JPWO2016158760A1 - Resin sheet for electronic parts, resin sheet for electronic parts with protective film, semiconductor device, and method for manufacturing the same - Google Patents
Resin sheet for electronic parts, resin sheet for electronic parts with protective film, semiconductor device, and method for manufacturing the same Download PDFInfo
- Publication number
- JPWO2016158760A1 JPWO2016158760A1 JP2016543102A JP2016543102A JPWO2016158760A1 JP WO2016158760 A1 JPWO2016158760 A1 JP WO2016158760A1 JP 2016543102 A JP2016543102 A JP 2016543102A JP 2016543102 A JP2016543102 A JP 2016543102A JP WO2016158760 A1 JPWO2016158760 A1 JP WO2016158760A1
- Authority
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- Prior art keywords
- resin sheet
- electronic parts
- semiconductor chip
- substrate
- resin
- 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
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- 229920005989 resin Polymers 0.000 title claims abstract description 129
- 239000011347 resin Substances 0.000 title claims abstract description 129
- 239000004065 semiconductor Substances 0.000 title claims description 65
- 230000001681 protective effect Effects 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 title abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 32
- 230000035699 permeability Effects 0.000 claims abstract description 22
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- 239000011256 inorganic filler Substances 0.000 claims abstract description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 11
- 125000003277 amino group Chemical group 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000000470 constituent Substances 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 51
- 238000010030 laminating Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 15
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- 229920000647 polyepoxide Polymers 0.000 description 23
- 239000003822 epoxy resin Substances 0.000 description 22
- 239000000126 substance Substances 0.000 description 20
- -1 alkyl methacrylate Chemical compound 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 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 12
- 239000002245 particle Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 6
- 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 6
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000005350 fused silica glass Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 3
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000004593 Epoxy Substances 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006059 cover glass Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 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
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
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- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 239000011889 copper foil Substances 0.000 description 1
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- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- BVURNMLGDQYNAF-UHFFFAOYSA-N dimethyl(1-phenylethyl)amine Chemical compound CN(C)C(C)C1=CC=CC=C1 BVURNMLGDQYNAF-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- UMSUVRQADXVIDD-UHFFFAOYSA-N ethyl 2-acetyloxyprop-2-enoate Chemical compound CCOC(=O)C(=C)OC(C)=O UMSUVRQADXVIDD-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
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- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
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- 230000005484 gravity Effects 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
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Abstract
水蒸気透過度が低く、且つ熱硬化前に高い弾性を有する接着剤シートを提供することによって電子機器の絶縁破壊試験の結果が良好になるなどの信頼性を向上させ、また中空構造を持つ電子機器でもその形状を容易に製造できる方法を提供する。（ａ）アクリル系共重合体、（ｂ）熱硬化性樹脂、（ｃ）無機充填材および（ｄ）アミノ基を有するシランカップリング剤を含有し、（ａ）アクリル系共重合体が構成モノマー単位中アクリロニトリル単位を３０モル％以上含有し、かつ電子部品用樹脂シート中の（ａ）アクリル系共重合体の含有率が２〜５重量％であることを特徴とする電子部品用樹脂シート。By providing an adhesive sheet with low water vapor permeability and high elasticity before thermosetting, the electronic device has improved reliability, such as improved results of dielectric breakdown tests of electronic devices, and has a hollow structure However, it provides a method by which the shape can be easily manufactured. (A) an acrylic copolymer, (b) a thermosetting resin, (c) an inorganic filler, and (d) a silane coupling agent having an amino group, wherein (a) the acrylic copolymer is a constituent monomer A resin sheet for electronic parts, wherein the unit contains acrylonitrile units in an amount of 30 mol% or more, and the content of the (a) acrylic copolymer in the resin sheet for electronic parts is 2 to 5% by weight.
Description
本発明は電子部品用樹脂シート、保護フィルム付電子部品用樹脂シートならびに半導体装置およびその製造方法に関する。 The present invention relates to a resin sheet for electronic parts, a resin sheet for electronic parts with a protective film, a semiconductor device, and a method for manufacturing the same.
近年の電子機器の小型化・薄型化に伴い、搭載される電子・電気部品にも、より小型化・薄膜化が求められるようになってきている。このため近年では、半導体の電子部品においても、従来のねじ止めやピン挿入型から、表面実装などの手法が採られるようになってきており、これにより小型化・薄膜化が実現されている。ＭＥＭＳ（ＭＩＣＲＯ ＥＬＥＣＴＲＯ ＭＥＣＨＡＮＩＣＡＬ ＳＹＳＴＥＭＳ）等の電子部品も例外ではなく、特にシート状の樹脂による表面実装によって、小型化・薄膜化を実現している（特許文献１、２参照）。
Along with the recent downsizing and thinning of electronic devices, there is an increasing demand for smaller and thinner electronic / electrical components to be mounted. For this reason, in recent years, methods such as surface mounting have been adopted from the conventional screwing and pin insertion type in semiconductor electronic components, and this has realized miniaturization and thinning. Electronic parts such as MEMS (MICRO ELECTRO MECHANICAL SYSTEMS) are no exception, and particularly, surface mounting with a sheet-like resin realizes miniaturization and thinning (see
ＭＥＭＳの中でも圧力センサや加速度センサ、ジャイロセンサ、ＳＡＷフィルタ等の電子部品の場合は、その機能上電子部品内部に中空を有していることが必要不可欠である。 Among MEMS, in the case of electronic components such as pressure sensors, acceleration sensors, gyro sensors, and SAW filters, it is indispensable to have a hollow inside the electronic components because of their functions.
図１は本発明の第一の半導体装置を示し、中空構造を有する電子部品の例であるが、この構造自体は従来から用いられているものである。ここで図１の電子部品用樹脂シート２に従来の樹脂材料を用いると、中空部分４に樹脂が入り込んで中空構造が損なわれることがあり、より高いレベルでの中空維持性が求められていた。
FIG. 1 shows a first semiconductor device of the present invention, which is an example of an electronic component having a hollow structure. This structure itself has been conventionally used. Here, when a conventional resin material is used for the
また図１に示すような電子部品の場合、基板１表面から半導体チップ３上面まで電子部品用樹脂シート２で完全に覆う構造となっている。そのため、電子部品用樹脂シート２を薄くする必要がある場合、外部の水蒸気が中空部分４に浸入しやすくなり、半導体チップ３の感度が損なわれるものであった。また薄い電子部品用樹脂シート２を硬化させる目的やパッケージ化の目的で加熱すると中空部分４に残存した気体が膨張し、電子部品用樹脂シート２が変形してしまうという問題があった。そのため薄くてもこのような問題の生じない電子部品用樹脂シートが求められていた。
Further, in the case of the electronic component as shown in FIG. 1, the electronic
また図２は本発明の第二の半導体装置を示し、中空構造を有する電子部品のもう１つの例であるが、この構造自体も従来から用いられているものである。図２に示すような電子部品の場合、中空部分９の空間容積が大きいため、中空部分９の残存気体の膨張がより大きくなる。一方で図２に示すような電子部品の場合、電子部品用樹脂シート７は半導体チップ搭載用基板６と中空構造形成用基板１０の間にのみ存在し、中空部分９と外部の距離が短いため、水蒸気が外部から中空部分９へ侵入する場合の移動距離が短くなる。しかしながら従来の樹脂材料は水蒸気透過度が十分低いとはいえず、図２の電子部品用樹脂シート７に従来の樹脂材料を用いた場合、水蒸気が透過して半導体チップ８の感度が損なわれることがあり、より高いレベルでの低水蒸気透過度が求められていた。
FIG. 2 shows a second semiconductor device according to the present invention, which is another example of an electronic component having a hollow structure. This structure itself is also conventionally used. In the case of the electronic component as shown in FIG. 2, since the space volume of the
これらに対して近年は樹脂材料の改良が進んでおり、上記中空維持性に関しては、電子部品用樹脂シートを２層構造として一方の層に粘度・伸度の高い樹脂材料を用い、これを中空構造と隣接する側に配置して樹脂が中空構造に入り込むことを防ぎ、これにより中空維持性を改善したものが開発されている（特許文献３）。なおこの電子部品用樹脂シートの他方の層は、中空維持性は劣るものの膜強度等の電子部品用樹脂シートが本来的に求められる物性に優れた樹脂材料を用いて、本来の目的も達成している。また上記水蒸気透過度については、無機充填剤の配合量等を制御することによって、水蒸気透過度を低くした技術が開発されている（特許文献４）。 In recent years, however, resin materials have been improved. With regard to the above-mentioned hollow maintainability, a resin sheet for electronic parts is made into a two-layer structure, and a resin material having a high viscosity and elongation is used for one layer. A resin that has been arranged on the side adjacent to the structure to prevent the resin from entering the hollow structure, thereby improving the hollow maintainability has been developed (Patent Document 3). The other layer of the resin sheet for electronic parts uses a resin material with excellent physical properties that are inherently required for the resin sheet for electronic parts, such as film strength, although the hollow maintainability is inferior. ing. Regarding the water vapor transmission rate, a technique has been developed in which the water vapor transmission rate is lowered by controlling the blending amount of the inorganic filler and the like (Patent Document 4).
