JP2004339277A - Phenol resin, curing agent for epoxy resin, and epoxy resin composition - Google Patents
Phenol resin, curing agent for epoxy resin, and epoxy resin composition Download PDFInfo
- Publication number
- JP2004339277A JP2004339277A JP2003134673A JP2003134673A JP2004339277A JP 2004339277 A JP2004339277 A JP 2004339277A JP 2003134673 A JP2003134673 A JP 2003134673A JP 2003134673 A JP2003134673 A JP 2003134673A JP 2004339277 A JP2004339277 A JP 2004339277A
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- JP
- Japan
- Prior art keywords
- group
- epoxy resin
- carbon atoms
- substituted
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 111
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 107
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 85
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 239000004065 semiconductor Substances 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 45
- 229920001568 phenolic resin Polymers 0.000 claims description 37
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 34
- -1 phenol compound Chemical class 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 229920003986 novolac Polymers 0.000 claims description 22
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 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 claims description 16
- 238000005538 encapsulation Methods 0.000 claims description 15
- 125000000101 thioether group Chemical group 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 150000002989 phenols Chemical class 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229930003836 cresol Natural products 0.000 claims description 9
- 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 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- 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 claims description 7
- LJBWJFWNFUKAGS-UHFFFAOYSA-N 2-[bis(2-hydroxyphenyl)methyl]phenol Chemical compound OC1=CC=CC=C1C(C=1C(=CC=CC=1)O)C1=CC=CC=C1O LJBWJFWNFUKAGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 150000003505 terpenes Chemical class 0.000 claims description 6
- 235000007586 terpenes Nutrition 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 3
- LMVLMHGTZULBRX-UHFFFAOYSA-N 2-[2,2,2-tris(2-hydroxyphenyl)ethyl]phenol Chemical compound OC1=CC=CC=C1CC(C=1C(=CC=CC=1)O)(C=1C(=CC=CC=1)O)C1=CC=CC=C1O LMVLMHGTZULBRX-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 150000001463 antimony compounds Chemical class 0.000 abstract description 11
- 229910000679 solder Inorganic materials 0.000 abstract description 11
- 150000002366 halogen compounds Chemical class 0.000 abstract description 10
- 238000007789 sealing Methods 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- 239000003063 flame retardant Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000006482 condensation reaction Methods 0.000 description 9
- 239000004593 Epoxy Substances 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 8
- 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 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- QRVYABWJVXXOTN-UHFFFAOYSA-N 4-methylsulfanylbenzaldehyde Chemical compound CSC1=CC=C(C=O)C=C1 QRVYABWJVXXOTN-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000012778 molding material Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 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
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- 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 4
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229940015043 glyoxal Drugs 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- 229960001755 resorcinol Drugs 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- ZUZAETTVAMCNTO-UHFFFAOYSA-N 2,3-dibutylbenzene-1,4-diol Chemical compound CCCCC1=C(O)C=CC(O)=C1CCCC ZUZAETTVAMCNTO-UHFFFAOYSA-N 0.000 description 2
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- HYCFWHIAROXTSC-UHFFFAOYSA-N 2-hydroxy-3-methylsulfanylbenzaldehyde Chemical compound CSC1=CC=CC(C=O)=C1O HYCFWHIAROXTSC-UHFFFAOYSA-N 0.000 description 2
- CTUPBAXICGISQP-UHFFFAOYSA-N 2-methylthiobenzaldehyde Chemical compound CC1=CC=CC=C1C=S CTUPBAXICGISQP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 150000001412 amines Chemical class 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-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
- 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
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-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
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-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
- NDOPHXWIAZIXPR-UHFFFAOYSA-N 2-bromobenzaldehyde Chemical compound BrC1=CC=CC=C1C=O NDOPHXWIAZIXPR-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- XOGKZGNRKVDVRK-UHFFFAOYSA-N 2-butylthiobenzaldehyde Chemical compound CCCCC1=CC=CC=C1C=S XOGKZGNRKVDVRK-UHFFFAOYSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- ZAZPXVLWYMDBIN-UHFFFAOYSA-N 2-ethylthiobenzaldehyde Chemical compound CCC1=CC=CC=C1C=S ZAZPXVLWYMDBIN-UHFFFAOYSA-N 0.000 description 1
- CDBMMUODDOBLJH-UHFFFAOYSA-N 2-hydroxy-4-methylsulfanylbenzaldehyde Chemical compound CSC1=CC=C(C=O)C(O)=C1 CDBMMUODDOBLJH-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
- CQSQMXIROIYTLO-UHFFFAOYSA-N 2-methylpropanethial Chemical compound CC(C)C=S CQSQMXIROIYTLO-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- YIVGJLBPCMXBOX-UHFFFAOYSA-N 2-phenylthiobenzaldehyde Chemical compound S=CC1=CC=CC=C1C1=CC=CC=C1 YIVGJLBPCMXBOX-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- WNWYSGOOKCRBTC-UHFFFAOYSA-N 2-propylthiobenzaldehyde Chemical compound CCCC1=CC=CC=C1C=S WNWYSGOOKCRBTC-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-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
