JP5240516B2 - Epoxy resin composition, cured product thereof, and build-up film insulating material - Google Patents
Epoxy resin composition, cured product thereof, and build-up film insulating material Download PDFInfo
- Publication number
- JP5240516B2 JP5240516B2 JP2008250203A JP2008250203A JP5240516B2 JP 5240516 B2 JP5240516 B2 JP 5240516B2 JP 2008250203 A JP2008250203 A JP 2008250203A JP 2008250203 A JP2008250203 A JP 2008250203A JP 5240516 B2 JP5240516 B2 JP 5240516B2
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- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- group
- curing agent
- hydrogen atom
- 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.)
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- 239000003822 epoxy resin Substances 0.000 title claims description 111
- 229920000647 polyepoxide Polymers 0.000 title claims description 111
- 239000000203 mixture Substances 0.000 title claims description 53
- 239000011810 insulating material Substances 0.000 title claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 50
- 229920005989 resin Polymers 0.000 claims description 46
- 239000011347 resin Substances 0.000 claims description 46
- 239000005011 phenolic resin Substances 0.000 claims description 32
- 239000003960 organic solvent Substances 0.000 claims description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 9
- 125000005129 aryl carbonyl group Chemical group 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 238000001723 curing Methods 0.000 description 45
- 239000010410 layer Substances 0.000 description 35
- 238000000034 method Methods 0.000 description 29
- 239000000047 product Substances 0.000 description 25
- -1 ester compound Chemical class 0.000 description 23
- 229920003986 novolac Polymers 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 150000002989 phenols Chemical class 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000758 substrate Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 11
- 239000011256 inorganic filler Substances 0.000 description 11
- 229910003475 inorganic filler Inorganic materials 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 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 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000004305 biphenyl Substances 0.000 description 9
- 239000004020 conductor Substances 0.000 description 9
- 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 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000012435 aralkylating agent Substances 0.000 description 8
- 230000001588 bifunctional effect Effects 0.000 description 8
- 235000010290 biphenyl Nutrition 0.000 description 8
- 229930003836 cresol Natural products 0.000 description 8
- 238000010030 laminating Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- 239000002313 adhesive film Substances 0.000 description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 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 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 125000004437 phosphorous atom Chemical group 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 229940035429 isobutyl alcohol Drugs 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 2
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- 229940093475 2-ethoxyethanol Drugs 0.000 description 2
- GSKNLOOGBYYDHV-UHFFFAOYSA-N 2-methylphenol;naphthalen-1-ol Chemical compound CC1=CC=CC=C1O.C1=CC=C2C(O)=CC=CC2=C1 GSKNLOOGBYYDHV-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XFSBVAOIAHNAPC-WSORPINJSA-N acetylbenzoylaconine Chemical compound O([C@H]1[C@]2(O)C[C@H]3C45[C@@H]6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)C4[C@]([C@@H](C[C@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-WSORPINJSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N beta-hydroxynaphthyl Natural products C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012796 inorganic flame retardant Chemical class 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- VSWALKINGSNVAR-UHFFFAOYSA-N naphthalen-1-ol;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C(O)=CC=CC2=C1 VSWALKINGSNVAR-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- 150000003003 phosphines Chemical group 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
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- 238000003786 synthesis reaction Methods 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
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- 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
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-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
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- 150000003918 triazines Chemical class 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- QLORRTLBSJTMSN-UHFFFAOYSA-N tris(2,6-dimethylphenyl) phosphate Chemical compound CC1=CC=CC(C)=C1OP(=O)(OC=1C(=CC=CC=1C)C)OC1=C(C)C=CC=C1C QLORRTLBSJTMSN-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
本発明は、硬化物のガラス領域、及び硬化物が暴される温度領域（サーマルサイクル条件下）における線膨張係数が極めて低いために寸法安定性に優れ、且つ熱的衝撃／物理的衝撃にも優れる（強靭性）エポキシ樹脂組成物に関する。 The present invention has excellent dimensional stability because of its extremely low coefficient of linear expansion in the glass region of the cured product and in the temperature region where the cured product is exposed (under thermal cycle conditions), and is also suitable for thermal shock / physical impact. The present invention relates to an excellent (toughness) epoxy resin composition.
エポキシ樹脂及びその硬化剤を必須成分とするエポキシ樹脂組成物は、その硬化物において優れた耐熱性と絶縁性を発現することから、半導体やプリント配線基板などの電子部品用途において広く用いられている。 An epoxy resin composition containing an epoxy resin and a curing agent as an essential component exhibits excellent heat resistance and insulation in the cured product, and is therefore widely used in electronic component applications such as semiconductors and printed wiring boards. .