しかしながらいずれも中空維持性と低水蒸気透過性を両立させたものではなく、さらなる改善が求められていた。 However, none of them achieved both hollow maintainability and low water vapor permeability, and further improvements were demanded.
本発明は、可撓性、膜強度を向上させることで中空維持性を改善し、さらに水蒸気透過度が低い電子部品用樹脂シートを提供することを課題とする。 It is an object of the present invention to provide a resin sheet for electronic parts that improves hollow maintainability by improving flexibility and film strength and has low water vapor permeability.
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（ａ）アクリル系共重合体、（ｂ）熱硬化性樹脂、（ｃ）無機充填材および（ｄ）アミノ基を有するシランカップリング剤を含有し、（ａ）アクリル系共重合体が構成モノマー単位中アクリロニトリル単位を３０モル％以上含有し、かつ電子部品用樹脂シート中の（ａ）アクリル系共重合体の含有率が２〜５重量％であることを特徴とする電子部品用樹脂シートである。 In order to solve the above problems, the present invention mainly has the following configuration. That is, it contains (a) an acrylic copolymer, (b) a thermosetting resin, (c) an inorganic filler, and (d) a silane coupling agent having an amino group, and (a) the acrylic copolymer is constituted. A resin sheet for electronic parts, comprising 30 mol% or more of acrylonitrile units in the monomer unit, and a content of (a) acrylic copolymer in the resin sheet for electronic parts is 2 to 5% by weight It is.
本発明により、中空維持性と低水蒸気透過性を両立させた電子部品用樹脂シートを得ることができる。これにより中空構造を有していても、電子部品用樹脂シートの硬化等のプロセスで中空構造が損なわれることが少なく、良好な半導体装置を得ることができる。また水蒸気の透過が低いため、半導体装置中の半導体チップの感度が損なわれることが少なくなる。 According to the present invention, it is possible to obtain a resin sheet for electronic parts that achieves both hollow maintainability and low water vapor permeability. Thereby, even if it has a hollow structure, the hollow structure is hardly damaged by a process such as curing of the resin sheet for electronic parts, and a good semiconductor device can be obtained. Moreover, since the water vapor transmission is low, the sensitivity of the semiconductor chip in the semiconductor device is less likely to be impaired.
本発明の電子部品用樹脂シートは、（ａ）アクリル系共重合体、（ｂ）熱硬化性樹脂、（ｃ）無機充填材および（ｄ）アミノ基を有するシランカップリング剤を含有し、（ａ）アクリル系共重合体が構成モノマー単位中アクリロニトリル単位を３０モル％以上含有し、かつ電子部品用樹脂シート中の（ａ）アクリル系共重合体の含有率が２〜５重量％であることを特徴とする。 The resin sheet for electronic parts of the present invention contains (a) an acrylic copolymer, (b) a thermosetting resin, (c) an inorganic filler, and (d) a silane coupling agent having an amino group. a) The acrylic copolymer contains 30 mol% or more of acrylonitrile units in the constituent monomer units, and the content of the (a) acrylic copolymer in the resin sheet for electronic parts is 2 to 5% by weight. It is characterized by.
本発明における（ａ）アクリル系共重合体は樹脂シートの可撓性、熱応力の緩和、低吸水性による絶縁性の向上等の機能を有する。また、構成モノマー単位中アクリロニトリル単位を３０モル％、好ましくは３５モル％以上含有することにより、電子部品用樹脂シートの可撓性を損なうことなく電子部品用樹脂シートの水蒸気透過度を効果的に抑え、更には絶縁性も向上させることができる。アクリロニトリル単位は疎水性を有したモノマー単位である。ポリマー中のアクリルニトリル単位が増加するにしたがってポリマーとしての疎水性が増加し、水蒸気透過度を抑制できる。アクリロニトリル単位を３０モル％以上とすることで樹脂シートの可撓性を維持しつつ、１００um厚の樹脂シートの４０℃／９０％ＲＨの環境下における水蒸気透過度を５０ｇ/（ｍ２・２４ｈ）以下にすることができる。The (a) acrylic copolymer in the present invention has functions such as flexibility of the resin sheet, relaxation of thermal stress, and improvement of insulation due to low water absorption. Further, by containing 30 mol%, preferably 35 mol% or more of acrylonitrile units in the constituent monomer units, the water vapor permeability of the resin sheet for electronic parts can be effectively reduced without impairing the flexibility of the resin sheet for electronic parts. In addition, the insulation can be improved. The acrylonitrile unit is a monomer unit having hydrophobicity. As the acrylonitrile unit in the polymer increases, the hydrophobicity of the polymer increases and the water vapor permeability can be suppressed. While maintaining the flexibility of the resin sheet by setting the acrylonitrile unit to 30 mol% or more, the water vapor permeability of the 100 um thick resin sheet in an environment of 40 ° C./90% RH is 50 g / (m 2 · 24 h). It can be:
ここでアクリロニトリル単位とは、モノマーを重合してアクリル系共重合体を得る際の原料モノマー中におけるアクリルニトリルに由来する構成単位をいう。またアクリロニトリル単位以外の構成単位とは、上記原料モノマー中におけるアクリルニトリル以外のモノマーに由来する構成単位をいう。 Here, the acrylonitrile unit refers to a structural unit derived from acrylonitrile in a raw material monomer when a monomer is polymerized to obtain an acrylic copolymer. The structural unit other than the acrylonitrile unit refers to a structural unit derived from a monomer other than acrylonitrile in the raw material monomer.
（ａ）アクリル系共重合体中のアクリロニトリル以外の構成単位の種類については特に限定されない。アクリル酸エステル、メタクリル酸エステルの例としては、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチル、アクリル酸プロピル、メタクリル酸プロピル、アクリル酸ブチル、メタクリル酸ブチル、アクリル酸ペンチル、メタクリル酸ペンチル、アクリル酸ヘキシル、メタクリル酸ヘキシル、アクリル酸−２−エチルヘキシル、メタクリル酸−２−エチルヘキシル、アクリル酸オクチル、メタクリル酸オクチルのようなアクリル酸アルキルエステル、メタクリル酸アルキルエステル等が挙げられる。またアクリル酸シクロヘキシルのようなアクリル酸の脂環属アルコールとのエステル等が挙げられる。 (A) The type of the structural unit other than acrylonitrile in the acrylic copolymer is not particularly limited. Examples of acrylic esters and methacrylic esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, methacrylic acid Examples include pentyl, hexyl acrylate, hexyl methacrylate, -2-ethylhexyl acrylate, -2-ethylhexyl methacrylate, octyl acrylate, acrylate alkyl acrylate, and alkyl methacrylate. Moreover, ester with the alicyclic alcohol of acrylic acid, such as cyclohexyl acrylate, etc. are mentioned.
また、上記アクリル酸エステル、メタクリル酸エステル以外の構成単位が含まれていてもよい。例えば、酢酸ビニル、スチレン、メチルスチレン、クロルスチレン、ビニリデンクロライド、エチルα―アセトキシアクリレート等が挙げられる。 Moreover, structural units other than the said acrylic acid ester and methacrylic acid ester may be contained. Examples thereof include vinyl acetate, styrene, methyl styrene, chlorostyrene, vinylidene chloride, ethyl α-acetoxy acrylate and the like.
