JP4984722B2 - Epoxy resin composition, epoxy resin molding material and semiconductor device - Google Patents
Epoxy resin composition, epoxy resin molding material and semiconductor device Download PDFInfo
- Publication number
- JP4984722B2 JP4984722B2 JP2006206013A JP2006206013A JP4984722B2 JP 4984722 B2 JP4984722 B2 JP 4984722B2 JP 2006206013 A JP2006206013 A JP 2006206013A JP 2006206013 A JP2006206013 A JP 2006206013A JP 4984722 B2 JP4984722 B2 JP 4984722B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- weight
- coupling agent
- resin composition
- silane coupling
- 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
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- 229920000647 polyepoxide Polymers 0.000 title claims description 126
- 239000003822 epoxy resin Substances 0.000 title claims description 125
- 239000000203 mixture Substances 0.000 title claims description 68
- 239000004065 semiconductor Substances 0.000 title claims description 33
- 239000012778 molding material Substances 0.000 title claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 60
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000005011 phenolic resin Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 17
- 150000007513 acids Chemical class 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 13
- 239000011256 inorganic filler Substances 0.000 claims description 12
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 12
- 238000005538 encapsulation Methods 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- -1 dicyclopentadiene modified phenol Chemical class 0.000 description 42
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 34
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- 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 26
- 229920005989 resin Polymers 0.000 description 25
- 239000011347 resin Substances 0.000 description 25
- 239000001993 wax Substances 0.000 description 25
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 24
- 229910000679 solder Inorganic materials 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- 239000004593 Epoxy Substances 0.000 description 21
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 20
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- 238000000034 method Methods 0.000 description 16
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 15
- 239000007822 coupling agent Substances 0.000 description 14
- 239000004698 Polyethylene Substances 0.000 description 13
- 238000000465 moulding Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 12
- 229940005561 1,4-benzoquinone Drugs 0.000 description 11
- 235000011054 acetic acid Nutrition 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 10
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 229910000077 silane Inorganic materials 0.000 description 9
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 5
- 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 5
- 229960001545 hydrotalcite Drugs 0.000 description 5
- 229910001701 hydrotalcite Inorganic materials 0.000 description 5
- 235000013872 montan acid ester Nutrition 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- BFXRJTDKPLPXSK-UHFFFAOYSA-N [SiH4].CO[Si](CCCS)(OC)OC Chemical compound [SiH4].CO[Si](CCCS)(OC)OC BFXRJTDKPLPXSK-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-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
- 229920003986 novolac Polymers 0.000 description 4
- 150000003003 phosphines Chemical class 0.000 description 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000005040 ion trap Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- GLTDLAUASUFHNK-UHFFFAOYSA-N n-silylaniline Chemical compound [SiH3]NC1=CC=CC=C1 GLTDLAUASUFHNK-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000001721 transfer moulding Methods 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 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001343 alkyl silanes Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 2
- CCMHRVVSKFCHAX-UHFFFAOYSA-N $l^{1}-azanylmethylbenzene Chemical group [N]CC1=CC=CC=C1 CCMHRVVSKFCHAX-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001448862 Croton Species 0.000 description 1
- 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 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical group [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- YOTZYFSGUCFUKA-UHFFFAOYSA-N dimethylphosphine Chemical compound CPC YOTZYFSGUCFUKA-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- JLHMVTORNNQCRM-UHFFFAOYSA-N ethylphosphine Chemical compound CCP JLHMVTORNNQCRM-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000019253 formic acid Nutrition 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
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- RMIODHQZRUFFFF-UHFFFAOYSA-N methoxyacetic acid Chemical compound COCC(O)=O RMIODHQZRUFFFF-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical class [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003918 triazines Chemical class 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
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- DMEUUKUNSVFYAA-UHFFFAOYSA-N trinaphthalen-1-ylphosphane Chemical compound C1=CC=C2C(P(C=3C4=CC=CC=C4C=CC=3)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 DMEUUKUNSVFYAA-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 235000019386 wax ester Nutrition 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Description
本発明は、エポキシ樹脂組成物、エポキシ樹脂成形材料及び半導体装置に関するものである。 The present invention relates to an epoxy resin composition, an epoxy resin molding material, and a semiconductor device.
ＩＣ、ＬＳＩ等の半導体素子の封止方法として、エポキシ樹脂組成物の成形材料（以下、「エポキシ樹脂成形材料」ともいう。）による成形封止が低コスト、大量生産に適しており、採用されている。さらに、信頼性の点でもエポキシ樹脂や硬化剤であるフェノール樹脂の改良により特性の向上が図られてきた。
しかし、近年の電子機器の小型化、軽量化、高性能化の市場動向において、半導体の高集積化も年々進み、また半導体装置の表面実装化が促進されるなかで、半導体封止用エポキシ樹脂組成物への要求は益々厳しいものとなってきている。このため、従来からのエポキシ樹脂組成物では解決出来ない問題点も出てきている。
As a sealing method for semiconductor elements such as IC and LSI, molding sealing with an epoxy resin composition molding material (hereinafter also referred to as “epoxy resin molding material”) is suitable for low cost and mass production. ing. Further, in terms of reliability, improvement of properties has been achieved by improving epoxy resins and phenol resins as curing agents.
However, due to the recent trend toward smaller, lighter, and higher performance electronic devices, semiconductors have been increasingly integrated and the surface mounting of semiconductor devices has been promoted. The demand for compositions has become increasingly severe. For this reason, the problem which cannot be solved with the conventional epoxy resin composition has also come out.
例えば、表面実装の採用により半導体装置が半田浸漬或いは半田リフロー工程で急激に２００℃以上の高温にさらされ、吸湿した水分が爆発的に気化する際の応力により、半導体装置内、特に半導体素子、リードフレーム、インナーリード上の金メッキや銀メッキ等の各種メッキされた各接合部分とエポキシ樹脂組成物の硬化物の界面で剥離が生じたりして、信頼性が著しく低下する現象である。
さらに、環境問題に端を発した有鉛半田から無鉛半田への移行に伴い、半田処理時の温度が高くなり、半導体装置中に含まれる水分の気化によって発生する爆発的な応力による耐半田性が、従来以上に大きな課題となってきている。
For example, by adopting surface mounting, the semiconductor device is suddenly exposed to a high temperature of 200 ° C. or higher in the solder dipping or solder reflow process, and the moisture inside the semiconductor device, particularly the semiconductor element, This is a phenomenon in which the reliability of the lead frame and the inner lead is remarkably lowered due to peeling at the interface between various plated joint portions such as gold plating and silver plating and the cured product of the epoxy resin composition.
In addition, with the transition from leaded solder to lead-free solder, which started with environmental problems, the temperature during soldering processing increased, and solder resistance due to explosive stress generated by vaporization of moisture contained in semiconductor devices However, it has become a bigger problem than before.
半田処理による信頼性低下を改善するために、メッキ部分とエポキシ樹脂組成物の硬化物との界面での剥離を防止する為、アミノシランやメルカプトシラン等のカップリング剤を添加して流動性と耐半田性の両立を図る手法も提案されている（例えば、特許文献２参照。）が、密着力が強くなるために、成形封止直後にランナー部をパッケージから切り離す工程（ゲートブレイク）で、基板からうまく樹脂が剥がれないという問題も起こっている。このようなことから、耐半田性とゲートブレイク性のバランスの取れた半導体封止用エポキシ樹脂組成物が求められている。 In order to improve reliability degradation due to solder processing, a coupling agent such as aminosilane or mercaptosilane is added to prevent peeling at the interface between the plated part and the cured product of the epoxy resin composition, thereby improving fluidity and resistance. A method for achieving both solderability has also been proposed (see, for example, Patent Document 2). However, in order to increase the adhesion, the substrate is separated in a process (gate break) in which the runner is separated from the package immediately after molding and sealing. There is also a problem that the resin does not peel off well. For these reasons, there is a need for an epoxy resin composition for semiconductor encapsulation that has a good balance between solder resistance and gate breakability.
本発明の目的は、耐半田性とゲートブレイク性のバランスに優れたエポキシ樹脂組成物を提供することにある。 An object of the present invention is to provide an epoxy resin composition having an excellent balance between solder resistance and gate breakability.
このような目的は、下記（１）〜（７）に記載の本発明により達成される。
（１）半導体封止に用いるエポキシ樹脂組成物であって、（Ａ）エポキシ樹脂、（Ｂ）硬化剤、（Ｃ）シランカップリング剤および（Ｄ）無機充填材を含み、前記（Ｃ）シランカップリング剤はシランカップリング剤と酸性化合物が予め混合されているものであり、含有する酸性化合物の量を前記シランカップリング剤（Ｃ）全体の０．００５重量％以上、１重量％以下に制御することにより、前記（Ｃ）シランカップリング剤を抽出処理した際の抽出水のｐＨが３．５以上３．９以下の範囲になるように調製されているものである
ことを特徴とするエポキシ樹脂組成物。
（２）前記（Ｃ）成分が、メルカプト基を有するシランカップリング剤と酸性化合物が予め混合されているものである上記（１）に記載のエポキシ樹脂組成物。
（３）さらに硬化促進剤（Ｅ）を含むものである上記（１）又は（２）に記載のエポキシ樹脂組成物。
（４）前記（Ａ）エポキシ樹脂が、一般式（１）で表されるエポキシ樹脂である上記（１）ないし（３）のいずれかに記載のエポキシ樹脂組成物。
（５）前記（Ｂ）硬化剤が、一般式（２）で表されるフェノール樹脂である上記（１）ないし（４）のいずれかに記載のエポキシ樹脂組成物。
（６）上記（１）ないし（５）のいずれかに記載のエポキシ樹脂組成物を混合及び／又は溶融混練してなることを特徴とするエポキシ樹脂成形材料。
（７）上記（６）に記載のエポキシ樹脂成形材料の硬化物で、半導体素子が封止されていることを特徴とする半導体装置。
Such an object is achieved by the present invention described in the following (1) to (7).
(1) An epoxy resin composition used for semiconductor encapsulation, comprising (A) an epoxy resin, (B) a curing agent, (C) a silane coupling agent, and (D) an inorganic filler, wherein (C) the silane In the coupling agent, a silane coupling agent and an acidic compound are preliminarily mixed, and the amount of the acidic compound to be contained is 0.005% by weight or more and 1% by weight or less of the entire silane coupling agent (C). by controlling, Ru Monodea pH of the extraction water when the extraction process the (C) a silane coupling agent is prepared such that from 3.5 to 3.9 or less <br/> An epoxy resin composition characterized by that.
(2) The epoxy resin composition according to (1) above, wherein the component (C) is a mixture of a silane coupling agent having a mercapto group and an acidic compound .
(3) The epoxy resin composition according to the above (1) or (2), which further contains a curing accelerator (E).
(4) The epoxy resin composition according to any one of (1) to (3), wherein the (A) epoxy resin is an epoxy resin represented by the general formula (1).
(5) The epoxy resin composition according to any one of (1) to (4), wherein the (B) curing agent is a phenol resin represented by the general formula (2).