この電子部品用途のなかでも半導体パッケージ基板材料におけるビルドアップ基板の技術分野では、絶縁材料に用いられる樹脂材料としてこれまでの液状材料に代わり、エポキシ樹脂及び硬化剤を必須成分とするエポキシ樹脂組成物からフィルム状に成形した所謂ビルドアップフィルムを基板上にラミネート、硬化させる技術が注目されている。然し乍ら、このようなフィルム単体で絶縁層を形成するためより硬化物自体に耐熱性、耐湿性、及び強度が求められている。
このような電子部品用途における高耐熱性、高耐湿性の樹脂材料として例えば、フェノール−ビフェニルアラルキル樹脂をエポキシ樹脂原料、或いはエポキシ樹脂用硬化剤として使用する技術が知られている（下記、特許文献１参照）。
しかしながら、近年、各種電子機器における信号の高速化、高周波数化が進んでいる為に、絶縁材料にもより低い誘電率、低誘電正接が求められているところ、エポキシ樹脂材料を用いた場合には、エポキシ樹脂硬化反応時に生じる水酸基の存在により誘電率や誘電正接が十分に低減できないものであった。
そこで、従来より、この硬化反応時に生成する水酸基を保護することによって、低誘電率・低誘電正接を実現し、加えて、耐湿性を一層改善する技術としてフェノール−フェニレンアラルキル樹脂をアリールエステル化して得られる活性エステル系化合物をエポキシ樹脂硬化剤として用いる技術が知られている（下記、特許文献２参照）。しかしながら、かかる活性エステル系化合物を硬化剤として用いた場合、低誘電率・低誘電正接を発現し、かつ、良好な耐湿性を発現させることが可能となるものの、該化合物のアラルキル基の存在により、硬化物の架橋密度が低くなってしまい、耐熱性が十分に発現されない他、芳香族性が高いにも関わらず、十分な難燃性が得られないものであった。
Among these electronic component applications, in the technical field of build-up substrates in semiconductor package substrate materials, epoxy resin compositions containing epoxy resin and curing agent as essential components instead of conventional liquid materials as resin materials used for insulating materials A so-called build-up film formed into a film is laminated and cured on a substrate. However, in order to form an insulating layer with such a single film, the cured product itself is required to have heat resistance, moisture resistance, and strength.
As a resin material having high heat resistance and high moisture resistance in such an electronic component application, for example, a technique using phenol-biphenyl aralkyl resin as an epoxy resin raw material or a curing agent for epoxy resin is known (the following patent document). 1).
However, in recent years, as signal speeds and frequencies have increased in various electronic devices, lower dielectric constants and lower dielectric loss tangents are also required for insulating materials. When epoxy resin materials are used, In this case, the dielectric constant and dielectric loss tangent cannot be sufficiently reduced due to the presence of a hydroxyl group produced during the epoxy resin curing reaction.
Therefore, by protecting the hydroxyl groups generated during this curing reaction, a low dielectric constant and low dielectric loss tangent have been realized, and in addition, phenol-phenylene aralkyl resins have been arylesterified as a technique for further improving moisture resistance. A technique using the resulting active ester compound as an epoxy resin curing agent is known (see Patent Document 2 below). However, when such an active ester compound is used as a curing agent, it can exhibit a low dielectric constant and a low dielectric loss tangent and can exhibit good moisture resistance, but due to the presence of an aralkyl group of the compound. In addition, the cross-linking density of the cured product is low, heat resistance is not sufficiently exhibited, and sufficient flame retardancy cannot be obtained despite high aromaticity.
従って、本発明が解決しようとする課題は、電子部品の絶縁材料として硬化物の誘電率及び誘電正接が十分に低く、かつ、硬化物の耐熱性及び難燃性に著しく優れるエポキシ樹脂組成物、及びその硬化物を提供することにある。 Therefore, the problem to be solved by the present invention is an epoxy resin composition that has a sufficiently low dielectric constant and dielectric loss tangent of a cured product as an insulating material for electronic parts, and is extremely excellent in heat resistance and flame retardancy of the cured product, And providing a cured product thereof.
本発明者等は上記課題を解決すべく鋭意検討を重ねた結果、エポキシ樹脂（Ａ）及び硬化剤（Ｂ）を必須成分とするエポキシ樹脂組成物であって、前記硬化剤（Ｂ）が、下記一般式１ As a result of intensive studies to solve the above-mentioned problems, the present inventors are an epoxy resin composition containing an epoxy resin (A) and a curing agent (B) as essential components, and the curing agent (B) is: The following general formula 1
（式中、Ｘは水素原子、アルキルカルボニル基、又は、アリールカルボニル基を表し、Ｒ１〜Ｒ３は、水素原子、炭素原子数１〜４のアルキル基、又はフェニル基を表し、Ｒ４は水素原子又はメチル基を表し、ｎは繰り返し単位の平均で０〜１０である。但し、Ｘのうち少なくとも１つはアルキルカルボニル基又はアリールカルボニル基である。）
で表される活性エステル樹脂（ｂ）を硬化剤として用いることにより、低誘電率・低誘電正接を実現すると共に、硬化物の耐熱性及び難燃性を飛躍的に改善できることを見出し、本発明を完成するに至った。
(In the formula, X represents a hydrogen atom, an alkylcarbonyl group, or an arylcarbonyl group, R 1 to R 3 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R 4 represents Represents a hydrogen atom or a methyl group, and n is an average of repeating units of 0 to 10, provided that at least one of X is an alkylcarbonyl group or an arylcarbonyl group.