- CHZAMJVESILJGH-UHFFFAOYSA-N 3-[bis(2-cyanoethyl)phosphanyl]propanenitrile Chemical compound N#CCCP(CCC#N)CCC#N CHZAMJVESILJGH-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
- MCUFTLAXJMCWPZ-UHFFFAOYSA-N 3-butyl-2-methylphenol Chemical compound CCCCC1=CC=CC(O)=C1C MCUFTLAXJMCWPZ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ROAPXILUYNNRQA-UHFFFAOYSA-N CCC1=NC=C(C)N1.C1=CN=CN1.C1=CN=CN1.C1=CN=CN1.C1=CN=CN1 Chemical class CCC1=NC=C(C)N1.C1=CN=CN1.C1=CN=CN1.C1=CN=CN1.C1=CN=CN1 ROAPXILUYNNRQA-UHFFFAOYSA-N 0.000 description 1
- 241001448862 Croton Species 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
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- 150000008065 acid anhydrides Chemical class 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N c1ccccc1 Chemical compound c1ccccc1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
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- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
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- 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
- 239000011521 glass Substances 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
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- 239000012796 inorganic flame retardant Substances 0.000 description 1
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
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- XKFPGUWSSPXXMF-UHFFFAOYSA-N tributyl(methyl)phosphanium Chemical compound CCCC[P+](C)(CCCC)CCCC XKFPGUWSSPXXMF-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、新規なフェノール樹脂及びその製造方法と、このフェノール樹脂を用いたエポキシ樹脂用硬化剤と、このエポキシ樹脂用硬化剤を用いたエポキシ樹脂組成物に関する。本発明のフェノール樹脂を用いたエポキシ樹脂組成物は、難燃性付与成分としてハロゲン化合物やアンチモン化合物を添加すること無しに優れた難燃性を有し、かつ成形性及び耐ハンダクラック性に優れる硬化物を与えることができ、特に半導体封止用途に有用である。
【０００２】
【従来の技術】
従来、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、これら半導体封止用エポキシ樹脂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性付与成分として、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とが組み合わせて配合されている。
【０００３】
しかしながら、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規制する動きが高まっている。このため、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。例えば、赤リンを配合する方法（特開平９−２２７７６５号公報）、リン酸エステル化合物を配合する方法（特開平９−２３５４４９号公報）、ホスファゼン化合物を配合する方法（特開平８−２２５７１４号公報）、金属水酸化物を配合する方法（特開平９−２４１４８３号公報）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や、充填剤の配合割合を高くする手法（特開平７−８２３４３号公報）などが検討されている。
【０００４】
しかし、半導体封止用エポキシ樹脂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があり、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。
【０００５】
一方で、半導体分野における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、低吸湿性及び密着性等にも十分配慮する必要がある。
【０００６】
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の架橋点間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（特開昭６１−４７７２５号公報）、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（特開昭６１−１２３６１８号公報）、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（特開平１−２７１４１５号公報）など、種々の提案がなされている。しかし、いずれ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することができない。
【０００７】
【特許文献１】
特開平９−２２７７６５号公報
【特許文献２】
特開平９−２３５４４９号公報
【特許文献３】
特開平８−２２５７１４号公報
【特許文献４】
特開平９−２４１４８３号公報
【特許文献５】
特開平７−８２３４３号公報
【特許文献６】
特開昭６１−４７７２５号公報
【特許文献７】
特開昭６１−１２３６１８号公報
【特許文献８】
特開平１−２７１４１５号公報
【０００８】
【本発明が解決しようとする課題】
本発明は、種々の用途に有用であり、特にエポキシ樹脂用硬化剤として使用した場合に、難燃性付与成分としてハロゲン化合物及びアンチモン化合物を添加すること無しに、優れた難燃性を有すると共に、成形性及び耐ハンダクラック性に優れた硬化物を与えることができる新規フェノール樹脂及びその製造方法と、このフェノール樹脂を用いたエポキシ樹脂用硬化剤と、このエポキシ樹脂用硬化剤を用いたエポキシ樹脂組成物、特に半導体封止用エポキシ樹脂組成物を提供することを目的とする。
【０００９】
【課題を解決するための手段】
本発明のフェノール樹脂は、下記一般式（Ｉ）で表されることを特徴とする。
【００１０】
【化３】
Ｒ１は互いに同一であっても異なっていても良く、炭素数１〜１０のアルキル基、置換又は無置換のフェニル基、或いは置換又は無置換のアラルキル基を示す。
Ｒ２は、（ａ＋１）価の、炭素数１〜１０の炭化水素基、置換又は無置換の芳香族炭化水素基、置換又は無置換のアラルキル基、或いは直接結合を示す。
Ｒ３は互いに同一であっても異なっていても良く、水素原子、炭素数１〜１０のアルキル基、或いは置換又は無置換のフェニル基を示す。
Ｒ４は互いに同一であっても異なっていても良く、水素原子、炭素数１〜１０のアルキル基、或いは置換又は無置換のフェニル基を示す。
Ｒ５は互いに同一であっても異なっていても良く、水素原子、炭素数１〜１０のアルキル基、置換又は無置換のフェニル基、置換又は無置換のアラルキル基、或いは炭素数１〜１０のアルコキシ基を示す。
Ｒ６は水素原子、炭素数１〜１０のアルキル基、置換又は無置換のフェニル基、置換又は無置換のアラルキル基、或いは炭素数１〜１０のアルコキシ基を示す。
ａは１〜３の、ｂは１〜２の、ｃ，ｄは０〜４の、ｊは１〜３の整数である。
ｌは平均値で１〜１０の数であり、ｍ、ｎは平均値で０〜１０の数である。
ただし、ここで「置換」とは、水素原子が炭素数１〜１０のアルキル基、水酸基、炭素数１〜１０のアルコキシ基に置き換わったものを示す。）
【００１１】
即ち、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、チオエーテル基を持つアルデヒド類とフェノール化合物との縮合反応により得られたチオエーテル基含有フェノール樹脂であれば、これをエポキシ樹脂用硬化剤として用いることにより、本発明の目的を達成し得ることを見出し、本発明を完成させた。
【００１２】
本発明のフェノール樹脂は、前記一般式（Ｉ）において、ｍ及びｎが０であることが好ましい。
【００１３】
このような本発明のフェノール樹脂は、フェノール化合物と、チオエーテル基を持つアルデヒドと、必要に応じて更に該チオエーテル基を持つアルデヒド以外の他のアルデヒド類及び／又は下記一般式（ＩＩ）で表される化合物とを、酸性触媒の存在下に反応させる本発明のフェノール樹脂の製造方法により、容易かつ高純度に製造することができる。
【００１４】
【化４】
【００１５】
本発明のエポキシ樹脂用硬化剤は、このような本発明のフェノール樹脂を含むエポキシ樹脂用硬化剤であって、該フェノール樹脂の含有量が５〜１００重量％であることを特徴とする。
【００１６】
本発明のエポキシ樹脂組成物は、エポキシ樹脂と、このエポキシ樹脂用硬化剤とを含むことを特徴とする。
【００１７】
本発明のエポキシ樹脂組成物において、エポキシ樹脂としては、ビスフェノールＡ、ビスフェノールＦ、ビフェノール、テトラメチルビフェノール、テルペンジフェノール、トリス（ヒドロキシルフェニル）メタン、テトラキス（ヒドロキシフェニル）エタン、ジシクロペンタジエンフェノール樹脂、ビフェニルアラルキル樹脂及びクレゾールノボラック樹脂よりなる群から選ばれた少なくとも１種類のフェノール化合物と、エピハロヒドリンとから製造されるエポキシ樹脂であることが好ましい。
【００１８】
本発明の半導体封止用エポキシ樹脂組成物は、このようなエポキシ樹脂組成物において、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含む半導体封止用のエポキシ樹脂組成物であって、該無機充填材の含有量が７０〜９５重量％であることを特徴とする。
【００１９】
【発明の実施の形態】
以下に本発明の実施の形態を詳細に説明する。
【００２０】
まず、下記一般式（Ｉ）で表される本発明の新規フェノール樹脂について説明する。
【００２１】
【化５】
上記一般式において、Ｒ１は互いに同一であっても異なっていても良く、炭素数１〜１０のアルキル基；炭素数１〜１０のアルキル基、水酸基、又は炭素数１〜１０のアルコキシ基で置換されていても良いフェニル基；或いは炭素数１〜１０のアルキル基、水酸基、又は炭素数１〜１０のアルコキシ基で置換されていても良いアラルキル基（例えば、ベンジル基、クミル基等）である。Ｒ１としては、特に、メチル基、フェニル基が好ましい。
【００２３】
Ｒ２は、（ａ＋１）価、好ましくは２価の、炭素数１〜１０のアルキル基、水酸基、又は炭素数１〜１０のアルコキシ基で置換されていても良い芳香族炭化水素基（例えば、フェニレン基、ヒドロキシフェニレン基、メトキシフェニレン基等）；炭素数１〜１０のアルキル基、水酸基、又は炭素数１〜１０のアルコキシ基で置換されていても良いアラルキル基（例えば、ｐ−キシリレン基、ｍ−キシリレン基等）；或いは直接結合である。Ｒ２としては、特に、フェニレン基、ヒドロキシフェニレン基が好ましい。
【００２４】
Ｒ３は互いに同一であっても異なっていても良く、水素原子；炭素数１〜１０のアルキル基；或いは炭素数１〜１０のアルキル基、水酸基、又は炭素数１〜１０のアルコキシ基で置換されていても良いフェニル基である。Ｒ３としては、特に、水素原子、メチル基が好ましい。
【００２５】