(6) An epoxy resin molding material obtained by mixing and / or melt-kneading the epoxy resin composition according to any one of (1) to (5) above.
(7) A semiconductor device, wherein a semiconductor element is sealed with a cured product of the epoxy resin molding material according to (6).
本発明によると、耐半田性とゲートブレイク性のバランスに優れたエポキシ樹脂組成物、エポキシ樹脂成形材料および半導体装置を得ることができる。 According to the present invention, it is possible to obtain an epoxy resin composition, an epoxy resin molding material, and a semiconductor device that have an excellent balance between solder resistance and gate breakability.
以下、本発明のエポキシ樹脂組成物、エポキシ樹脂成形材料および半導体装置について詳細に説明する。
本発明のエポキシ樹脂組成物は、半導体封止に用いるエポキシ樹脂組成物であって、（Ａ）エポキシ樹脂、（Ｂ）硬化剤および（Ｃ）シランカップリング剤を含み、前記（Ｃ）シランカップリング剤として、該シランカップリング剤を抽出処理した際の抽出水のｐＨが３．５以上４．７以下となるものを用いることを特徴とする。
また、本発明のエポキシ樹脂成形材料は、上記に記載のエポキシ樹脂組成物を混合及び／又は溶融混練してなることを特徴とする。
また、本発明の半導体装置は、上記に記載のエポキシ樹脂成形材料の硬化物で、半導体素子が封止されていることを特徴とする
Hereinafter, the epoxy resin composition, the epoxy resin molding material, and the semiconductor device of the present invention will be described in detail.
The epoxy resin composition of the present invention is an epoxy resin composition used for semiconductor encapsulation, and includes (A) an epoxy resin, (B) a curing agent, and (C) a silane coupling agent. The ring agent is characterized in that the pH of the extracted water when the silane coupling agent is extracted is 3.5 or more and 4.7 or less.
The epoxy resin molding material of the present invention is characterized by mixing and / or melt-kneading the above-described epoxy resin composition.
A semiconductor device of the present invention is characterized in that a semiconductor element is sealed with a cured product of the above-described epoxy resin molding material.
まず、エポキシ樹脂組成物、エポキシ樹脂成形材料について説明する。
前記エポキシ樹脂組成物は、エポキシ樹脂（Ａ）を含む。前記エポキシ樹脂（Ａ）は、１分子内にエポキシ基を２個以上有するモノマー、オリゴマー、ポリマー全般であり、その分子量、分子構造は特に限定するものではないが、例えば、ビフェニル型エポキシ樹脂、ビスフェノール型エポキシ樹脂、スチルベン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、アルキル変性トリフェノールメタン型エポキシ樹脂、トリアジン核含有エポキシ樹脂、ジシクロペンタジエン変性フェノール型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂（フェニレン骨格、ビフェニレン骨格等を有する）等が挙げられ、これらは１種類を単独で用いても２種以上を併用しても差し支えない。このようなエポキシ樹脂の中でも下記一般式（１）で表されるフェノールアラルキル型エポキシ樹脂が好ましい。これにより、耐燃性、耐半田性を特に向上することができる。
First, the epoxy resin composition and the epoxy resin molding material will be described.
The said epoxy resin composition contains an epoxy resin (A). The epoxy resin (A) includes all monomers, oligomers, and polymers having two or more epoxy groups in one molecule, and the molecular weight and molecular structure thereof are not particularly limited. For example, biphenyl type epoxy resin, bisphenol Type epoxy resin, stilbene type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene modified phenol type epoxy Examples thereof include resins, phenol aralkyl type epoxy resins (having a phenylene skeleton, a biphenylene skeleton, etc.), and these may be used alone or in combination of two or more. Among such epoxy resins, a phenol aralkyl type epoxy resin represented by the following general formula (1) is preferable. Thereby, especially flame resistance and solder resistance can be improved.
前記エポキシ樹脂組成物は、硬化剤（Ｂ）を含む。前記硬化剤（Ｂ）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ず、それらの具体例としてはフェノール系樹脂、ビスフェノールＡなどのビスフェノール化合物、無水マレイン酸、無水フタル酸、無水ピロメリット酸などの酸無水物およびメタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホンなどの芳香族アミンなどが挙げられこれらを単独で用いても、２種以上の硬化剤を併用しても良い。 The said epoxy resin composition contains a hardening | curing agent (B). The curing agent (B) is not particularly limited as long as it is cured by reacting with an epoxy resin, and specific examples thereof include phenolic resins, bisphenol compounds such as bisphenol A, maleic anhydride, phthalic anhydride, Examples include acid anhydrides such as pyromellitic anhydride and aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. These may be used alone or in combination of two or more curing agents.
これらの硬化剤の中でも特にフェノール系樹脂を用いることが好ましい。本発明に用いるフェノール系樹脂は、１分子内にフェノール性水酸基を２個以上有するモノマー、オリゴマー、ポリマー全般であり、その分子量、分子構造を特に限定するものではないが、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、ジシクロペンタジエン変性フェノール樹脂、テルペン変性フェノール樹脂、トリフェノールメタン型樹脂、フェノールアラルキル樹脂（フェニレン骨格、ビフェニレン骨格等を有する）等が挙げられ、これらは１種類を単独で用いても２種以上を併用しても差し支えない。このようなフェノール系樹脂の中でも下記一般式（２）で表されるフェノールアラルキル樹脂が好ましい。これにより、耐燃性、耐半田性を特に向上することができる。 Among these curing agents, it is particularly preferable to use a phenolic resin. The phenolic resin used in the present invention is a monomer, oligomer or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, phenol novolak resin, cresol Examples include novolak resins, dicyclopentadiene-modified phenol resins, terpene-modified phenol resins, triphenolmethane resins, phenol aralkyl resins (having a phenylene skeleton, biphenylene skeleton, etc.). You can use more than one species together. Among such phenol resins, a phenol aralkyl resin represented by the following general formula (2) is preferable. Thereby, especially flame resistance and solder resistance can be improved.
エポキシ樹脂と硬化剤であるフェノール系樹脂の配合割合としては、全エポキシ樹脂のエポキシ基数（Ｅｐ）と全フェノール系樹脂のフェノール性水酸基数（Ｐｈ）との比（Ｅｐ／Ｐｈ）が０．８以上、１．３以下であることが好ましく、特に０．９以上、１．２５以下であることが好ましい。比が上記範囲内であると、エポキシ樹脂成形材料の硬化性の低下、或いは硬化物のガラス転移温度の低下、耐湿信頼性の低下等を引き起こす可能性が低い。 As a blending ratio of the epoxy resin and the phenolic resin as the curing agent, the ratio (Ep / Ph) of the number of epoxy groups (Ep) of all epoxy resins to the number of phenolic hydroxyl groups (Ph) of all phenolic resins is 0.8. As mentioned above, it is preferable that it is 1.3 or less, and it is especially preferable that it is 0.9 or more and 1.25 or less. When the ratio is within the above range, there is a low possibility of causing a decrease in the curability of the epoxy resin molding material, a decrease in the glass transition temperature of the cured product, a decrease in moisture resistance reliability, or the like.
前記エポキシ樹脂組成物は、シランカップリング剤（Ｃ）を含み、このシランカップリング剤は抽出処理した際の抽出水のｐＨが３．５〜４．７であることを特徴とする。
一般のシランカップリング剤を抽出処理した際の抽出水のｐＨは、３〜１２と広範囲のものである。これに対して、本発明では、このような抽出水のｐＨが３．５〜４．７となる範囲のシランカップリング剤（Ｃ）を選択及び／又は調製することにより、耐半田性とゲートブレイク性（成形後の基板上からのカル及びランナー部樹脂の除去の容易さ）のバランスに優れたエポキシ樹脂組成物を得ることができるものである。
このように、抽出処理した際の抽出水のｐＨが３．５〜４．７となるシランカップリング剤（Ｃ）を用いることにより、耐半田性とゲートブレイク性とのバランスに優れる理由は、以下のように考えられる。
一般的に多くのシランカップリング剤は、中性のときに最も反応性が低く、酸性にすると加水分解反応が促進されて反応性が高まる。したがって、中性のシランカップリング剤を用いると、シランカップリング剤と無機充填材との反応性に乏しく、未反応のシランカップリング剤が封止樹脂中に存在することになる。そうすると、成形（封止）する際に、未反応のシランカップリング剤とパッケージ基板やその他の部材とが反応してしまう場合がある。そのため、樹脂と、基板のゲート部金属との密着性が必要以上に高くなるため、ゲートブレイク性が低下する。
これに対して、本発明では抽出処理した際の抽出水のｐＨが３．５〜４．７となるシランカップリング剤（Ｃ）を用いるため、シランカップリング剤（Ｃ）と無機充填材との反応が適度に進行し、成形時の密着性が適切な範囲となりゲートブレイク性が向上するものである。さらに、具体的には、抽出処理した際の抽出水のｐＨが３．７〜４．５となるシランカップリング剤（Ｃ）を用いることが好ましく、特にｐＨ３．９〜４．３となるシランカップリング剤（Ｃ）を用いることが好ましい。これにより、耐半田性とゲートブレイク性とのバランスに優れるのに加え、耐湿信頼性に優れる。
なお、シランカップリング剤の抽出は、例えば次のような条件で行い、抽出水のｐＨを測定した。シランカップリング剤１重量部と精製水５０重量部をガラス瓶中で１０分間攪拌し、上澄み液をｐＨの測定に使用した。
The epoxy resin composition includes a silane coupling agent (C), and this silane coupling agent has a pH of 3.5 to 4.7 when extracted water is extracted.
The pH of the extraction water when a general silane coupling agent is extracted is 3 to 12 in a wide range. On the other hand, in the present invention, by selecting and / or preparing the silane coupling agent (C) in such a range that the pH of the extracted water is 3.5 to 4.7, solder resistance and gate It is possible to obtain an epoxy resin composition having an excellent balance of breakability (ease of removing the cal and runner resin from the molded substrate).
Thus, by using the silane coupling agent (C) having a pH of 3.5 to 4.7 when the extraction water is extracted, the reason for the excellent balance between solder resistance and gate breakability is as follows. It is considered as follows.
In general, many silane coupling agents have the lowest reactivity when they are neutral, and when acidified, the hydrolysis reaction is promoted to increase the reactivity. Therefore, when a neutral silane coupling agent is used, the reactivity between the silane coupling agent and the inorganic filler is poor, and an unreacted silane coupling agent is present in the sealing resin. Then, when molding (sealing), the unreacted silane coupling agent may react with the package substrate and other members. Therefore, the adhesiveness between the resin and the gate part metal of the substrate becomes higher than necessary, so that the gate breakability is lowered.
On the other hand, in this invention, since the silane coupling agent (C) from which the pH of the extraction water at the time of an extraction process becomes 3.5-4.7 is used, a silane coupling agent (C) and an inorganic filler The reaction proceeds moderately, the adhesion at the time of molding is in an appropriate range, and the gate breakability is improved. Furthermore, specifically, it is preferable to use a silane coupling agent (C) having a pH of 3.7 to 4.5 when the extraction water is extracted, and particularly a silane having a pH of 3.9 to 4.3. It is preferable to use a coupling agent (C). Thereby, in addition to being excellent in balance between solder resistance and gate breakability, it is excellent in moisture resistance reliability.