By using the active ester resin (b) represented by the formula (I) as a curing agent, it has been found that the low dielectric constant and low dielectric loss tangent can be achieved, and the heat resistance and flame retardancy of the cured product can be dramatically improved. It came to complete.
即ち、本発明は、エポキシ樹脂（Ａ）及び硬化剤（Ｂ）を必須成分とするエポキシ樹脂組成物であって、前記硬化剤（Ｂ）が、下記一般式１ That is, this invention is an epoxy resin composition which has an epoxy resin (A) and a hardening | curing agent (B) as an essential component, Comprising: The said hardening | curing agent (B) is the following general formula 1
（式中、Ｘは水素原子、アルキルカルボニル基、又は、アリールカルボニル基を表し、Ｒ１〜Ｒ３は、水素原子、炭素原子数１〜４のアルキル基、又はフェニル基を表し、Ｒ４は水素原子又はメチル基を表し、ｎは繰り返し単位の平均で０〜１０である。但し、Ｘのうち少なくとも１つはアルキルカルボニル基又はアリールカルボニル基である。）
で表される活性エステル樹脂（ｂ）を含有することを特徴とするエポキシ樹脂組成物に関する。
(In the formula, X represents a hydrogen atom, an alkylcarbonyl group, or an arylcarbonyl group, R 1 to R 3 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R 4 represents Represents a hydrogen atom or a methyl group, and n is an average of repeating units of 0 to 10, provided that at least one of X is an alkylcarbonyl group or an arylcarbonyl group.
The epoxy resin composition characterized by containing the active ester resin (b) represented by these.
本発明は、更に、該エポキシ樹脂組成物を硬化させてなることを特徴とするエポキシ樹脂硬化物に関する。 The present invention further relates to an epoxy resin cured product obtained by curing the epoxy resin composition.
本発明は、更に、該エポキシ樹脂組成物からなることを特徴とするビルドアップフィルム絶縁材料に関する。 The present invention further relates to a build-up film insulating material comprising the epoxy resin composition.
本発明によれば、電子部品の絶縁材料として硬化物の誘電率及び誘電正接が十分に低く、かつ、硬化物の耐熱性及び難燃性に著しく優れるエポキシ樹脂組成物、及びその硬化物を提供できる。 According to the present invention, there are provided an epoxy resin composition having a sufficiently low dielectric constant and dielectric loss tangent of a cured product as an insulating material for an electronic component, and a cured product that is remarkably excellent in heat resistance and flame retardancy of the cured product. it can.
本発明のエポキシ樹脂組成物で用いるエポキシ樹脂（Ａ）としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂；ビフェニル型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂等のビフェニル型エポキシ樹脂；フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、フェノール類とフェノール性水酸基を有する芳香族アルデヒドとの縮合物のエポキシ化物、ビフェニルノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂；トリフェニルメタン型エポキシ樹脂；テトラフェニルエタン型エポキシ樹脂；ジシクロペンタジエン−フェノール付加反応型エポキシ樹脂；フェノールアラルキル型エポキシ樹脂；ナフトールノボラック型エポキシ樹脂、
ナフトールアラルキル型エポキシ樹脂、ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂、ジグリシジルオキシナフタレン、下記構造式
Examples of the epoxy resin (A) used in the epoxy resin composition of the present invention include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins; biphenyl type epoxy resins and tetramethylbiphenyl type epoxy resins. Biphenyl type epoxy resin; phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, epoxidized product of condensate of phenols and aromatic aldehyde having phenolic hydroxyl group, biphenyl novolak type epoxy resin, etc. Novolac type epoxy resin; Triphenylmethane type epoxy resin; Tetraphenylethane type epoxy resin; Dicyclopentadiene-phenol addition reaction type epoxy resin; Phenol aralkyl type Epoxy resins; naphthol novolak type epoxy resin,
Naphthol aralkyl epoxy resin, naphthol-phenol co-condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, diglycidyloxynaphthalene, structural formula
で表される４官能ナフタレン型エポキシ樹脂等の分子構造中にナフタレン骨格を有するエポキシ樹脂；リン原子含有エポキシ樹脂等が挙げられる。また、これらのエポキシ樹脂は単独で用いてもよく、２種以上を混合してもよい。
An epoxy resin having a naphthalene skeleton in a molecular structure such as a tetrafunctional naphthalene type epoxy resin represented by: a phosphorus atom-containing epoxy resin. Moreover, these epoxy resins may be used independently and may mix 2 or more types.