さらに、上記（ａ）アクリル系共重合体はエポキシ基、水酸基、アミノ基、ヒドロキシアルキル基、ビニル基、シラノール基およびイソシアネート基から選ばれた少なくとも１種の官能基を有することが好ましい。これにより、後述の（ｂ）熱硬化性樹脂との結合が強固になり、絶縁性が向上することによって電子機器の信頼性が向上する。特にエポキシ基はエポキシ樹脂との相溶性の観点からより好ましい。 Furthermore, the (a) acrylic copolymer preferably has at least one functional group selected from an epoxy group, a hydroxyl group, an amino group, a hydroxyalkyl group, a vinyl group, a silanol group, and an isocyanate group. Thereby, the coupling | bonding with the below-mentioned (b) thermosetting resin becomes firm, and the reliability of an electronic device improves by improving insulation. In particular, an epoxy group is more preferable from the viewpoint of compatibility with an epoxy resin.
本発明における（ａ）アクリル系共重合体の含有率は電子部品用樹脂シート全体に対して２〜５重量％であり、２〜３．５重量％であることが好ましい。（ａ）アクリル系共重合体の含有量を２重量％以上とすることにより樹脂組成物に可撓性を与え、シート状としての形状が維持できるようになる。また、（ａ）アクリル系共重合体を５重量％以下にすることで電子部品用樹脂シートの水蒸気透過度を効果的に低下させることができ、また絶縁性を向上させることができる。これは電子部品用樹脂シートの構成単位中で最も水蒸気透過度の高い構成単位であるアクリル系共重合体の含有量を少なくすることによって、電子部品用樹脂シートとしての水蒸気透過度を抑制できることによるものである。アクリル系共重合体を５重量％以下にすることによって、１００μｍ厚の樹脂シートの４０℃／９０％RHにおける水蒸気透過度を５０ｇ／（ｍ２・２４ｈ）以下にすることができる。In the present invention, the content of the (a) acrylic copolymer is 2 to 5% by weight, preferably 2 to 3.5% by weight, based on the entire resin sheet for electronic parts. (A) By setting the content of the acrylic copolymer to 2% by weight or more, the resin composition is given flexibility, and the shape as a sheet can be maintained. Moreover, (a) By making an acrylic type copolymer into 5 weight% or less, the water vapor transmission rate of the resin sheet for electronic components can be reduced effectively, and insulation can be improved. This is because the water vapor permeability as a resin sheet for electronic parts can be suppressed by reducing the content of the acrylic copolymer that is the structural unit having the highest water vapor permeability among the structural units of the resin sheet for electronic parts. Is. By making the
本発明における（ｂ）熱硬化性樹脂は特に限定されないが、エポキシ樹脂であることが好ましい。 The (b) thermosetting resin in the present invention is not particularly limited, but is preferably an epoxy resin.
本発明で好ましく使用されるエポキシ樹脂は１分子中に２個以上のエポキシ基を有するものが好ましい。これらの具体例としては、たと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、ビフェニル型エポキシ樹脂、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、ナフタレン型エポキシ樹脂、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などが挙げられる。 The epoxy resin preferably used in the present invention preferably has two or more epoxy groups in one molecule. Specific examples thereof include, for example, cresol novolac type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, wire And aliphatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, and the like.
これらのエポキシ樹脂の中で、本発明において好ましく用いられるものは、含有塩素量が少なく、低軟化点であり柔軟性のある２官能成分の多いエポキシ樹脂であるビフェニル型エポキシ樹脂、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、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂である。もちろんこれらエポキシ樹脂を混合して用いてもよい。 Among these epoxy resins, those that are preferably used in the present invention are biphenyl type epoxy resins and bisphenol A type epoxies that are low in softening point and low in softening point and flexible in many bifunctional components. Resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin. Of course, these epoxy resins may be mixed and used.
また本発明では（ｂ）熱硬化性樹脂とあわせて、硬化剤を使用してもよい。本発明で好ましく使用される硬化剤は、エポキシ樹脂と反応して硬化させるものであれば特に限定されないお。これらの具体例としては、例えばフェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールＡやレゾルシンから合成される各種ノボラック樹脂、無水マレイン酸、無水ピロメリット酸などの酸無水物およびジアミノジフェニルスルホンなどの芳香族アミンが挙げられる。これら硬化剤の中で、好ましく用いられるものは、耐熱性、耐湿性の点から、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールＡ、ジアミノジフェニルスルホンである。 In the present invention, a curing agent may be used in combination with (b) the thermosetting resin. The curing agent preferably used in the present invention is not particularly limited as long as it is cured by reacting with an epoxy resin. Specific examples thereof include phenol novolac resins, cresol novolac resins, various novolac resins synthesized from bisphenol A and resorcin, acid anhydrides such as maleic anhydride and pyromellitic anhydride, and aromatic amines such as diaminodiphenyl sulfone. Is mentioned. Among these curing agents, those that are preferably used are phenol novolac resin, cresol novolac resin, bisphenol A, and diaminodiphenyl sulfone from the viewpoint of heat resistance and moisture resistance.
また本発明では（ｂ）熱硬化性樹脂とあわせて、硬化促進剤を使用してもよい。本発明で好ましく使用される硬化促進剤は、硬化反応を促進させるものであれば特に限定されない。その具体例としては、例えば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および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−メチルベンジルジメチルアミン、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）フェノールおよび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、トリフェニルスルフォン、トリエチルスルフォン、トリブチルスルフォンなどの有機スルフォン化合物が好ましく、特にイミダゾール化合物、トリフェニルスルフォン、１，８−ジアザビシクロ（５，４，０）ウンデセン−７などが好ましく用いられる。なお、これら硬化促進剤は、用途によっては２種類以上を併用してもよく、その添加量は（ｂ）熱硬化性樹脂１００重量部に対して０．１〜３０重量部、より好ましくは５〜２５重量部の範囲が好ましい。これにより、保存安定性が向上する。また、硬化促進剤を用いることで熱硬化性樹脂の架橋密度が増加し、樹脂シートに可撓性が付与され、さらには水蒸気透過度を抑制し、絶縁性を向上させることができる。 In the present invention, a curing accelerator may be used in combination with (b) the thermosetting resin. The curing accelerator preferably used in the present invention is not particularly limited as long as it accelerates the curing reaction. Specific examples thereof 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-methylbenzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol and 1,8-diazabicyclo (5,4,0) Tertiary amine compounds such as undecene-7, and organic sulfone compounds such as triphenyl sulfone, triethyl sulfone, and tributyl sulfone are preferred. In particular, imidazole compounds, triphenyl sulfone, 1,8-diazabicyclo (5, , 0) undecene-7 is preferably used. These curing accelerators may be used in combination of two or more depending on the application, and the addition amount thereof is 0.1 to 30 parts by weight, more preferably 5 parts per 100 parts by weight of (b) thermosetting resin. A range of ˜25 parts by weight is preferred. Thereby, storage stability improves. Moreover, the crosslinking density of a thermosetting resin increases by using a hardening accelerator, flexibility is provided to a resin sheet, Furthermore, water vapor permeability can be suppressed and insulation can be improved.