Ｒ４は互いに同一であっても異なっていても良く、水素原子；炭素数１〜１０のアルキル基；或いは炭素数１〜１０のアルキル基、水酸基、又は炭素数１〜１０のアルコキシ基で置換されていても良いフェニル基である。Ｒ４としては、特に、水素原子、メチル基が好ましい。
【００２６】
Ｒ５は互いに同一であっても異なっていても良く、水素原子；炭素数１〜１０のアルキル基；炭素数１〜１０のアルキル基、水酸基、又は炭素数１〜１０のアルコキシ基で置換されていても良いフェニル基；炭素数１〜１０のアルキル基、水酸基、又は炭素数１〜１０のアルコキシ基で置換されていても良いアラルキル基（例えば、ベンジル基、クミル基等）；或いは炭素数１〜１０のアルコキシ基である。Ｒ５としては、特に、水素原子、メチル基が好ましい。
【００２７】
Ｒ６は水素原子、炭素数１〜１０のアルキル基；炭素数１〜１０のアルキル基、水酸基、又は炭素数１〜１０のアルコキシ基で置換されていても良いフェニル基；炭素数１〜１０のアルキル基、水酸基、又は炭素数１〜１０のアルコキシ基で置換されていても良いアラルキル基（例えば、ベンジル基、クミル基等）；或いは炭素数１〜１０のアルコキシ基である。Ｒ６としては、特に、水素原子、フェニル基が好ましい。
【００２８】
ａは１〜３の整数であり、好ましくは１である。ｂは１〜２の整数であり、好ましくは１である。ｃ，ｄは０〜４の整数であり、好ましくは０、１である。ｊは１〜３の整数であり、好ましくは１、２である。
【００２９】
ｌは平均値で１〜１０の、ｍ、ｎは平均値で０〜１０の数である。好ましくはｌは平均値で１〜５であり、ｍ、ｎは０である。ｍ、ｎが０であると、フェノール樹脂中の硫黄含有量が高くなる為、難燃性の効果が大である点において好ましい。
【００３０】
このような本発明のフェノール樹脂を製造する方法に制約はないが、本発明のフェノール樹脂の製造方法に従って、フェノール化合物と、チオエーテル基を持つアルデヒド類とを、酸性触媒の存在下に付加縮合反応させる方法、或いは、フェノール化合物と、チオエーテル基を持つアルデヒド類と、他のアルデヒド類（即ち、チオエーテル基を持つアルデヒド類以外のアルデヒド類）及び／又は下記一般式（ＩＩ）で表される化合物とを、酸性触媒の存在下に付加縮合反応させる方法が、容易な操作で純度の良いフェノール樹脂が得られる点で好ましい。
【００３１】
【化６】
【００３２】
ここで用いられるチオエーテル基を持つアルデヒド類の具体例としては、メチルチオベンズアルデヒド、エチルチオベンズアルデヒド、プロピルチオベンズアルデヒド、ブチルチオベンズアルデヒド、フェニルチオベンズアルデヒド、メチルチオヒドロキシベンズアルデヒド、メチルチオプロピオンアルデヒド等が挙げられ、これらは１種を単独で用いても良く、２種以上を併用しても良い。これらのチオエーテル基を持つアルデヒド類の中では、物性や入手の容易さから、メチルチオベンズアルデヒド又はメチルチオヒドロキシベンズアルデヒドが好ましい。
【００３３】
ここで用いられるフェノール化合物の具体例としては、フェノール、クレゾール、キシレノール、プロピルフェノール、ブチルフェノール、ブチルクレゾール、フェニルフェノール、クミルフェノール、メトキシフェノール、ブロモフェノール等が挙げられ、これらは１種を単独で用いても良く、２種以上を併用しても良い。これらのフェノール化合物の中では、物性や入手の容易さから、フェノール又はクレゾールが好ましい。
【００３４】
また、ここで用いられる他のアルデヒド類の具体例としては、ホルムアルデヒド、アセトアルデヒド、プロピルアルデヒド、ブチルアルデヒド、バレルアルデヒド、カプロンアルデヒド、ベンズアルデヒド、クロルベンズアルデヒド、ブロムベンズアルデヒド、グリオキザール、マロンアルデヒド、スクシンアルデヒド、グルタルアルデヒド、アジピンアルデヒド、ピメリンアルデヒド、セバシンアルデヒド、アクロレイン、クロトンアルデヒド、サリチルアルデヒド、フタルアルデヒド、ヒドロキシベンズアルデヒド等が挙げられ、これらは１種を単独で用いても良く、２種以上を併用しても良い。
【００３５】
また、ここで用いられる前記一般式（ＩＩ）で表される化合物の具体例としては、α，α’−キシレングリコール、α，α’−キシレンジクロライド、α，α’−ジクロロエチルベンゼン、α，α’−ジクロロプロピルベンゼン、或いはα，α’−ジハロアルキルベンゼン類のアルキル置換体などが挙げられ、これらは１種を単独で用いても良く、２種以上を併用しても良い。
【００３６】
上述のフェノール化合物とチオエーテル基を持つアルデヒド類、必要に応じて用いられる他のアルデヒド類及び／又は一般式（ＩＩ）で表される化合物を付加縮合反応させる際、フェノール化合物に対するチオエーテル基を持つアルデヒド類、他のアルデヒド類、一般式（ＩＩ）で表される化合物の使用割合は、多くなるほど得られるフェノール樹脂が高分子量化し、硬化物の耐熱性向上などに寄与する一方で、樹脂が高粘度となるため、これを用いた組成物の流れ性が悪化する。従って、その使用割合は使用目的に応じて調整する必要があるが、通常は、上述のフェノール化合物１モルに対して、チオエーテル基を持つアルデヒド類、他のアルデヒド類、一般式（ＩＩ）で表される化合物の合計の割合が好ましくは０．１〜２．０モル、より好ましくは０．１５〜１．０モルである。
【００３７】
付加縮合反応に用いられる酸性触媒としては、例えば、塩酸、硫酸等の鉱酸類；シュウ酸、トルエンスルホン酸等の有機酸類；珪タングステン酸、リンタングステン酸等のヘテロポリ酸；活性白土；その他酸性を示す有機酸塩類等の、ノボラック樹脂製造用の通常の酸性触媒の１種又は２種以上を使用することができる。このような酸性触媒の使用量は、フェノール化合物１００重量部に対して好ましくは０．１〜５重量部、より好ましくは０．３〜３重量部である。
【００３８】
この付加縮合反応の反応条件としては、一般のノボラック化反応条件を用いることができる。即ち酸性触媒の存在下に、２０〜２００℃の温度で１〜２０時間反応させる条件が好ましい。
【００３９】
なお、この付加縮合反応においては、芳香族炭化水素類、アルコール類、エーテル類等の不活性溶剤、更に反応条件を選択することにより、ケトン系溶剤等の溶剤を用いることができる。
【００４０】
反応終了後は、必要に応じて、酸性触媒、酸性触媒を中和した場合はその塩、未反応のフェノール化合物及び反応溶媒などを除去することにより、本発明のフェノール樹脂を得ることができる。このようにして製造された本発明のフェノール樹脂を半導体封止材用に使用する場合には、酸性触媒又はその塩を水洗、濾過、吸着等の方法で十分に除去することが、半導体の腐食を防止する上で好ましい。
【００４１】
以上のようにして製造される本発明のフェノール樹脂の品質性状は、各原料の種類、使用割合、反応条件、精製方法等により変化するため、用途に応じて適宜調製されるが、このフェノール樹脂をエポキシ樹脂用硬化剤として使用する場合には、水酸基当量が１２０〜３００ｇ／ｅｑ．、好ましくは１３０〜２５０ｇ／ｅｑ．、軟化点が５０〜１４０℃、好ましくは６０〜１２０℃、１５０℃の溶融粘度が０．８Ｐａ・ｓ以下、好ましくは０．５Ｐａ・ｓ以下となるよう各種条件等を調整することが好ましい。
【００４２】
本発明のエポキシ樹脂用硬化剤は、このような本発明のフェノール樹脂を含むものであり、難燃性付与成分としてハロゲン化合物やアンチモン化合物を添加すること無しに、優れた難燃性を付与すると共に、成形性及び耐ハンダクラック性に優れたエポキシ樹脂硬化物を与えることができる。
【００４３】
本発明のエポキシ樹脂用硬化剤は、本発明のフェノール樹脂を単独で用いたものであっても良いし、本発明のフェノール樹脂の２種以上を混合したものであっても良く、本発明のフェノール樹脂に他のエポキシ樹脂用硬化剤を混合したものであっても良い。併用し得る他のエポキシ樹脂用硬化剤としては、例えば、ビスフェノールＡ、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、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、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、ビフェニルアラルキル樹脂、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、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、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等の各種のフェノール樹脂；テトラヒドロ無水フタル酸、無水ピロメリット酸等の酸無水物類；ジアミノジフェニルメタン等のアミン類等が挙げられ、これらは１種を単独で用いても良く、２種以上を併用しても良い。本発明のエポキシ樹脂用硬化剤を半導体封止用に使用する場合には、併用される他の硬化剤としては、ノボラック型フェノール樹脂、フェノールアラルキル樹脂、ビフェニルアラルキル樹脂、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等のフェノール樹脂類が好ましい。
【００４４】
このような他の硬化剤を併用する場合、併用される他の硬化剤の使用量は、全硬化剤量に対して、９０重量％以下、好ましくは５０重量％以下、さらに好ましくは３０重量％以下である。他の硬化剤の併用量が多すぎると、本発明のフェノール樹脂を用いることによる効果が十分発揮されなくなる。
【００４５】
このような他の硬化剤を併用する場合、他の硬化剤は、本発明のフェノール樹脂と、エポキシ樹脂組成物を調製する前に予め混合してから用いても良く、エポキシ樹脂組成物の配合時にそれぞれの必要量を配合しても良い。
【００４６】
本発明のエポキシ樹脂用硬化剤の品質性状は、各成分の種類、使用割合等により変化するが、水酸基当量が１２０〜３００ｇ／ｅｑ．、好ましくは１３０〜２５０ｇ／ｅｑ．、軟化点が５０〜１４０℃、好ましくは６０〜１２０℃、１５０℃の溶融粘度が０．８Ｐａ・ｓ以下、好ましくは０．５Ｐａ・ｓ以下となるよう各種条件等を調整することが好ましい。この水酸基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。また、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、高すぎるとエポキシ樹脂等との混合が困難になる。また、溶融粘度が高すぎると成形時の流動性が損なわれる。
【００４７】
次に、このような本発明のエポキシ樹脂用硬化剤を用いた本発明のエポキシ樹脂組成物について説明する。本発明のエポキシ樹脂組成物は、エポキシ樹脂と本発明のエポキシ樹脂用硬化剤とを必須成分として配合してなるものである。
【００４８】
このエポキシ樹脂組成物に用いるエポキシ樹脂としては、一般のエポキシ樹脂を使用することができる。そのエポキシ樹脂としては例えば、ビスフェノールＡ、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、テルペンジフェノール、トリス（ヒドロキシルフェニル）メタン、テトラキス（ヒドロキシフェニル）エタン、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、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、ビフェニルアラルキル樹脂、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、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、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等の各種のフェノール化合物と、エピハロヒドリンとから製造されるエポキシ樹脂や、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の種々のアミン化合物と、エピハロヒドリンとから製造されるエポキシ樹脂、メチルヘキサヒドロキシフタル酸、ダイマー酸などの種々のカルボン酸類と、エピハロヒドリンとから製造されるエポキシ樹脂などが挙げられ、これらは１種を単独で用いても良く、２種以上を併用しても良い。
【００４９】
特に、本発明のエポキシ樹脂組成物を半導体封止用に使用する場合には、エポキシ樹脂として、ビスフェノールＡ、ビスフェノールＦ、ビフェノール、テトラメチルビフェノール、テルペンジフェノール、トリス（ヒドロキシルフェニル）メタン、テトラキス（ヒドロキシフェニル）エタン、ジシクロペンタジエンフェノール樹脂、ビフェニルアラルキル樹脂及びクレゾールノボラック樹脂よりなる群から選ばれた少なくとも１種類のフェノール化合物と、エピハロヒドリンとから製造されるエポキシ樹脂の１種又は２種以上を使用することが好ましい。
【００５０】
本発明のエポキシ樹脂組成物に使用される本発明のエポキシ樹脂用硬化剤の使用量は、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。
【００５１】
