JP4451129B2 - Epoxy resin composition - Google Patents
Epoxy resin composition Download PDFInfo
- Publication number
- JP4451129B2 JP4451129B2 JP2003416443A JP2003416443A JP4451129B2 JP 4451129 B2 JP4451129 B2 JP 4451129B2 JP 2003416443 A JP2003416443 A JP 2003416443A JP 2003416443 A JP2003416443 A JP 2003416443A JP 4451129 B2 JP4451129 B2 JP 4451129B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- group
- resin composition
- general formula
- phenol
- 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 - Lifetime
Links
- 229920000647 polyepoxide Polymers 0.000 title claims description 131
- 239000003822 epoxy resin Substances 0.000 title claims description 130
- 239000000203 mixture Substances 0.000 title claims description 57
- 239000005011 phenolic resin Substances 0.000 claims description 33
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000004593 Epoxy Substances 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- -1 full Eniru group Chemical group 0.000 claims description 20
- 239000003063 flame retardant Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001463 antimony compounds Chemical class 0.000 claims description 11
- 150000002366 halogen compounds Chemical class 0.000 claims description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 63
- 229920005989 resin Polymers 0.000 description 42
- 239000011347 resin Substances 0.000 description 42
- 229920003986 novolac Polymers 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 16
- 238000002156 mixing Methods 0.000 description 14
- 150000002989 phenols Chemical class 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 10
- 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 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000155 melt Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 239000012778 molding material Substances 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- 235000013824 polyphenols Nutrition 0.000 description 6
- 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 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
- 238000005538 encapsulation Methods 0.000 description 5
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 4
- 229910000410 antimony oxide Inorganic materials 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 4
- 150000003003 phosphines Chemical class 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- OIAUFEASXQPCFE-UHFFFAOYSA-N formaldehyde;1,3-xylene Chemical compound O=C.CC1=CC=CC(C)=C1 OIAUFEASXQPCFE-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- HYNDYAQJODYUGF-UHFFFAOYSA-N 1,2,3,4,5,7,8,9-octahydropyrido[1,2-a][1,4]diazepine Chemical compound C1NCCCN2CCCC=C21 HYNDYAQJODYUGF-UHFFFAOYSA-N 0.000 description 1
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- YTIPFUNXZCIVBV-UHFFFAOYSA-N 1-butyl-1,2,3,3-tetramethylguanidine Chemical compound CCCCN(C)C(=NC)N(C)C YTIPFUNXZCIVBV-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- ZUZAETTVAMCNTO-UHFFFAOYSA-N 2,3-dibutylbenzene-1,4-diol Chemical compound CCCCC1=C(O)C=CC(O)=C1CCCC ZUZAETTVAMCNTO-UHFFFAOYSA-N 0.000 description 1
- HIKRJHFHGKZKRI-UHFFFAOYSA-N 2,4,6-trimethylbenzaldehyde Chemical compound CC1=CC(C)=C(C=O)C(C)=C1 HIKRJHFHGKZKRI-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- VSYYOSUMBQANGJ-UHFFFAOYSA-N 2-(aminomethyl)-3,4-dimethylphenol Chemical compound CC1=CC=C(O)C(CN)=C1C VSYYOSUMBQANGJ-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
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- QCGVOGKSFYKSDS-UHFFFAOYSA-N 2-ethyl-5-methyl-1h-imidazole;2-undecyl-1h-imidazole Chemical compound CCC1=NC=C(C)N1.CCCCCCCCCCCC1=NC=CN1 QCGVOGKSFYKSDS-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-O 2-methyl-1h-imidazol-3-ium Chemical compound CC=1NC=C[NH+]=1 LXBGSDVWAMZHDD-UHFFFAOYSA-O 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 description 1
- WINNTJDLRWGRLM-UHFFFAOYSA-N 3,4,5-trihydroxy-6-methoxybenzene-1,2-dicarboperoxoic acid Chemical compound COC1=C(C(C(=O)OO)=C(C(=C1O)O)O)C(=O)OO WINNTJDLRWGRLM-UHFFFAOYSA-N 0.000 description 1
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 1
- YICAEXQYKBMDNH-UHFFFAOYSA-N 3-[bis(3-hydroxypropyl)phosphanyl]propan-1-ol Chemical compound OCCCP(CCCO)CCCO YICAEXQYKBMDNH-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 244000249914 Hemigraphis reptans Species 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 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
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- BULOCEWDRJUMEL-UHFFFAOYSA-N benzene formaldehyde Chemical compound C=O.C1=CC=CC=C1.C=O BULOCEWDRJUMEL-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000185 dioxinlike effect Effects 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
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SLAFUPJSGFVWPP-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SLAFUPJSGFVWPP-UHFFFAOYSA-M 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- FVKGRHSPCZORQC-UHFFFAOYSA-N formaldehyde;toluene Chemical compound O=C.CC1=CC=CC=C1 FVKGRHSPCZORQC-UHFFFAOYSA-N 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 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
- 150000007974 melamines Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- PRQMIJVEENXPNQ-UHFFFAOYSA-N n,n-dimethyl-3,4-dihydro-2h-pyrrol-5-amine Chemical compound CN(C)C1=NCCC1 PRQMIJVEENXPNQ-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000011160 research Methods 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-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
- PADOFXALCIVUFS-UHFFFAOYSA-N tris(2,3-dimethoxyphenyl)phosphane Chemical compound COC1=CC=CC(P(C=2C(=C(OC)C=CC=2)OC)C=2C(=C(OC)C=CC=2)OC)=C1OC PADOFXALCIVUFS-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Description
本発明は、エポキシ樹脂組成物に関する。この組成物は、難燃付与成分としてハロゲン化合物、アンチモン化合物を添加することなしに、又は少量添加するだけで優れた難燃性を有し、かつ低吸湿性、密着性に優れる硬化物を与えることができ、特に半導体封止の用途に有用である。 The present invention relates to an epoxy resin composition. This composition has excellent flame retardancy without adding a halogen compound or antimony compound as a flame retardant imparting component, or by adding a small amount, and gives a cured product having excellent low moisture absorption and adhesion. Particularly useful for semiconductor encapsulation applications.
半導体素子の封止には、信頼性、生産性及びコストの面から、エポキシ樹脂組成物が広く用いられている。一般のプラスチック材料と同じく、これら組成物にも難燃性が要求されており、そのために主成分とは別に難燃付与成分として、テトラブロモビスフェノールＡ型エポキシ樹脂やブロム化フェノールノボラック型エポキシ樹脂などのブロム化エポキシ樹脂と酸化アンチモンが組み合わせて配合されている。 For sealing semiconductor elements, epoxy resin compositions are widely used in terms of reliability, productivity, and cost. Like general plastic materials, these compositions are also required to be flame retardant. For this reason, as a flame retardant component apart from the main component, tetrabromobisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, etc. This is a combination of brominated epoxy resin and antimony oxide.
近年、環境保護の観点からダイオキシン類似化合物を発生する危惧のある含ハロゲン化合物や毒性の高いアンチモン化合物の使用を量規制する動きが高まっており、半導体封止用組成物に関しては、上述のブロム化エポキシ樹脂をはじめとするハロゲン化合物や酸化アンチモンを使用することなしに難燃性を達成させる技術が検討されるようになった。たとえば、赤リンを配合する方法（特許文献１）、リン酸エステル化合物を配合する方法（特許文献２）、ホスファゼン化合物を配合する方法（特許文献３）、金属水酸化物を配合する方法（特許文献４）などのハロゲン化合物や酸化アンチモンに代わる難燃剤を配合する手法及び充填剤の配合割合を高くする手法（特許文献５）などが検討されている。 In recent years, from the viewpoint of environmental protection, there is an increasing movement to regulate the use of halogen-containing compounds that are likely to generate dioxin-like compounds and highly toxic antimony compounds. Techniques for achieving flame retardancy without using epoxy compounds and other halogen compounds and antimony oxide have been studied. For example, a method of blending red phosphorus (Patent Document 1), a method of blending a phosphate ester compound (Patent Document 2), a method of blending a phosphazene compound (Patent Document 3), a method of blending a metal hydroxide (Patent Document 3) A method of blending a halogen compound such as literature 4) or a flame retardant in place of antimony oxide and a method of increasing the blending ratio of the filler (Patent Literature 5) have been studied.
しかし、半導体封止用エポキシ組成物に赤リンを用いた場合は耐湿信頼性の低下や赤リンの打撃発火性に起因する安全性の問題、燐酸エステルやホスファゼン化合物を用いた場合は可塑化による成形性の低下や耐湿信頼性の低下の問題、金属水酸化物を用いた場合や充填剤の配合割合を高くした場合は流動性の低下の問題がそれぞれにあり、いずれの場合もブロム化エポキシ樹脂と酸化アンチモンを併用した封止用エポキシ樹脂組成物と同等の成形性、信頼性を得るに至っていない。 However, when red phosphorus is used in the epoxy composition for semiconductor encapsulation, it is caused by deterioration of moisture resistance reliability and safety problems due to red phosphorus impact ignition, and plasticization when phosphate ester or phosphazene compound is used. There is a problem of deterioration of moldability and moisture resistance reliability, and there is a problem of decrease in fluidity when using metal hydroxide or when the blending ratio of the filler is increased. In either case, brominated epoxy Moldability and reliability equivalent to those of an epoxy resin composition for sealing using a combination of a resin and antimony oxide have not been obtained.
一方で、高度化した実装方式に対応するため、封止用エポキシ樹脂組成物にはなお一層の成形性、耐ハンダクラック性が要求されており、これらを達成するためには、組成物の速硬化性、流動性、低熱線膨張化、低吸湿性及び密着性等にも十分配慮する必要がある。 On the other hand, in order to cope with advanced mounting methods, the epoxy resin composition for sealing is required to have further moldability and solder crack resistance. To achieve these, the speed of the composition is required. It is necessary to give sufficient consideration to curability, fluidity, low thermal linear expansion, low hygroscopicity, adhesion, and the like.