The extraction of the silane coupling agent was performed under the following conditions, for example, and the pH of the extracted water was measured. 1 part by weight of a silane coupling agent and 50 parts by weight of purified water were stirred in a glass bottle for 10 minutes, and the supernatant was used for pH measurement.
このようなシランカップリング剤（Ｃ）は、例えば含有する酸性化合物の量を制御することにより抽出水のｐＨを３．５〜４．７に調製することができる。
前記酸性化合物としては、例えば、無機酸としては塩酸、硝酸、硫酸、燐酸など、有機酸としては蟻酸、酢酸、プロピオン酸、酪酸、モノクロロ酢酸、ジクロロ酢酸、トリクロロ酢酸、メトキシ酢酸、シアノ酢酸、クロトン酸などの脂肪族カルボン酸、安息香酸、トルイル酸、フタル酸、ナフタレンカルボン酸、ナフタレンジカルボン酸などの芳香族カルボン酸、メタンスルホン酸、エタンスルホン酸、プロパンスルホン酸などの脂肪族スルホン酸及びベンゼンスルホン酸、トルエンスルホン酸、ナフタレンスルホン酸などの芳香族スルホン酸等が挙げられる。また、これらの化合物は１種類を単独で用いても２種類以上を併用してもよい。これらの酸性化合物は予めシランカップリング剤と混合されていても、前記エポキシ樹脂組成物を混合・混練する工程の中で混合されても良い。
Such a silane coupling agent (C) can adjust the pH of the extraction water to 3.5 to 4.7 by controlling the amount of the acidic compound contained, for example.
Examples of the acidic compound include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid as inorganic acids, and formic acid, acetic acid, propionic acid, butyric acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, methoxyacetic acid, cyanoacetic acid, and croton as organic acids. Aliphatic carboxylic acids such as acids, benzoic acid, toluic acid, aromatic carboxylic acids such as phthalic acid, naphthalene carboxylic acid, naphthalene dicarboxylic acid, aliphatic sulfonic acids such as methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, and benzene Aromatic sulfonic acids such as sulfonic acid, toluene sulfonic acid, naphthalene sulfonic acid and the like can be mentioned. Moreover, these compounds may be used individually by 1 type, or may use 2 or more types together. These acidic compounds may be mixed in advance with a silane coupling agent, or may be mixed in the step of mixing and kneading the epoxy resin composition.
前記酸性化合物の含有量は、特に限定されないが、前記シランカップリング剤（Ｃ）全体の０．００５重量％以上、１重量％以下が好ましく、特に０．０１重量％以上、０．５重量％以下が好ましい。含有量が前記範囲内であると、耐半田性とゲートブレイク性のバランスが取れ、酸性化合物に起因する信頼性低下や凝集物の増加の懸念も少ない。 The content of the acidic compound is not particularly limited, but is preferably 0.005% by weight or more and 1% by weight or less of the entire silane coupling agent (C), particularly 0.01% by weight or more and 0.5% by weight. The following is preferred. When the content is within the above range, the solder resistance and the gate breakability are balanced, and there is little concern about a decrease in reliability and an increase in aggregate due to the acidic compound.
前記シランカップリング剤（Ｃ）は、中性、あるいは酸性のシランカップリング剤に、前記酸性化合物を混合して用いることができ、例えばエポキシシラン、メルカプトシラン、アルキルシラン、ビニルシラン等を用いることが出来る。具体的には、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、メチルトリメトキシシラン、ビニルトリエトキシシランなどが挙げられる。これらのうちエポキシシラン、メルカプトシランが好ましく、またこれらは２種以上併用した方がより効果が高く、特にエポキシシラン又はメルカプトシランを併用するのが好ましい。 The silane coupling agent (C) can be used by mixing the acidic compound with a neutral or acidic silane coupling agent. For example, epoxy silane, mercapto silane, alkyl silane, vinyl silane or the like is used. I can do it. Specifically, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, vinyltriethoxysilane and the like can be mentioned. Of these, epoxy silane and mercapto silane are preferable, and it is more effective to use two or more of these together, and it is particularly preferable to use epoxy silane or mercapto silane together.
前記シランカップリング剤（Ｃ）の配合量は、特に限定されないが、エポキシ樹脂組成物全体の０．０１重量％以上、１重量％以下が好ましく、より好ましくは０.０５重量％以上、０．８重量％以下である。シランカップリング剤（Ｃ）の配合量が上記範囲内であると、さらなる低粘度化と流動性向上効果が期待でき、良好なゲートブレイク性が保たれる。また、上記範囲内であれば、硬化性の低下を引き起こす可能性が低い。 Although the compounding quantity of the said silane coupling agent (C) is not specifically limited, 0.01 weight% or more and 1 weight% or less of the whole epoxy resin composition are preferable, More preferably, it is 0.05 weight% or more, 0.0. 8% by weight or less. When the blending amount of the silane coupling agent (C) is within the above range, further lowering of viscosity and improvement in fluidity can be expected, and good gate breakability can be maintained. Moreover, if it is in the said range, possibility that a curability fall will be low is low.
前記エポキシ樹脂組成物には、抽出水のｐＨを３．５〜４．７に調製したシランカップリング剤（Ｃ）の他に、必要に応じて抽出水のｐＨが３．５〜４．７以外のエポキシシラン、メルカプトシラン、アミノシラン、アルキルシラン、ウレイドシラン、ビニルシラン等のシランカップリング剤を併用することが出来る。具体的な化合物としては、例えば、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルメチルジメトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリエトキシシラン、Ｎ−６−（アミノヘキシル）−３−アミノプロピルトリメトキシシラン、Ｎ−（３−トリメトキシシリルプロピル）−１，３−ベンゼンジメタナミン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、メチルトリメトキシシランン、γ−ウレイドプロピルトリエトキシシラン、ビニルトリエトキシシランなどが挙げられる。これらのうちエポキシシラン、メルカプトシラン、アミノシランが好ましく、アミノシランとしては、１級アミノシラン又はアニリノシランが好ましい。またこれらは２種以上併用した方がより効果が高く、特にアニリノシランとエポキシシラン又はメルカプトシラン又は１級アミノシランを併用するのが好ましく、エポキシシラン、メルカプトシラン、１級アミノシラン、アニリノシラン４種類併用するのが最も好ましい。 In addition to the silane coupling agent (C) prepared by adjusting the pH of the extraction water to 3.5 to 4.7, the epoxy resin composition may have a pH of 3.5 to 4.7 as necessary. Other silane coupling agents such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane can be used in combination. Specific examples of the compound include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl). -Γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-6- (aminohexyl) -3-aminopropyltrimethoxysilane, N- (3-trimethoxysilylpropyl) -1,3-benzenedimethamine, γ-glycidoxypropyltriethoxysilane, γ-glycine Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane Emissions, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, .gamma.-mercaptopropyltrimethoxysilane, methyltrimethoxysilane down, .gamma.-ureidopropyltriethoxysilane, and vinyl triethoxysilane. Of these, epoxy silane, mercapto silane, and amino silane are preferable. As the amino silane, primary amino silane or anilino silane is preferable. In addition, it is more effective to use two or more of these in combination, and it is particularly preferable to use anilinosilane in combination with epoxy silane, mercaptosilane or primary aminosilane, and to use together four types of epoxysilane, mercaptosilane, primary aminosilane, and anilinosilane. Is most preferred.
このような抽出水のｐＨが３．５〜４．７以外のシランカップリング剤の配合量は、特に限定されないが、前記エポキシ樹脂組成物全体の０．０１重量％以上、１重量％以下が好ましく、特に０．０３重量％以上、０．５重量％以下が好ましい。抽出水のｐＨが３．５〜４．７以外のシランカップリング剤の配合量が上記範囲内であると、さらなる低粘度化と流動性向上効果が期待できる。また、上記範囲内であれば、硬化性の低下を引き起こす可能性が低い。また、これらシランカップリング剤は、予め水或いは必要に応じて酸又はアルカリを添加して、加水分解処理して用いてもよく、また予め無機充填材に処理されていてもよい。 The blending amount of the silane coupling agent having a pH other than 3.5 to 4.7 is not particularly limited, but is 0.01% by weight or more and 1% by weight or less of the total epoxy resin composition. Particularly preferred is 0.03% by weight or more and 0.5% by weight or less. When the blending amount of the silane coupling agent having a pH other than 3.5 to 4.7 in the extracted water is within the above range, further viscosity reduction and fluidity improvement effects can be expected. Moreover, if it is in the said range, possibility that a curability fall will be low is low. In addition, these silane coupling agents may be used after being hydrolyzed by adding water or an acid or an alkali as necessary, or may be previously treated with an inorganic filler.
本発明に用いることができる無機充填材（Ｄ）としては、一般に半導体封止用エポキシ樹脂組成物に使用されているものを用いることができる。例えば、溶融シリカ、結晶シリカ、タルク、アルミナ、窒化珪素等が挙げられ、最も好適に使用されるものとしては、球状の溶融シリカである。これらの無機充填剤は、１種類を単独で用いても２種以上を併用しても差し支えない。 As an inorganic filler (D) which can be used for this invention, what is generally used for the epoxy resin composition for semiconductor sealing can be used. Examples thereof include fused silica, crystalline silica, talc, alumina, silicon nitride and the like, and the most preferably used is spherical fused silica. These inorganic fillers may be used alone or in combination of two or more.
前記無機充填材（Ｄ）の平均粒子径は、特に限定されないが、５μｍ以上、５０μｍ以下が好ましく、特に１０μｍ以上、４５μｍ以下が好ましい。平均粒子径が上記範囲内であると、流動性は良好で、下限値を下回ると十分な流動性が得られず、上限値を上回ると成形時の充填性が悪くなり、空隙が多く生じる恐れがある。 Although the average particle diameter of the said inorganic filler (D) is not specifically limited, 5 micrometers or more and 50 micrometers or less are preferable, and 10 micrometers or more and 45 micrometers or less are especially preferable. When the average particle size is within the above range, the fluidity is good, and when the average particle size is below the lower limit, sufficient fluidity cannot be obtained. There is.
前記無機充填材（Ｄ）の含有量は、特に限定されないが、前記エポキシ樹脂組成物全体の７５重量％以上、９４重量％以下が好ましく、特に８０重量％以上、９２重量％以下が好ましい。含有量が上記範囲内であると、耐半田性の低下や流動性の低下を引き起こす可能性が低い。 Although content of the said inorganic filler (D) is not specifically limited, 75 weight% or more and 94 weight% or less of the whole said epoxy resin composition are preferable, and 80 weight% or more and 92 weight% or less are especially preferable. When the content is within the above range, there is a low possibility of causing a decrease in solder resistance and a decrease in fluidity.