ここで、リン原子含有エポキシ樹脂としては、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド（以下、「ＨＣＡ」と略記する。）のエポキシ化物、ＨＣＡとキノン類とを反応させて得られるフェノール樹脂のエポキシ化物、フェノールノボラック型エポキシ樹脂をＨＣＡで変性したエポキシ樹脂、クレゾールノボラック型エポキシ樹脂をＨＣＡで変性したエポキシ樹脂、また、ビスフェノールＡ型エポキシ樹脂を、ＨＣＡとキノン類とを反応させて得られるフェノール樹脂で変成して得られるエポキシ樹脂、及びビスフェニールＡ型エポキシ樹脂を、ＨＣＡとキノン類とを反応させて得られるフェノール樹脂で変成して得られるエポキシ樹脂等が挙げられる。 Here, as the phosphorus atom-containing epoxy resin, epoxidized product of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as “HCA”), HCA and quinones Epoxy product of phenol resin obtained by reacting phenolic resin, epoxy resin obtained by modifying phenol novolac type epoxy resin with HCA, epoxy resin obtained by modifying cresol novolac type epoxy resin with HCA, and bisphenol A type epoxy resin using HCA and quinone Resin obtained by modification with a phenol resin obtained by reacting with a phenol, an epoxy resin obtained by modifying a bisphenyl A type epoxy resin with a phenol resin obtained by reacting an HCA with a quinone, etc. Is mentioned.
上記したエポキシ樹脂（Ａ）のなかでも、特にエポキシ樹脂組成物にした際の加工性に優れる点、特にビルドアップ用接着フィルム用途における成形加工性に優れる点からビスフェノール型エポキシ樹脂が好ましく、特にエポキシ当量１６０〜２００ｇ／ｅｑ．のビスフェノール型エポキシ樹脂が好ましく、特に成形加工性及び耐熱性の点からビスフェノールＡ型エポキシ樹脂が好ましい。 Among the above-described epoxy resins (A), bisphenol type epoxy resins are preferable, particularly from the viewpoint of excellent processability when used as an epoxy resin composition, and particularly excellent moldability in use for build-up adhesive films. Equivalent 160-200 g / eq. The bisphenol A type epoxy resin is particularly preferable from the viewpoints of moldability and heat resistance.
また、耐熱性の点からは、分子構造中にナフタレン骨格を有するエポキシ樹脂、分子構造中にリン原始を有するエポキシ樹脂であることが好ましい。これらナフタレン骨格を有するエポキシ樹脂、分子構造中にリン原始を有するエポキシ樹脂のエポキシ当量は、耐熱性の点から１，０００ｇ／当量以下、中でも７００ｇ／当量以下、とりわけ５００ｇ／当量以下であることが好ましい。 From the viewpoint of heat resistance, an epoxy resin having a naphthalene skeleton in the molecular structure and an epoxy resin having a phosphorus primitive in the molecular structure are preferable. The epoxy equivalent of the epoxy resin having a naphthalene skeleton and the epoxy resin having a phosphorus primitive in the molecular structure is 1,000 g / equivalent or less, particularly 700 g / equivalent or less, particularly 500 g / equivalent or less from the viewpoint of heat resistance. preferable.
次に、本発明で用いる前記硬化剤（Ｂ）は、下記一般式１ Next, the curing agent (B) used in the present invention is represented by the following general formula 1
（式中、Ｘは水素原子、アルキルカルボニル基、又は、アリールカルボニル基を表し、Ｒ１〜Ｒ３は、水素原子、炭素原子数１〜４のアルキル基、又はフェニル基を表し、Ｒ４は水素原子又はメチル基を表し、ｎは繰り返し単位の平均で０〜１０である。）
で表される活性エステル樹脂（ｂ）である。
(In the formula, X represents a hydrogen atom, an alkylcarbonyl group, or an arylcarbonyl group, R 1 to R 3 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R 4 represents Represents a hydrogen atom or a methyl group, and n is an average of 0 to 10 repeating units.)
It is active ester resin (b) represented by these.
また、前記一般式１におけるｎの平均値は、特に硬化物の耐熱性に優れる点から１．５〜４であることが好ましい。 Moreover, it is preferable that the average value of n in the said General formula 1 is 1.5-4 from the point which is excellent in the heat resistance of hardened | cured material especially.