これらの要求を満足させるために、テトラメチルビフェノール型エポキシ樹脂とフェノールアラルキル樹脂など架橋間点の長い硬化物を与えるフェノール樹脂からなる組成物を用い、吸湿性及び低応力性を改良すること（特許文献６）、吸湿性を改善するためにジシクロペンタジエンフェノールを原料とするエポキシ樹脂を主成分に用いること（特許文献７）、耐湿性と耐熱性のバランスを取るためにオルソ−クレゾールとベンズアルデヒドの共縮合ノボラック樹脂のエポキシ物を主成分として用いること（特許文献８）など、種々の検討が提案されている。 In order to satisfy these requirements, a composition comprising a phenol resin that gives a cured product having a long cross-linking point such as a tetramethylbiphenol type epoxy resin and a phenol aralkyl resin is used to improve hygroscopicity and low stress (patents). Document 6), using epoxy resin based on dicyclopentadienephenol as the main component in order to improve hygroscopicity (Patent Document 7), ortho-cresol and benzaldehyde to balance moisture resistance and heat resistance. Various studies have been proposed such as using an epoxy compound of a co-condensed novolac resin as a main component (Patent Document 8).
また、芳香族炭化水素ホルムアルデヒド樹脂変性ノボラック型エポキシ樹脂を用いたものでは、通常のエポキシ樹脂と芳香族炭化水素ホルムアルデヒド樹脂変性ノボラック型エポキシ樹脂の組成物を用い、耐熱性、接着性を改良すること（特許文献９）、芳香族炭化水素樹脂変性ノボラックエポキシ樹脂と多官能性シアン酸エステル系の組成物を用い、耐熱性を改良すること（特許文献１０）、（特許文献１１）などが提案されている。 In addition, in the case of using an aromatic hydrocarbon formaldehyde resin-modified novolac type epoxy resin, use a composition of a normal epoxy resin and an aromatic hydrocarbon formaldehyde resin-modified novolak type epoxy resin to improve heat resistance and adhesion. (Patent Document 9), using an aromatic hydrocarbon resin-modified novolak epoxy resin and a polyfunctional cyanate ester-based composition to improve heat resistance (Patent Document 10), (Patent Document 11), etc. ing.
しかし、どの提案も環境に配慮した提案とは言えず、難燃剤としてハロゲン化合物やアンチモン化合物を用いないと十分な難燃性を達成できない。
本発明は、種々の用途に使用でき、難燃付与成分としてハロゲン化合物、アンチモン化合物を添加することなしに、又は少量添加するだけで優れた難燃性を有し、かつ低吸湿性、密着性に優れた硬化物を与えるエポキシ樹脂組成物を提供しようとするものである。 The present invention can be used in various applications, has excellent flame retardancy without adding a halogen compound or antimony compound as a flame retardant imparting component, or only by adding a small amount, and has low moisture absorption and adhesion. It is intended to provide an epoxy resin composition that gives an excellent cured product.
本発明者等は、前記の課題を解決するために種々研究を重ねた結果、エポキシ樹脂として特定の芳香族炭化水素ホルムアルデヒド樹脂変性ノボラック型エポキシ樹脂を製造し、該エポキシ樹脂を、硬化剤として特定の芳香族基を多く含むフェノール樹脂を用いることによりその目的を達成できたのである。本発明は、以下の各発明を包含する。 As a result of repeated researches to solve the above-mentioned problems, the present inventors manufactured a specific aromatic hydrocarbon formaldehyde resin-modified novolak type epoxy resin as an epoxy resin , and specified the epoxy resin as a curing agent. The purpose could be achieved by using a phenol resin containing a large amount of aromatic groups. The present invention includes the following inventions.
（１）（Ａ）エポキシ樹脂、（Ｂ）フェノール系硬化剤、及び（Ｃ）硬化促進剤を必須成分とし、（Ａ）エポキシ樹脂が下記一般式（１）で表わされるフェノール樹脂とエピハロヒドリンを反応させることにより得られる、エポキシ当量が１５０〜３３０ｇ／ｅｑ．、且つ一般式（１）で表わされるフェノール樹脂の水酸基当量から計算した理論値の１．００倍〜１．５０倍であるエポキシ樹脂を含有してなるエポキシ樹脂組成物。
（２）前記（Ｂ）フェノール系硬化剤が前記一般式（１）又は下記一般式（２）で表わされるフェノール樹脂であることを特徴とする（１）項記載のエポキシ樹脂組成物。
（３）前記（Ａ）エポキシ樹脂として、下記一般式（６）で表わされる結晶性エポキシ樹脂、又は前記一般式（２）で表わされるフェノール樹脂とエピハロヒドリンを反応させることにより得られるエポキシ樹脂を含有してなる（１）項又は（２）項に記載のエポキシ樹脂組成物。
（４）前記一般式(１)で表わされるフェノール樹脂の遊離フェノールが３質量％以下であることを特徴とする（１）項〜（３）項のいずれか１項に記載のエポキシ樹脂組成物。 ( 4 ) The epoxy resin composition according to any one of items (1) to ( 3 ), wherein a free phenol of the phenol resin represented by the general formula (1) is 3% by mass or less. .
（５）前記（Ａ）エポキシ樹脂、（Ｂ）硬化剤の１５０℃における混合溶融粘度が０．９Ｐａ・ｓ以下である（１）項〜（４）項のいずれか１項に記載のエポキシ樹脂組成物。 ( 5 ) The epoxy resin according to any one of (1) to ( 4 ), wherein the (A) epoxy resin and (B) the curing agent have a mixed melt viscosity at 150 ° C. of 0.9 Pa · s or less. Composition.
（６）前記一般式（１）で表わされるフェノール樹脂とエピハロヒドリンを反応させることにより得られるエポキシ樹脂がエポキシ樹脂全体の７０質量％より多いことを特徴とする（１）項〜（５）項のいずれか１項に記載のエポキシ樹脂組成物。 (6) the general formula (1) an epoxy resin obtained by reacting a phenolic resin with an epihalohydrin represented by is equal to or greater than 70% by weight of the total epoxy resin (1) to (5) of claim The epoxy resin composition according to any one of the above.
（７）無機充填材として、破砕型及び／又は球状の、溶融及び／又は結晶シリカ粉末を組成物の７０〜９５質量％配合してなる（１）項〜（６）項のいずれか１項に記載のエポキシ樹脂組成物。 ( 7 ) Any one of items (1) to ( 6 ), wherein 70 to 95% by mass of the composition of crushed and / or spherical, fused and / or crystalline silica powder is blended as the inorganic filler. The epoxy resin composition described in 1.
（８）難燃付与成分としてハロゲン化合物及び／又はアンチモン化合物を含まず、その硬化物がＵＬ−９４規格のＶ−０を満足する難燃性を有する（１）項〜（７）項のいずれか１項に記載のエポキシ樹脂組成物。 ( 8 ) Any of the items (1) to ( 7 ), which does not contain a halogen compound and / or an antimony compound as a flame retardant imparting component, and the cured product has flame retardancy satisfying V-0 of UL-94 standard. The epoxy resin composition according to claim 1.
（９）前記（７）項又は（８）項のいずれか１項に記載のエポキシ樹脂組成物を含有する硬化性樹脂組成物を硬化してなるエポキシ樹脂硬化物。 ( 9 ) An epoxy resin cured product obtained by curing a curable resin composition containing the epoxy resin composition according to any one of ( 7 ) or ( 8 ).
本発明のエポキシ樹脂組成物は、難燃付与成分としてハロゲン化合物、アンチモン化合物を添加することなしに、又は少量添加するだけで優れた難燃性を有し、かつ低吸湿性、密着性に優れる硬化物を与えるので、電気電子分野、特に半導体封止の用途に有用である。 The epoxy resin composition of the present invention has excellent flame retardancy without adding a halogen compound or antimony compound as a flame retardant imparting component, or just by adding a small amount, and is excellent in low moisture absorption and adhesion. Since it gives a cured product, it is useful in the electrical and electronic field, particularly in semiconductor encapsulation applications.
前記一般式（１）で表わされる化合物は、芳香族炭化水素ホルムアルデヒド樹脂、フェノール類及びホルムアルデヒドを反応させることによって得られる。芳香族炭化水素ホルムアルデヒド樹脂の具体例としては、メシチレン-ホルムアルデヒド樹脂、キシレン-ホルムアルデヒド樹脂、トルエン-ホルムアルデヒド樹脂、ベンゼン-ホルムアルデヒド樹脂などが挙げられる。フェノール類としてはフェノール、クレゾール、キシレノールなどが挙げられる。 The compound represented by the general formula (1) can be obtained by reacting an aromatic hydrocarbon formaldehyde resin, phenols and formaldehyde. Specific examples of the aromatic hydrocarbon formaldehyde resin include mesitylene-formaldehyde resin, xylene-formaldehyde resin, toluene-formaldehyde resin, and benzene-formaldehyde resin. Phenols include phenol, cresol, xylenol and the like.
一般式（１）で表わされる化合物の製造方法は、前述した芳香族炭化水素ホルムアルデヒド樹脂とフェノールとを硫酸、塩酸、硝酸などの無機酸、トルエンスルホン酸、キシレンスルホン酸、シュウ酸などの酸性触媒により反応させた後、更にその酸性触媒を使用するか或いは酢酸カルシウム、酢酸マグネシウム、酢酸亜鉛、その他有機酸金属塩、酸化亜鉛などの中性触媒を使用して、ホルムアルデヒドと反応させる方法が挙げられる。また、フェノール類とホルムアルデヒドとを反応させた後、芳香族炭化水素ホルムアルデヒドと反応させる方法や芳香族炭化水素ホルムアルデヒド樹脂、フェノール類、及びホルムアルデヒドを同時に反応させる方法でも実施できる。 The method for producing the compound represented by the general formula (1) comprises the above-described aromatic hydrocarbon formaldehyde resin and phenol, an inorganic acid such as sulfuric acid, hydrochloric acid or nitric acid, an acidic catalyst such as toluenesulfonic acid, xylenesulfonic acid or oxalic acid. After the reaction, a method in which the acid catalyst is further used, or a neutral catalyst such as calcium acetate, magnesium acetate, zinc acetate, other organic acid metal salt, zinc oxide or the like is used to react with formaldehyde. . Moreover, after reacting phenols and formaldehyde, it can also implement by the method of reacting with aromatic hydrocarbon formaldehyde, or the method of reacting aromatic hydrocarbon formaldehyde resin, phenols, and formaldehyde simultaneously.