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、硬化促進剤、無機充填材、カップリング剤、難燃剤、可塑剤、反応性希釈剤、顔料等が挙げられ、必要に応じて適宜に配合することができる。
【００５２】
その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、これらの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、これらは１種を単独で用いても良く、２種以上を併用しても良い。こ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。これらの硬化促進剤は、全エポキシ樹脂１００重量部に対して０．１〜８重量部用いることが好ましく、０．３〜５重量部用いることがより好ましい。
【００５３】
また、その無機充填材としては例えば、溶融シリカ、結晶性シリカ、ガラス粉、アルミナ、炭酸カルシウムなどが挙げられ、これらは１種を単独で用いても良く、２種以上を併用しても良い。特に、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重量％配合することが好ましい。
【００５４】
また、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、これらは１種を単独で用いても良く、２種以上を併用しても良い。しかし、本発明のエポキシ樹脂用硬化剤を用いた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或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ことが好ましい。
【００５５】
本発明の新規なフェノール樹脂は種々の用途に使用することができるが、特に、このフェノール樹脂をエポキシ樹脂用硬化剤の主成分として用いた場合、難燃性付与成分としてハロゲン化合物やアンチモン化合物を添加すること無しに、優れた難燃性を有し、かつ成形性及び耐ハンダクラック性に優れるエポキシ樹脂硬化物を与える。従って、この硬化剤を用いた本発明のエポキシ樹脂組成物は、電気電子分野、特に半導体封止の用途に有用である。
【００５６】
【実施例】
以下に実施例及び比較例を挙げて、本発明をより具体的に説明する。
【００５７】
［フェノール樹脂の製造］
＜実施例１＞
温度計、撹拌装置、及び冷却管を備えた内容量２Ｌの三ッ口フラスコに、フェノール１７５ｇ、パラトルエンスルホン酸５ｇを仕込み、８０℃に昇温した。撹拌しながら、４−（メチルチオ）ベンズアルデヒド９４ｇを１時間かけて滴下した。滴下終了後、温度を８０℃に保ちながら１時間保持して反応を行わせた。更に、温度を１２０℃まで昇温し、３時間反応を行わせた。続いて、８０℃まで冷却した後、トルエン９００ｇを加え、系内が中性になるまで水洗した。その後、１６０℃、５ｔｏｒｒ（０．６７ｋＰａ）の減圧下でトルエンと未反応のフェノールを留去し、目的のフェノール樹脂を得た。このフェノール樹脂は前記一般式（Ｉ）における各記号が表１に示すフェノール樹脂であり、そのフェノール性水酸基当量、軟化点、１５０℃での溶融粘度、及び外観は表１に示す通りであった。このフェノール樹脂のＧＰＣチャートを図１に、ＩＲチャートを図２に示す。
【００５８】
＜実施例２＞
実施例１において、フェノールの使用量を１１７ｇとしたこと以外は、実施例１と同様の操作を行い、目的のフェノール樹脂を得た。このフェノール樹脂は前記一般式（Ｉ）における各記号が表１に示すフェノール樹脂であり、そのフェノール性水酸基当量、軟化点、１５０℃での溶融粘度、及び外観は表１に示す通りであった。
【００５９】
＜実施例３＞
実施例１において、フェノール１７５ｇの代りにクレゾール１８５ｇを用い、４−（メチルチオ）ベンズアルデヒドの使用量を８７ｇとしたこと以外は、実施例１と同様の操作を行い、目的のフェノール樹脂を得た。このフェノール樹脂は前記一般式（Ｉ）における各記号が表１に示すフェノール樹脂であり、そのフェノール性水酸基当量、軟化点、１５０℃での溶融粘度、及び外観は表１に示す通りであった。
【００６０】
＜実施例４＞
実施例１において、４−（メチルチオ）ベンズアルデヒド９４ｇの代りに、４−（メチルチオ）サリチルアルデヒド１０４ｇを用いたこと以外は、実施例１と同様の操作を行い、目的のフェノール樹脂を得た。このフェノール樹脂は前記一般式（Ｉ）における各記号が表１に示すフェノール樹脂であり、そのフェノール性水酸基当量、軟化点、１５０℃での溶融粘度、及び外観は表１に示すとおりであった。
【００６１】
＜実施例５＞
実施例１において４−（メチルチオ）ベンズアルデヒドの使用量を４７ｇとし、さらに４−（メチルチオ）ベンズアルデヒドと同時に３７重量％ホルムアルデヒド水溶液２５ｇを１時間かけて滴下したこと以外は、実施例１と同様の操作を行い、目的のフェノール樹脂を得た。このフェノール樹脂は前記一般式（Ｉ）における各記号が表１に示すフェノール樹脂であり、そのフェノール性水酸基当量、軟化点、１５０℃での溶融粘度、及び外観は表１に示すとおりであった。このフェノール樹脂のＧＰＣチャートを図３に、ＩＲチャートを図４に示す。
【００６２】
【表１】
［エポキシ樹脂組成物の製造］
＜実施例６〜１３、比較例１，２＞
表２に示したように、エポキシ樹脂として、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、トリス（ヒドロキシフェニル）メタンから誘導されたエポキシ樹脂、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、又は臭素化資エポキシ樹脂を用い、エポキシ樹脂用硬化剤として実施例１〜５で製造した各フェノール樹脂、フェノールアラルキル樹脂、又はフェノールノボラック樹脂を用い、無機充填剤としてシリカ粉末を用い、硬化促進剤としてトリフェニルホスフィンを用い、更にカップリング剤としてエポキシシラン、着色剤としてカーボンブラック、離型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。
【００６４】
なお、実施例１１，１３における、実施例１で製造されたフェノール樹脂と、フェノールアルキル樹脂Ｆとの併用系のエポキシ樹脂用硬化剤の水酸基当量は１７４ｇ／ｅｑ．であり、軟化点は８２℃であり、１５０℃の溶融粘度は０．２８Ｐａ・ｓである。
【００６５】
また、実施例１２における、実施例３で製造されたフェノール樹脂と、フェノールノボラック樹脂Ｇとの併用系のエポキシ樹脂用硬化剤の水酸基当量は１４０ｇ／ｅｑ．であり、軟化点は８５℃であり、１５０℃の溶融粘度は０．２５Ｐａ・ｓである。
【００６６】
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。各溶融混練物のスパイラルフローは表２に示す通りであった。得られた各溶融混練物を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。
【００６７】
ポストキュア後の各試験片の吸湿率、ガラス転移温度、及び難燃性を試験した結果を表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２に示した。
【００６８】
なお、各試験方法は下記の通りである。
［スパイラルフロー（ｃｍ）］
ＥＭＭ−１−６６に準じたスパイラルフロー測定用金型を用いて成形し、流動距離（ｃｍ）を求めた。
［吸湿率（％）］
８５℃、８５％ＲＨ、７２時間後の吸湿率
［ガラス転移温度（℃）］
ＴＭＡ法
［耐ハンダクラック性］
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。
【００６９】
また、表２中の※１〜※５は次の通りである。
※１：Ａ；テトラメチル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「エピコートＹＸ４０００Ｈ」、エポキシ当量：１９３ｇ／ｅｑ）
Ｂ；クレゾールノボラック型エポキシ樹脂（ジャパンエポキシレジン（株）製商品名「エピコート１８０Ｓ６２」、エポキシ当量：１９７ｇ／ｅｑ）
Ｃ；トリス（ヒドロキシルフェニル）メタン型エポキシ樹脂（ジャパンエポキシレジン（株）製商品名「エピコート１０３２Ｓ５０」、エポキシ当量： １６９ｇ／ｅｑ）
Ｄ；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 「エピコートＹＬ６１２１Ｈ」、エポキシ当量：１７２ｇ／ｅｑ）
※２：Ｅ；臭素化エポキシ樹脂（日本化薬社製商品名「ＢＲＥＮ−Ｓ」、エポキシ当量： ３８５ｇ／ｅｑ，臭素含量：４８％）
※３：Ｆ；フェノールアラルキル樹脂（明和化成社製商品名「ＭＥＨ−７８００Ｓ」」、水酸基当量：１７５ｇ／ｅｑ，軟化点：７５℃）
Ｇ；フェノールノボラック樹脂（群栄化学社製商品名「レヂトップＰＳＭ４２６１」 、水酸基当量：１０３ｇ／ｅｑ，軟化点：８５℃）
※４：溶融シリカ粉末（龍森社製商品名「ＲＤ−８」）
※５：エポキシシラン（信越化学工業社製商品名「ＫＢＭ−４０３」）
【００７０】
【表２】
表２より明らかなように、本発明のフェノール樹脂を用いた実施例６〜１３の各成形材料は、比較例１，２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無しに、優れた難燃性を有すると共に、低吸湿性、低応力性のバランスに優れ、特に半導体封止用に用いられた場合、耐ハンダクラック性に優れている。
【００７２】
【発明の効果】
以上詳述した通り、本発明の新規フェノール樹脂は、エポキシ樹脂用硬化剤の主成分として用いた場合に、難燃性付与成分としてハロゲン化合物やアンチモン化合物を添加すること無しに優れた難燃性を付与すると共に、成形性及び耐ハンダクラック性等に優れた硬化物を与えることができる。従って、本発明のフェノール樹脂を含むエポキシ樹脂用硬化剤を用いた本発明のエポキシ樹脂組成物は半導体封止等の用途に有用である。
【図面の簡単な説明】
【図１】実施例１で製造したフェノール樹脂のＧＰＣチャート図である。
【図２】実施例１で製造したフェノール樹脂のＩＲチャート図である。
【図３】実施例５で製造したフェノール樹脂のＧＰＣチャート図である。
【図４】実施例５で製造したフェノール樹脂のＩＲチャート図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel phenol resin and a method for producing the same, a curing agent for an epoxy resin using the phenol resin, and an epoxy resin composition using the curing agent for an epoxy resin. The epoxy resin composition using the phenolic resin of the present invention has excellent flame retardancy without adding a halogen compound or an antimony compound as a flame retardant-imparting component, and has excellent moldability and solder crack resistance. It can provide a cured product, and is particularly useful for semiconductor encapsulation applications.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, epoxy resin compositions have been widely used for encapsulating semiconductor elements from the viewpoints of reliability, productivity, and cost. As with general plastic materials, these epoxy resin compositions for semiconductor encapsulation are required to have flame retardancy. Therefore, apart from the main component, as a flame retardancy-imparting component, a tetrabromobisphenol A-type epoxy resin or bromide is used. A brominated epoxy resin such as a phenolized novolak type epoxy resin and antimony oxide are combined.