本発明における（ｃ）無機充填材としては、溶融シリカ、結晶性シリカ、炭酸カルシウム、炭酸マグネシウム、アルミナ、窒化珪素、酸化チタンなどが挙げられるが、その低透湿性から溶融シリカが好ましく用いられる。ここでいう溶融シリカとは、真比重が２．３以下の非晶性シリカを意味する。この溶融シリカの製造方法は、必ずしも溶融状態を経る必要はなく、任意の製造方法を用いることができる。たとえば結晶性シリカを溶融する方法、および各種原料から合成する方法などで製造することができる。本発明に用いる溶融シリカの粒径は、接着剤厚みや搭載される部品間距離に影響を与えるサイズのものでなければ特に限定されないが、通常、その平均粒径が２０μｍ以下のものが用いられる。また、溶融時の流動性を向上させる目的で、２種類以上の平均粒径を有する溶融球状シリカを併用することがさらに好ましい。中でも、平均粒径３μｍ以上の溶融球状シリカおよび平均粒径２μｍ以下の溶融球状シリカを併用することが好ましい。平均粒径３μｍ以上の溶融球状シリカおよび平均粒径２μｍ以下の溶融球状シリカを９５／５〜３０／７０の重量比で混合して用いることがさらに好ましい。 Examples of the inorganic filler (c) in the present invention include fused silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, silicon nitride, and titanium oxide. Fused silica is preferably used because of its low moisture permeability. The fused silica here means amorphous silica having a true specific gravity of 2.3 or less. The manufacturing method of this fused silica does not necessarily need to go through a molten state, and any manufacturing method can be used. For example, it can be produced by a method of melting crystalline silica and a method of synthesizing from various raw materials. The particle size of the fused silica used in the present invention is not particularly limited as long as it does not have a size that affects the adhesive thickness and the distance between mounted components. Usually, the average particle size is 20 μm or less. . Further, for the purpose of improving the fluidity at the time of melting, it is more preferable to use fused spherical silica having two or more kinds of average particle diameters in combination. Among them, it is preferable to use together fused spherical silica having an average particle size of 3 μm or more and fused spherical silica having an average particle size of 2 μm or less. It is more preferable to use fused spherical silica having an average particle size of 3 μm or more and fused spherical silica having an average particle size of 2 μm or less in a weight ratio of 95/5 to 30/70.
また、本発明において上記（ｃ）無機充填材の含有率は水蒸気透過度の観点から６０〜９０重量％であることが好ましい。下限としては７０重量％以上であることがより好ましく、７５重量％以上であることがさらに好ましい。また上限としては８８重量％以下であることがより好ましく、８３重量％以下であることがさらに好ましい。無機充填材を６０重量％以上とすることで電子部品用樹脂シートの水蒸気透過度をより低くすることができ、また９０重量％以下とすることで電子部品用樹脂シートをより容易にシート状に加工することができ、さらには１００μｍ以下の薄いシート状にすることができる。 In the present invention, the content of the inorganic filler (c) is preferably 60 to 90% by weight from the viewpoint of water vapor permeability. As a minimum, it is more preferable that it is 70 weight% or more, and it is further more preferable that it is 75 weight% or more. The upper limit is more preferably 88% by weight or less, and still more preferably 83% by weight or less. By making the inorganic filler 60% by weight or more, the water vapor permeability of the resin sheet for electronic parts can be lowered, and by making it 90% by weight or less, the resin sheet for electronic parts can be made into a sheet more easily. It can be processed and can be made into a thin sheet of 100 μm or less.
本発明における（ｄ）アミノ基を有するシランカップリング剤は、アミノ基を有しているため（ａ）アクリル系共重合体中のアクリロニトリル単位との相溶性が優れている。これにより本発明の電子部品用樹脂シートは、硬化前の状態においてその可撓性、膜強度が向上する。中空構造を有する電子部品の貼り合せや保護に用いて電子部品用樹脂シートを熱硬化させた場合にも、中空部分の残存気体の熱膨張によって電子部品用樹脂シートがおこす変形が少なく、幅広い加工条件において良好な貼り合せや保護を行うことができる。 Since the (d) silane coupling agent having an amino group in the present invention has an amino group, the compatibility with the acrylonitrile unit in the (a) acrylic copolymer is excellent. As a result, the flexibility and film strength of the resin sheet for electronic parts of the present invention are improved in a state before curing. Even when a resin sheet for electronic parts is heat-cured for bonding and protecting electronic parts having a hollow structure, there is little deformation caused by the thermal expansion of residual gas in the hollow part, and a wide range of processing Good bonding and protection can be performed under the conditions.
（ｄ）アミノ基を有するシランカップリング剤の具体例としては、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メトキシシラン、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−フェニルー３−アミノプロピルトリメトキシシラン、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、Ｎ−（ビニルベンジル）−２−アミノエチル−３−アミノプロピルトリメトキシシラン塩酸塩等が挙げられる。中でもＮ−フェニルー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メトキシシラン、３−アミノプロピルトリエトキシシランを用いると（ａ）アクリル系共重合体中のアクリロニトリル単位との相溶性がより優れているため好ましい。アミノ基を有するシランカップリング剤はアクリル系共重合体中のアクリロニトリル単位とシランカップリング剤の相溶性が優れているため、電子部品用樹脂シートの可撓性を向上させることができる。 (D) Specific examples of the silane coupling agent having an amino group include N-2 (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N- ( Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride and the like. Among these, when N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane are used, the compatibility with the acrylonitrile unit in the acrylic copolymer is more excellent. Therefore, it is preferable. Since the silane coupling agent having an amino group has excellent compatibility between the acrylonitrile unit in the acrylic copolymer and the silane coupling agent, the flexibility of the resin sheet for electronic parts can be improved.
本発明において、上記（ｄ）アミノ基を有するシランカップリング剤の含有量は、（ｃ）無機充填材の比表面積に対して用いられるシランカップリング剤の最小被覆面積（ｍ２／ｇ）の割合として、０．４〜３．０であることが好ましい。また下限としては０．８以上であることがより好ましく、上限としては２．０以下であることがより好ましい。In the present invention, the content of the (d) amino group-containing silane coupling agent is (c) the minimum covering area (m 2 / g) of the silane coupling agent used for the specific surface area of the inorganic filler. The ratio is preferably 0.4 to 3.0. The lower limit is more preferably 0.8 or more, and the upper limit is more preferably 2.0 or less.
本発明の電子部品用樹脂シートは、さらに各種添加剤を含有させてもよい。例えばハロゲン化合物、リン化合物などの難燃剤、カーボンブラック、オレフィン系共重合体、変性ニトリルゴム、変性ブタジエンゴム、変性ポリブタジエンゴムなどの各種エラストマー、チタネート系カップリング剤などの充填材表面処理剤、ハイドロタルサイト類などのイオン捕捉剤などを挙げることができる。 The resin sheet for electronic parts of the present invention may further contain various additives. For example, flame retardants such as halogen compounds and phosphorus compounds, carbon black, olefin copolymers, various elastomers such as modified nitrile rubber, modified butadiene rubber and modified polybutadiene rubber, filler surface treatment agents such as titanate coupling agents, hydro Examples include ion scavengers such as talcite.
本発明の電子部品用樹脂シートは、１００μｍ厚の４０℃／９０％ＲＨでの水蒸気透過度が、５０ｇ／（ｍ２・２４ｈ）以下であることが好ましく、３５ｇ／（ｍ２・２４ｈ）以下であることがより好ましく、２０ｇ／（ｍ２・２４ｈ）以下であることがさらに好ましい。水蒸気透過度を低くすることにより、絶縁性が向上し電子機器の信頼性を向上させることができる。また水蒸気透過度については、ＪＩＳ Ｚ ０２０８（１９７６）（カップ法）の記載の方法に従って、測定することができる。The resin sheet for electronic parts of the present invention preferably has a water vapor permeability at 40 ° C./90% RH of 100 μm thickness of 50 g / (m 2 · 24 h) or less, and 35 g / (m 2 · 24 h) or less. It is more preferable that it is 20 g / (m 2 · 24 h) or less. By reducing the water vapor permeability, the insulation can be improved and the reliability of the electronic device can be improved. The water vapor permeability can be measured according to the method described in JIS Z 0208 (1976) (cup method).
なお電子部品用樹脂シートの厚みが１００μｍでない場合は、上記方法にて水蒸気透過度を測定し、以下の計算式で換算すればよい。 When the thickness of the resin sheet for electronic parts is not 100 μm, the water vapor permeability is measured by the above method and converted by the following formula.