このようにして得られる一般式（１）で表わされる化合物は、この後エポキシ化したものの品質性状を考えると、各成分の種類、使用割合等により変化するが、水酸基当量が１００〜２７０ｇ／ｅｑ．、好ましくは１２０〜２４０ｇ／ｅｑ．、より好ましくは１４０〜２２０ｇ／ｅｑ．、１５０℃の溶融粘度が１．１Ｐａ・ｓ以下、好ましくは０．９Ｐａ・ｓ以下、より好ましくは０．７Ｐａ・ｓ以下、軟化点が７０〜１６０℃、好ましくは８０〜１３０℃、より好ましくは８０〜１００℃、となるよう各種条件等を調整することが好ましい。 The compound represented by the general formula (1) thus obtained varies depending on the type of each component, the use ratio, etc. in view of the quality properties of the epoxidized product, but the hydroxyl group equivalent is 100 to 270 g / eq. . , Preferably 120 to 240 g / eq. , More preferably 140 to 220 g / eq. The melt viscosity at 150 ° C. is 1.1 Pa · s or less, preferably 0.9 Pa · s or less, more preferably 0.7 Pa · s or less, and the softening point is 70 to 160 ° C., preferably 80 to 130 ° C., more preferably. It is preferable to adjust various conditions so that the temperature is 80 to 100 ° C.
また、一般式（１）のフェノール樹脂に含まれる遊離フェノールは３質量％以下、好ましくは２質量％以下、より好ましくは１質量％以下が好ましい。遊離フェノールが多すぎるとエポキシ樹脂組成物の硬化物の耐熱性が低下するだけでなく、高温での取り扱い時の作業環境の悪化にもつながる。
水酸基当量はＪＩＳ Ｋ００７０、軟化点はＪＩＳ Ｋ７２３４、遊離フェノールはＧＣ法にて測定した。
Moreover, the free phenol contained in the phenol resin of the general formula (1) is 3% by mass or less, preferably 2% by mass or less, more preferably 1% by mass or less. If there is too much free phenol, not only will the heat resistance of the cured product of the epoxy resin composition be reduced, but it will also lead to a deterioration of the working environment during handling at high temperatures.
The hydroxyl equivalent was measured by JIS K0070, the softening point was measured by JIS K7234, and the free phenol was measured by the GC method.
一般式（１）で表わされる化合物とエピハロヒドリンの反応によって得られるエポキシ樹脂は公知の方法によって製造することができる。代表的な例を以下に詳述する。まず、フェノール性水酸基１モル当たり３〜２０モルに相当する量のエピハロヒドリンに溶解させて均一な溶液とする。ついで、その溶液を撹拌しながら、これにフェノール性水酸基１モル当たり０．９〜２．０モル量のアルカリ金属水酸化物を固体又は水溶液で加えて反応させる．この反応は、常圧下又は減圧下で行わせることができ、反応温度は通常、常圧下の反応の場合は３０〜１５０℃であり、減圧下の反応の場合は３０〜８０℃である。反応は必要に応じて所定の温度を保持しながら反応液を共沸させ、揮発する蒸気を冷却して得られた凝縮液を油／水分離し、水分を除いた油分を反応系へ戻す方法により脱水する。アルカリ金属水酸化物の添加は、急激な反応を抑えるために、１〜８時間かけて少量ずつを断続的もしくは連続的に添加する。その全反応時間は通常、１〜１０時間である。 The epoxy resin obtained by the reaction of the compound represented by the general formula (1) and epihalohydrin can be produced by a known method. Representative examples are described in detail below. First, it is dissolved in an amount of epihalohydrin corresponding to 3 to 20 mol per mol of phenolic hydroxyl group to obtain a uniform solution. Then, while stirring the solution, 0.9 to 2.0 moles of alkali metal hydroxide per mole of phenolic hydroxyl group is added as a solid or an aqueous solution to react. This reaction can be carried out under normal pressure or reduced pressure, and the reaction temperature is usually 30 to 150 ° C. for a reaction under normal pressure and 30 to 80 ° C. for a reaction under reduced pressure. In the reaction, the reaction liquid is azeotroped while maintaining a predetermined temperature as required, the condensed liquid obtained by cooling the vaporized vapor is separated into oil / water, and the oil component excluding moisture is returned to the reaction system. To dehydrate. Addition of the alkali metal hydroxide is intermittently or continuously added little by little over 1 to 8 hours in order to suppress a rapid reaction. The total reaction time is usually 1 to 10 hours.
反応終了後、不溶性の副生塩を濾別して除くか、水洗により除去した後、未反応のエピハロヒドリンを減圧留去して除くと、目的のエポキシ樹脂が得られる。この反応におけるエピハロヒドリンとしては、通常、エピクロルヒドリン又はエピブロモヒドリンが用いられる。アルカリ金属水酸化物としては通常、水酸化ナトリウム又は水酸化カリウムが用いられる。 After completion of the reaction, the insoluble by-product salt is removed by filtration or removed by washing with water, and then the unreacted epihalohydrin is removed by distillation under reduced pressure to obtain the desired epoxy resin. As epihalohydrin in this reaction, epichlorohydrin or epibromohydrin is usually used. As the alkali metal hydroxide, sodium hydroxide or potassium hydroxide is usually used.
また、この反応においては、テトラメチルアンモニウムクロリド、テトラエチルアンモニウムブロミドなどの第四級アンモニウム塩；ベンジルジメチルアミン、２，４，６−トリス（ジメチルアミノメチル）フェノールなどの第三級アミン；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などのイミダゾール類；エチルトリフェニルホスホニウムアイオダイドなどのホスホニウム塩；トリフェニルホスフィンなどのホスフィン類等の触媒を用いても良い。 In this reaction, quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide; tertiary amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; 2-ethyl Catalysts such as imidazoles such as -4-methylimidazole and 2-phenylimidazole; phosphonium salts such as ethyltriphenylphosphonium iodide; phosphines such as triphenylphosphine may be used.
さらに、この反応においては、エタノール、イソプロピルアルコールなどのアルコール類；アセトン、メチルエチルケトンなどのケトン類；ジオキサン、エチレングリコールジメチルエーテルなどのエーテル類；メトキシプロパノールなどのグリコールエーテル類；ジメチルスルホキシド、ジメチルホルムアミドなどの非プロトン性極性溶媒等の不活性な有機溶媒を使用しても良い。 Further, in this reaction, alcohols such as ethanol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and ethylene glycol dimethyl ether; glycol ethers such as methoxypropanol; non-dimethyls such as dimethyl sulfoxide and dimethylformamide An inert organic solvent such as a protic polar solvent may be used.
さらに、上記のようにして得られたエポキシ樹脂の可鹸化ハロゲン量が多すぎる場合は、再処理して十分に可鹸化ハロゲン量が低下した精製エポキシ樹脂を得ることができる。つまり、その粗製エポキシ樹脂を、イソプロピルアルコール、メチルエチルケトン、メチルイソブチルケトン、トルエン、キシレン、ジオキサン、メトキシプロパノール、ジメチルスルホキシドなどの不活性な有機溶媒に再溶解しアルカリ金属水酸化物を固体又は水溶液で加えて約３０〜１２０℃の温度で０．５〜８時間再閉環反応を行った後、水洗等の方法で過剰のアルカリ金属水酸化物や副性塩を除去し、さらに有機溶媒を減圧留去して除くと、精製されたエポキシ樹脂が得られる。 Furthermore, when the amount of saponifiable halogen in the epoxy resin obtained as described above is too large, a purified epoxy resin having a sufficiently reduced amount of saponifiable halogen can be obtained by reprocessing. That is, the crude epoxy resin is redissolved in an inert organic solvent such as isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dioxane, methoxypropanol, dimethyl sulfoxide, and the alkali metal hydroxide is added as a solid or aqueous solution. After re-ringing reaction at a temperature of about 30 to 120 ° C. for 0.5 to 8 hours, excess alkali metal hydroxide and secondary salts are removed by a method such as washing with water, and the organic solvent is distilled off under reduced pressure. When removed, a purified epoxy resin is obtained.
以上のようにして製造される一般式（１）とエピハロヒドリンの反応によって得られるエポキシ樹脂の品質性状は、各成分の種類、使用割合等により変化するが、エポキシ当量が１５０〜３３０ｇ／ｅｑ．、好ましくは１８０〜３００ｇ／ｅｑ．、より好ましくは２００〜２８０ｇ／ｅｑ．、１５０℃の溶融粘度が０．９Ｐａ・ｓ以下、好ましくは０．７Ｐａ・ｓ以下、より好ましくは０．５Ｐａ・ｓ以下、軟化点が５０〜１２０℃、好ましくは６０〜１１０℃、より好ましくは６２〜１００℃、加水分解性ハロゲンが１０００ｐｐｍ以下、好ましくは８００ｐｐｍ以下、より好ましくは６００ｐｐｍ以下、揮発性分（水も含む）は０．９質量％以下、好ましくは０．６質量％以下、より好ましくは０．３質量％以下となるよう各種条件等を調整することが好ましい。 The quality properties of the epoxy resin obtained by the reaction of the general formula (1) and epihalohydrin produced as described above vary depending on the type of each component, the use ratio, and the like, but the epoxy equivalent is 150 to 330 g / eq. , Preferably 180 to 300 g / eq. , More preferably 200 to 280 g / eq. The melt viscosity at 150 ° C. is 0.9 Pa · s or less, preferably 0.7 Pa · s or less, more preferably 0.5 Pa · s or less, and the softening point is 50 to 120 ° C., preferably 60 to 110 ° C., more preferably. Is 62 to 100 ° C., hydrolyzable halogen is 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less, volatile content (including water) is 0.9 mass% or less, preferably 0.6 mass% or less, More preferably, various conditions and the like are adjusted so as to be 0.3% by mass or less.