ここで、前記一般式１におけるｎの平均値は、下記の方法により求めることができる。［ｎの平均値の求め方］
下記の条件にて行ったＧＰＣ測定によりｎ＝１、ｎ＝２、ｎ＝３、ｎ＝４のそれぞれに対応するスチレン換算分子量（α１、α２、α３、α４）と、ｎ＝１、ｎ＝２、ｎ＝３、ｎ＝４のそれぞれの理論分子量（β１、β２、β３、β４）との比率（β１／α１、β２／α２、β３／α３、β４／α４）を求め、これら（β１／α１〜β４／α４）の平均値を求める。ＧＰＣで求めた数平均分子量（Ｍｎ）にこの平均値を掛け合わせた数値を平均分子量として、ｎの値を算出する。
Here, the average value of n in the general formula 1 can be obtained by the following method. [How to find the average value of n]
According to GPC measurement performed under the following conditions, styrene equivalent molecular weights (α1, α2, α3, α4) corresponding to n = 1, n = 2, n = 3, and n = 4, and n = 1 and n = The ratios (β1 / α1, β2 / α2, β3 / α3, β4 / α4) to the respective theoretical molecular weights (β1, β2, β3, β4) of 2, n = 3, and n = 4 were determined, and these (β1 / The average value of α1 to β4 / α4) is obtained. The value of n is calculated by taking the value obtained by multiplying the average value by the number average molecular weight (Mn) determined by GPC as the average molecular weight.
（ＧＰＣ測定条件）
測定装置 ：東ソー株式会社製「ＨＬＣ−８２２０ ＧＰＣ」、
カラム：東ソー株式会社製ガードカラム「ＨＸＬ−Ｌ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ３０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ４０００ＨＸＬ」
検出器： ＲＩ（示差屈折径）
データ処理：東ソー株式会社製「ＧＰＣ−８０２０モデルIIバージョン４．１０」
測定条件： カラム温度 ４０℃
展開溶媒 テトラヒドロフラン
流速 １．０ｍｌ／分
標準 ： 前記「ＧＰＣ−８０２０モデルIIバージョン４．１０」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
（使用ポリスチレン）
東ソー株式会社製「Ａ−５００」
東ソー株式会社製「Ａ−１０００」
東ソー株式会社製「Ａ−２５００」
東ソー株式会社製「Ａ−５０００」
東ソー株式会社製「Ｆ−１」
東ソー株式会社製「Ｆ−２」
東ソー株式会社製「Ｆ−４」
東ソー株式会社製「Ｆ−１０」
東ソー株式会社製「Ｆ−２０」
東ソー株式会社製「Ｆ−４０」
東ソー株式会社製「Ｆ−８０」
東ソー株式会社製「Ｆ−１２８」
試料 ： 樹脂固形分換算で１．０質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（５０μｌ）。
(GPC measurement conditions)
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
また、前記活性エステル樹脂（ｂ）は、具体的には、下記一般式１’ Further, the active ester resin (b) specifically includes the following general formula 1 '
（式中、Ｒ１〜Ｒ３は、水素原子、炭素原子数１〜４のアルキル基、又はフェニル基を表し、Ｒ４は水素原子又はメチル基を表し、ｎは繰り返し単位の平均で０〜１０である。但し、Ｘのうち少なくとも１つはアルキルカルボニル基又はアリールカルボニル基である。）で表されるフェノール樹脂（ｂ’）のフェノール性水酸基をアルキルエステル化又はアリールエステル化した構造のものであり、フェノール性水酸基に対するアルキルエステル化又はアリールエステル化の割合は、特に限定されるものではないが、８０〜９８％の範囲であることが硬化性や活性エステル樹脂（ｂ）の硬化物における耐湿性に優れる点から好ましい。
(Wherein R 1 to R 3 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, R 4 represents a hydrogen atom or a methyl group, and n represents an average of 0 to 0 repeating units. 10 wherein, at least one of X is an alkylcarbonyl group or an arylcarbonyl group), the phenolic hydroxyl group of the phenol resin (b ′) represented by the alkyl ester or aryl ester structure. The ratio of alkyl esterification or aryl esterification with respect to the phenolic hydroxyl group is not particularly limited, but it is in the range of 80 to 98% in the cured product of the curability and active ester resin (b). It is preferable from the point which is excellent in moisture resistance.
上記した活性エステル樹脂（ｂ）を製造する際に用いるフェノール樹脂（ｂ’）は、具体的には、フェノール類（ｂ１）と、下記構造式 Specifically, the phenol resin (b ′) used in producing the active ester resin (b) specifically includes phenols (b1) and the following structural formula.
（式中、Ｙはメトキシメチル基、クロロメチル基、ブロモメチル基、又はビニル基を表す。）で表される２官能性アラルキル化剤（ｂ２）とを、触媒の存在下に下記工程１〜工程４を必須の工程とする方法により製造することができる。
(Wherein Y represents a methoxymethyl group, a chloromethyl group, a bromomethyl group, or a vinyl group) and a bifunctional aralkylating agent (b2) represented by the following steps 1 to step in the presence of a catalyst: 4 can be produced by a method in which 4 is an essential step.