前記エポキシ樹脂組成物は、特に限定されないが、硬化促進剤（Ｅ）を含むことが好ましい。これにより、エポキシ樹脂と硬化剤との反応を促進することができ、良好な流動性と硬化性を併せ持つことができる。
前記硬化促進剤（Ｅ）は、エポキシ樹脂のエポキシ基と硬化剤（例えば、フェノール系樹脂のフェノール性水酸基）との反応を促進するものであればよく、一般に半導体素子の封止材であるエポキシ樹脂組成物に使用されているものを利用することができる。具体例としては、有機ホスフィン、テトラ置換ホスホニウム化合物、ホスホベタイン化合物、ホスフィン化合物とキノン化合物との付加物等のリン原子含有化合物、１，８−ジアザビシクロ（５，４，０）ウンデセン−７、ベンジルジメチルアミン、２−メチルイミダゾール等の窒素原子含有化合物が挙げられる。これらの硬化促進剤は、１種類を単独で用いても２種以上を併用して差し支えない。これらのうち、リン原子含有化合物が好ましく、特に流動性という点を考慮するとテトラ置換ホスホニウム化合物が好ましく、またエポキシ樹脂組成物の硬化物の高温下における低弾性率化という点を考慮するとホスホベタイン化合物、ホスフィン化合物とキノン化合物との付加物がより好ましい。
Although the said epoxy resin composition is not specifically limited, It is preferable that a hardening accelerator (E) is included. Thereby, reaction of an epoxy resin and a hardening | curing agent can be accelerated | stimulated and it can have favorable fluidity | liquidity and sclerosis | hardenability.
The curing accelerator (E) may be anything that promotes the reaction between the epoxy group of the epoxy resin and the curing agent (for example, the phenolic hydroxyl group of the phenolic resin), and is generally an epoxy that is a sealing material for semiconductor elements. What is used for the resin composition can be utilized. Specific examples include organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, phosphorus atom-containing compounds such as adducts of phosphine compounds and quinone compounds, 1,8-diazabicyclo (5,4,0) undecene-7, benzyl Nitrogen atom-containing compounds such as dimethylamine and 2-methylimidazole can be mentioned. These curing accelerators may be used alone or in combination of two or more. Among these, a phosphorus atom-containing compound is preferable, and a tetra-substituted phosphonium compound is preferable in consideration of fluidity, and a phosphobetaine compound in consideration of lowering a modulus of elasticity of a cured product of an epoxy resin composition at a high temperature. An adduct of a phosphine compound and a quinone compound is more preferable.
前記有機ホスフィンとしては、例えば、エチルホスフィン、フェニルホスフィン等の第１ホスフィン、ジメチルホスフィン、ジフェニルホスフィン等の第２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、トリブチルホスフィン、トリフェニルホスフィン等の第３ホスフィンが挙げられる。 Examples of the organic phosphine include a first phosphine such as ethylphosphine and phenylphosphine, a second phosphine such as dimethylphosphine and diphenylphosphine, and a third phosphine such as trimethylphosphine, triethylphosphine, tributylphosphine, and triphenylphosphine. .
前記テトラ置換ホスホニウム化合物としては、例えば、一般式（３）で表される化合物が挙げられる。 As said tetra substituted phosphonium compound, the compound represented by General formula (3) is mentioned, for example.
上記一般式（３）で表される化合物は、例えば以下のようにして得られる。まず、テトラ置換ホスホニウムブロマイドと芳香族有機酸と塩基を有機溶剤に混ぜ均一に混合し、その溶液系内に芳香族有機酸アニオンを発生させる。次いで水を加える。すると、上記一般式（３）で表される化合物を沈殿させることができる。上記一般式（３）で表される化合物において、リン原子に結合するＲ１、Ｒ２、Ｒ３およびＲ４がフェニル基であり、かつＡＨはヒドロキシル基を芳香環に有する化合物、すなわちフェノール類であり、かつＡは該フェノール類のアニオンであるのが好ましい。 The compound represented by the general formula (3) is obtained as follows, for example. First, a tetra-substituted phosphonium bromide, an aromatic organic acid, and a base are mixed in an organic solvent and mixed uniformly to generate an aromatic organic acid anion in the solution system. Then add water. Then, the compound represented by the general formula (3) can be precipitated. In the compound represented by the general formula (3), R1, R2, R3 and R4 bonded to the phosphorus atom are phenyl groups, and AH is a compound having a hydroxyl group in an aromatic ring, that is, a phenol, and A is preferably an anion of the phenol.
前記ホスホベタイン化合物としては、例えば、下記一般式（４）で表される化合物が挙げられる。 As said phosphobetaine compound, the compound represented by following General formula (4) is mentioned, for example.
上記一般式（４）で表される化合物は、例えば以下のようにして得られる。まず、第三ホスフィンであるトリ芳香族置換ホスフィンとジアゾニウム塩とを接触させ、前記トリ芳香族置換ホスフィンと前記ジアゾニウム塩が有するジアゾニウム基とを置換させる工程を経て得られる。しかしこれに限定されるものではない。一般式（４）で表される化合物としては、例えば、Ｘが水素又はメチル基であり、かつＹが水素又はヒドロキシル基であるものが好ましい。 The compound represented by the general formula (4) is obtained, for example, as follows. First, it is obtained through a step of bringing a triaromatic substituted phosphine, which is a third phosphine, into contact with a diazonium salt and replacing the triaromatic substituted phosphine with a diazonium group of the diazonium salt. However, the present invention is not limited to this. As the compound represented by the general formula (4), for example, those in which X is hydrogen or a methyl group and Y is hydrogen or a hydroxyl group are preferable.
前記ホスフィン化合物とキノン化合物との付加物としては、例えば、下記一般式（５）で表される化合物等が挙げられる。 Examples of the adduct of the phosphine compound and the quinone compound include compounds represented by the following general formula (5).
前記ホスフィン化合物と前記キノン化合物との付加物に用いるホスフィン化合物としては、例えば、トリフェニルホスフィン、トリス（アルキルフェニル）ホスフィン、トリス（アルコキシフェニル）ホスフィン、トリナフチルホスフィン、トリス（ベンジル）ホスフィン等の芳香環に無置換あるいはアルキル基、アルコキシル基等の置換基が存在するものが好ましく、アルキル基、アルコキシル基の有機基としては１〜６の炭素数を有するものが挙げられる。入手しやすさの観点からはトリフェニルホスフィンが好ましい。
また前記ホスフィン化合物と前記キノン化合物との付加物に用いるキノン化合物としては、例えば、ｏ−ベンゾキノン、ｐ−ベンゾキノン、アントラキノン類が挙げられ、中でもｐ−ベンゾキノンが保存安定性の点から好ましい。
前記ホスフィン化合物と前記キノン化合物との付加物の製造方法としては、有機第三ホスフィンとキノン化合物の両者が溶解することができる溶媒中で接触、混合させることにより付加物を得ることができる。溶媒としてはアセトンやメチルエチルケトン等のケトン類で付加物への溶解性が低いものがよい。しかしこれに限定されるものではない。
前記一般式（５）で表される化合物において、リン原子に結合するＲ１、Ｒ２およびＲ３がフェニル基であり、かつＲ３、Ｒ４およびＲ５が水素原子である化合物、すなわち１,４−ベンゾキノンとトリフェニルホスフィンを付加させた化合物が好ましい。
Examples of the phosphine compound used for the adduct of the phosphine compound and the quinone compound include aromatic compounds such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine. The ring is preferably unsubstituted or has a substituent such as an alkyl group or alkoxyl group, and examples of the organic group of the alkyl group and alkoxyl group include those having 1 to 6 carbon atoms. From the viewpoint of availability, triphenylphosphine is preferable.
Examples of the quinone compound used in the adduct of the phosphine compound and the quinone compound include o-benzoquinone, p-benzoquinone, and anthraquinone, and among them, p-benzoquinone is preferable from the viewpoint of storage stability.
As a method for producing an adduct of the phosphine compound and the quinone compound, the adduct can be obtained by contacting and mixing in a solvent capable of dissolving both the organic tertiary phosphine and the quinone compound. The solvent is preferably a ketone such as acetone or methyl ethyl ketone, which has low solubility in the adduct. However, the present invention is not limited to this.
In the compound represented by the general formula (5), R1, R2 and R3 bonded to the phosphorus atom are phenyl groups, and R3, R4 and R5 are hydrogen atoms, that is, 1,4-benzoquinone and tri A compound to which phenylphosphine is added is preferable.
前記硬化促進剤（Ｄ）の配合量は、特に限定されないが、前記エポキシ樹脂組成物全体の０．１重量％以上、１重量％以下が好ましい。配合量が上記範囲内であると、流動性を損なうことなく、良好な硬化性を得ることができる。 Although the compounding quantity of the said hardening accelerator (D) is not specifically limited, 0.1 to 1 weight% of the whole said epoxy resin composition is preferable. When the blending amount is within the above range, good curability can be obtained without impairing fluidity.
前記エポキシ樹脂組成物には、必要に応じて離型剤が用いられる。前記離型剤としては、従来公知のものを用いることができるが、例えば、高級脂肪酸、高級脂肪酸金属塩、エステル系ワックス、ポリエチレン系ワックス等が挙げられ、これらは１種類を単独で用いても２種以上を併用しても構わない。これらのうちポリエチレン系ワックスが好ましく、ポリエチレン系ワックスとモンタン酸エステル系ワックスを併用した方がより好ましい。前記離型剤の配合量は、特に制限されないが、前記エポキシ樹脂組成物全体の０．０５重量％以上３重量％以下が好ましく、より好ましくは０.１重量％以上１重量％以下である。配合量が前記下限値を下回ると離型性が低下する場合があり、前記上限値を上回ると密着性および耐半田性が低下する場合がある。 A release agent is used in the epoxy resin composition as necessary. As the mold release agent, conventionally known ones can be used, and examples thereof include higher fatty acids, higher fatty acid metal salts, ester waxes, polyethylene waxes and the like, and these may be used alone. Two or more kinds may be used in combination. Of these, polyethylene waxes are preferable, and it is more preferable to use polyethylene wax and montanic acid ester wax in combination. The blending amount of the release agent is not particularly limited, but is preferably 0.05% by weight or more and 3% by weight or less, more preferably 0.1% by weight or more and 1% by weight or less of the entire epoxy resin composition. If the blending amount is less than the lower limit value, the releasability may be lowered, and if it exceeds the upper limit value, adhesion and solder resistance may be lowered.