エポキシ当量が小さすぎると低吸湿性に劣り、大きすぎると硬化性が悪化する。溶融粘度が高すぎると成型時の流動性が損なわれる。軟化点が低すぎると固体としての取り扱いが困難になり、高すぎるとフェノール樹脂等との混合が困難になる。加水分解性ハロゲンが多すぎると封止材中のハロゲンイオンなどが原因で半導体集積回路のアルミ配線の腐食による不良を起こしてしまう可能性がある。揮発成分が多いと硬化不良を起こしてしまう可能性があると同時に高温での取り扱い時の作業環境の悪化にもつながる。 If the epoxy equivalent is too small, the low hygroscopicity is poor, and if it is too large, the curability deteriorates. If the melt viscosity is too high, fluidity during molding is impaired. If the softening point is too low, handling as a solid becomes difficult, and if it is too high, mixing with a phenol resin or the like becomes difficult. If there is too much hydrolyzable halogen, there is a possibility of causing a defect due to corrosion of the aluminum wiring of the semiconductor integrated circuit due to halogen ions in the sealing material. If there are many volatile components, curing failure may occur, and at the same time, the working environment during handling at high temperatures may be deteriorated.
さらに、エポキシ当量は一般式（１）のフェノール樹脂の水酸基当量から計算した理論値の１．００〜１．５０倍、好ましくは１．００〜１．２０倍なるよう各種条件等を調整することが好ましい。ここでの理論値とは、一般式（１）のフェノール樹脂のヒドロキシル基が全てグリシジル化した時の値であり、エポキシ当量が理論値より大きすぎることは、ヒドロキシル基がエピハロヒドリン以外のものと反応し、高分子化している等の原因が考えられ、硬化性の悪化や不純物の存在が懸念される。 Furthermore, various conditions are adjusted so that the epoxy equivalent is 1.00 to 1.50 times, preferably 1.00 to 1.20 times the theoretical value calculated from the hydroxyl equivalent of the phenol resin of the general formula (1). Is preferred. The theoretical value here is a value when all the hydroxyl groups of the phenol resin of the general formula (1) are glycidylated, and the epoxy equivalent is larger than the theoretical value. The hydroxyl group reacts with something other than epihalohydrin. However, there are causes such as polymerization, and there are concerns about deterioration of curability and the presence of impurities.
揮発成分はＧＣ法で測定した揮発分とＪＩＳ Ｋ００６８で測定した水分の合計とした。
加水分解性ハロゲンは以下の電位差滴定法にて測定した。
ビーカーに試料1.0 gを精評し、ジオキサン３０ｍｌを加え、完全に溶解した。１Ｎアルコール性ＫＯＨ ５ｍｌをホールピペットで加えた後、ビーカーに冷却管をつけ、オイルバス中で３０分間煮沸還流した。１Ｎアルコール性ＫＯＨは事前に１Ｌメスフラスコに水酸化カリウム５６．１ｇを秤量し、９５．０％エタノールで溶解し調整した。その後ビーカーを冷却し、メタノール５ｍｌ、８０％アセトン水１００ｍｌを加えた。ビーカーに回転子を入れ、硝酸２ｍｌを加え、０．０１Ｎ硝酸銀標準溶液を用い、電位差滴定装置にて滴定した。次式より加水分解性ハロゲンを計算した。
The volatile component was the sum of the volatile content measured by the GC method and the water content measured by JIS K0068.
Hydrolyzable halogen was measured by the following potentiometric titration method.
Sample 1.0 g was put into a beaker and 30 ml of dioxane was added and completely dissolved. After adding 5 ml of 1N alcoholic KOH with a whole pipette, a condenser was attached to the beaker, and the mixture was boiled and refluxed for 30 minutes in an oil bath. 1N alcoholic KOH was prepared by weighing 56.1 g of potassium hydroxide in a 1 L volumetric flask in advance and dissolving in 95.0% ethanol. Thereafter, the beaker was cooled, and 5 ml of methanol and 100 ml of 80% acetone water were added. The rotor was placed in a beaker, 2 ml of nitric acid was added, and titration was performed using a 0.01N silver nitrate standard solution with a potentiometric titrator. The hydrolyzable halogen was calculated from the following formula.
加水分解性ハロゲン(ｐｐｍ) ＝〔(Ａ−Ｂ)×Ｃ×Ｆ×１０3〕／Ｗ
但し、Ａ：試料の滴定に要した０．０１Ｎ硝酸銀標準溶液の量(ｍｌ)、Ｂ：空試験の滴定に要した０．０１Ｎ硝酸銀標準溶液の量(ｍｌ)、Ｃ：ハロゲンの原子量、Ｎ:硝酸銀標準溶液の規定度、Ｆ：硝酸銀標準溶液の力価、Ｗ：サンプル量(ｇ)。
Hydrolyzable halogen (ppm) = [(AB) × C × F × 10 3 ] / W
However, A: Amount of 0.01N silver nitrate standard solution required for titration of sample (ml), B: Amount of 0.01N silver nitrate standard solution required for titration of blank test (ml), C: Atom atomic weight, N : Normality of silver nitrate standard solution, F: titer of silver nitrate standard solution, W: sample amount (g).
本発明のエポキシ樹脂組成物のエポキシ樹脂は、一般式（１）で表わされるフェノール樹脂とエピハロヒドリンから得られるエポキシ樹脂以外のエポキシ樹脂を混合することができるが、それぞれを個別に製造した後、混合しても良いし、一般式（１）で表わされるフェノール樹脂とその他のエポキシ樹脂の原料である化合物を混合使用してエピハロヒドリンと反応させ、混合エポキシ樹脂として同時に製造しても良い。 The epoxy resin of the epoxy resin composition of the present invention can be mixed with a phenol resin represented by the general formula (1) and an epoxy resin other than an epoxy resin obtained from epihalohydrin. Alternatively, the phenol resin represented by the general formula (1) and a compound that is a raw material of another epoxy resin may be mixed and reacted with epihalohydrin to be simultaneously produced as a mixed epoxy resin.
その混合することができるエポキシ樹脂としては、公知のものが使用できるが、具体例としては、次のフェノール類あるいはフェノール樹脂とエピハロヒドリンから製造されるエポキシ樹脂；ビスフェノールＦ、ビスフェノールＡＤ、ビフェノール、テトラメチルビフェノール、ビス（４−ヒドロキシフェニル）メタン、ビス（４−ヒドロキシフェニル）プロパン、テルペンジフェノール、ハイドロキノン、メチルハイドロキノン、ジブチルハイドロキノン、レゾルシン、メチルレゾルシン、ビスフェノールＳ、チオジフェノール、ジヒドロキシジフェニルエーテル、ジヒドロキシナフタレン、フェノールノボラック樹脂、オルソ−クレゾールノボラック樹脂、ビスフェノールＡノボラック樹脂、ジシクロペンタジエンフェノール樹脂、テルペンフェノール樹脂、フェノールアラルキル樹脂、ナフトールノボラック樹脂などの種々のフェノール類や、種々のフェノール類と、ベンズアルデヒド、ヒドロキシベンズアルデヒド、クロトンアルデヒド、グリオキザールなどの種々のアルデヒド類との縮合反応で得られる多価フェノール樹脂等の各種のフェノール化合物や、石油系重質油又はピッチ類とホルムアルデヒド重合物とフェノール類とを酸触媒の存在下に重縮合させた変性フェノール樹脂など。次のアミン化合物とエピハロヒドリンとから製造されるエポキシ樹脂；ジアミノジフェニルメタン、アミノフェノール、キシレンジアミンなど、次のカルボン酸類とエピハロヒドリンとから製造されるエポキシ樹脂；メチルヘキサヒドロキシフタル酸、ダイマー酸などが挙げられ、これらを２種以上併用しても良い。 As the epoxy resin that can be mixed, known resins can be used. Specific examples include the following phenols or epoxy resins produced from phenol resins and epihalohydrins; bisphenol F, bisphenol AD, biphenol, tetramethyl. Biphenol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) propane, terpene diphenol, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, methylresorcin, bisphenol S, thiodiphenol, dihydroxydiphenyl ether, dihydroxynaphthalene, Phenol novolac resin, ortho-cresol novolac resin, bisphenol A novolac resin, dicyclopentadiene phenol resin, tellurium Polyphenols obtained by condensation reaction of various phenols such as polyphenol resin, phenol aralkyl resin, naphthol novolak resin, and various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, and glyoxal Various phenolic compounds such as resins, and modified phenolic resins obtained by polycondensation of petroleum heavy oil or pitches, formaldehyde polymers and phenols in the presence of an acid catalyst. Epoxy resins produced from the following amine compounds and epihalohydrins; epoxy resins produced from the following carboxylic acids and epihalohydrins such as diaminodiphenylmethane, aminophenol, and xylenediamine; methyl hexahydroxyphthalic acid, dimer acid, etc. Two or more of these may be used in combination.
一般式（１）で表わされる化合物とエピハロヒドリンの反応によって得られるエポキシ樹脂と混合できるそれ以外のエポキシ樹脂の混合割合は特にその制限はないが、一般式（１）で表わされる化合物とエピハロヒドリンの反応によって得られるエポキシ樹脂がエポキシ樹脂全体の７０質量％より多いことが好ましい。一般式（１）で表わされる化合物とエピハロヒドリンの反応によって得られるエポキシ樹脂の混合割合が少なすぎると、本発明のエポキシ樹脂組成物に十分な性能を付与することができない。 The mixing ratio of the other epoxy resin that can be mixed with the epoxy resin obtained by the reaction of the compound represented by the general formula (1) and the epihalohydrin is not particularly limited, but the reaction of the compound represented by the general formula (1) and the epihalohydrin. It is preferable that the epoxy resin obtained by is more than 70 mass% of the whole epoxy resin. If the mixing ratio of the epoxy resin obtained by the reaction of the compound represented by the general formula (1) and epihalohydrin is too small, sufficient performance cannot be imparted to the epoxy resin composition of the present invention.