[0003]
However, in recent years, there has been an increasing movement to restrict the use of halogen-containing compounds and highly toxic antimony compounds which may generate dioxin-like compounds from the viewpoint of environmental protection. For this reason, with respect to the composition for semiconductor encapsulation, a technique for achieving flame retardancy without using a halogen compound such as the above-mentioned brominated epoxy resin or antimony oxide has been studied. For example, a method of blending red phosphorus (JP-A-9-227765), a method of blending a phosphate ester compound (JP-A-9-235449), and a method of blending a phosphazene compound (JP-A-8-225714) ), A method of blending a metal hydroxide (JP-A-9-241483), a method of blending a flame retardant instead of a halogen compound or antimony oxide, or a method of increasing the blending ratio of a filler (JP-A-7-241). No. 82343) has been studied.
[0004]
However, when red phosphorus is used in the epoxy resin composition for semiconductor encapsulation, there is a problem of safety due to a decrease in moisture resistance reliability and the impact and ignition properties of red phosphorus, and when a phosphoric ester or a phosphazene compound is used. The problems of reduced moldability and moisture resistance reliability due to plasticization, the problem of reduced fluidity when using a metal hydroxide or increasing the blending ratio of the filler, respectively, In this case, the moldability and reliability equivalent to those of the epoxy resin composition for encapsulation using a brominated epoxy resin and antimony oxide in combination have not been obtained.
[0005]
On the other hand, in order to respond to advanced mounting methods in the semiconductor field, epoxy resin compositions for encapsulation require even more moldability and solder crack resistance. It is necessary to give due consideration to the rapid curability, fluidity, low hygroscopicity and adhesion of the product.
[0006]
In order to satisfy these requirements, a composition comprising a phenol resin which gives a long cured product between cross-linking points, such as a tetramethyl biphenol type epoxy resin and a phenol aralkyl resin, is used to improve moisture absorption and low stress ( Japanese Patent Application Laid-Open No. Sho 61-47725), an epoxy resin using dicyclopentadiene phenol as a raw material is used as a main component to improve moisture absorption (Japanese Patent Application Laid-Open No. 61-123618). Various proposals have been made, such as using an epoxy compound of a co-condensed novolak resin of ortho-cresol and benzaldehyde as a main component in order to achieve a balance (Japanese Patent Application Laid-Open No. 1-271415). However, none of these proposals can be said to be environmentally friendly proposals, and sufficient flame retardancy cannot be achieved unless a halogen compound or an antimony compound is used as a flame retardant.
[0007]
[Patent Document 1]
JP-A-9-227765
[Patent Document 2]
JP-A-9-235449
[Patent Document 3]
JP-A-8-225714
[Patent Document 4]
JP-A-9-241483
[Patent Document 5]
JP-A-7-82343
[Patent Document 6]
JP-A-61-47725
[Patent Document 7]
JP-A-61-123618
[Patent Document 8]
JP-A-1-271415
[0008]
[Problems to be solved by the present invention]
The present invention is useful for various applications, especially when used as a curing agent for epoxy resins, without adding a halogen compound and an antimony compound as a flame retardant component, and has excellent flame retardancy Phenolic resin capable of providing a cured product excellent in moldability and solder crack resistance, a method for producing the same, a curing agent for an epoxy resin using the phenolic resin, and an epoxy using the curing agent for an epoxy resin An object of the present invention is to provide a resin composition, particularly an epoxy resin composition for semiconductor encapsulation.
[0009]
[Means for Solving the Problems]
The phenol resin of the present invention is characterized by being represented by the following general formula (I).
[0010]
Embedded image
R 1 May be the same or different, and represent an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted aralkyl group.
R 2 Represents a (a + 1) -valent hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aralkyl group, or a direct bond.
R 3 May be the same or different, and represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenyl group.
R 4 May be the same or different, and represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenyl group.
R 5 May be the same or different from each other, and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, or an alkoxy group having 1 to 10 carbon atoms. Is shown.
R 6 Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, or an alkoxy group having 1 to 10 carbon atoms.
a is an integer of 1 to 3, b is an integer of 1 to 2, c and d are an integer of 0 to 4, and j is an integer of 1 to 3.
1 is a number of 1 to 10 on average, and m and n are numbers of 0 to 10 on average.
Here, the term "substituted" means that a hydrogen atom is replaced by an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. )
[0011]
That is, the present inventors have conducted various studies in order to solve the above-mentioned problems, and as a result, as long as the thioether group-containing phenol resin is obtained by a condensation reaction between an aldehyde having a thioether group and a phenol compound, It has been found that the object of the present invention can be achieved by using as a curing agent for an epoxy resin, and the present invention has been completed.
[0012]
In the phenol resin of the present invention, m and n in the general formula (I) are preferably 0.
[0013]
Such a phenolic resin of the present invention is represented by a phenolic compound, an aldehyde having a thioether group, and if necessary, other aldehydes other than the aldehyde having the thioether group and / or the following general formula (II). Can be easily and highly purified by the method for producing a phenolic resin of the present invention in which the compound is reacted in the presence of an acidic catalyst.
[0014]
Embedded image
[0015]
The curing agent for epoxy resin of the present invention is a curing agent for epoxy resin containing such a phenolic resin of the present invention, wherein the content of the phenolic resin is 5 to 100% by weight.
[0016]
The epoxy resin composition of the present invention is characterized by containing an epoxy resin and a curing agent for the epoxy resin.
[0017]
In the epoxy resin composition of the present invention, as the epoxy resin, bisphenol A, bisphenol F, biphenol, tetramethylbiphenol, terpene diphenol, tris (hydroxylphenyl) methane, tetrakis (hydroxyphenyl) ethane, dicyclopentadiene phenol resin, An epoxy resin produced from at least one phenol compound selected from the group consisting of biphenylaralkyl resins and cresol novolak resins and epihalohydrin is preferred.
[0018]
The epoxy resin composition for semiconductor encapsulation of the present invention is an epoxy resin for semiconductor encapsulation which comprises a crushed and / or spherical, fused and / or crystalline silica powder as an inorganic filler in such an epoxy resin composition. A composition, wherein the content of the inorganic filler is 70 to 95% by weight.
[0019]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
[0020]
First, the novel phenolic resin of the present invention represented by the following general formula (I) will be described.
[0021]
Embedded image
In the above general formula, R 1 May be the same or different from each other, and may be an alkyl group having 1 to 10 carbon atoms; phenyl which may be substituted with an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. A aralkyl group (eg, a benzyl group, a cumyl group, etc.) which may be substituted with an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. R 1 Particularly, a methyl group and a phenyl group are preferable.