前記エポキシ樹脂組成物には、必要に応じてイオントラップ剤が用いられる。前記イオントラップ剤としては従来公知のものを用いることができるが、例えば、ハイドロタルサイト類やマグネシウム、アルミニウム、ビスマス、チタン、ジルコニウムから選ばれる元素の含水酸化物等が挙げられ、これらは１種類を単独で用いても２種以上を併用しても構わない。これらのうちハイドロタルサイト類が好ましい。前記イオントラップ剤の配合量は、特に制限されないが、前記エポキシ樹脂組成物全体の０．０５重量％以上３重量％以下が好ましく、より好ましくは０.１重量％以上１重量％以下である。配合量が前記範囲内であると、充分なイオン補足作用を発揮し、他の材料特性に対する悪影響も少ない。 An ion trap agent is used for the epoxy resin composition as necessary. As the ion trapping agent, conventionally known ones can be used. Examples thereof include hydrotalcites and hydrated oxides of elements selected from magnesium, aluminum, bismuth, titanium, and zirconium. May be used alone or in combination of two or more. Of these, hydrotalcites are preferred. The blending amount of the ion trapping agent is not particularly limited, but is preferably 0.05% by weight or more and 3% by weight or less, more preferably 0.1% by weight or more and 1% by weight or less of the entire epoxy resin composition. When the blending amount is within the above range, sufficient ion scavenging action is exhibited and there is little adverse effect on other material properties.
前記エポキシ樹脂組成物は、エポキシ樹脂、フェノール樹脂、シランカップリング剤、硬化促進剤、及び無機質充填材を主成分とし、更に必要に応じて、離型剤、イオントラップ剤を用いるが、カーボンブラック等の着色剤、シリコーンオイル、ゴム等の低応力添加剤、臭素化エポキシ樹脂や三酸化アンチモン、水酸化アルミニウム、水酸化マグネシウム、ほう酸亜鉛、モリブデン酸亜鉛、フォスファゼン等の難燃剤等の添加剤を適宜配合しても差し支えない。 The epoxy resin composition is mainly composed of an epoxy resin, a phenol resin, a silane coupling agent, a curing accelerator, and an inorganic filler, and a mold release agent and an ion trap agent are used as necessary. Additives such as colorants such as silicone oils, low stress additives such as rubber, flame retardants such as brominated epoxy resins, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene It may be blended appropriately.
このようなエポキシ樹脂組成物を、例えば、ミキサー等を用いて原料を充分に均一に混合した後、更に熱ロール又はニーダー等で溶融混練し、冷却後粉砕してエポキシ樹脂成形材料とすることができる。 Such an epoxy resin composition, for example, after mixing the raw materials sufficiently uniformly using a mixer or the like, further melt-kneaded with a hot roll or kneader, etc., cooled and pulverized to obtain an epoxy resin molding material it can.
また、上述のエポキシ樹脂成形材料を用いて、半導体素子等の各種の電子部品を封止し、半導体装置を製造するには、トランスファーモールド、コンプレッションモールド、インジェクションモールド等の従来からの成形方法で硬化成形して半導体装置を得ることができる。 In addition, using the above-mentioned epoxy resin molding material, various electronic parts such as semiconductor elements are sealed, and a semiconductor device is manufactured by a conventional molding method such as a transfer mold, a compression mold, or an injection mold. A semiconductor device can be obtained by molding.
以下に本発明を実施例および比較例に基づいて詳細に説明するが、本発明はこれらに限定されるものではない。配合割合は重量部とした。 Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples, but the present invention is not limited thereto. The blending ratio was parts by weight.
（実施例１）
エポキシ樹脂として前記一般式（１）で表されるエポキシ樹脂１（ビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂：日本化薬（株）製、商品名ＮＣ３０００Ｐ、軟化点５８℃、エポキシ当量２７３、ｎ＝２．３）７．６重量部と、フェノール樹脂として前記一般式（２）で表されるビフェニレン骨格を有するフェノールアラルキル樹脂（明和化成（株）製、商品名ＭＥＨ−７８５１ＳＳ、軟化点６５℃、水酸基当量２０４、式（２）においてｎ＝１．６）５．１重量部と、硬化促進剤：トリフェニルホスフィンと１，４−ベンゾキノンとの付加物０．２重量部と、溶融球状シリカ（平均粒径３０μｍ）８６．０重量部と、シランカップリング剤（Ｃ）としてメルカプトシラン１：γ−メルカプトプロピルトリメトキシシラン（９９．９重量部）と酢酸（０．１重量部）の混合物（抽出水のｐＨ３．９）０．２重量部と、他のカップリング剤としてＮ−フェニル−γ−アミノプロピルトリメトキシシラン０．１重量部と、離型剤としてポリエチレン系ワックス（離型剤１）０．２重量部と、モンタン酸エステル系ワックス（離型剤２）０．１重量部と、イオントラップ剤としてハイドロタルサイト（協和化学工業（株）製、ＤＨＴ−４Ｈ）０．２重量部と、カーボンブラック０．３重量部とをミキサーにて混合し、熱ロールを用いて、９５℃で８分間混練して冷却後粉砕し、エポキシ樹脂成形材料を得た。
Example 1
Epoxy resin 1 represented by the general formula (1) as an epoxy resin (phenol aralkyl type epoxy resin having a biphenylene skeleton: manufactured by Nippon Kayaku Co., Ltd., trade name NC3000P, softening point 58 ° C., epoxy equivalent 273, n = 2.3) Phenol aralkyl resin having a biphenylene skeleton represented by the above general formula (2) as a phenol resin (made by Meiwa Kasei Co., Ltd., trade name: MEH-7851SS, softening point: 65 ° C., 2.3) Hydroxyl equivalent weight 204, n = 1.6 in formula (2) 5.1 parts by weight, curing accelerator: 0.2 part by weight of adduct of triphenylphosphine and 1,4-benzoquinone, fused spherical silica ( 86.0 parts by weight of an average particle size of 30 μm) and mercaptosilane 1: γ-mercaptopropyltrimethoxysilane (silane) as a silane coupling agent (C) 99.9 parts by weight) and acetic acid (0.1 part by weight) (extracted water pH 3.9) 0.2 part by weight, and N-phenyl-γ-aminopropyltrimethoxysilane 0 as another coupling agent 0.1 part by weight, 0.2 part by weight of a polyethylene wax (release agent 1) as a release agent, 0.1 part by weight of a montanate ester wax (release agent 2), and hydrotal as an ion trapping agent 0.2 part by weight of sight (Kyowa Chemical Industry Co., Ltd., DHT-4H) and 0.3 part by weight of carbon black are mixed with a mixer and kneaded at 95 ° C. for 8 minutes using a hot roll. After cooling, the mixture was pulverized to obtain an epoxy resin molding material.
（実施例２）
シランカップリング剤（Ｃ）として以下のものを用いた以外は、実施例１と同様にした。
シランカップリング剤（Ｃ）として、メルカプトシラン２：γ−メルカプトプロピルトリメトキシシラン（９９．９７重量部）と酢酸（０．０３重量部）の混合物（抽出水のｐＨ４．３）を用いた。
(Example 2)
The procedure was the same as Example 1 except that the following silane coupling agent (C) was used.
As a silane coupling agent (C), a mixture of mercaptosilane 2: γ-mercaptopropyltrimethoxysilane (99.97 parts by weight) and acetic acid (0.03 parts by weight) (pH 4.3 of extracted water) was used.
（実施例３）
シランカップリング剤（Ｃ）として以下のものを用いた以外は、実施例１と同様にした。
シランカップリング剤（Ｃ）として、メルカプトシラン３：γ−メルカプトシラン（９９．０重量部）と酢酸（１．０重量部）の混合物（抽出水のｐＨ３．７）を用いた。
Example 3
The procedure was the same as Example 1 except that the following silane coupling agent (C) was used.
As a silane coupling agent (C), a mixture of mercaptosilane 3: γ-mercaptosilane (99.0 parts by weight) and acetic acid (1.0 parts by weight) (pH 3.7 of extracted water) was used.
（実施例４）
シランカップリング剤（Ｃ）として以下のものを用いた以外は、実施例１と同様にした。
シランカップリング剤（Ｃ）として、メルカプトシラン４：γ−メルカプトプロピルトリメトキシシラン（９９．０重量部）とプロピオン酸（１．０重量部）の混合物（抽出水のｐＨ４．２）を用いた。
Example 4
The procedure was the same as Example 1 except that the following silane coupling agent (C) was used.
As the silane coupling agent (C), a mixture of mercaptosilane 4: γ-mercaptopropyltrimethoxysilane (99.0 parts by weight) and propionic acid (1.0 parts by weight) (pH 4.2 of extracted water) was used. .
（実施例５）
他のカップリング剤の配合量を多くし、全体の配合を以下のようにした以外は実施例１と同様にした。
エポキシ樹脂として前記一般式（１）で表されるエポキシ樹脂１（ビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂：日本化薬（株）製、商品名ＮＣ３０００Ｐ、軟化点５８℃、エポキシ当量２７３、ｎ＝２．３）７．３重量部と、フェノール樹脂として前記一般式（２）で表されるビフェニレン骨格を有するフェノールアラルキル樹脂（明和化成（株）製、商品名ＭＥＨ−７８５１ＳＳ、軟化点６５℃、水酸基当量２０４、式（２）においてｎ＝１．６）４．９重量部と、硬化促進剤：トリフェニルホスフィンと１，４−ベンゾキノンとの付加物０．２重量部と、溶融球状シリカ（平均粒径３０μｍ）８６．０重量部と、シランカップリング剤（Ｃ）としてメルカプトシラン１：γ−メルカプトプロピルトリメトキシシラン（９９．９重量部）と酢酸（０．１重量部）の混合物（抽出水のｐＨ３．９）０．２重量部と、他のカップリング剤としてＮ−フェニル−γ−アミノプロピルトリメトキシシラン０．６重量部と、離型剤としてポリエチレン系ワックス（離型剤１）０．２重量部と、モンタン酸エステル系ワックス（離型剤２）０．１重量部と、イオントラップ剤としてハイドロタルサイト（協和化学工業（株）製、ＤＨＴ−４Ｈ）０．２重量部と、カーボンブラック０．３重量部とした。
(Example 5)
The same procedure as in Example 1 was performed except that the amount of the other coupling agent was increased and the total formulation was as follows.
Epoxy resin 1 represented by the general formula (1) as an epoxy resin (phenol aralkyl type epoxy resin having a biphenylene skeleton: manufactured by Nippon Kayaku Co., Ltd., trade name NC3000P, softening point 58 ° C., epoxy equivalent 273, n = 2.3) Phenol aralkyl resin having a biphenylene skeleton represented by the general formula (2) as a phenol resin (7.3) by weight (Maywa Kasei Co., Ltd., trade name: MEH-7851SS, softening point: 65 ° C., Hydroxyl equivalent 204, n = 1.6 in formula (2), 4.9 parts by weight, curing accelerator: 0.2 part by weight of adduct of triphenylphosphine and 1,4-benzoquinone, fused spherical silica ( 86.0 parts by weight of an average particle size of 30 μm) and mercaptosilane 1: γ-mercaptopropyltrimethoxysilane (silane) as a silane coupling agent (C) 99.9 parts by weight) and acetic acid (0.1 part by weight) (extracted water pH 3.9) 0.2 part by weight, and N-phenyl-γ-aminopropyltrimethoxysilane 0 as another coupling agent .6 parts by weight, 0.2 part by weight of a polyethylene wax (release agent 1) as a release agent, 0.1 part by weight of a montanate ester wax (release agent 2), and hydrotal as an ion trapping agent 0.2 parts by weight of a site (DHT-4H manufactured by Kyowa Chemical Industry Co., Ltd.) and 0.3 parts by weight of carbon black were used.