１００μｍ厚の４０℃／９０％ＲＨでの水蒸気透過度＝水蒸気透過度の測定値×（測定に用いた電子部品用樹脂シートの厚み（μｍ）／１００）
また、本発明の電子部品用樹脂シートは、電子部品において中空構造を形成する場合に、好適に用いることができる。本発明の電子部品用樹脂シートは、硬化前の状態における可撓性、膜強度が優れている。そのため本発明の電子部品用樹脂シートを、中空構造を有する電子部品の貼り合せや保護に用いた場合、中空部分に残存した気体が熱硬化時に膨張したとしても、形状の変化が少ないという効果を有する。Water vapor transmission rate at 40 ° C./90% RH of 100 μm thickness = measured value of water vapor transmission rate × (thickness of resin sheet for electronic parts used for measurement (μm) / 100)
Moreover, the resin sheet for electronic parts of this invention can be used suitably, when forming a hollow structure in an electronic part. The resin sheet for electronic parts of the present invention is excellent in flexibility and film strength before being cured. Therefore, when the resin sheet for electronic parts of the present invention is used for bonding and protecting electronic parts having a hollow structure, even if the gas remaining in the hollow part expands at the time of thermosetting, there is an effect that there is little change in shape. Have.
次に、本発明の電子部品用樹脂シートの製造方法について説明する。本発明の電子部品用樹脂シートの製造方法としては溶融混練、例えばバンバリーミキサー、ニーダーロール、単軸もしくは二軸の押し出し機およびコニーダーなどの公知の混練方法を用いて溶融混練した後にシート状に成型する方法が挙げられる。また原材料を有機溶剤、例えば、トルエン、キシレン、クロルベンゼンなどの芳香族系、メチルエチルケトン、メチルケトン、メチルイソブチルケトンなどのケトン系、ジメチルホルムアミド、ジメチルアセトアミド、Ｎメチルピロリドンなどの非プロトン系極性溶剤単独あるいは混合物に溶解・分散した後に、基材層、例えばシリコーン、フッ素、アルキド化合物などを処理したポリエステルフィルムに、塗布し乾燥することによって作製することもできる。特に溶剤に溶解・分散させてから基材層に塗布し乾燥させる方法は、より薄い膜を形成できることから好ましい。 Next, the manufacturing method of the resin sheet for electronic components of this invention is demonstrated. As a method for producing the resin sheet for electronic parts of the present invention, melt kneading, for example, melt kneading using a known kneading method such as a Banbury mixer, a kneader roll, a single or biaxial extruder and a kneader, and then molding into a sheet shape The method of doing is mentioned. The raw materials are organic solvents such as aromatic solvents such as toluene, xylene and chlorobenzene, ketones such as methyl ethyl ketone, methyl ketone and methyl isobutyl ketone, aprotic polar solvents such as dimethylformamide, dimethylacetamide and N methylpyrrolidone alone or After dissolving / dispersing in the mixture, it can also be produced by applying to a base material layer such as a polyester film treated with silicone, fluorine, alkyd compound, etc. and drying. In particular, the method of dissolving and dispersing in a solvent and then applying to the substrate layer and drying is preferable because a thinner film can be formed.
本発明の保護フィルム付電子部品用樹脂シートは、上記電子部品用樹脂シートおよび保護フィルムを有することを特徴とする。保護フィルムは電子部品用樹脂シートの片面のみ有していてもよいし、両面に有していてもよい。本発明で言う保護フィルムとは、電子部品用樹脂シートの表面を保護し、また電子部品用樹脂シートから剥離できれば特に限定されない。例えばシリコーン、フッ素化合物、アルキド化合物などをコーティングしたポリエステルフィルム、ポリオレフィンフィルムなどが挙げられる。保護フィルムの厚みは特に限定されないが、１０〜１００μｍが一般的である。 The resin sheet for electronic parts with a protective film of this invention has the said resin sheet for electronic parts, and a protective film, It is characterized by the above-mentioned. The protective film may have only one side of the resin sheet for electronic parts, or may have on both sides. The protective film referred to in the present invention is not particularly limited as long as it protects the surface of the resin sheet for electronic parts and can be peeled off from the resin sheet for electronic parts. Examples thereof include polyester films and polyolefin films coated with silicone, fluorine compounds, alkyd compounds, and the like. Although the thickness of a protective film is not specifically limited, 10-100 micrometers is common.
本発明の第一の半導体装置は、基板、前記基板上に形成された半導体チップおよび前記基板上に形成された半導体チップを覆うように積層された上記電子部品用樹脂シートを有しており、前記基板と前記半導体チップとの間に中空構造が形成されていることを特徴とする。 The first semiconductor device of the present invention includes a substrate, a semiconductor chip formed on the substrate, and the resin sheet for electronic components stacked so as to cover the semiconductor chip formed on the substrate, A hollow structure is formed between the substrate and the semiconductor chip.
また本発明の第二の半導体装置は、半導体チップ搭載面を囲む形状を有する半導体チップ搭載用基板、前記半導体チップ搭載用基板上に形成された半導体チップおよび中空構造形成用基板を有しており、前記半導体チップ搭載用基板と前記中空構造形成用基板が、上記電子部品用樹脂シートを介して接続されていることを特徴とする。 A second semiconductor device of the present invention includes a semiconductor chip mounting substrate having a shape surrounding a semiconductor chip mounting surface, a semiconductor chip formed on the semiconductor chip mounting substrate, and a hollow structure forming substrate. The semiconductor chip mounting substrate and the hollow structure forming substrate are connected via the resin sheet for electronic parts.
本発明の第一の半導体装置の製造方法は、（１）基板上に半導体チップを形成する工程、および（２）前記基板上に形成された半導体チップを覆うように、前記半導体チップ側から電子部品用樹脂シートを積層する工程をこの順に含み、前記基板と前記半導体チップとの間に中空構造が形成されるように電子部品用樹脂シートを積層することを特徴とする。 The first semiconductor device manufacturing method of the present invention includes (1) a step of forming a semiconductor chip on a substrate, and (2) an electron from the semiconductor chip side so as to cover the semiconductor chip formed on the substrate. The step of laminating resin sheets for components is included in this order, and the resin sheets for electronic components are laminated so that a hollow structure is formed between the substrate and the semiconductor chip.
また本発明の第二の半導体装置の製造方法は、（１’）半導体チップ搭載面を囲む形状を有する半導体チップ搭載用基板上に半導体チップを形成する工程、（２’）半導体チップ搭載用基板の中空構造形成用基板との接続面または中空構造形成用基板の半導体チップ搭載用基板との接続面に、電子部品用樹脂シートを積層する工程、および（３’）半導体チップ搭載用基板と中空構造形成用基板を、前記電子部品用樹脂シートを介して接続する工程、をこの順に含むことを特徴とする。 According to the second method of manufacturing a semiconductor device of the present invention, (1 ′) a step of forming a semiconductor chip on a semiconductor chip mounting substrate having a shape surrounding the semiconductor chip mounting surface, and (2 ′) a semiconductor chip mounting substrate. A step of laminating a resin sheet for electronic parts on the connection surface with the hollow structure forming substrate or the connection surface with the semiconductor chip mounting substrate of the hollow structure forming substrate, and (3 ′) the semiconductor chip mounting substrate and the hollow It includes a step of connecting the structure forming substrate via the resin sheet for electronic parts in this order.
上記電子部品用樹脂シートを用いて上記半導体装置を製造することで、上記半導体装置に形成された中空構造への水蒸気の透過が抑制され、半導体チップの感度が損なわれることが少なくなる。これにより感度等の性能の高い半導体装置とすることができる。また、中空構造を作製するために上記電子部品用樹脂シートを用いても、その貼り合せ時や熱硬化時に樹脂が変形することなく、所定の形状を容易に作製することができるため生産性に優れている。 By manufacturing the semiconductor device using the resin sheet for electronic parts, the permeation of water vapor to the hollow structure formed in the semiconductor device is suppressed, and the sensitivity of the semiconductor chip is reduced. Thus, a semiconductor device with high performance such as sensitivity can be obtained. Moreover, even if the resin sheet for electronic parts is used to produce a hollow structure, the resin can be easily produced without deforming at the time of bonding or thermosetting. Are better.
以下に、本発明を実施例に基づいて具体的に説明するが、本発明はこれに限定されるものではない。なお、各実施例において略号で示した原料の詳細を以下に示す。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto. In addition, the detail of the raw material shown by the abbreviation in each Example is shown below.