[0023]
R 2 Is an (a + 1) -valent, preferably divalent, aromatic hydrocarbon group which may be substituted by an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms (for example, a phenylene group) , A hydroxyphenylene group, a methoxyphenylene group, etc.); an aralkyl group which may be substituted by an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms (for example, p-xylylene group, m- Or a direct bond. R 2 Particularly, a phenylene group and a hydroxyphenylene group are preferable.
[0024]
R 3 May be the same or different and are each substituted with a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; or an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. Is a phenyl group. R 3 Particularly, a hydrogen atom and a methyl group are preferable.
[0025]
R 4 May be the same or different and are each substituted with a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; or an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. May be a phenyl group. R 4 Particularly, a hydrogen atom and a methyl group are preferable.
[0026]
R 5 May be the same or different, and each represents a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; substituted with an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. A phenyl group; an aralkyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms (for example, a benzyl group, a cumyl group, etc.); 10 alkoxy groups. R 5 Particularly, a hydrogen atom and a methyl group are preferable.
[0027]
R 6 Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms; a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms; A aralkyl group (for example, a benzyl group, a cumyl group, etc.) which may be substituted with a group, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms; or an alkoxy group having 1 to 10 carbon atoms. R 6 Particularly, a hydrogen atom and a phenyl group are preferable.
[0028]
a is an integer of 1 to 3, and is preferably 1. b is an integer of 1 to 2, preferably 1. c and d are integers of 0 to 4, preferably 0 and 1. j is an integer of 1 to 3, preferably 1, 2.
[0029]
1 is a number of 1 to 10 on average, and m and n are numbers of 0 to 10 on average. Preferably, 1 is 1 to 5 on average, and m and n are 0. When m and n are 0, the sulfur content in the phenol resin increases, which is preferable in that the flame retardant effect is large.
[0030]
The method for producing the phenolic resin of the present invention is not limited, but according to the method for producing the phenolic resin of the present invention, a phenol compound and an aldehyde having a thioether group are subjected to an addition condensation reaction in the presence of an acidic catalyst. Or a phenol compound, an aldehyde having a thioether group, another aldehyde (that is, an aldehyde other than the aldehyde having a thioether group) and / or a compound represented by the following general formula (II). Is preferred in that an addition condensation reaction is carried out in the presence of an acidic catalyst in that a phenol resin having high purity can be obtained by a simple operation.
[0031]
Embedded image
[0032]
Specific examples of the aldehyde having a thioether group used herein include methylthiobenzaldehyde, ethylthiobenzaldehyde, propylthiobenzaldehyde, butylthiobenzaldehyde, phenylthiobenzaldehyde, methylthiohydroxybenzaldehyde, and methylthiopropionaldehyde. The seeds may be used alone or in combination of two or more. Among these aldehydes having a thioether group, methylthiobenzaldehyde or methylthiohydroxybenzaldehyde is preferable from the viewpoint of physical properties and availability.
[0033]
Specific examples of the phenol compound used herein include phenol, cresol, xylenol, propylphenol, butylphenol, butylcresol, phenylphenol, cumylphenol, methoxyphenol, bromophenol, and the like. They may be used, or two or more kinds may be used in combination. Among these phenol compounds, phenol or cresol is preferred from the viewpoint of physical properties and availability.
[0034]
Further, specific examples of other aldehydes used herein include formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chlorbenzaldehyde, bromobenzaldehyde, glyoxal, malonaldehyde, succinaldehyde, and glutaraldehyde. Aldehyde, adipaldehyde, pimeraldehyde, sebacinaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde, etc., may be used alone or in combination of two or more. good.
[0035]
Specific examples of the compound represented by the general formula (II) used herein include α, α′-xylene glycol, α, α′-xylene dichloride, α, α′-dichloroethylbenzene, α, α. Examples include '-dichloropropylbenzene or alkyl-substituted α, α'-dihaloalkylbenzenes, and these may be used alone or in combination of two or more.
[0036]
When the above-mentioned phenol compound and an aldehyde having a thioether group, another aldehyde used as necessary and / or an addition condensation reaction of the compound represented by the general formula (II), an aldehyde having a thioether group with respect to the phenol compound , The other aldehydes, and the compound represented by the general formula (II), the higher the ratio, the higher the phenol resin obtained has a higher molecular weight and contributes to the improvement of heat resistance of the cured product. Therefore, the flowability of the composition using this becomes worse. Therefore, the use ratio must be adjusted according to the purpose of use, but usually, the aldehyde having a thioether group, other aldehydes, and the general formula (II) are represented by 1 mole of the phenol compound. The total ratio of the compounds obtained is preferably 0.1 to 2.0 mol, more preferably 0.15 to 1.0 mol.
[0037]
Examples of the acidic catalyst used for the addition condensation reaction include mineral acids such as hydrochloric acid and sulfuric acid; organic acids such as oxalic acid and toluenesulfonic acid; heteropolyacids such as silicotungstic acid and phosphotungstic acid; activated clay; One or more of ordinary acidic catalysts for producing novolak resins, such as the organic acid salts shown below, can be used. The use amount of such an acidic catalyst is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the phenol compound.
[0038]
As the reaction conditions for this addition condensation reaction, general novolak reaction conditions can be used. That is, it is preferable to carry out the reaction at a temperature of 20 to 200 ° C. for 1 to 20 hours in the presence of an acidic catalyst.
[0039]
In this addition condensation reaction, an inert solvent such as aromatic hydrocarbons, alcohols and ethers, and a solvent such as a ketone solvent can be used by selecting the reaction conditions.
[0040]
After completion of the reaction, the phenolic resin of the present invention can be obtained by removing the acidic catalyst, the salt thereof, the unreacted phenolic compound, the reaction solvent, and the like, if necessary, when the acidic catalyst is neutralized. When the phenolic resin of the present invention thus produced is used for a semiconductor encapsulant, it is necessary to sufficiently remove the acidic catalyst or a salt thereof by a method such as washing with water, filtration, and adsorption. This is preferable in preventing
[0041]
The quality properties of the phenolic resin of the present invention produced as described above vary depending on the type of each raw material, the proportion used, the reaction conditions, the purification method, and the like, and thus are appropriately prepared depending on the application. Is used as a curing agent for epoxy resins, the hydroxyl equivalent is 120 to 300 g / eq. , Preferably 130 to 250 g / eq. It is preferable to adjust various conditions so that the melt viscosity at a softening point of 50 to 140 ° C., preferably 60 to 120 ° C. and 150 ° C. is 0.8 Pa · s or less, preferably 0.5 Pa · s or less.
[0042]
The curing agent for an epoxy resin of the present invention contains such a phenolic resin of the present invention, and imparts excellent flame retardancy without adding a halogen compound or an antimony compound as a flame retardancy-imparting component. At the same time, it is possible to provide an epoxy resin cured product having excellent moldability and solder crack resistance.
[0043]
The curing agent for an epoxy resin of the present invention may be one using the phenolic resin of the present invention alone, or may be a mixture of two or more of the phenolic resins of the present invention. A mixture of a phenolic resin and another curing agent for an epoxy resin may be used. Other curing agents for epoxy resins that can be used in combination include, for example, bisphenol A, bisphenol F, bisphenol AD, biphenol, tetramethylbiphenol, terpene diphenol, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcinol, methylresorcinol, bisphenol S, Various phenols such as thiodiphenol, dihydroxydiphenyl ether, dihydroxynaphthalene, phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, dicyclopentadiene phenol resin, terpene phenol resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol novolak resin And various phenols, hydroxybenzaldehyde, croton alde Phenolic resin obtained by the condensation reaction with various aldehydes such as aldehydes, glyoxal, etc., modified phenol obtained by polycondensing petroleum heavy oil or pitches with formaldehyde polymer and phenols in the presence of an acid catalyst Various phenolic resins such as resins; acid anhydrides such as tetrahydrophthalic anhydride and pyromellitic anhydride; amines such as diaminodiphenylmethane; these may be used alone or in combination of two or more. May be used together. When the epoxy resin curing agent of the present invention is used for semiconductor encapsulation, other curing agents used in combination include novolak phenol resins, phenol aralkyl resins, biphenyl aralkyl resins, dicyclopentadiene phenol resins, and terpenes. Phenolic resins such as phenolic resins are preferred.
[0044]
When such another curing agent is used in combination, the amount of the other curing agent used is 90% by weight or less, preferably 50% by weight or less, more preferably 30% by weight, based on the total amount of the curing agent. It is as follows. If the combined amount of the other curing agents is too large, the effect of using the phenolic resin of the present invention will not be sufficiently exhibited.
[0045]
When such another curing agent is used in combination, the other curing agent may be used after being mixed in advance with the phenolic resin of the present invention before preparing the epoxy resin composition. At times, the respective required amounts may be blended.