（実施例６）
他のカップリング剤を用いずに、全体の配合を以下のようにした以外は実施例１と同様にした。
エポキシ樹脂として前記一般式（１）で表されるエポキシ樹脂１（ビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂：日本化薬（株）製、商品名ＮＣ３０００Ｐ、軟化点５８℃、エポキシ当量２７３、ｎ＝２．３）７．６重量部と、フェノール樹脂として前記一般式（２）で表されるビフェニレン骨格を有するフェノールアラルキル樹脂（明和化成（株）製、商品名ＭＥＨ−７８５１ＳＳ、軟化点６５℃、水酸基当量２０４、式（２）においてｎ＝１．６）５．２重量部と、硬化促進剤：トリフェニルホスフィンと１，４−ベンゾキノンとの付加物０．２重量部と、溶融球状シリカ（平均粒径３０μｍ）８６．０重量部と、シランカップリング剤（Ｃ）としてメルカプトシラン１：γ−メルカプトプロピルトリメトキシシラン（９９．９重量部）と酢酸（０．１重量部）の混合物（抽出水のｐＨ３．９）０．２重量部と、離型剤としてポリエチレン系ワックス（離型剤１）０．２重量部と、モンタン酸エステル系ワックス（離型剤２）０．１重量部と、イオントラップ剤としてハイドロタルサイト（協和化学工業（株）製、ＤＨＴ−４Ｈ）０．２重量部と、カーボンブラック０．３重量部とした。
(Example 6)
The same procedure as in Example 1 was carried out except that the entire formulation was as follows without using other coupling agents.
Epoxy resin 1 represented by the general formula (1) as an epoxy resin (phenol aralkyl type epoxy resin having a biphenylene skeleton: manufactured by Nippon Kayaku Co., Ltd., trade name NC3000P, softening point 58 ° C., epoxy equivalent 273, n = 2.3) Phenol aralkyl resin having a biphenylene skeleton represented by the above general formula (2) as a phenol resin (made by Meiwa Kasei Co., Ltd., trade name: MEH-7851SS, softening point: 65 ° C., 2.3) Hydroxyl group equivalent 204, n = 1.6 in formula (2) 5.2 parts by weight, curing accelerator: 0.2 part by weight of adduct of triphenylphosphine and 1,4-benzoquinone, fused spherical silica ( 86.0 parts by weight of an average particle size of 30 μm) and mercaptosilane 1: γ-mercaptopropyltrimethoxysilane (silane) as a silane coupling agent (C) 99.9 parts by weight) and acetic acid (0.1 part by weight) mixture (extracted water pH 3.9) 0.2 part by weight, and a polyethylene wax (release agent 1) 0.2 part by weight as a release agent And 0.1 parts by weight of a montanic acid ester wax (release agent 2), 0.2 parts by weight of hydrotalcite (Kyowa Chemical Industry Co., Ltd., DHT-4H) as an ion trapping agent, and carbon black 0 3 parts by weight.
（実施例７）
エポキシ樹脂として以下のものを用い、全体の配合を以下のようにした以外は実施例１と同様にした。
エポキシ樹脂としてエポキシ樹脂２：ビフェニル型エポキシ樹脂（ジャパンエポキシレジン（株）製、商品名ＹＸ−４０００、エポキシ当量１９０、融点１０５℃）６．４重量部と、フェノール樹脂として前記一般式（２）で表されるビフェニレン骨格を有するフェノールアラルキル樹脂（明和化成（株）製、商品名ＭＥＨ−７８５１ＳＳ、軟化点６５℃、水酸基当量２０４、式（２）においてｎ＝１．６）６．３重量部と、硬化促進剤：トリフェニルホスフィンと１，４−ベンゾキノンとの付加物０．２重量部と、溶融球状シリカ（平均粒径３０μｍ）８６．０重量部と、シランカップリング剤（Ｃ）としてメルカプトシラン１：γ−メルカプトプロピルトリメトキシシラン（９９．９重量部）と酢酸（０．１重量部）の混合物（抽出水のｐＨ３．９）０．２重量部と、他のカップリング剤としてＮ−フェニル−γ−アミノプロピルトリメトキシシラン０．１重量部と、離型剤としてポリエチレン系ワックス（離型剤１）０．２重量部と、モンタン酸エステル系ワックス（離型剤２）０．１重量部と、イオントラップ剤としてハイドロタルサイト（協和化学工業（株）製、ＤＨＴ−４Ｈ）０．２重量部と、カーボンブラック０．３重量部とした。
(Example 7)
The following were used as the epoxy resin, and the same as Example 1 except that the entire formulation was as follows.
Epoxy resin as an epoxy resin 2: 6.4 parts by weight of a biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name YX-4000, epoxy equivalent 190, melting point 105 ° C.) and the general formula (2) as a phenol resin Phenol aralkyl resin having a biphenylene skeleton represented by the formula (Maywa Kasei Co., Ltd., trade name MEH-7851SS, softening point 65 ° C., hydroxyl group equivalent 204, n = 1.6 in formula (2)) 6.3 parts by weight And curing accelerator: 0.2 part by weight of an adduct of triphenylphosphine and 1,4-benzoquinone, 86.0 parts by weight of fused spherical silica (average particle size 30 μm), and silane coupling agent (C) Mercaptosilane 1: mixture of γ-mercaptopropyltrimethoxysilane (99.9 parts by weight) and acetic acid (0.1 parts by weight) H3.9) 0.2 parts by weight, 0.1 parts by weight of N-phenyl-γ-aminopropyltrimethoxysilane as another coupling agent, and polyethylene wax (release agent 1) as a release agent. 2 parts by weight, 0.1 parts by weight of a montanic acid ester wax (release agent 2), 0.2 parts by weight of hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd., DHT-4H) as an ion trapping agent, Carbon black was 0.3 parts by weight.
（実施例８）
フェノール樹脂として以下のものを用い、全体の配合を以下のようにした以外は実施例１と同様にした。
エポキシ樹脂として前記一般式（１）で表されるエポキシ樹脂１（ビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂：日本化薬（株）製、商品名ＮＣ３０００Ｐ、軟化点５８℃、エポキシ当量２７３、ｎ＝２．３）８．２重量部と、フェノール樹脂としてフェノール樹脂２：フェノールアラルキル樹脂（三井化学（株）製、商品名ＸＬＣ−ＬＬ、水酸基当量１６５、軟化点７９℃、式（７）においてｎ＝５）４．５重量部と、硬化促進剤：トリフェニルホスフィンと１，４−ベンゾキノンとの付加物０．２重量部と、溶融球状シリカ（平均粒径３０μｍ）８６．０重量部と、シランカップリング剤（Ｃ）としてメルカプトシラン１：γ−メルカプトプロピルトリメトキシシラン（９９．９重量部）と酢酸（０．１重量部）の混合物（抽出水のｐＨ３．９）０．２重量部と、他のカップリング剤としてＮ−フェニル−γ−アミノプロピルトリメトキシシラン０．１重量部と、離型剤としてポリエチレン系ワックス（離型剤１）０．２重量部と、モンタン酸エステル系ワックス（離型剤２）０．１重量部と、イオントラップ剤としてハイドロタルサイト（協和化学工業（株）製、ＤＨＴ−４Ｈ）０．２重量部と、カーボンブラック０．３重量部とした。
(Example 8)
The following was used as a phenol resin, and the same as Example 1 except that the whole composition was as follows.
Epoxy resin 1 represented by the general formula (1) as an epoxy resin (phenol aralkyl type epoxy resin having a biphenylene skeleton: manufactured by Nippon Kayaku Co., Ltd., trade name NC3000P, softening point 58 ° C., epoxy equivalent 273, n = 2.3) 8.2 parts by weight and phenol resin 2: phenol aralkyl resin (trade name XLC-LL, hydroxyl group equivalent 165, softening point 79 ° C., n-type in formula (7) = 5) 4.5 parts by weight, curing accelerator: 0.2 part by weight of adduct of triphenylphosphine and 1,4-benzoquinone, fused spherical silica (average particle size 30 μm) 86.0 parts by weight, Mercaptosilane 1: γ-mercaptopropyltrimethoxysilane (99.9 parts by weight) and acetic acid (0.1 parts by weight) as silane coupling agent (C) 0.2 parts by weight of the product (pH 3.9 of the extraction water), 0.1 part by weight of N-phenyl-γ-aminopropyltrimethoxysilane as another coupling agent, and polyethylene wax (release) as the release agent Agent 1) 0.2 part by weight, montanic acid ester wax (release agent 2) 0.1 part by weight, and hydrotalcite (Kyowa Chemical Industry Co., Ltd., DHT-4H) as an ion trapping agent. 2 parts by weight and 0.3 parts by weight of carbon black were used.
（実施例９）
無機充填材の含有量を少なくして、全体の配合を以下のようにした以外は実施例１と同様にした。
エポキシ樹脂として前記一般式（１）で表されるエポキシ樹脂１（ビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂：日本化薬（株）製、商品名ＮＣ３０００Ｐ、軟化点５８℃、エポキシ当量２７３、ｎ＝２．３）１２．９重量部と、フェノール樹脂として前記一般式（２）で表されるビフェニレン骨格を有するフェノールアラルキル樹脂（明和化成（株）製、商品名ＭＥＨ−７８５１ＳＳ、軟化点６５℃、水酸基当量２０４、式（２）においてｎ＝１．６）８．８重量部と、硬化促進剤：トリフェニルホスフィンと１，４−ベンゾキノンとの付加物０．２重量部と、溶融球状シリカ（平均粒径３０μｍ）７７．０重量部と、シランカップリング剤（Ｃ）としてメルカプトシラン１：γ−メルカプトプロピルトリメトキシシラン（９９．９重量部）と酢酸（０．１重量部）の混合物（抽出水のｐＨ３．９）０．２重量部と、他のカップリング剤としてＮ−フェニル−γ−アミノプロピルトリメトキシシラン０．１重量部と、離型剤としてポリエチレン系ワックス（離型剤１）０．２重量部と、モンタン酸エステル系ワックス（離型剤２）０．１重量部と、イオントラップ剤としてハイドロタルサイト（協和化学工業（株）製、ＤＨＴ−４Ｈ）０．２重量部と、カーボンブラック０．３重量部とした。
Example 9
The same procedure as in Example 1 was carried out except that the content of the inorganic filler was reduced and the overall formulation was as follows.