＜アクリル系共重合体１＞
混合機及び冷却器を備えた反応器に窒素雰囲気下にて、アクリロニトリル（和光純薬社製、特級）１０６ｇ（２．００モル）、ブチルアクリレート（和光純薬社製、特級）２３１ｇ（１．８０モル）、グリシジルメタクリレート（和光純薬社製、特級）２８ｇ（０．２０モル）、溶媒としてメチルエチルケトン（和光純薬社製、一級）を２９００ｇ入れ、大気圧（１０１３ｈＰａ）下、８５℃に加熱し、さらに連鎖移動剤として２―エチルヘキシルメルカプトアセテート（和光純薬社製）を０．００１ｇ、重合開始剤としてアゾビスイソブチロニトリル（和光純薬社製、Ｖ−６０）を０．００２ｇ加え、重量平均分子量が７０万となるまで重合した。重量平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）法（装置：東ソー社製ＧＥＬＰＥＲＭＥＡＴＩＯＮ ＣＨＲＯＭＡＴＯＧＲＡＰＨ、カラム：東ソー社製ＴＳＫ−ＧＥＬ ＧＭＨＸＬ７．８×３００ｍｍ）により測定し、ポリスチレン換算で算出した。<
Under a nitrogen atmosphere in a reactor equipped with a mixer and a cooler, 106 g (2.00 mol) of acrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd., special grade), 231 g (1. 80 mol), 28 g (0.20 mol) of glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 2900 g of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd., first grade) as a solvent, and heated to 85 ° C. under atmospheric pressure (1013 hPa). Further, 0.001 g of 2-ethylhexyl mercaptoacetate (manufactured by Wako Pure Chemical Industries, Ltd.) is added as a chain transfer agent, and 0.002 g of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd., V-60) is added as a polymerization initiator. The polymerization was continued until the weight average molecular weight reached 700,000. The weight average molecular weight was measured by a GPC (gel permeation chromatography) method (apparatus: GELPERMATION CHROMATOGRAPH, manufactured by Tosoh Corporation, column: TSK-GEL GMHXL 7.8 × 300 mm, manufactured by Tosoh Corporation), and calculated in terms of polystyrene.
これにより、モル比がアクリロニトリル：ブチルアクリレート：グリシジルメタクリレート＝５０：４５：５（重量平均分子量７０万）のアクリル系共重合体１を得た。
Thereby, the
＜アクリル系共重合体２＞
混合機及び冷却器を備えた反応器に窒素雰囲気下にて、アクリロニトリル（和光純薬社製、特級）１０６ｇ（２．００モル）、ブチルアクリレート（和光純薬社製、特級）５０５ｇ（３．９４モル）、グリシジルメタクリレート（和光純薬社製、特級）４４ｇ（０．３１モル）、溶媒としてメチルエチルケトン（和光純薬社製、一級）を６６００ｇ入れ、大気圧（１０１３ｈＰａ）下、８５℃に加熱し、さらに連鎖移動剤として２―エチルヘキシルメルカプトアセテート（和光純薬社製）を０．００１ｇ、重合開始剤としてアゾビスイソブチロニトリル（和光純薬社製、Ｖ−６０）を０．００２ｇ加え、重量平均分子量が８６万となるまで重合した。重量平均分子量の測定方法は上記アクリル系共重合体１と同様の方法で行った。<
In a nitrogen atmosphere in a reactor equipped with a mixer and a cooler, 106 g (2.00 mol) of acrylonitrile (manufactured by Wako Pure Chemical Industries, special grade), 505 g of butyl acrylate (manufactured by Wako Pure Chemical Industries, special grade) (3. 94 mol), 44 g (0.31 mol) of glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 6600 g of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd., first grade) as a solvent, and heated to 85 ° C. under atmospheric pressure (1013 hPa). Further, 0.001 g of 2-ethylhexyl mercaptoacetate (manufactured by Wako Pure Chemical Industries, Ltd.) is added as a chain transfer agent, and 0.002 g of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd., V-60) is added as a polymerization initiator. The polymerization was continued until the weight average molecular weight reached 860,000. The weight average molecular weight was measured by the same method as for the
これにより、モル比がアクリロニトリル：ブチルアクリレート：グリシジルメタクリレート＝３２：６３：５（重量平均分子量８６万）のアクリル系共重合体２を得た。
As a result, an
＜アクリル系共重合体３＞
混合機及び冷却器を備えた反応器に窒素雰囲気下にて、エチルアクリレート（和光純薬社製、特級）２００ｇ（２．００モル）、ブチルアクリレート（和光純薬社製、特級）１１８ｇ（０．９２０モル）、グリシジルメタクリレート（和光純薬社製、特級）２２ｇ（０．１５５モル）、溶媒としてメチルエチルケトン（和光純薬社製、一級）を３０００ｇ入れ、大気圧（１０１３ｈＰａ）下、８５℃に加熱し、さらに連鎖移動剤として２―エチルヘキシルメルカプトアセテート（和光純薬社製）を０．００１ｇ、重合開始剤としてアゾビスイソブチロニトリル（和光純薬社製、Ｖ−６０）を０．００１ｇ加え、重量平均分子量が１２０万となるまで重合した。重量平均分子量の測定方法は上記アクリル系共重合体１と同様の方法で行った。<
In a reactor equipped with a mixer and a cooler, in a nitrogen atmosphere, 200 g (2.00 mol) of ethyl acrylate (special grade) manufactured by Wako Pure Chemical Industries, and 118 g (0 grade) of butyl acrylate (special grade manufactured by Wako Pure Chemical Industries, Ltd.) 920 mol), 22 g (0.155 mol) of glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., special grade) and 3000 g of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd., first grade) as a solvent, and at 85 ° C. under atmospheric pressure (1013 hPa). Then, 0.001 g of 2-ethylhexyl mercaptoacetate (manufactured by Wako Pure Chemical Industries, Ltd.) is used as a chain transfer agent, and 0.001 g of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd., V-60) is used as a polymerization initiator. In addition, polymerization was performed until the weight average molecular weight reached 1,200,000. The weight average molecular weight was measured by the same method as for the
これにより、モル比がエチルアクリレート：ブチルアクリレート：グリシジルメタクリレート＝６５：３０：５（重量平均分子量１２０万）のアクリル系共重合体３を得た。
Thereby, the
＜熱硬化性樹脂＞
ビスフェノールＡ型エポキシ樹脂（ｊＥＲ−８２８、エポキシ当量：１９０、三菱化学株式会社製、常温で液状、２５℃での粘度：１４Ｐａ・ｓ）。<Thermosetting resin>
Bisphenol A type epoxy resin (jER-828, epoxy equivalent: 190, manufactured by Mitsubishi Chemical Corporation, liquid at normal temperature, viscosity at 25 ° C .: 14 Pa · s).
＜硬化剤＞
ノボラックフェノール（Ｈ−１、明和化成株式会社製）。<Curing agent>
Novolak phenol (H-1, manufactured by Meiwa Kasei Co., Ltd.).
＜硬化促進剤＞
２−ヘプタデシルイミダゾール（Ｃ１７Ｚ、四国化成株式会社製）。<Curing accelerator>
2-heptadecylimidazole (C17Z, manufactured by Shikoku Kasei Co., Ltd.).
＜無機充填材＞
溶融球状シリカ（ＦＢ−５Ｄ、平均粒径５．０μｍ、電気化学工業株式会社製）
溶融球状シリカ（ＳＯ−Ｃ２、平均粒径０．５μｍ、株式会社アドマテックス製）。<Inorganic filler>
Fused spherical silica (FB-5D, average particle size 5.0 μm, manufactured by Denki Kagaku Kogyo Co., Ltd.)
Fused spherical silica (SO-C2, average particle size 0.5 μm, manufactured by Admatex Co., Ltd.).