また、混合できるその他のエポキシ樹脂の中では、混合しても本発明のエポキシ樹脂組成物の特性を損なうことが少なく、流動性を低下させる効果のある結晶性のビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、テトラメチルビフェノール型エポキシ樹脂及び４，４’−ビフェノール型エポキシ樹脂、難燃性を向上させる効果のあるビフェニルフェノール型のエポキシ樹脂が特に好ましい。 Among other epoxy resins that can be mixed, the crystalline bisphenol A type epoxy resin, bisphenol F, which is less likely to damage the properties of the epoxy resin composition of the present invention even when mixed, has the effect of reducing fluidity. Type epoxy resin, tetramethylbiphenol type epoxy resin, 4,4′-biphenol type epoxy resin, and biphenylphenol type epoxy resin having an effect of improving flame retardancy are particularly preferable.
本発明のエポキシ樹脂組成物において必須成分として使用される(Ｂ)硬化剤の具体例としては、芳香族炭化水素ホルムアルデヒド樹脂変性ノボラック型フェノール樹脂、フェノールノボラック樹脂、クレゾールノボラック樹脂、フェノールアラルキル樹脂、ビフェニルアラルキル樹脂、ナフトールアラルキル樹脂などの種々の多価フェノール類や、種々のフェノール類とベンズアルデヒド、ヒドロキシベンズアルデヒドなどの種々のアルデヒド類との縮合反応で得られる多価フェノール樹脂等があげられ、これらは１種単独でも、２種以上併用しても良い。 Specific examples of the curing agent (B) used as an essential component in the epoxy resin composition of the present invention include aromatic hydrocarbon formaldehyde resin-modified novolak type phenol resin, phenol novolak resin, cresol novolak resin, phenol aralkyl resin, biphenyl. Examples include various polyhydric phenols such as aralkyl resins and naphthol aralkyl resins, and polyhydric phenol resins obtained by condensation reactions of various phenols with various aldehydes such as benzaldehyde and hydroxybenzaldehyde. One species may be used alone, or two or more species may be used in combination.
また、（Ａ）エポキシ樹脂と（Ｂ）硬化剤の１５０℃における混合溶融粘度は０．９Ｐａ・ｓ以下、好ましくは０．７Ｐａ・ｓ以下、より好ましくは０．５Ｐａ・ｓ以下となるように各種条件などを調整する事が好ましい。溶融粘度が高すぎると成形時の流動性が損なわれる。 Further, the mixed melt viscosity at 150 ° C. of (A) the epoxy resin and (B) the curing agent is 0.9 Pa · s or less, preferably 0.7 Pa · s or less, more preferably 0.5 Pa · s or less. It is preferable to adjust various conditions. If the melt viscosity is too high, fluidity during molding is impaired.
本発明のエポキシ樹脂組成物に使用される硬化剤の使用量は、全エポキシ樹脂成分中のエポキシ基１モルに対して、全硬化剤中のエポキシ基と反応する基が０．５〜２．０モルになる量が好ましく、より好ましくは０．７〜１．２モルである。 The amount of the curing agent used in the epoxy resin composition of the present invention is such that the group that reacts with the epoxy group in the total curing agent is 0.5-2. The amount to be 0 mol is preferred, more preferably 0.7 to 1.2 mol.
本発明のエポキシ樹脂組成物において必須成分として使用される(Ｃ)硬化促進剤としては、例えば、トリブチルホスフィン、トリフェニルホスフィン、トリス（ジメトキシフェニル)ホスフィン、トリス（ヒドロキシプロピル）ホスフィン、トリス（シアノエチル)ホスフィンなどのホスフィン化合物、テトラフェニルホスホニウムテトラフェニルボレート、メチルトリブチルホスホニウムテトラフェニルボレート、メチルトリシアノエチルホスホニウムテトラフェニルボレートなどのホスホニウム塩、２−メチルイミダゾール、２−フェニルイミダゾール、２−エチル−４−メチルイミダゾール、２−ウンデシルイミダゾール、１−シアノエチル−２−メチルイミダゾール、２,４−ジシアノ−６−［２−メチルイミダゾリル−（１）］−エチル−Ｓ−トリアジン、２,４−ジシアノ−６−［２−ウンデシルイミダゾリル−（１）］−エチル−Ｓ−トリアジンなどのイミダゾール類、１−シアノエチル−２−ウンデシルイミダゾリウムトリメリテ−ト、２−メチルイミダゾリウムイソシアヌレート、２−エチル−４−メチルイミダゾリウムテトラフェニルボレート、２−エチル−１,４−ジメチルイミダゾリウムテトラフェニルボレートなどのイミダゾリウム塩、２,４,６−トリス(ジメチルアミノメチル)フェノール、ベンジルジメチルアミン、テトラメチルブチルグアニジン、Ｎ−メチルピペラジン、２−ジメチルアミノ−１−ピロリンなどのアミン類、トリエチルアンモニウムテトラフェニルボレートなどのアンモニウム塩、１,５−ジアザビシクロ（５,４,０）−７−ウンデセン、１,５−ジアザビシクロ（４,３,０）−５−ノネン、１,４−ジアザビシクロ（２,２,２）−オクタンなどのジアザビシクロ化合物、それらジアザビシクロ化合物のテトラフェニルボレート、フェノール塩、フェノールノボラック塩、２−エチルヘキサン酸塩などが挙げられる。それらの硬化促進剤となる化合物の中では、ホスフィン化合物、イミダゾール化合物、ジアザビシクロ化合物、及びそれらの塩が好ましい。
これらの促進剤の使用量は効果促進効果が得られれば特に制限はないが、（Ａ）エポキシ樹脂と（Ｂ）硬化剤の総量に対して０．１〜１０重量％が好ましく、１〜７重量％がより好ましい。
Examples of the (C) curing accelerator used as an essential component in the epoxy resin composition of the present invention include tributylphosphine, triphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, and tris (cyanoethyl). Phosphine compounds such as phosphine, phosphonium salts such as tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium tetraphenylborate, methyltricyanoethylphosphonium tetraphenylborate, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl- (1)]-eth Imidazoles such as -S-triazine, 2,4-dicyano-6- [2-undecylimidazolyl- (1)]-ethyl-S-triazine, 1-cyanoethyl-2-undecylimidazolium trimellitate, Imidazolium salts such as 2-methylimidazolium isocyanurate, 2-ethyl-4-methylimidazolium tetraphenylborate, 2-ethyl-1,4-dimethylimidazolium tetraphenylborate, 2,4,6-tris (dimethyl (Aminomethyl) phenol, benzyldimethylamine, tetramethylbutylguanidine, N-methylpiperazine, amines such as 2-dimethylamino-1-pyrroline, ammonium salts such as triethylammonium tetraphenylborate, 1,5-diazabicyclo (5, 4,0) -7-undecene, 1, -Diazabicyclo (4,3,0) -5-nonene, diazabicyclo compounds such as 1,4-diazabicyclo (2,2,2) -octane, tetraphenylborate, phenol salt, phenol novolak salt of these diazabicyclo compounds, 2- Examples include ethyl hexanoate. Among these compounds serving as curing accelerators, phosphine compounds, imidazole compounds, diazabicyclo compounds, and salts thereof are preferable.
Although there is no restriction | limiting in particular if the usage-amount of these accelerators is acquired, if an effect promotion effect is acquired, 0.1-10 weight% is preferable with respect to the total amount of (A) epoxy resin and (B) hardening | curing agent, and 1-7 Weight percent is more preferred.
本発明のエポキシ樹脂組成物において使用される無機充填剤としては例えば、溶融シリカ、結晶性シリカ、ガラス粉、アルミナ、炭酸カルシウム、硫酸カルシウム、タルクなどが挙げられる。また、本発明のエポキシ樹脂組成物を半導体封止の用途に用いる場合には、無機充填材として、破砕型及び／又は球状の、溶融及び／又は結晶性シリカ粉末充填材を組成物全体の７０〜９５質量％配合することが好ましい。無機充填剤を使用することにより、封止材の熱膨張係数を内部のシリコンチップやリードフレームに近づけることができ、また封止材全体の吸湿量を減らす事ができるため、耐はんだクラック性を向上させることができる。またその平均粒径は１〜５０μｍ、好ましくは１．５〜４０μｍ、より好ましくは２〜３０μｍである。粒径が細かすぎると溶融粘度が高くなり流動性が低下してしまい、粒径が大きくなると成形時に金型の狭い隙間に充填剤が目詰まりし材料の充填性を低下させてしまう。 Examples of the inorganic filler used in the epoxy resin composition of the present invention include fused silica, crystalline silica, glass powder, alumina, calcium carbonate, calcium sulfate, and talc. In addition, when the epoxy resin composition of the present invention is used for semiconductor encapsulation, a crushed and / or spherical, fused and / or crystalline silica powder filler is used as the inorganic filler. It is preferable to add to 95% by mass. By using an inorganic filler, the thermal expansion coefficient of the encapsulant can be brought close to that of the internal silicon chip and lead frame, and the moisture absorption amount of the entire encapsulant can be reduced. Can be improved. Moreover, the average particle diameter is 1-50 micrometers, Preferably it is 1.5-40 micrometers, More preferably, it is 2-30 micrometers. If the particle size is too fine, the melt viscosity becomes high and the fluidity is lowered, and if the particle size is large, the filler is clogged in the narrow gap of the mold at the time of molding and the filling property of the material is lowered.
本発明のエポキシ樹脂組成物には、他の一般のエポキシ樹脂組成物と同様に、各種添加剤を配合することができる。それら各種添加剤としては例えば、カップリング剤、難燃剤、可塑剤、反応性希釈剤、顔料等があげられ、必要に応じて適宜に配合することができる。その難燃剤としては、臭素化エポキシ樹脂、臭素化フェノール樹脂などのハロゲン系難燃剤、三酸化アンチモンなどのアンチモン化合物、赤燐、リン酸エステル類、ホスフィン類などのリン系難燃剤、メラミン誘導体などの窒素系難燃剤及び水酸化アルミニウム、水酸化マグネシウムなどの無機系難燃剤などが挙げられる。 Various additives can be mix | blended with the epoxy resin composition of this invention similarly to other general epoxy resin compositions. Examples of these various additives include coupling agents, flame retardants, plasticizers, reactive diluents, pigments, and the like, which can be appropriately blended as necessary. The flame retardants include halogenated flame retardants such as brominated epoxy resins and brominated phenolic resins, antimony compounds such as antimony trioxide, red flame retardants such as red phosphorus, phosphate esters and phosphines, melamine derivatives, etc. Nitrogen-based flame retardants, and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.