[0046]
The quality properties of the curing agent for epoxy resin of the present invention vary depending on the type of each component, the usage ratio, etc., but the hydroxyl equivalent is 120 to 300 g / eq. , Preferably 130 to 250 g / eq. It is preferable to adjust various conditions so that the melt viscosity at a softening point of 50 to 140 ° C., preferably 60 to 120 ° C. and 150 ° C. is 0.8 Pa · s or less, preferably 0.5 Pa · s or less. If the hydroxyl group equivalent is too small, low hygroscopicity is inferior, and if it is too large, curability deteriorates. On the other hand, if the softening point is too low, handling as a solid becomes difficult, and if it is too high, mixing with an epoxy resin or the like becomes difficult. On the other hand, if the melt viscosity is too high, the fluidity during molding is impaired.
[0047]
Next, the epoxy resin composition of the present invention using such a curing agent for an epoxy resin of the present invention will be described. The epoxy resin composition of the present invention comprises an epoxy resin and a curing agent for an epoxy resin of the present invention as essential components.
[0048]
As the epoxy resin used for the epoxy resin composition, a general epoxy resin can be used. Examples of the epoxy resin include bisphenol A, bisphenol F, bisphenol AD, biphenol, tetramethylbiphenol, terpenediphenol, tris (hydroxyphenyl) methane, tetrakis (hydroxyphenyl) ethane, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcinol, Methyl resorcin, bisphenol S, thiodiphenol, dihydroxydiphenyl ether, dihydroxynaphthalene, phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, dicyclopentadiene phenol resin, terpene phenol resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol novolak resin Such as various phenols, various Polyphenolic resin obtained by condensation reaction of phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, petroleum heavy oil or pitch, formaldehyde polymer and phenol in the presence of an acid catalyst Various phenolic compounds such as modified phenolic resin polycondensed underneath, epoxy resins produced from epihalohydrin and various amine compounds such as diaminodiphenylmethane, aminophenol, xylene diamine and epoxy produced from epihalohydrin Resins, various carboxylic acids such as methylhexahydroxyphthalic acid and dimer acid, and epoxy resins produced from epihalohydrin. These may be used alone or in combination of two or more. Is also good.
[0049]
In particular, when the epoxy resin composition of the present invention is used for encapsulating semiconductors, bisphenol A, bisphenol F, biphenol, tetramethylbiphenol, terpenediphenol, tris (hydroxyphenyl) methane, tetrakis ( (Hydroxyphenyl) ethane, dicyclopentadiene phenol resin, biphenyl aralkyl resin and cresol novolak resin, at least one kind of phenol compound selected from the group consisting of epoxy resin and one or more kinds of epoxy resins produced from epihalohydrin Is preferred.
[0050]
The amount of the epoxy resin curing agent of the present invention used in the epoxy resin composition of the present invention is such that the group reacting with the epoxy group in the entire curing agent is 1 mol of the epoxy group in the entire epoxy resin component. The amount is preferably 0.5 to 2.0 mol, more preferably 0.7 to 1.2 mol.
[0051]
Various additives can be added to the epoxy resin composition of the present invention, similarly to other general epoxy resin compositions. These various additives include, for example, a curing accelerator, an inorganic filler, a coupling agent, a flame retardant, a plasticizer, a reactive diluent, a pigment, and the like, and can be appropriately added as needed.
[0052]
Examples of the curing accelerator include phosphine compounds such as tributylphosphine, triphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, and tris (cyanoethyl) phosphine, tetraphenylphosphonium tetraphenylborate, and methyltributylphosphonium tetra. Phosphonium salts such as phenylborate and methyltricyanoethylphosphonium tetraphenylborate, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, 2 , 4-dicyano-6- [2-methylimidazolyl- (1)]-ethyl-S-triazine, 2,4-dicyano-6- [2-undeci Imidazoles such as imidazolyl- (1)]-ethyl-S-triazine, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-ethyl-4-methylimidazolium tetra Imidazolium salts such as phenylborate, 2-ethyl-1,4-dimethylimidazolium tetraphenylborate, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, tetramethylbutylguanidine, N-methylpiperazine , 2-dimethylamino-1-pyrroline and other amines, ammonium salts such as triethylammonium tetraphenylborate, 1,5-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo (4,3 , 0) -5-none , 1,4-diazabicyclo (2,2,2) -octane and the like; tetraphenylborate, phenol salt, phenol novolak salt, 2-ethylhexanoate and the like of these diazabicyclo compounds. The seeds may be used alone or in combination of two or more. Among these compounds that serve as curing accelerators, phosphine compounds, imidazole compounds, diazabicyclo compounds, and salts thereof are preferable. These curing accelerators are preferably used in an amount of 0.1 to 8 parts by weight, more preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the total epoxy resin.
[0053]
Examples of the inorganic filler include fused silica, crystalline silica, glass powder, alumina, calcium carbonate, and the like. These may be used alone or in combination of two or more. . In particular, when the epoxy resin composition of the present invention is used for semiconductor encapsulation, a crushable and / or spherical, fused and / or crystalline silica powder filler is used as the inorganic filler. It is preferable to mix it by 95% by weight.
[0054]
Examples of the flame retardant include halogen-based flame retardants such as brominated epoxy resins and brominated phenol resins, antimony compounds such as antimony trioxide, phosphorus-based flame retardants such as red phosphorus, phosphate esters, and phosphines, and melamine. Examples include nitrogen-based flame retardants such as derivatives and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide. These may be used alone or in combination of two or more. However, since the cured product of the epoxy resin composition using the epoxy resin curing agent of the present invention is excellent in flame retardancy, among the above, brominated epoxy resins and brominated phenol resins, which are particularly concerned with environmental safety, are mentioned. With respect to the halogen-based flame retardants and antimony compounds such as antimony trioxide, these flame retardants do not need to be blended or can be used in a small amount. However, since the flame retardancy varies depending on the type and blending amount of each component in the composition, selection of each component and adjustment of the blending amount so as to secure the flame retardancy of V-0 of UL-94 standard or the equivalent. Is preferred.
[0055]
Although the novel phenolic resin of the present invention can be used for various applications, particularly when this phenolic resin is used as a main component of a curing agent for an epoxy resin, a halogen compound or an antimony compound is used as a flame-retardant component. An epoxy resin cured product having excellent flame retardancy and excellent moldability and solder crack resistance can be obtained without addition. Therefore, the epoxy resin composition of the present invention using this curing agent is useful in the field of electric and electronic fields, particularly for semiconductor encapsulation.
[0056]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
[0057]
[Production of phenolic resin]
<Example 1>
A two-liter three-necked flask equipped with a thermometer, a stirrer, and a condenser was charged with phenol (175 g) and paratoluenesulfonic acid (5 g), and heated to 80 ° C. While stirring, 94 g of 4- (methylthio) benzaldehyde was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction was carried out for 1 hour while maintaining the temperature at 80 ° C. Further, the temperature was raised to 120 ° C., and the reaction was performed for 3 hours. Subsequently, after cooling to 80 ° C., 900 g of toluene was added, and the system was washed with water until the inside of the system became neutral. Thereafter, toluene and unreacted phenol were distilled off at 160 ° C. under a reduced pressure of 5 torr (0.67 kPa) to obtain a target phenol resin. This phenol resin is a phenol resin in which each symbol in the general formula (I) is shown in Table 1, and its phenolic hydroxyl equivalent, softening point, melt viscosity at 150 ° C., and appearance are as shown in Table 1. . FIG. 1 shows a GPC chart and FIG. 2 shows an IR chart of the phenol resin.
[0058]
<Example 2>
The same operation as in Example 1 was carried out except that the amount of phenol used in Example 1 was changed to 117 g, to obtain a target phenol resin. This phenol resin is a phenol resin in which each symbol in the general formula (I) is shown in Table 1, and its phenolic hydroxyl equivalent, softening point, melt viscosity at 150 ° C., and appearance are as shown in Table 1. .
[0059]
<Example 3>
A target phenolic resin was obtained in the same manner as in Example 1 except that 185 g of cresol was used instead of 175 g of phenol and the amount of 4- (methylthio) benzaldehyde used was 87 g. This phenol resin is a phenol resin in which each symbol in the general formula (I) is shown in Table 1, and its phenolic hydroxyl equivalent, softening point, melt viscosity at 150 ° C., and appearance are as shown in Table 1. .
[0060]
<Example 4>
In Example 1, the same operation as in Example 1 was carried out except that 104 g of 4- (methylthio) salicylaldehyde was used instead of 94 g of 4- (methylthio) benzaldehyde, to obtain a target phenol resin. This phenol resin is a phenol resin in which each symbol in the general formula (I) is shown in Table 1, and its phenolic hydroxyl equivalent, softening point, melt viscosity at 150 ° C., and appearance are as shown in Table 1. .
[0061]
<Example 5>
The same operation as in Example 1 except that the amount of 4- (methylthio) benzaldehyde used in Example 1 was 47 g and 25 g of a 37% by weight aqueous solution of formaldehyde was added dropwise over 1 hour simultaneously with 4- (methylthio) benzaldehyde. Was carried out to obtain a desired phenol resin. This phenol resin is a phenol resin in which each symbol in the general formula (I) is shown in Table 1, and its phenolic hydroxyl equivalent, softening point, melt viscosity at 150 ° C., and appearance are as shown in Table 1. . FIG. 3 shows a GPC chart of this phenol resin, and FIG. 4 shows an IR chart thereof.