＜シランカップリング剤＞
Ｎ−フェニル−３−アミノプロピルトリメトキシシラン（ＫＢＭ−５７３、信越化学工業株式会社製）
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（ＫＢＭ−６０２、信越化学工業株式会社製）
ビニルトリス（２−メトキシエトキシ）シラン（Ｖ００４８、東京化成工業株式会社製）。<Silane coupling agent>
N-phenyl-3-aminopropyltrimethoxysilane (KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.)
N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.)
Vinyltris (2-methoxyethoxy) silane (V0048, manufactured by Tokyo Chemical Industry Co., Ltd.).
＜シート化膜評価＞
各実施例・比較例で得られた積層体（電子部品用樹脂シート厚み５０μｍ）を直径が３インチのコア、直径が６インチのコアに巻き取らせて、シート化膜評価を行った。評価基準は下記のとおりである。なお巻き取りの際に、樹脂シート中に１ｍｍ以上のピンホール状の穴が開いた場合は、巻き取れなかったものとして評価した。
◎：直径が３インチのコアにも直径が６インチのコアにもロール状に巻き取れたもの。
○：直径が３インチのコアにはロール状に巻き取れなかったが、直径が６インチのコアにロール状に巻き取れたもの。
×：直径が３インチのコアにも直径が６インチのコアにもロール状に巻き取れなかったもの。<Evaluation of sheet film>
The laminates (resin sheet thickness for electronic parts 50 μm) obtained in each of the examples and comparative examples were wound around a core having a diameter of 3 inches and a core having a diameter of 6 inches, and a sheeted film was evaluated. The evaluation criteria are as follows. In the case of winding, when a pinhole-shaped hole of 1 mm or more was opened in the resin sheet, it was evaluated as not being wound.
A: A core having a diameter of 3 inches or a core having a diameter of 6 inches is wound into a roll.
○: A core having a diameter of 3 inches could not be wound into a roll, but a core having a diameter of 6 inches was wound into a roll.
X: Neither a core with a diameter of 3 inches nor a core with a diameter of 6 inches could be wound in a roll shape.
＜水蒸気透過度測定＞
各実施例・比較例で得られた積層体（電子部品用樹脂シート厚み１００μｍ）のシリコーン離型剤付き厚さ３８μｍのポリエチレンテレフタレートフィルム（リンテック株式会社製ＰＥＴ３８）および保護フィルム（藤森工業（株）製“フィルムバイナ”ＧＴ）を剥がし、１７０℃で２時間加熱硬化し、得られた電子部品用樹脂シートの硬化物についてＪＩＳ Ｚ ０２０８（カップ法）の規定に従って、水蒸気透過度測定を行った。測定条件は４０℃／９０％ＲＨ、９６時間とした。<Water vapor permeability measurement>
38 μm thick polyethylene terephthalate film (Lintec Co., Ltd. PET38) and protective film (Fujimori Kogyo Co., Ltd.) with a silicone release agent of the laminates (resin sheet thickness for electronic parts 100 μm) obtained in each Example and Comparative Example “Film Binder” GT) was peeled off, heat-cured at 170 ° C. for 2 hours, and the cured product of the obtained resin sheet for electronic parts was subjected to water vapor permeability measurement according to JIS Z 0208 (cup method). The measurement conditions were 40 ° C./90% RH and 96 hours.
＜中空封止試験＞
各実施例・比較例で得られた積層体（電子部品用樹脂シート厚み５０μｍ）を２０ｍｍ角に切り出し、中央に５ｍｍの丸穴を金型で打ち抜いた。この穴の空いた積層体（電子部品用樹脂シート厚み５０μｍ）から、シリコーン離型剤付き厚さ３８μｍのポリエチレンテレフタレートフィルム（リンテック株式会社製ＰＥＴ３８）および保護フィルム（藤森工業（株）製“フィルムバイナ”ＧＴ）を剥がし、穴の空いた電子部品用樹脂シート単膜とした。これを２枚のカバーグラス（松浪硝子工業株式会社製：マイクロカバーグラス Ｎｏ．４）で挟み、６０℃、０．３ＭＰａで１分間プレスし２枚のカバーグラスと穴の空いた電子部品用樹脂シート単膜を貼りあわせ、中空封止試験用試験片とした。この試験片を１５０℃で２時間加熱し、２枚のカバーグラスと電子部品用樹脂シートで囲まれた中空の穴の辺の長さを測定し、初期値である５ｍｍを超えた長さを記録した。<Hollow sealing test>
The laminates (resin sheet thickness for electronic parts 50 μm) obtained in each of the examples and comparative examples were cut into 20 mm squares, and a 5 mm round hole was punched out with a mold in the center. From this perforated laminate (resin sheet thickness for electronic parts 50 μm), a 38 μm thick polyethylene terephthalate film (PET38 manufactured by Lintec Co., Ltd.) with a silicone release agent and a protective film (“Fujimori Kogyo Co., Ltd.,“ film binder ” "GT) was peeled off to obtain a resin sheet single film for electronic parts having holes. This is sandwiched between two cover glasses (Matsunami Glass Industry Co., Ltd .: Micro Cover Glass No. 4), pressed at 60 ° C. and 0.3 MPa for 1 minute, and two cover glasses and a resin for electronic parts with holes are provided. A sheet single membrane was bonded to obtain a test piece for hollow sealing test. This test piece was heated at 150 ° C. for 2 hours, and the length of the side of the hollow hole surrounded by the two cover glasses and the resin sheet for electronic parts was measured, and the length exceeding the initial value of 5 mm was measured. Recorded.
中空の穴の中に残存した気体は１５０℃加熱中に膨張し、中空部分を囲む電子部品用樹脂シートを押し広げる。つまり、この中空の穴の加熱後の直径の増加量を測定することによって電子部品用樹脂シートが加熱中に気体膨脹によってどれだけ変形するかを測ることができる。この直径の増加量が少ないほど、初期の形状を維持しており、中空構造の維持性能が高いと言える。 The gas remaining in the hollow hole expands during heating at 150 ° C., and spreads the resin sheet for electronic parts surrounding the hollow portion. That is, it is possible to measure how much the resin sheet for electronic parts is deformed by gas expansion during heating by measuring the increase in diameter of the hollow hole after heating. It can be said that the smaller the increase in diameter, the higher the initial shape is maintained and the higher the maintenance performance of the hollow structure.
＜絶縁破壊試験＞
まず３５ｍｍ角のセラミック基板を用意し、この中央に２層フレキシブル基板（東レフィルム加工株式会社製：メタロイヤル、ポリイミド樹脂層２５μｍ、銅箔８μｍ）を用いてＬ／Ｓ＝１５／１５μｍのくし型電極を作製した。<Dielectric breakdown test>
First, a 35 mm square ceramic substrate is prepared, and a comb layer of L / S = 15/15 μm using a two-layer flexible substrate (manufactured by Toray Film Processing Co., Ltd .: Meta Royal, polyimide resin layer 25 μm,
続いて各実施例・比較例で得られた積層体（電子部品用樹脂シート厚み５０μｍ）を３０ｍｍ角に切り出し、その中央に、２０ｍｍ角の穴を金型で打ち抜いた。次に積層体（電子部品用樹脂シート厚み５０μｍ）から、シリコーン離型剤付き厚さ３８μｍのポリエチレンテレフタレートフィルム（リンテック株式会社製ＰＥＴ３８）および保護フィルム（藤森工業（株）製“フィルムバイナ”ＧＴ）を剥離し、穴の空いた電子部品用樹脂シート単膜にした。これを前記のセラミック基板上のくし型電極の周りを囲むようにセラミック基板上に貼り付け、さらにこの上から別の３５ｍｍ角のセラミック基板を貼りあわせて、セラミック基板／電子部品用樹脂シート・くし型電極／セラミック基板の構成体を作製した。 Subsequently, the laminates (resin sheet thickness for electronic parts 50 μm) obtained in each of the examples and comparative examples were cut into 30 mm squares, and a 20 mm square hole was punched out in the center with a die. Next, from the laminated body (resin sheet thickness for electronic parts 50 μm), a 38 μm thick polyethylene terephthalate film (PET38 manufactured by Lintec Corporation) with a silicone release agent and a protective film (“Film Vina” GT manufactured by Fujimori Kogyo Co., Ltd.) Was peeled off to form a single-layer resin sheet for electronic parts with holes. This is pasted on the ceramic substrate so as to surround the comb-shaped electrode on the ceramic substrate, and another 35 mm square ceramic substrate is further laminated on the ceramic substrate, so that the ceramic substrate / resin sheet for electronic parts / comb A structure of a mold electrode / ceramic substrate was produced.