本発明のエポキシ樹脂組成物の硬化物は難燃性に優れるため、上記のうち特に環境安全性が危惧されている臭素化エポキシ樹脂、臭素化フェノール樹脂などのハロゲン系難燃剤、三酸化アンチモンなどのアンチモン化合物について、これらの難燃剤を配合する必要がないか、少量にすることができる。ただし、組成物中の各成分の種類や配合量により難燃性は変化するので、ＵＬ−９４規格のＶ−０あるいはそれに準じた難燃性を確保できるよう各成分の選択や配合量の調整をする必要がある。 Since the cured product of the epoxy resin composition of the present invention is excellent in flame retardancy, among the above, halogenated flame retardants such as brominated epoxy resins and brominated phenol resins that are particularly concerned about environmental safety, antimony trioxide, etc. These antimony compounds do not need to be blended with these flame retardants or can be made in a small amount. However, since flame retardancy varies depending on the type and blending amount of each component in the composition, selection of each component and adjustment of blending amount so as to ensure flame retardancy according to UL-94 V-0 or equivalent. It is necessary to do.
本発明のエポキシ樹脂組成物の硬化物を封止材として用いた際の吸湿率は０．４質量％以下、好ましくは０．３質量％以下、より好ましくは０．２質量％以下である。吸湿率が高いと硬化物中の水分が急激に気化し、その結果、パッケージに大きな応力が発生しクラックが生じてしまう。吸湿率は以下の通り測定した。
直径５０ｍｍ高さ３ｍｍの円柱の試験片を成形し、１０５℃で２時間乾燥した。その後、試験片の質量を精秤した後、８５℃／８５％ＲＨの恒温恒湿槽に入れた。７２時間後に質量を測定し、その質量変化を測定した。
The moisture absorption when the cured product of the epoxy resin composition of the present invention is used as a sealing material is 0.4% by mass or less, preferably 0.3% by mass or less, more preferably 0.2% by mass or less. If the moisture absorption rate is high, moisture in the cured product is rapidly vaporized, resulting in a large stress in the package and cracks. The moisture absorption rate was measured as follows.
A cylindrical test piece having a diameter of 50 mm and a height of 3 mm was molded and dried at 105 ° C. for 2 hours. Thereafter, the mass of the test piece was precisely weighed and then placed in a constant temperature and humidity chamber of 85 ° C./85% RH. The mass was measured after 72 hours, and the change in mass was measured.
本発明のエポキシ樹脂組成物の硬化物を封止材として用いた際のガラス転移点以下の線膨張係数α１は５〜２５μｍ／ｍ℃、好ましくは５〜２０μｍ／ｍ℃、より好ましくは５〜１５μｍ／ｍ℃である。ガラス転移点以下の線膨張係数α２は２０〜６０μｍ／ｍ℃、好ましくは２０〜５０μｍ／ｍ℃、より好ましくは20〜40μm/m℃である。線膨張係数がこれらの範囲から外れると封止樹脂中に熱応力が増大し、パッシベーションやチップの損傷、アルミ配線のスライド、パッケージクラックなどの不良を起こしてしまう。
線膨張係数はＴＭＡ法（ＴＡ ｉｎｓｔｒｕｍｅｎｔｓ社製 ＴＭＡ ２９４０ Ｔｈｅｒｍｏｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｚｅｒを使用）にて測定した。
The linear expansion coefficient α1 below the glass transition point when the cured product of the epoxy resin composition of the present invention is used as a sealing material is 5 to 25 μm / m ° C., preferably 5 to 20 μm / m ° C., more preferably 5 to 5 μm / m ° C. 15 μm / m ° C. The linear expansion coefficient α2 below the glass transition point is 20 to 60 μm / m ° C., preferably 20 to 50 μm / m ° C., more preferably 20 to 40 μm / m ° C. If the linear expansion coefficient is out of these ranges, thermal stress increases in the sealing resin, causing defects such as passivation, chip damage, aluminum wiring slides, and package cracks.
The linear expansion coefficient was measured by the TMA method (using TMA 2940 Thermoanalyzer manufactured by TA instruments).
本発明のエポキシ樹脂組成物は、難燃付与成分としてハロゲン化合物、アンチモン化合物を添加することなしに、又は少量添加するだけで優れた難燃性を有し、かつ低吸湿性、密着性に優れる硬化物を与えるので、電気電子分野、特に半導体封止の用途に有用である。 The epoxy resin composition of the present invention has excellent flame retardancy without adding a halogen compound or antimony compound as a flame retardant imparting component, or just by adding a small amount, and is excellent in low moisture absorption and adhesion. Since it gives a cured product, it is useful in the electrical and electronic field, particularly in semiconductor encapsulation applications.
以下に、本発明で使用される芳香族炭化水素ホルムアルデヒド樹脂変性ノボラック型エポキシ樹脂の製造例、本発明のエポキシ樹脂組成物の実施例及び比較例を挙げてさらに詳述する。 The production examples of the aromatic hydrocarbon formaldehyde resin-modified novolak type epoxy resins used in the present invention, examples of the epoxy resin composition of the present invention, and comparative examples will be described in further detail below.
〔予備製造例〕
温度計、撹拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、キシレン２２０ｇ、硫酸１３０ｇ、を仕込み、９０℃に昇温して均一に溶解させた後、３５％ホルムアルデヒド水溶液２４０ｇを１時間かけて滴下した。滴下終了後、９０℃で５時間保持し反応を完了させ、水洗により硫酸を除去した。系内が中性になるまで水洗を繰り返した後、生成物から減圧下でキシレンを留去してキシレン-ホルムアルデヒド樹脂を得た。以後、このキシレン−ホルムアルデヒド樹脂をＸＦ樹脂とする。
[Preliminary production example]
A 2 L three-necked flask equipped with a thermometer, a stirrer, and a cooling tube was charged with 220 g of xylene and 130 g of sulfuric acid, heated to 90 ° C. and uniformly dissolved, and then 240 g of 35% formaldehyde aqueous solution was added for 1 hour. It was dripped over. After completion of the dropwise addition, the reaction was completed by maintaining at 90 ° C. for 5 hours, and sulfuric acid was removed by washing with water. Washing with water was repeated until the system became neutral, and then xylene was distilled off from the product under reduced pressure to obtain a xylene-formaldehyde resin. Hereinafter, this xylene-formaldehyde resin is referred to as XF resin.
〔製造例1〕
温度計、撹拌装置、冷却管を備えた内容量２Ｌの三口フラスコに、先に得られたＸＦ樹脂２００ｇにフェノール３００ｇ、ｐ−トルエンスルホン酸０．１ｇを加え、１００℃で２時間攪拌した。その後、ホルマリン３５ｇ、シュウ酸１．５ｇを加え３時間攪拌した。反応混合物をメチルイソブチルケトン５００ｇに溶解し、６５℃で中性になるまで水洗を繰り返した。次いで減圧下でメチルイソブチルケトン、フェノールを１６０℃、減圧下で留去して芳香族炭化水素ホルムアルデヒド樹脂変性ノボラック型フェノール樹脂を得た。水酸基当量１６３ｇ／ｅｑ．、１５０℃における溶融粘度０．２１Ｐａ・ｓ、軟化点８４℃、遊離フェノール０．１質量％以下であった。またこの樹脂は一般式（１）においてＲ2＝ＣＨ3、ｉ＝０、ｊ＝２、ｍ＝２．３、ｎ＝１．６であった。
(Production Example 1)
300 g of phenol and 0.1 g of p-toluenesulfonic acid were added to 200 g of the previously obtained XF resin in a 2 L three-necked flask equipped with a thermometer, a stirrer, and a condenser, and stirred at 100 ° C. for 2 hours. Thereafter, 35 g of formalin and 1.5 g of oxalic acid were added and stirred for 3 hours. The reaction mixture was dissolved in 500 g of methyl isobutyl ketone and washed repeatedly with water until neutral at 65 ° C. Subsequently, methyl isobutyl ketone and phenol were distilled off under reduced pressure at 160 ° C. under reduced pressure to obtain an aromatic hydrocarbon formaldehyde resin-modified novolak type phenol resin. Hydroxyl equivalent weight 163 g / eq. The melt viscosity at 150 ° C. was 0.21 Pa · s, the softening point was 84 ° C., and the free phenol was 0.1% by mass or less. The resin in the general formula (1) R 2 = CH 3 , i = 0, j = 2, m = 2.3, was n = 1.6.
