗料溶液の粘度が非常に高いためミキサーでの攪拌はできず、３本ロールで混合を行った。このときの固形分濃度は８２重量％であった。この塗料を“フィルムバイナ”（登録商標）ＧＴに乾燥厚みが３０μｍとなるよう塗布・乾燥し、接着剤シートを得た。接着剤層の断面を観察したが、空隙は観察されなかった。接着剤シートの評価結果を表１に示す。
Comparative Example 1
In the paint prepared in 1-i of Example 1, the amount of the dilution solvent was changed to 50 parts by weight to prepare. At this time, since the viscosity of the coating solution was very high, stirring with a mixer was not possible, and mixing was performed with three rolls. The solid content concentration at this time was 82% by weight. This paint was applied to “Film Binner” (registered trademark) GT and dried to a dry thickness of 30 μm to obtain an adhesive sheet. Although the cross section of the adhesive layer was observed, no voids were observed. The evaluation results of the adhesive sheet are shown in Table 1.
比較例２
比較例１で作製した接着剤層の両面に、実施例１の１−iiと同様に厚み２μｍの接着剤層を形成した。接着剤シートの評価結果を表１に示す。
Comparative Example 2
Similar to 1-ii of Example 1, an adhesive layer having a thickness of 2 μm was formed on both surfaces of the adhesive layer produced in Comparative Example 1. The evaluation results of the adhesive sheet are shown in Table 1.
比較例３
熱伝導性充填剤として窒化アルミニウム粉末（Ｈグレード）とＡＯ５０２を８：２の重量比で混合し、この熱伝導性充填剤１００重量部を０．５重量部のＫＢＭ４０３で乾式処理を行った。この表面処理を行った熱伝導性充填剤を８１重量部、樹脂成分として、“エピコート”（登録商標）８２８を６．８重量部、ＰＳＭ４３２６を２．３重量部、ＳＧＰ−３を９重量部、エポキシ樹脂硬化触媒（トリフェニルホスフィン）０．０６重量部に希釈溶媒としてＤＭＦ／モノクロルベンゼン／ＭＩＢＫ等量混合溶媒を１３３重量部添加し、４０℃の条件下でミキサーで均一となるまで攪拌し塗料とした。このときの固形分濃度は３５重量％、塗料中の熱伝導性充填剤の含有量は全固形分中６３体積％であった。
Comparative Example 3
Aluminum nitride powder (H grade) and AO502 were mixed at a weight ratio of 8: 2 as a thermally conductive filler, and 100 parts by weight of this thermally conductive filler was dry-treated with 0.5 part by weight of KBM403. 81 parts by weight of the thermally conductive filler subjected to this surface treatment, 6.8 parts by weight of “Epicoat” (registered trademark) 828, 2.3 parts by weight of PSM 4326, and 9 parts by weight of SGP-3 as resin components Then, 133 parts by weight of DMF / monochlorobenzene / MIBK equivalent mixed solvent as a diluent solvent was added to 0.06 part by weight of epoxy resin curing catalyst (triphenylphosphine), and stirred with a mixer at 40 ° C. until uniform. Paint was used. At this time, the solid content concentration was 35% by weight, and the content of the heat conductive filler in the paint was 63% by volume in the total solid content.
次にこの塗料を “フィルムバイナ”（登録商標）ＧＴにバーコータで約３０μｍの乾燥厚さとなるように塗布し、１２０℃で５分間乾燥し、接着剤層を形成した。 Next, this paint was applied to “Film Binner” (registered trademark) GT with a bar coater to a dry thickness of about 30 μm, and dried at 120 ° C. for 5 minutes to form an adhesive layer.
この接着剤層の断面を観察すると、樹脂成分中に熱伝導性充填剤が均一に分散していた。 When the cross section of the adhesive layer was observed, the heat conductive filler was uniformly dispersed in the resin component.
比較例４
空隙を有する接着剤層（ａ）を実施例１の１−ｉと同様に作製した。
Comparative Example 4
An adhesive layer (a) having voids was prepared in the same manner as 1-i in Example 1.
次いで、接着剤組成物としてＡＯ５０２：１００重量部をＫＢＭ４０３：０．５重量部でシラン処理した熱伝導性充填剤を３３重量部、“エピコート”（登録商標）８２８を１３重量部、ＰＳＭ４３２６を５重量部、ＳＧＰ−３を１８重量部、トリフェニルホスフィンを０．１重量部配合し、更に希釈溶媒としてＭＩＢＫを２４０重量部添加し、４０℃の条件下でミキサーで均一となるまで攪拌し塗料とした。このときの固形分濃度は１７重量％、塗料中の熱伝導性充填剤の含有量は全固形分中２５体積％であった。 Next, as an adhesive composition, AO502: 100 parts by weight of KBM403: 0.5 parts by weight of silane-treated heat conductive filler 33 parts by weight, “Epicoat” (registered trademark) 828 13 parts by weight, and PSM4326 5 parts Part by weight, 18 parts by weight of SGP-3 and 0.1 part by weight of triphenylphosphine are added, and further 240 parts by weight of MIBK is added as a diluent solvent, and the mixture is stirred with a mixer at 40 ° C. until uniform. It was. At this time, the solid content concentration was 17% by weight, and the content of the heat conductive filler in the paint was 25% by volume in the total solid content.
次に、この塗料を、空隙を有する接着剤層（ａ）の表面にバーコータで塗布し、１２０℃で５分間乾燥し、接着剤層を形成した。このときの塗布厚みは、乾燥時に最表面に５μｍの該接着剤組成物の層が形成されるよう調整した。 Next, this paint was applied to the surface of the adhesive layer (a) having voids with a bar coater and dried at 120 ° C. for 5 minutes to form an adhesive layer. The coating thickness at this time was adjusted so that a 5 μm layer of the adhesive composition was formed on the outermost surface during drying.
その後、保護フィルムを塗布面に貼り合わせ、空隙を有する接着剤層を形成する際に使用した保護フィルム層を剥がし、上記と同様の方法で接着剤層の形成、保護フィルムの貼り合わせを行った。 Thereafter, the protective film was bonded to the coated surface, the protective film layer used when forming the adhesive layer having voids was peeled off, and the adhesive layer was formed and the protective film was bonded in the same manner as described above. .
得られた接着剤シートの接着剤層の断面を観察すると、接着剤層（ａ）の中心付近に充填されていない空隙が存在した。また、接着剤層（ａ）の両面に５μｍの該接着剤組成物の層が形成されていた。 When the cross section of the adhesive layer of the obtained adhesive sheet was observed, there was an unfilled void near the center of the adhesive layer (a). Further, 5 μm of the adhesive composition layer was formed on both sides of the adhesive layer (a).
表１から明らかなように、本発明により得られた接着剤シートは熱伝導性が高く、更に高い接着力、良好な取り扱い性を併せ持つ。 As is apparent from Table 1, the adhesive sheet obtained according to the present invention has high thermal conductivity, and further has high adhesive strength and good handleability.
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