これを６０℃、０．３ＭＰａで１分間の条件でプレスして接着し、さらにオーブンにて１５０℃／２ｈ加熱して電子部品用樹脂シートを熱硬化させ、絶縁破壊試験用試験片とした。この試験片を４０℃９０％ＲＨの環境下に置き、マイグレーションテスター（ＩＭＶ社製ＭＩＧ−８６００Ｂ）を用いてくし型電極に１２Ｖの直流電圧をかけ、３３６ｈ後の絶縁抵抗値を測定した。 This was pressed and bonded at 60 ° C. and 0.3 MPa for 1 minute, and further heated in an oven at 150 ° C./2 h to thermally cure the resin sheet for electronic parts to obtain a test piece for dielectric breakdown test. The test piece was placed in an environment of 40 ° C. and 90% RH, and a DC voltage of 12 V was applied to the comb electrode using a migration tester (IMG MIG-8600B), and the insulation resistance value after 336 h was measured.
実施例１
溶融球状シリカ（ＳＯ−Ｃ２、平均粒径０．５μｍ、株式会社アドマテックス製）２８．８ｇ、溶融球状シリカ（ＦＢ−５Ｄ、平均粒径５．０μｍ、電気化学工業株式会社製）５１．９ｇをミキサー内で入れ、メチルイソブチルケトンを４０ｇ加えた。続いてＮ−フェニル−３−アミノプロピルトリメトキシシラン（ＫＢＭ−５７３、信越化学工業株式会社製）０．８ｇを霧吹きで噴射し、ミキサー内で混合した。これにアクリル系共重合体１を２．５ｇ、ビスフェノールＡ型エポキシ樹脂（ｊＥＲ−８２８、エポキシ当量：１９０、三菱化学株式会社製、常温で液状、２５℃での粘度：１４Ｐａ・ｓ）１１．９ｇ、ノボラックフェノール（Ｈ−１、明和化成株式会社製）４ｇ、２−ヘプタデシルイミダゾール（Ｃ１７Ｚ、四国化成株式会社製）０．１ｇを加えて、固形分濃度７０重量％となるようにメチルイソブチルケトンを加え、３０℃で撹拌、ホモミキサーで処理をして接着剤溶液を作製した。Example 1
28.8 g of fused spherical silica (SO-C2, average particle size 0.5 μm, manufactured by Admatex Co., Ltd.), 51.9 g of fused spherical silica (FB-5D, average particle size 5.0 μm, manufactured by Denki Kagaku Kogyo Co., Ltd.) Was added in a mixer, and 40 g of methyl isobutyl ketone was added. Subsequently, 0.8 g of N-phenyl-3-aminopropyltrimethoxysilane (KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed with a spray and mixed in a mixer. 10. 2.5 g of
この接着剤溶液をバーコータで、シリコーン離型剤付き厚さ３８μｍのポリエチレンテレフタレートフィルム（リンテック株式会社製ＰＥＴ３８）に乾燥後の厚みが５０μｍになるように塗布し、１１０℃で５分間乾燥し、保護フィルム（藤森工業（株）製“フィルムバイナ”ＧＴ）を貼り合わせて、シリコーン離型剤付き厚さ３８μｍのポリエチレンテレフタレートフィルム（リンテック株式会社製ＰＥＴ３８）、電子部品用樹脂シートおよび保護フィルム（藤森工業（株）製“フィルムバイナ”ＧＴ）がこの順に積層された積層体（電子部品用樹脂シート厚み５０μｍ）を作製した。 This adhesive solution was applied to a 38 μm thick polyethylene terephthalate film (PET38 manufactured by Lintec Corporation) with a silicone release agent with a bar coater so that the thickness after drying was 50 μm, and dried at 110 ° C. for 5 minutes to protect. Film (Fujimori Kogyo Co., Ltd. “Film Binner” GT) is bonded to a 38 μm thick polyethylene terephthalate film with a silicone release agent (Lintec Co., Ltd. PET38), resin sheet for electronic parts and protective film (Fujimori Kogyo) A laminate (resin sheet thickness for electronic parts 50 μm) in which “Film Binner” GT) manufactured in this manner was laminated in this order was produced.
また接着剤溶液の塗布の際に、乾燥後の厚みが１００μｍとなるようにした以外は積層体（電子部品用樹脂シート厚み５０μｍ）と同様にして、積層体（電子部品用樹脂シート厚み１００μｍ）を作製した。 The laminate (electronic component resin sheet thickness 100 μm) is the same as the laminate (electronic component resin sheet thickness 50 μm) except that the thickness after drying is 100 μm when the adhesive solution is applied. Was made.
得られた積層体（電子部品用樹脂シート厚み５０μｍ）を用いて、上記シート化膜評価、中空封止試験、絶縁破壊試験の各評価を行った。また得られた積層体（電子部品用樹脂シート厚み１００μｍ）を用いて、上記水蒸気透過度測定を行った。結果を表１に示す。 Using the obtained laminate (resin sheet thickness for electronic parts 50 μm), each evaluation of the sheet-formed film evaluation, the hollow sealing test, and the dielectric breakdown test was performed. Moreover, the said water-vapor-permeation measurement was performed using the obtained laminated body (resin sheet | seat thickness for electronic components 100 micrometers). The results are shown in Table 1.
実施例２〜１１、比較例１〜５
各組成の種類、配合量を表１、２に記載のとおり変更した以外は実施例１と同様にして、シリコーン離型剤付き厚さ３８μｍのポリエチレンテレフタレートフィルム（リンテック株式会社製ＰＥＴ３８）、電子部品用樹脂シートおよび保護フィルム（藤森工業（株）製“フィルムバイナ”ＧＴ）がこの順に積層された積層体（電子部品用樹脂シート厚み５０μｍ）および積層体（電子部品用樹脂シート厚み１００μｍ）を作製した。Examples 2-11, Comparative Examples 1-5
Except for changing the type and amount of each composition as described in Tables 1 and 2, in the same manner as in Example 1, a 38 μm thick polyethylene terephthalate film with a silicone release agent (PET38 manufactured by Lintec Corporation), electronic component A laminated body (resin sheet thickness for electronic parts 50 μm) and a laminated body (resin sheet thickness for electronic parts 100 μm) in which resin sheets and protective films (“Film Binner” GT manufactured by Fujimori Kogyo Co., Ltd.) are laminated in this order are prepared. did.
得られた積層体（電子部品用樹脂シート厚み５０μｍ）を用いて、上記シート化膜評価、中空封止試験、絶縁破壊試験の各評価を行った。また得られた積層体（電子部品用樹脂シート厚み１００μｍ）を用いて、上記水蒸気透過度測定を行った。結果を表１、２に示す。なお比較例１については、バーコータにて塗った膜に１ｍｍ以上のピンホール状の穴があるため、水蒸気透過度測定、中空封止試験、絶縁破壊試験の各評価を行うことはできなかった。 Using the obtained laminate (resin sheet thickness for electronic parts 50 μm), each evaluation of the sheet-formed film evaluation, the hollow sealing test, and the dielectric breakdown test was performed. Moreover, the said water-vapor-permeation measurement was performed using the obtained laminated body (resin sheet | seat thickness for electronic components 100 micrometers). The results are shown in Tables 1 and 2. In Comparative Example 1, since a film coated with a bar coater had a pinhole-shaped hole of 1 mm or more, each evaluation of water vapor permeability measurement, hollow sealing test, and dielectric breakdown test could not be performed.
１ 基板
２ 電子部品用樹脂シート
３ 半導体チップ
４ 中空部分
５ 半田ボール
６ 半導体チップ搭載用基板
７ 電子部品用樹脂シート
８ 半導体チップ
９ 中空部分
１０ 中空構造形成用基板DESCRIPTION OF
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