Epoxy resin 1 represented by the general formula (1) as an epoxy resin (phenol aralkyl type epoxy resin having a biphenylene skeleton: manufactured by Nippon Kayaku Co., Ltd., trade name NC3000P, softening point 58 ° C., epoxy equivalent 273, n = 2.3) 12.9 parts by weight and a phenol aralkyl resin having a biphenylene skeleton represented by the general formula (2) as a phenol resin (Maywa Kasei Co., Ltd., trade name: MEH-7851SS, softening point: 65 ° C., Hydroxyl equivalent 204, n = 1.6 in formula (2) 8.8 parts by weight, curing accelerator: 0.2 part by weight of adduct of triphenylphosphine and 1,4-benzoquinone, fused spherical silica ( (Average particle size 30 μm) 77.0 parts by weight and mercaptosilane 1: γ-mercaptopropyltrimethoxysilane as silane coupling agent (C) (99.9 parts by weight) and acetic acid (0.1 parts by weight) mixture (pH 3.9 of extracted water) 0.2 parts by weight, and N-phenyl-γ-aminopropyltrimethoxysilane as another coupling agent 0.1 part by weight, 0.2 part by weight of a polyethylene wax (release agent 1) as a release agent, 0.1 part by weight of a montanate ester wax (release agent 2), and hydro as an ion trapping agent The amount was 0.2 parts by weight of talcite (manufactured by Kyowa Chemical Industry Co., Ltd., DHT-4H) and 0.3 parts by weight of carbon black.
（実施例１０）
無機充填材の含有量を多くして、全体の配合を以下のようにした以外は実施例１と同様にした。
エポキシ樹脂として前記一般式（１）で表されるエポキシ樹脂１（ビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂：日本化薬（株）製、商品名ＮＣ３０００Ｐ、軟化点５８℃、エポキシ当量２７３、ｎ＝２．３）３．４重量部と、フェノール樹脂として前記一般式（２）で表されるビフェニレン骨格を有するフェノールアラルキル樹脂（明和化成（株）製、商品名ＭＥＨ−７８５１ＳＳ、軟化点６５℃、水酸基当量２０４、式（２）においてｎ＝１．６）２．３重量部と、硬化促進剤：トリフェニルホスフィンと１，４−ベンゾキノンとの付加物０．２重量部と、溶融球状シリカ（平均粒径３０μｍ）９３．０重量部と、シランカップリング剤（Ｃ）としてメルカプトシラン１：γ−メルカプトプロピルトリメトキシシラン（９９．９重量部）と酢酸（０．１重量部）の混合物（抽出水のｐＨ３．９）０．２重量部と、他のカップリング剤としてＮ−フェニル−γ−アミノプロピルトリメトキシシラン０．１重量部と、離型剤としてポリエチレン系ワックス（離型剤１）０．２重量部と、モンタン酸エステル系ワックス（離型剤２）０．１重量部と、イオントラップ剤としてハイドロタルサイト（協和化学工業（株）製、ＤＨＴ−４Ｈ）０．２重量部と、カーボンブラック０．３重量部とした。
(Example 10)
The same procedure as in Example 1 was carried out except that the content of the inorganic filler was increased and the overall formulation was as follows.
Epoxy resin 1 represented by the general formula (1) as an epoxy resin (phenol aralkyl type epoxy resin having a biphenylene skeleton: manufactured by Nippon Kayaku Co., Ltd., trade name NC3000P, softening point 58 ° C., epoxy equivalent 273, n = 2.3) A phenol aralkyl resin having 3.4 parts by weight and a biphenylene skeleton represented by the general formula (2) as a phenol resin (Maywa Kasei Co., Ltd., trade name: MEH-7851SS, softening point: 65 ° C., Hydroxyl equivalent 204, n = 1.6 in formula (2) 2.3 parts by weight, curing accelerator: 0.2 part by weight of adduct of triphenylphosphine and 1,4-benzoquinone, fused spherical silica ( 93.0 parts by weight of an average particle size of 30 μm) and mercaptosilane 1: γ-mercaptopropyltrimethoxysilane (silane) as the silane coupling agent (C) 99.9 parts by weight) and acetic acid (0.1 part by weight) (extracted water pH 3.9) 0.2 part by weight, and N-phenyl-γ-aminopropyltrimethoxysilane 0 as another coupling agent 0.1 part by weight, 0.2 part by weight of a polyethylene wax (release agent 1) as a release agent, 0.1 part by weight of a montanate ester wax (release agent 2), and hydrotal as an ion trapping agent 0.2 parts by weight of a site (DHT-4H manufactured by Kyowa Chemical Industry Co., Ltd.) and 0.3 parts by weight of carbon black were used.
（比較例１）
抽出水のｐＨが３．５〜４．７の範囲にあるシランカップリング剤（Ｃ）を用いずに、全体の配合を以下のようにした以外は実施例１と同様にした。
エポキシ樹脂として前記一般式（１）で表されるエポキシ樹脂１（ビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂：日本化薬（株）製、商品名ＮＣ３０００Ｐ、軟化点５８℃、エポキシ当量２７３、ｎ＝２．３）７．７重量部と、フェノール樹脂として前記一般式（２）で表されるビフェニレン骨格を有するフェノールアラルキル樹脂（明和化成（株）製、商品名ＭＥＨ−７８５１ＳＳ、軟化点６５℃、水酸基当量２０４、式（２）においてｎ＝１．６）５．２重量部と、硬化促進剤：トリフェニルホスフィンと１，４−ベンゾキノンとの付加物０．２重量部と、溶融球状シリカ（平均粒径３０μｍ）８６．０重量部と、他のカップリング剤としてＮ−フェニル−γ−アミノプロピルトリメトキシシラン０．１重量部と、離型剤としてポリエチレン系ワックス（離型剤１）０．２重量部と、モンタン酸エステル系ワックス（離型剤２）０．１重量部と、イオントラップ剤としてハイドロタルサイト（協和化学工業（株）製、ＤＨＴ−４Ｈ）０．２重量部と、カーボンブラック０．３重量部とした。
(Comparative Example 1)
The same procedure as in Example 1 was carried out except that the entire formulation was as follows without using the silane coupling agent (C) in which the pH of the extracted water was in the range of 3.5 to 4.7.
Epoxy resin 1 represented by the general formula (1) as an epoxy resin (phenol aralkyl type epoxy resin having a biphenylene skeleton: manufactured by Nippon Kayaku Co., Ltd., trade name NC3000P, softening point 58 ° C., epoxy equivalent 273, n = 2.3) 7.7 parts by weight and a phenol aralkyl resin having a biphenylene skeleton represented by the above general formula (2) as a phenol resin (Maywa Kasei Co., Ltd., trade name: MEH-7851SS, softening point: 65 ° C., Hydroxyl group equivalent 204, n = 1.6 in formula (2) 5.2 parts by weight, curing accelerator: 0.2 part by weight of adduct of triphenylphosphine and 1,4-benzoquinone, fused spherical silica ( (Average particle size 30 μm) 86.0 parts by weight, 0.1 parts by weight of N-phenyl-γ-aminopropyltrimethoxysilane as another coupling agent, mold release 0.2 parts by weight of a polyethylene wax (release agent 1) as an agent, 0.1 part by weight of a montanate ester wax (release agent 2), and hydrotalcite (Kyowa Chemical Industry Co., Ltd.) as an ion trap agent Made by DHT-4H) and 0.3 parts by weight of carbon black.
（比較例２）
シランカップリング剤（Ｃ）として以下のものを用いた以外は、実施例１と同様にした。
エポキシ樹脂として前記一般式（１）で表されるエポキシ樹脂１（ビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂：日本化薬（株）製、商品名ＮＣ３０００Ｐ、軟化点５８℃、エポキシ当量２７３、ｎ＝２．３）７．６重量部と、フェノール樹脂として前記一般式（２）で表されるビフェニレン骨格を有するフェノールアラルキル樹脂（明和化成（株）製、商品名ＭＥＨ−７８５１ＳＳ、軟化点６５℃、水酸基当量２０４、式（２）においてｎ＝１．６）５．１重量部と、硬化促進剤：トリフェニルホスフィンと１，４−ベンゾキノンとの付加物０．２重量部と、溶融球状シリカ（平均粒径３０μｍ）８６．０重量部と、シランカップリング剤（Ｃ）としてメルカプトシラン５：γ−メルカプトプロピルトリメトキシシラン（抽出水のｐＨ４．９）０．２重量部と、他のカップリング剤としてＮ−フェニル−γ−アミノプロピルトリメトキシシラン０．１重量部と、離型剤としてポリエチレン系ワックス（離型剤１）０．２重量部と、モンタン酸エステル系ワックス（離型剤２）０．１重量部と、イオントラップ剤としてハイドロタルサイト（協和化学工業（株）製、ＤＨＴ−４Ｈ）０．２重量部と、カーボンブラック０．３重量部とした。
(Comparative Example 2)
The procedure was the same as Example 1 except that the following silane coupling agent (C) was used.
Epoxy resin 1 represented by the general formula (1) as an epoxy resin (phenol aralkyl type epoxy resin having a biphenylene skeleton: manufactured by Nippon Kayaku Co., Ltd., trade name NC3000P, softening point 58 ° C., epoxy equivalent 273, n = 2.3) Phenol aralkyl resin having a biphenylene skeleton represented by the above general formula (2) as a phenol resin (made by Meiwa Kasei Co., Ltd., trade name: MEH-7851SS, softening point: 65 ° C., 2.3) Hydroxyl equivalent weight 204, n = 1.6 in formula (2) 5.1 parts by weight, curing accelerator: 0.2 part by weight of adduct of triphenylphosphine and 1,4-benzoquinone, fused spherical silica ( 86.0 parts by weight of an average particle size of 30 μm) and mercaptosilane 5: γ-mercaptopropyltrimethoxysilane (C) as the silane coupling agent (C) PH 4.9) 0.2 parts by weight of extracted water, 0.1 parts by weight of N-phenyl-γ-aminopropyltrimethoxysilane as another coupling agent, and polyethylene wax (release agent 1) as a release agent ) 0.2 parts by weight, 0.1 parts by weight of a montanic acid ester wax (release agent 2), and 0.2% by weight of hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd., DHT-4H) as an ion trapping agent Parts and carbon black 0.3 parts by weight.
（比較例３）
シランカップリング剤（Ｃ）として以下のものを用いた以外は、実施例１と同様にした。
エポキシ樹脂として前記一般式（１）で表されるエポキシ樹脂１（ビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂：日本化薬（株）製、商品名ＮＣ３０００Ｐ、軟化点５８℃、エポキシ当量２７３、ｎ＝２．３）７．６重量部と、フェノール樹脂として前記一般式（２）で表されるビフェニレン骨格を有するフェノールアラルキル樹脂（明和化成（株）製、商品名ＭＥＨ−７８５１ＳＳ、軟化点６５℃、水酸基当量２０４、式（２）においてｎ＝１．６）５．１重量部と、硬化促進剤：トリフェニルホスフィンと１，４−ベンゾキノンとの付加物０．２重量部と、溶融球状シリカ（平均粒径３０μｍ）８６．０重量部と、シランカップリング剤（Ｃ）としてメルカプトシラン６：γ−メルカプトプロピルトリメトキシシラン（９９．０重量部）と塩酸（１．０重量部）の混合物（抽出水のｐＨ２．９）０．２重量部と、他のカップリング剤としてＮ−フェニル−γ−アミノプロピルトリメトキシシラン０．１重量部と、離型剤としてポリエチレン系ワックス（離型剤１）０．２重量部と、モンタン酸エステル系ワックス（離型剤２）０．１重量部と、イオントラップ剤としてハイドロタルサイト（協和化学工業（株）製、ＤＨＴ−４Ｈ）０．２重量部と、カーボンブラック０．３重量部とした。
(Comparative Example 3)
The procedure was the same as Example 1 except that the following silane coupling agent (C) was used.