[0062]
[Table 1]
[Production of epoxy resin composition]
<Examples 6 to 13, Comparative Examples 1 and 2>
As shown in Table 2, as the epoxy resin, an epoxy resin derived from tetramethylbiphenol, an epoxy resin derived from biphenol and tetramethylbiphenol, an epoxy resin derived from tris (hydroxyphenyl) methane, and orthocresol novolak Using an epoxy resin derived from a resin, or a brominated epoxy resin, using each phenolic resin, phenol aralkyl resin, or phenol novolak resin produced in Examples 1 to 5 as a curing agent for the epoxy resin, as an inorganic filler Each epoxy resin composition was compounded using silica powder, triphenylphosphine as a curing accelerator, epoxysilane as a coupling agent, carbon black as a coloring agent, and carnauba wax as a release agent.
[0064]
In addition, in Examples 11 and 13, the phenol resin produced in Example 1 and the phenol alkyl resin F used together with the epoxy resin curing agent had a hydroxyl equivalent of 174 g / eq. The softening point is 82 ° C. and the melt viscosity at 150 ° C. is 0.28 Pa · s.
[0065]
In addition, in Example 12, the hydroxyl equivalent of the curing agent for the epoxy resin of the combined use of the phenol resin produced in Example 3 and the phenol novolak resin G was 140 g / eq. The softening point is 85 ° C. and the melt viscosity at 150 ° C. is 0.25 Pa · s.
[0066]
Next, each compound was melt-kneaded at a temperature of 70 to 120 ° C. for 5 minutes using a mixing roll. The spiral flow of each melt-kneaded product was as shown in Table 2. Each of the obtained melt-kneaded products was taken out into a thin plate, 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.
[0067]
Table 2 shows the results of testing the moisture absorption, the glass transition temperature, and the flame retardancy of each test piece after the post cure. Table 2 shows the results of a test on the solder crack resistance of the simulated semiconductor device sealed with each molding material.
[0068]
In addition, each test method is as follows.
[Spiral flow (cm)]
Molding was performed using a mold for measuring spiral flow according to EMM-1-66, and the flow distance (cm) was determined.
[Moisture absorption (%)]
85 ° C, 85% RH, moisture absorption after 72 hours
[Glass transition temperature (° C)]
TMA method
[Solder crack resistance]
Sixteen 80-pin QFPs were absorbed at 85 ° C. and 85% RH for 72 hours, then immersed in a 260 ° C. solder bath for 10 seconds, and the number of cracks generated was determined.
[0069]
* 1 to * 5 in Table 2 are as follows.
* 1: A: Tetramethyl biphenyl type epoxy resin (trade name “Epicoat YX4000H” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 193 g / eq)
B; Cresol novolak type epoxy resin (trade name “Epicoat 180S62” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 197 g / eq)
C: Tris (hydroxylphenyl) methane type epoxy resin (trade name “Epicoat 1032S50”, manufactured by Japan Epoxy Resins Co., Ltd., epoxy equivalent: 169 g / eq)
D: Biphenyl type epoxy resin (trade name “Epicoat YL6121H”, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 172 g / eq)
* 2: E: Brominated epoxy resin (trade name “BREN-S” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 385 g / eq, bromine content: 48%)
* 3: F: phenol aralkyl resin (trade name “MEH-7800S” manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent: 175 g / eq, softening point: 75 ° C.)
G: phenol novolak resin (trade name “Letop PSM4261”, manufactured by Gunei Chemical Co., hydroxyl equivalent: 103 g / eq, softening point: 85 ° C.)
* 4: Fused silica powder (trade name “RD-8” manufactured by Tatsumori)
* 5: Epoxysilane (brand name “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.)
[0070]
[Table 2]
As is clear from Table 2, each of the molding materials of Examples 6 to 13 using the phenolic resin of the present invention did not contain a halogen compound and an antimony compound as compared with the molding materials of Comparative Examples 1 and 2. In addition to having excellent flame retardancy, it has an excellent balance of low moisture absorption and low stress. Especially when used for semiconductor encapsulation, it has excellent solder crack resistance.
[0072]
【The invention's effect】
As described in detail above, the novel phenolic resin of the present invention, when used as a main component of a curing agent for an epoxy resin, has excellent flame retardancy without adding a halogen compound or an antimony compound as a flame retardancy-imparting component. And a cured product excellent in moldability, solder crack resistance, and the like. Therefore, the epoxy resin composition of the present invention using the epoxy resin curing agent containing the phenolic resin of the present invention is useful for applications such as semiconductor encapsulation.
[Brief description of the drawings]
FIG. 1 is a GPC chart of a phenol resin produced in Example 1.
FIG. 2 is an IR chart of the phenolic resin produced in Example 1.
FIG. 3 is a GPC chart of a phenol resin produced in Example 5.
FIG. 4 is an IR chart of a phenol resin produced in Example 5.
Claims (8)
Ｒ１は互いに同一であっても異なっていても良く、炭素数１〜１０のアルキル基、置換又は無置換のフェニル基、或いは置換又は無置換のアラルキル基を示す。
Ｒ２は、（ａ＋１）価の、炭素数１〜１０の炭化水素基、置換又は無置換の芳香族炭化水素基、置換又は無置換のアラルキル基、或いは直接結合を示す。
Ｒ３は互いに同一であっても異なっていても良く、水素原子、炭素数１〜１０のアルキル基、或いは置換又は無置換のフェニル基を示す。
Ｒ４は互いに同一であっても異なっていても良く、水素原子、炭素数１〜１０のアルキル基、或いは置換又は無置換のフェニル基を示す。
Ｒ５は互いに同一であっても異なっていても良く、水素原子、炭素数１〜１０のアルキル基、置換又は無置換のフェニル基、置換又は無置換のアラルキル基、或いは炭素数１〜１０のアルコキシ基を示す。
Ｒ６は水素原子、炭素数１〜１０のアルキル基、置換又は無置換のフェニル基、置換又は無置換のアラルキル基、或いは炭素数１〜１０のアルコキシ基を示す。
ａは１〜３の、ｂは１〜２の、ｃ，ｄは０〜４の、ｊは１〜３の整数である。
ｌは平均値で１〜１０の数であり、ｍ、ｎは平均値で０〜１０の数である。
ただし、ここで「置換」とは、水素原子が炭素数１〜１０のアルキル基、水酸基、炭素数１〜１０のアルコキシ基に置き換わったものを示す。）A phenol resin represented by the following general formula (I).
R 1 may be the same or different, and represents an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted aralkyl group.
R 2 represents a (a + 1) -valent hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aralkyl group, or a direct bond.
R 3 may be the same or different, and represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenyl group.
R 4 may be the same or different, and represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenyl group.
R 5 may be the same or different from each other, and may be a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, or a group having 1 to 10 carbon atoms. Shows an alkoxy group.
R 6 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, or an alkoxy group having 1 to 10 carbon atoms.
a is an integer of 1 to 3, b is an integer of 1 to 2, c and d are an integer of 0 to 4, and j is an integer of 1 to 3.
1 is a number of 1 to 10 on average, and m and n are numbers of 0 to 10 on average.
Here, the term "substituted" means that a hydrogen atom is replaced by an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms. )
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006112438A1 (en) * | 2005-04-15 | 2006-10-26 | Dainippon Ink And Chemicals, Inc. | Epoxy resin composition, hardening product thereof, semiconductor sealing material, novel epoxy resin, novel polyhydroxy compound and process for producing the same |
| WO2007097209A1 (en) * | 2006-02-22 | 2007-08-30 | Ajinomoto Co., Inc. | Epoxy resin composition |
| JP2010070471A (en) * | 2008-09-17 | 2010-04-02 | Air Water Inc | Phenolic polymer, method of producing the same, and use therefor |
| CN110461938A (en) * | 2017-03-31 | 2019-11-15 | 日立化成株式会社 | Composition epoxy resin and electronic part apparatus |
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2003
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006112438A1 (en) * | 2005-04-15 | 2006-10-26 | Dainippon Ink And Chemicals, Inc. | Epoxy resin composition, hardening product thereof, semiconductor sealing material, novel epoxy resin, novel polyhydroxy compound and process for producing the same |
| WO2007097209A1 (en) * | 2006-02-22 | 2007-08-30 | Ajinomoto Co., Inc. | Epoxy resin composition |
| JP2010070471A (en) * | 2008-09-17 | 2010-04-02 | Air Water Inc | Phenolic polymer, method of producing the same, and use therefor |
| CN110461938A (en) * | 2017-03-31 | 2019-11-15 | 日立化成株式会社 | Composition epoxy resin and electronic part apparatus |
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