具体的には、前記フェノール樹脂（ｂ’）は、
工程１： 触媒（ｃ）の存在下に、前記フェノール類（ｂ１）と、前記２官能性アラルキル化剤（ｂ２）とを反応させる工程、
工程２： 反応終了後、得られた反応生成物を、質量基準で１．５〜８倍量の非水溶性有機溶媒に溶解させてフェノール樹脂溶液とする工程、
工程３： 工程２で得られたフェノール樹脂溶液を水洗する工程、
工程４： 次いで、フェノール樹脂溶液から非水溶性有機溶媒を除去する
ことにより工業的に製造することができる。
Specifically, the phenol resin (b ′) is
Step 1: reacting the phenols (b1) with the bifunctional aralkylating agent (b2) in the presence of the catalyst (c),
Step 2: After completion of the reaction, the obtained reaction product is dissolved in 1.5 to 8 times the amount of a water-insoluble organic solvent on a mass basis to obtain a phenol resin solution,
Step 3: A step of washing the phenol resin solution obtained in Step 2 with water,
Process 4: It can manufacture industrially by removing a water-insoluble organic solvent from a phenol resin solution then.
ここで前記フェノール類（ｂ１）は、例えば、フェノール、クレゾール、エチルフェノール、ｉ−プロピルフェノール、ｔ−ブチルフェノール、ｏ−フェニルフェノール、ｐ−フェニルフェノール、２，４，６−トリメチルフェノールが挙げられる。これらの中でも特に耐熱性及び難燃性の点からフェノール、クレゾールが好ましい。これらの中でも特に耐熱性及び難燃性の点からフェノール、クレゾールが好ましい。 Here, examples of the phenols (b1) include phenol, cresol, ethylphenol, i-propylphenol, t-butylphenol, o-phenylphenol, p-phenylphenol, and 2,4,6-trimethylphenol. Among these, phenol and cresol are particularly preferable from the viewpoint of heat resistance and flame retardancy. Among these, phenol and cresol are particularly preferable from the viewpoint of heat resistance and flame retardancy.
次に、前記２官能性アラルキル化剤（ｂ２）は、具体的には、４，４’−ビフェニレン−ビスメトキシメチル、４，４’−ジビニルビフェニル、４，４’−ビフェニレン−ビスクロロメチル、及び４，４’−ビフェニレン−ビスブロモメチルが挙げられる。 Next, the bifunctional aralkylating agent (b2) specifically includes 4,4′-biphenylene-bismethoxymethyl, 4,4′-divinylbiphenyl, 4,4′-biphenylene-bischloromethyl, And 4,4′-biphenylene-bisbromomethyl.
前記第１工程は、触媒の存在下に、前記フェノール類（ｂ１）と、前記２官能性アラルキル化剤（ｂ２）とを反応させる工程である。ここで用いる触媒は酸触媒が好ましく、例えば、塩酸、硫酸、リン酸などの無機酸、メタンスルホン酸、ｐ−トルエンスルホン酸、シュウ酸などの有機酸、三弗化ホウ素、無水塩化アルミニウム、塩化亜鉛などのルイス酸などが挙げられる。その使用量は仕込み原料の総質量に対して、０．１〜５質量％なる範囲であることが好ましい。 The first step is a step of reacting the phenols (b1) with the bifunctional aralkylating agent (b2) in the presence of a catalyst. The catalyst used here is preferably an acid catalyst, for example, an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid, an organic acid such as methanesulfonic acid, p-toluenesulfonic acid or oxalic acid, boron trifluoride, anhydrous aluminum chloride, or chloride. Examples include Lewis acids such as zinc. The amount used is preferably in the range of 0.1 to 5% by mass with respect to the total mass of the charged raw materials.
ここで、前記フェノール類（ｂ１）と、前記２官能性アラルキル化剤（ｂ２）との仕込み割合は、質量基準で前者／後者＝１０／１〜１．１／１の範囲であることが、反応して得られるフェノール樹脂の軟化点が５０〜１８０℃の範囲であることから好ましい。 Here, the charging ratio of the phenols (b1) and the bifunctional aralkylating agent (b2) is in the range of the former / the latter = 10/1 to 1.1 / 1 on a mass basis. The softening point of the phenol resin obtained by the reaction is preferably in the range of 50 to 180 ° C.
また、第１工程の反応は、水や有機溶剤の存在下に行うことが好ましい。有機溶媒としては特に限定されないが、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブチルアルコール等のアルコール類、メチルセロソルブ、エチルセロソルブ等のセロソルブ類、トルエン、キシレン等の芳香族炭化水素類、メチルエチルケトン、メチルイソブチルケトン等のケトン類が挙げられる。水と有機溶媒を併用しても構わない。具体的には、例えば、攪拌機を内部に具備する反応容器内に、前記フェノール類（ｂ１）、前記２官能性アラルキル化剤（ｂ２）、水とアルコール類（例：イソプロピルアルコール）とを仕込み、不活性ガス雰囲気下で攪拌を開始する。この際に加える、水、アルコール類は、系内が攪拌可能となるような量である。系内が分散された状態となった後、触媒を加えて昇温し、リフラックス温度（９５℃）を超えない温度でホールドして反応せしめる方法等が挙げられる。 The reaction in the first step is preferably performed in the presence of water or an organic solvent. The organic solvent is not particularly limited, but alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutyl alcohol, cellosolves such as methyl cellosolve and ethyl cellosolve, and aromatic hydrocarbons such as toluene and xylene , Ketones such as methyl ethyl ketone and methyl isobutyl ketone. Water and an organic solvent may be used in combination. Specifically, for example, the phenols (b1), the bifunctional aralkylating agent (b2), water and alcohols (eg, isopropyl alcohol) are charged in a reaction vessel equipped with a stirrer. Start stirring under inert gas atmosphere. The amount of water and alcohol added at this time is such that the system can be stirred. Examples include a method in which after the system is dispersed, the temperature is increased by adding a catalyst, and the reaction is held at a temperature not exceeding the reflux temperature (95 ° C.).