こうして得られた芳香族炭化水素ホルムアルデヒド樹脂変性ノボラック型フェノール樹脂１５０ｇ、エピクロルヒドリン５１０ｇ、イソプロピルアルコール２００ｇを温度計、撹拌装置、冷却管を備えた内容量２Ｌの三口フラスコに仕込み、４０℃に昇温して均一に溶解させた後、４８．５質量％の水酸化ナトリウム水溶液９０ｇを６０分かけて滴下した。その間に徐々に昇温し、滴下終了後には系内が６５℃になるようにした。その後、６５℃で３０分保持し反応を完了させ、水洗により副生塩及び過剰の水酸化ナトリウムを除去した。ついで、生成物から減圧下で過剰のエピクロルヒドリンとイソプロパノールを留去して、粗製エポキシ樹脂を得た。この粗製エポキシ樹脂をメチルイソブチルケトン３００ｇに溶解させ、４８．５質量％の水酸化ナトリウム水溶液９ｇを加え、６５℃の温度で１時間反応させた。その後、反応液に第一リン酸ナトリウム水溶液を加えて、過剰の水酸化ナトリウムを中和し、水洗して副生塩を除去した。次いで、減圧下でメチルイソブチルケトンを完全に除去して、目的のエポキシ樹脂１８０ｇを得た。得られた樹脂はエポキシ当量２４７ｇ／ｅｑ．（水酸基当量から計算した理論値は２１９ｇ／ｅｑ．）、加水分解性ハロゲン４００ｐｐｍ、１５０℃における溶融粘度は０．１８Ｐａ・ｓ、軟化点は６３℃であった。 The thus obtained aromatic hydrocarbon formaldehyde resin-modified novolak-type phenolic resin 150 g, epichlorohydrin 510 g, and isopropyl alcohol 200 g were charged into a 2 L three-necked flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was raised to 40 ° C. Then, 90 g of a 48.5% by mass aqueous sodium hydroxide solution was added dropwise over 60 minutes. During this time, the temperature was gradually raised, and the temperature inside the system was adjusted to 65 ° C. after the dropping was completed. Thereafter, the reaction was completed by maintaining at 65 ° C. for 30 minutes, and by-product salt and excess sodium hydroxide were removed by washing with water. Subsequently, excess epichlorohydrin and isopropanol were distilled off from the product under reduced pressure to obtain a crude epoxy resin. This crude epoxy resin was dissolved in 300 g of methyl isobutyl ketone, 9 g of 48.5 mass% sodium hydroxide aqueous solution was added, and the mixture was reacted at a temperature of 65 ° C. for 1 hour. Thereafter, an aqueous sodium phosphate solution was added to the reaction solution to neutralize excess sodium hydroxide and washed with water to remove by-product salts. Next, methyl isobutyl ketone was completely removed under reduced pressure to obtain 180 g of the desired epoxy resin. The obtained resin had an epoxy equivalent of 247 g / eq. (Theoretical value calculated from hydroxyl group equivalent was 219 g / eq.), Hydrolyzable halogen 400 ppm, melt viscosity at 150 ° C. was 0.18 Pa · s, and softening point was 63 ° C.
〔製造例２〕
製造例１においてホルマリンの量を５５ｇに置き換えた以外は、製造例１と同様の操作を行い、芳香族炭化水素ホルムアルデヒド樹脂変性ノボラック型フェノール樹脂を得た。得られた樹脂は水酸基当量１７０ｇ／ｅｑ．、１５０℃における溶融粘度０．６２Ｐａ・ｓ、軟化点９５℃、遊離フェノール０．１質量％以下であった。またこの樹脂は一般式（１）においてＲ２＝ＣＨ３、ｉ＝０、ｊ＝２、ｍ＝２．９、ｎ＝２．１であった。つづいて製造例１と同様の操作を行い、エポキシ樹脂を得た。得られた樹脂はエポキシ当量２４９ｇ／ｅｑ．（水酸基当量から計算した理論値は２２６ｇ／ｅｑ．）、加水分解性ハロゲン５００ｐｐｍ、１５０℃における溶融粘度は０．４８Ｐａ・ｓ、軟化点は８０℃であった。
[Production Example 2]
Except that the amount of formalin was replaced with 55 g in Production Example 1, the same operation as in Production Example 1 was performed to obtain an aromatic hydrocarbon formaldehyde resin-modified novolak type phenol resin. The obtained resin had a hydroxyl equivalent weight of 170 g / eq. The melt viscosity at 150 ° C. was 0.62 Pa · s, the softening point was 95 ° C., and the free phenol was 0.1% by mass or less. The resin in the general formula (1) R 2 = CH 3 , i = 0, j = 2, m = 2.9, was n = 2.1. Subsequently, the same operation as in Production Example 1 was performed to obtain an epoxy resin. The obtained resin had an epoxy equivalent of 249 g / eq. (Theoretical value calculated from hydroxyl group equivalent was 226 g / eq.), Hydrolyzable halogen 500 ppm, melt viscosity at 150 ° C. was 0.48 Pa · s, and softening point was 80 ° C.
〔製造例３〕
製造例１においてホルマリンの量を７０ｇ、メチルイソブチルケトン、フェノールの留去の温度を１２０℃に置き換えた以外は、製造例１と同様の操作を行い、芳香族炭化水素ホルムアルデヒド樹脂変性ノボラック型フェノール樹脂を得た。得られた樹脂は水酸基当量１９０ｇ・／ｅｑ．、１５０℃における溶融粘度４．２Ｐａ・ｓ、軟化点１０９℃、遊離フェノール３．６質量％であった。またこの樹脂は一般式（１）においてＲ２＝ＣＨ３、ｉ＝０、ｊ＝２、ｍ＝９．８、ｎ＝７．５であった。つづいて、製造例１において、エピクロロヒドリンの量を４４０ｇ、イソプロピルアルコールの量を１７０ｇ、４８．５質量％の水酸化ナトリウム水溶液の量を７０ｇとした以外は、製造例１と同様の操作を行い、エポキシ樹脂を得た。得られた樹脂はエポキシ当量２９６ｇ／ｅｑ．（水酸基当量から計算した理論値は２４６ｇ／ｅｑ．）、加水分解性ハロゲン７００ｐｐｍ、１５０℃における溶融粘度は２．４Ｐａ・ｓ、軟化点は９７℃であった。
[Production Example 3]
The same procedure as in Production Example 1 was performed except that the amount of formalin in Production Example 1 was replaced with 70 g, methyl isobutyl ketone, and phenol distillation temperature at 120 ° C., and an aromatic hydrocarbon formaldehyde resin-modified novolak phenol resin Got. The resulting resin had a hydroxyl equivalent weight of 190 g · eq. The melt viscosity at 150 ° C. was 4.2 Pa · s, the softening point was 109 ° C., and the free phenol was 3.6% by mass. The resin in the general formula (1) R 2 = CH 3 , i = 0, j = 2, m = 9.8, was n = 7.5. Subsequently, in Production Example 1, the same operation as in Production Example 1 except that the amount of epichlorohydrin was 440 g, the amount of isopropyl alcohol was 170 g, and the amount of 48.5 mass% sodium hydroxide aqueous solution was 70 g. To obtain an epoxy resin. The obtained resin had an epoxy equivalent of 296 g / eq. (Theoretical value calculated from hydroxyl group equivalent was 246 g / eq.), 700 ppm hydrolyzable halogen, melt viscosity at 150 ° C. was 2.4 Pa · s, and softening point was 97 ° C.
〔製造例４〕
製造例３においてエピクロロヒドリンの量を２３０ｇ、イソプロピルアルコールの量を９０ｇ、４８．５質量％の水酸化ナトリウム水溶液の量を７０ｇとした以外は、製造例１と同様の操作を行い、エポキシ樹脂を得た。得られた樹脂はエポキシ当量３７２ｇ／ｅｑ．（水酸基当量から計算した理論値は２４６ｇ／ｅｑ．）、加水分解性ハロゲン１１００ｐｐｍ、１５０℃における溶融粘度は５．４Ｐａ・ｓ、軟化点は１２２℃であった。
[Production Example 4]
The same operation as in Production Example 1 was carried out except that the amount of epichlorohydrin was 230 g, the amount of isopropyl alcohol was 90 g, and the amount of 48.5 mass% sodium hydroxide aqueous solution was 70 g in Production Example 3. A resin was obtained. The obtained resin had an epoxy equivalent of 372 g / eq. (Theoretical value calculated from hydroxyl group equivalent was 246 g / eq.), Hydrolyzable halogen was 1100 ppm, melt viscosity at 150 ° C. was 5.4 Pa · s, and softening point was 122 ° C.
〔エポキシ樹脂組成物実施例１〜６及び比較例１〜４〕
表１に示したように、エポキシ樹脂として製造例１〜４で得られたエポキシ樹脂、テトラメチルビフェノールから誘導されたエポキシ樹脂、ビフェノールとテトラメチルビフェノールから誘導されたエポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、テトラブロモビスフェノールＡ型エポキシ樹脂又はオルソクレゾールノボラック樹脂から誘導されたエポキシ樹脂、エポキシ樹脂用硬化剤として一般式（１）で表わされるフェノール樹脂、フェノールアラルキル樹脂、ビフェニルフェノール樹脂、フェノール／ベンズアルデヒドノボラック型樹脂、ナフトールアラルキル樹脂、フェノールノボラック樹脂、無機充填剤としてシリカ粉末、硬化促進剤としてトリフェニルホスフィンを用い、さらにカップリング剤としてエポキシシラン、離形剤としてカルナバワックスをそれぞれ用いて、各エポキシ樹脂組成物を配合した。次いで、各配合物をミキシングロールを用いて７０〜１２０℃の温度で５分間溶融混練した。得られた各溶融混合物は薄板状に取り出し冷却した後、粉砕して各成形材料を得た。これらの各成形材料を用い低圧トランスファー成形機で金型温度１７５℃、成形時間１８０秒で成形して、各試験片を得、１８０℃で８時間ポストキュアさせた。ポストキュア後の各試験片の吸湿率、ガラス転移温度、及び密着性、難燃性を試験した結果を表１及び表２に示した。さらに各成形材料により封止された模擬半導体装置の耐ハンダクラック性を試験した結果を表１及び表２に示した。またエポキシ樹脂と硬化剤の混合溶融粘度を表１及び表２に示した。
[Epoxy Resin Composition Examples 1 to 6 and Comparative Examples 1 to 4]
As shown in Table 1, the epoxy resin obtained in Production Examples 1 to 4 as an epoxy resin, an epoxy resin derived from tetramethylbiphenol, an epoxy resin derived from biphenol and tetramethylbiphenol, and a bisphenol A type epoxy resin , Epoxy resin derived from tetrabromobisphenol A type epoxy resin or orthocresol novolak resin, phenol resin represented by general formula (1) as a curing agent for epoxy resin, phenol aralkyl resin, biphenylphenol resin, phenol / benzaldehyde novolak type Resin, naphthol aralkyl resin, phenol novolak resin, silica powder as inorganic filler, triphenylphosphine as curing accelerator, epoxy silane as release agent, mold release agent Using carnauba wax each was formulated each epoxy resin composition. Subsequently, each compound was melt-kneaded for 5 minutes at a temperature of 70 to 120 ° C. using a mixing roll. Each obtained molten mixture was taken out into a thin plate shape, cooled, and then pulverized to obtain each molding material. Each of these molding materials was molded by a low pressure transfer molding machine at a mold temperature of 175 ° C. and a molding time of 180 seconds to obtain each test piece, which was post-cured at 180 ° C. for 8 hours. Tables 1 and 2 show the results of testing the moisture absorption rate, glass transition temperature, adhesion, and flame retardancy of each test piece after post cure. Furthermore, Table 1 and Table 2 show the results of testing the solder crack resistance of the simulated semiconductor device sealed with each molding material. Tables 1 and 2 show the mixed melt viscosity of the epoxy resin and the curing agent.