Epoxy resin 1 represented by the general formula (1) as an epoxy resin (phenol aralkyl type epoxy resin having a biphenylene skeleton: manufactured by Nippon Kayaku Co., Ltd., trade name NC3000P, softening point 58 ° C., epoxy equivalent 273, n = 2.3) Phenol aralkyl resin having a biphenylene skeleton represented by the above general formula (2) as a phenol resin (made by Meiwa Kasei Co., Ltd., trade name: MEH-7851SS, softening point: 65 ° C., 2.3) Hydroxyl equivalent weight 204, n = 1.6 in formula (2) 5.1 parts by weight, curing accelerator: 0.2 part by weight of adduct of triphenylphosphine and 1,4-benzoquinone, fused spherical silica ( 86.0 parts by weight of an average particle size of 30 μm) and mercaptosilane 6: γ-mercaptopropyltrimethoxysilane (C) as the silane coupling agent (C) 99.0 parts by weight) and hydrochloric acid (1.0 part by weight) (extracted water pH 2.9) 0.2 part by weight, and N-phenyl-γ-aminopropyltrimethoxysilane 0 as another coupling agent 0.1 part by weight, 0.2 part by weight of a polyethylene wax (release agent 1) as a release agent, 0.1 part by weight of a montanate ester wax (release agent 2), and hydrotal as an ion trapping agent 0.2 parts by weight of a site (DHT-4H manufactured by Kyowa Chemical Industry Co., Ltd.) and 0.3 parts by weight of carbon black were used.
各実施例および比較例で得られたエポキシ樹脂成形材料を用いて、以下の方法で評価した。結果を表１に示す。 Using the epoxy resin molding materials obtained in each Example and Comparative Example, evaluation was performed by the following methods. The results are shown in Table 1.
１．スパイラルフロー
低圧トランスファー成形機を用いて、ＥＭＭＩ−１−６６に準じたスパイラルフロー測定用金型に、金型温度１７５℃、注入圧力６．９ＭＰa、硬化時間１２０秒の条件でエポキシ樹脂組成物を注入し、流動長を測定した。単位をｃｍとした。
1. Spiral flow Using a low-pressure transfer molding machine, the epoxy resin composition was applied to a spiral flow measurement mold according to EMMI-1-66 under conditions of a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds. The flow length was measured. The unit was cm.
２．ゲートブレイク性
低圧トランスファー成形機を用いて、成形温度１７５℃、圧力８．３ＭＰａ、硬化時間１２０秒の条件で、８０ｐＱＦＰ（プレプレーティッド フレーム）を成形した直後に、ゲート部の樹脂を外した後の基板の色を目視で評価した。色が元の基板に近いほど良好であり、樹脂が残っていると封止材の色（通常はカーボンが含まれているために黒色）になる。各符号は、以下の通りである。
◎：樹脂残りが全く見られず、元の金属と区別できない状態。
○：薄く樹脂が残ってやや白く見える状態。
△：さらに樹脂が残って灰色に見える状態。
×：厚く樹脂が残って、ほぼ黒色に見える状態。
2. Gate breakability After removing 80pQFP (pre-plated frame) using a low-pressure transfer molding machine under conditions of a molding temperature of 175 ° C, a pressure of 8.3 MPa, and a curing time of 120 seconds. The color of the substrate was visually evaluated. The closer the color is to the original substrate, the better. The remaining resin becomes the color of the sealing material (usually black because carbon is contained). Each code is as follows.
A: No resin residue is seen and cannot be distinguished from the original metal.
○: A state in which the resin remains thin and looks slightly white.
(Triangle | delta): The state which resin remains and looks gray.
X: A state where the resin remains thick and appears almost black.
３．耐湿信頼性
１６ピンＤＩＰ（Dual Inline Package）の半導体パッケージを、１２５℃、相対湿度１００％の水蒸気中で、２０Ｖの電圧を、１６ピンＤＩＰに印加し、断線不良を調べた。１５個のパッケージのうち、８個以上に不良が出るまでの時間を、不良時間とした。単位は時間とした。なお、測定時間は、最長で５００時間とし、その時点で不良パッケージ数が８個未満であったものは、不良時間を５００時間以上と示した。不良時間が長いほど、耐湿信頼性に優れる。
3. Moisture resistance reliability A 16-pin DIP (Dual Inline Package) semiconductor package was applied to a 16-pin DIP with a voltage of 20 V in water vapor at 125 ° C. and a relative humidity of 100%, and the disconnection failure was examined. Of the 15 packages, the time until 8 or more defects were detected was defined as the defect time. The unit was time. Note that the measurement time was 500 hours at the longest, and when the number of defective packages was less than 8 at that time, the defective time was 500 hours or more. The longer the defect time, the better the moisture resistance reliability.
４．アセトン不溶分
最大径４ｍｍ以下に篩分したものを約３００ｇ精秤したものに対し、アセトン２００〜５００ｇを混合し振とう機にて２０分間振とうさせた後、溶解液をＪＩＳ篩い６５メッシュ（目開き２１２μｍ）に通し、篩い上の残存物の風乾サンプル重量を元の３００ｇで除した値を、アセトン不溶分とした。アセトン不溶分が多いと、成形封止時に充填不良が発生しやすくなる傾向があり、この値は小さいほど良い。単位は％。
4). Acetone-insoluble matter About 300 g of a sieve that has been sieved to a maximum diameter of 4 mm or less, 200-500 g of acetone is mixed and shaken for 20 minutes with a shaker, and then the solution is JIS sieve 65 mesh ( The value obtained by dividing the air-dried sample weight of the residue on the sieve by the original 300 g was passed through the mesh (212 μm), and was defined as acetone insoluble matter. When there is much acetone insoluble content, there exists a tendency which a filling defect tends to generate | occur | produce at the time of shaping | molding sealing, and this value is so good that it is small. Units%.
５．耐半田性
低圧トランスファー成形機を用いて、成形温度１７５℃、圧力８．３ＭＰａ、硬化時間１２０秒の条件で、８０ｐＱＦＰ（Ｃｕフレーム、チップサイズ６．０ｍｍ×６．０ｍｍ）を成形し、アフターベークとして１７５℃、８時間加熱処理した後、８５℃、相対湿度８５％で１２０時間の加湿処理を行った後、２６０℃のＩＲリフロー処理をした。パッケージ内部の剥離とクラックを超音波探傷機で確認し、剥離、クラックのいずれか一方でもあったものを不良とした。評価した１０個のパッケージ中の不良パッケージ数を示す。
5. Solder resistance Using a low-pressure transfer molding machine, 80pQFP (Cu frame, chip size 6.0 mm x 6.0 mm) was molded after baking at a molding temperature of 175 ° C, a pressure of 8.3 MPa, and a curing time of 120 seconds. After heat treatment at 175 ° C. for 8 hours, a humidification treatment was performed at 85 ° C. and a relative humidity of 85% for 120 hours, followed by an IR reflow treatment at 260 ° C. Peeling and cracks inside the package were confirmed with an ultrasonic flaw detector, and those that had either peeling or cracking were considered defective. The number of defective packages among the 10 packages evaluated is shown.
表１から明らかなように実施例１〜１０で得られたエポキシ成形材料を用いて成形した半導体パッケージは、ゲートブレイク性および耐半田性のバランスに優れていた。
また、実施例２、４、５および７ないし９で得られたエポキシ成形材料は、スパイラルフローにも優れており、流動性に優れることが示された。
また、実施例１、２、４、６ないし８および１０で得られたエポキシ成形材料は、アセトン不溶分が無く、成形時の充填不良が発生しにくいことが示唆された。
上記のように本発明に従う実施例はいずれも、良好な保存安定性を有し、半導体素子等の封止成形時において良好な流動性、硬化性を有し、かつ無鉛半田に対応する高温の半田処理によっても剥離やクラックが発生しない良好な耐半田性を有する半導体封止用エポキシ樹脂組成物が得られるものである。
As is apparent from Table 1, the semiconductor package molded using the epoxy molding material obtained in Examples 1 to 10 was excellent in the balance between gate breakability and solder resistance.
In addition, the epoxy molding materials obtained in Examples 2, 4, 5 and 7 to 9 were also excellent in spiral flow and were shown to be excellent in fluidity.
In addition, it was suggested that the epoxy molding materials obtained in Examples 1, 2, 4, 6 to 8 and 10 have no acetone insoluble content and hardly cause poor filling during molding.
As described above, all of the examples according to the present invention have good storage stability, have good fluidity and curability at the time of sealing molding of semiconductor elements and the like, and have a high temperature corresponding to lead-free solder. An epoxy resin composition for semiconductor encapsulation having good solder resistance that does not cause peeling or cracking even by soldering treatment can be obtained.
本発明に従うと、半導体素子等の封止成形時において良好な流動性、硬化性を有し、かつ無鉛半田に対応する高温の半田処理によっても剥離やクラックが発生しない良好な耐半田性を有し、成形直後のゲートブレイク性の良好な半導体封止用エポキシ樹脂組成物が得られるので、特に表面実装型の半導体装置の製造用として好適に用いることができる。 According to the present invention, it has good fluidity and curability during sealing molding of semiconductor elements and the like, and has good solder resistance that does not cause peeling or cracking even with high-temperature solder processing corresponding to lead-free solder. And since the epoxy resin composition for semiconductor sealing with the favorable gate break property immediately after shaping | molding is obtained, it can use suitably especially for manufacture of a surface mount type semiconductor device.
Claims (7)
（Ａ）エポキシ樹脂、（Ｂ）硬化剤、（Ｃ）シランカップリング剤および（Ｄ）無機充填材を含み、
前記（Ｃ）シランカップリング剤はシランカップリング剤と酸性化合物が予め混合されているものであり、含有する酸性化合物の量を前記シランカップリング剤（Ｃ）全体の０．００５重量％以上、１重量％以下に制御することにより、前記（Ｃ）シランカップリング剤を抽出処理した際の抽出水のｐＨが３．５以上３．９以下の範囲になるように調製されているものである
ことを特徴とするエポキシ樹脂組成物。 An epoxy resin composition used for semiconductor encapsulation,
(A) an epoxy resin, (B) a curing agent, (C) a silane coupling agent, and (D) an inorganic filler,
The (C) silane coupling agent is a mixture of a silane coupling agent and an acidic compound in advance, and the amount of the acidic compound contained is 0.005% by weight or more of the entire silane coupling agent (C), by controlling the 1 wt% or less, wherein (C) Monodea the pH of the extraction water when the extraction process the silane coupling agent is prepared such that from 3.5 to 3.9 or less that <br/> epoxy resin composition, characterized by.
A semiconductor device, wherein a semiconductor element is sealed with a cured product of the epoxy resin molding material according to claim 6.
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