この工程１の反応において得られるフェノール樹脂の着色を抑制する点から、この反応系に酸化防止剤や還元剤を添加しても良い。酸化防止剤としては特に限定されないが、例えば２，６−ジアルキルフェノール誘導体などのヒンダートフェノール系化合物や２価のイオウ系化合物や３価のリン原子を含む亜リン酸エステル系化合物などを挙げることができる。還元剤としては、次亜リン酸、亜リン酸、チオ硫酸、亜硫酸、ハイドロサルファイトまたはこれらの塩などが挙げられる。 From the viewpoint of suppressing coloring of the phenol resin obtained in the reaction of Step 1, an antioxidant or a reducing agent may be added to the reaction system. Although it does not specifically limit as antioxidant, For example, a hindered phenol type compound, such as a 2, 6- dialkylphenol derivative, a bivalent sulfur type compound, a phosphite type compound containing a trivalent phosphorus atom, etc. are mentioned. Can do. Examples of the reducing agent include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, and salts thereof.
次に、工程２は、上記工程１による反応が終了した後、得られた反応生成物を、前記２官能性アラルキル化剤（ｂ２）に対して、質量基準で１．５〜８倍量の非水溶性有機溶媒に溶解させてフェノール樹脂溶液とする工程である。ここで用いる非水溶性有機溶媒の中でも、目的物であるフェノール樹脂の抽出効率が良好となる点から、非水溶性の脂肪族アルコール、脂肪族エーテル、及び脂肪族ケトン有機溶媒が好ましい。ここで、非水溶性の脂肪族アルコールとしては、１−ブタノール、２−ブタノール、イソブチルアルコール、イソペンチルアルコール、シクロヘキサノール、２-メトキシエタノール、２−エトキシエタノール、及びジエチレングリコールが挙げられる。非水溶性の脂肪族エーテルとしては、ジエチレングリコールジエチルエーテルが挙げられる。非水溶性の脂肪族ケトンとしては、メチルイソブチルケトン、シクロヘキサノンが挙げられる。 Next, in Step 2, after the reaction in Step 1 is completed, the obtained reaction product is 1.5 to 8 times the amount of the bifunctional aralkylating agent (b2) on a mass basis. This is a step of dissolving in a water-insoluble organic solvent to obtain a phenol resin solution. Among the water-insoluble organic solvents used here, water-insoluble aliphatic alcohols, aliphatic ethers, and aliphatic ketone organic solvents are preferable because the extraction efficiency of the target phenol resin is good. Here, examples of the water-insoluble aliphatic alcohol include 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, 2-methoxyethanol, 2-ethoxyethanol, and diethylene glycol. Examples of the water-insoluble aliphatic ether include diethylene glycol diethyl ether. Examples of water-insoluble aliphatic ketones include methyl isobutyl ketone and cyclohexanone.
これらの中でも、特に沸点が１００〜１３０℃の範囲であることが工程２における作業効率が良好な点から好ましく、具体的には、１−ブタノール、２−ブタノール、イソブチルアルコール、イソペンチルアルコール、２−メトキシエタノール、２−エトキシエタノール、ジエチレングリコール、メチルイソブチルケトンが好ましい。 Among these, a boiling point in the range of 100 to 130 ° C. is preferable from the viewpoint of good working efficiency in step 2, and specifically, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, 2 -Methoxyethanol, 2-ethoxyethanol, diethylene glycol and methyl isobutyl ketone are preferred.
工程１において、水や有機溶媒を併用した場合では、反応に供した水や縮合水を脱水させた後、非水溶性有機溶媒を用いて溶解させることが好ましい。上述した通り、前記２官能性アラルキル化剤（ｂ２）に対して、質量基準で１．５〜８倍量の非水溶性有機溶媒で反応生成物から目的物たるフェノール樹脂を抽出してフェノール樹脂溶液とする工程である。 In step 1, when water or an organic solvent is used in combination, it is preferable to dehydrate water used for the reaction or condensed water and then dissolve it using a water-insoluble organic solvent. As described above, the phenol resin, which is the target product, is extracted from the reaction product with a water-insoluble organic solvent in an amount of 1.5 to 8 times the mass of the bifunctional aralkylating agent (b2). This is a process of making a solution.