名 エピコートYX4000H，エポキシ当量：193(g/eq)）
＊２： Ｂ；ビフェニル型エポキシ樹脂（ジャパンエポキシレジン社商品名 エピコー
トYL6121H，エポキシ当量：172(g/eq)，）
＊３： Ｃ；ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン社商品名
エピコートYL6810，エポキシ当量：172(g/eq)，）
＊４： Ｄ；クレゾ−ルノボラック型エポキシ樹脂（ジャパンエポキシレジン社商品名
エピコート180S62，エポキシ当量：197(g/eq)）
＊５： Ｅ；臭素化エポキシ樹脂（日本化薬社商品名 BREN-S、エポキシ当量：385
(g/eq)、臭素含量：48%）
＊６： Ｆ；フェノールアラルキル樹脂（明和化成社商品名 MEH-7800S，水酸基当
量：175(g/eq)，軟化点：75(℃）
＊７： Ｇ；芳香族炭化水素ホルムアルデヒド樹脂変性ノボラック型フェノール樹脂
（三菱瓦斯化学社商品名 ニカノールGLP，水酸基当量：163(g/eq)，
軟化点：86(℃）
＊８： Ｈ；フェノール/ベンズアルデヒドノボラック型樹脂（ジャパンエポキシレジ ン社商品名 エピキュアＹＬＨ１０２７，水酸基当量：150(g/eq)），軟 化点：82(℃）
＊９： Ｉ；ビフェニルフェノール樹脂（明和化成社商品名 MEH-7851S，水酸基当 量：205(g/eq)，軟化点：75(℃）
＊１０： Ｊ；ナフトールアラルキル樹脂（明和化成社商品名 MEH-7700，水酸基当量：
140(g/eq)，軟化点：96(℃）
＊１１： Ｋ；フェノールノボラック樹脂（群栄化学社商品名 レヂトップPSM4261，水酸
基当量：103(g/eq)，軟化点：85℃）
＊１２： 溶融シリカ粉末（龍森社商品名 RD-8）
＊１３： エポキシシラン（信越化学工業社商品名 KBM-403）
＊１４： エポキシ樹脂と硬化剤のみを混合溶融させてICI粘度計により測定。
＊１５： ＥＭＭＩ−１−６６
＊１６： ＴＭＡ法
＊１７： 85℃、85%RH、72時間後の吸湿率
＊１８： アルミピール試験
＊１９： 80ピンQFP16個を85℃、85%RHにおいて72時間吸湿後、260℃ハンダ浴に10秒
間浸漬し、クラックの発生した個数を求めた。
＊２０： ＵＬ９４
Name Epicoat YX4000H, epoxy equivalent: 193 (g / eq))
* 2: B: Biphenyl type epoxy resin (Japan Epoxy Resin product name EPICO
YL6121H, epoxy equivalent: 172 (g / eq),)
* 3: C: Bisphenol A type epoxy resin (trade name of Japan Epoxy Resin Co., Ltd.)
Epicoat YL6810, epoxy equivalent: 172 (g / eq),)
* 4: D: Cresol-Lenovorac type epoxy resin (Japan Epoxy Resin product name)
Epicoat 180S62, epoxy equivalent: 197 (g / eq))
* 5: E: Brominated epoxy resin (Nippon Kayaku Co., Ltd. trade name BREN-S, epoxy equivalent: 385
(g / eq), bromine content: 48%)
* 6: F: Phenol aralkyl resin (Maywa Kasei Co., Ltd., MEH-7800S, hydroxyl group)
Amount: 175 (g / eq), softening point: 75 (° C)
* 7: G: Aromatic hydrocarbon formaldehyde resin-modified novolak phenol resin
(Product name: Mitsubishi Gas Chemical Company, Nikanol GLP, hydroxyl equivalent: 163 (g / eq),
Softening point: 86 (℃)
* 8: H: Phenol / benzaldehyde novolak resin (trade name: EpiCure YLH1027, hydroxyl equivalent: 150 (g / eq)), Softening point: 82 (° C)
* 9: I: Biphenylphenol resin (Maywa Kasei Co., Ltd. trade name MEH-7851S, hydroxyl group equivalent: 205 (g / eq), softening point: 75 (° C)
* 10: J: Naphthol aralkyl resin (Maywa Kasei Co., Ltd. trade name MEH-7700, hydroxyl equivalent:
140 (g / eq), softening point: 96 (℃)
* 11: K: Phenol novolac resin (Gunei Chemical Co., Ltd., trade name Resitop PSM4261, Hydroxic Acid
Base equivalent: 103 (g / eq), softening point: 85 ° C)
* 12: Fused silica powder (trade name RD-8, Tatsumori)
* 13: Epoxy silane (trade name KBM-403, Shin-Etsu Chemical Co., Ltd.)
* 14: Measured with ICI viscometer after mixing and melting only epoxy resin and curing agent.
* 15: EMMI-1-66
* 16: TMA method * 17: Moisture absorption rate after 72 hours at 85 ° C, 85% RH * 18: Aluminum peel test * 19: Solder at 260 ° C after absorbing 80 pin QFP at 85 ° C and 85% RH for 72 hours 10 seconds to bath
It was immersed for a while and the number of cracks was determined.
* 20: UL94
上記表１及び表２から明らかなように、実施例１〜６の各成形材料は、比較例１〜４の成形材料と比較してハロゲン化合物、アンチモン化合物を添加することなしに、優れた難燃性を有するとともに、低吸湿性、密着性のバランスに優れ、さらに耐ハンダクラック性に優れていた。また比較例３、４の成形材料は低吸湿性、密着性には優れていたが、混合溶融粘度が高いため、スパイラルフローが短く、著しく流動性に劣っていた。 As apparent from Table 1 and Table 2 above, the molding materials of Examples 1 to 6 were superior to the molding materials of Comparative Examples 1 to 4 without adding a halogen compound or an antimony compound. In addition to being flammable, it was excellent in the balance between low moisture absorption and adhesion, and also excellent in solder crack resistance. In addition, the molding materials of Comparative Examples 3 and 4 were excellent in low moisture absorption and adhesion, but because of the high mixed melt viscosity, the spiral flow was short and the fluidity was remarkably inferior.
Claims (9)
（Ａ）エポキシ樹脂として、下記一般式（１）で表されるフェノール樹脂とエピハロヒドリンを反応させることにより得られるエポキシ樹脂であって、そのエポキシ当量が１５０〜３３０ｇ／ｅｑ．で、下記一般式（１）で表されるフェノール樹脂の水酸基当量から計算した理論値の１．００倍〜１．５０倍であり、且つ、加水分解性ハロゲンが１０００ｐｐｍ以下、１５０℃における溶融粘度が０．９Ｐａ・ｓ以下、及び軟化点が５０〜１２０℃のエポキシ樹脂を含有することを特徴とするエポキシ樹脂組成物。
(A) as an epoxy resin, an epoxy resin obtained by reacting a phenolic resin with an epihalohydrin represented by the following general formula (1), its epoxy equivalent 150~330g / eq. In, Ri 1.00 times 1.50 Baidea the theoretical values calculated from the hydroxyl equivalent of the phenolic resin represented by the following general formula (1), and, hydrolyzable halogens 1000ppm or less, melting at 0.99 ° C. An epoxy resin composition comprising an epoxy resin having a viscosity of 0.9 Pa · s or less and a softening point of 50 to 120 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003416443A JP4451129B2 (en) | 2003-12-15 | 2003-12-15 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003416443A JP4451129B2 (en) | 2003-12-15 | 2003-12-15 | Epoxy resin composition |
Related Child Applications (1)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006176595A (en) * | 2004-12-21 | 2006-07-06 | Matsushita Electric Works Ltd | Epoxy resin composition for sealing semiconductor and semiconductor apparatus |
| JP2007138128A (en) * | 2005-10-20 | 2007-06-07 | Matsushita Electric Works Ltd | Epoxy resin composition for sealing semiconductor and semiconductor device |
| JP2007262235A (en) * | 2006-03-28 | 2007-10-11 | Matsushita Electric Works Ltd | Semiconductor-sealing epoxy resin and semiconductor device |
| WO2008047613A1 (en) * | 2006-10-11 | 2008-04-24 | Nipponkayaku Kabushikikaisha | Epoxy resin, method for producing the epoxy resin, epoxy resin composition using the epoxy resin, and cured product of the epoxy resin composition |
| JP5473209B2 (en) * | 2007-10-29 | 2014-04-16 | 日本化薬株式会社 | Phenolic resin, epoxy resin, epoxy resin composition and cured product thereof |
| JP5268606B2 (en) * | 2008-12-08 | 2013-08-21 | 日本化薬株式会社 | Phenolic resin, epoxy resin, epoxy resin composition and cured product thereof |
| JP5413127B2 (en) * | 2009-10-29 | 2014-02-12 | 住友ベークライト株式会社 | Semiconductor sealing resin composition, semiconductor device using the same, and method for producing semiconductor sealing resin composition |
| JP5353636B2 (en) * | 2009-10-29 | 2013-11-27 | 住友ベークライト株式会社 | Semiconductor sealing resin composition and semiconductor device using the same |
| JP5673237B2 (en) * | 2011-03-10 | 2015-02-18 | 住友ベークライト株式会社 | Resin composition for sealing and electronic component device |
| JP2017132897A (en) * | 2016-01-27 | 2017-08-03 | 三菱ケミカル株式会社 | Epoxy resin composition containing phenolic resin as curing agent, cured product of the same, and electric and electronic component using the cured product |
| WO2020129248A1 (en) * | 2018-12-21 | 2020-06-25 | 日立化成株式会社 | Sealing resin composition and electronic component device |
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