次に、工程３は、工程２で得られたフェノール樹脂溶液を水洗する工程である。水洗は常法に従って行うことができるが、フェノール樹脂溶液のｐＨが３〜７、好ましくは５〜７になるまで行うことが好ましい。また、工程３では、水洗の前、及び水洗時において、反応に用いた触媒を中和剤によって予め中和処理を行っても良い。ここで用いられる中和剤は、水酸化ナトリウム、水酸化カリウム、炭酸カリウム、トリエチルアミン等が挙げられる。 Next, step 3 is a step of washing the phenol resin solution obtained in step 2 with water. The washing with water can be performed according to a conventional method, but it is preferably performed until the pH of the phenol resin solution is 3 to 7, preferably 5 to 7. In Step 3, the catalyst used for the reaction may be preliminarily neutralized with a neutralizing agent before and during washing with water. Examples of the neutralizing agent used here include sodium hydroxide, potassium hydroxide, potassium carbonate, triethylamine and the like.
次に工程４は、フェノール樹脂溶液から非水溶性有機溶媒を除去して目的物たるフェノール樹脂を得る工程である。フェノール樹脂溶液から非水溶性有機溶媒を除去する方法は、具体的には、加熱減圧蒸留によって非水溶性有機溶媒を除去すれば良い。この際の条件は、１５０〜２００℃、３ｋＰａ以下の範囲であることが好ましい。 Next, step 4 is a step of removing the water-insoluble organic solvent from the phenol resin solution to obtain the target phenol resin. Specifically, the water-insoluble organic solvent may be removed from the phenol resin solution by removing the water-insoluble organic solvent by heating and distillation under reduced pressure. The conditions at this time are preferably in the range of 150 to 200 ° C. and 3 kPa or less.
以上の工程１〜工程４を経て、下記一般式１’ Through the above steps 1 to 4, the following general formula 1 '
（式中、Ｒ１〜Ｒ３は、水素原子、炭素原子数１〜４のアルキル基、又はフェニル基を表し、Ｒ４は水素原子又はメチル基を表し、ｎは繰り返し単位の平均で０〜１０である。但し、Ｘのうち少なくとも１つはアルキルカルボニル基又はアリールカルボニル基である。）で表されるフェノール樹脂（ｂ’）を得ることができる。
(Wherein R 1 to R 3 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, R 4 represents a hydrogen atom or a methyl group, and n represents an average of 0 to 0 repeating units. It is possible to obtain a phenol resin (b ′) represented by the formula: wherein at least one of X is an alkylcarbonyl group or an arylcarbonyl group.
この様にして得られたフェノール樹脂（ｂ’）を、次いで、アルキルエステル化剤又はアリールエステル化剤と反応させることにより目的とする活性エステル樹脂（ｂ）を得ることができる。 The phenol resin (b ') thus obtained is then reacted with an alkyl esterifying agent or an aryl esterifying agent to obtain the desired active ester resin (b).
また、フェノール樹脂（ｂ’）に反応させる、アルキルエステル化剤又はアリールエステル化剤としては、安息香酸、或いは、フェニル安息香酸、メチル安息香酸、エチル安息香酸、ｎ−プロピル安息香酸、ｉ−プロピル安息香酸及びｔ−ブチル安息香酸等のアルキル安息香酸、並びにこれらの酸フッ化物、酸塩化物、酸臭化物、酸ヨウ化物等の酸ハロゲン化物が挙げられるが、フェノール性水酸基との反応性が良好なものとなる点から安息香酸塩化物又はアルキル安息香酸塩基物であることが好ましい。 Examples of the alkyl esterifying agent or aryl esterifying agent to be reacted with the phenol resin (b ′) include benzoic acid, phenylbenzoic acid, methylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, and i-propyl. Alkyl benzoic acids such as benzoic acid and t-butyl benzoic acid, and acid halides such as acid fluorides, acid chlorides, acid bromides, and acid iodides are mentioned, but the reactivity with phenolic hydroxyl groups is good. From the point of becoming a thing, it is preferable that it is a benzoic acid chloride or an alkylbenzoic acid base.
そして、フェノール樹脂（ｂ’）と、アルキルエステル化剤又はアリールエステル化剤とを反応させる方法は、具体的には、これらの各成分をアルカリ触媒の存在下に反応させることができる。
ここで使用し得るアルカリ触媒としては、水酸化ナトリウム、水酸化カリウム、トリエチルアミン、ピリジン等が挙げられる。これらのなかでも特に水酸化ナトリウム、水酸化カリウムが水溶液の状態で使用することができ、生産性が良好となる点から好ましい。
The method of reacting the phenol resin (b ′) with the alkyl esterifying agent or the aryl esterifying agent can specifically react these components in the presence of an alkali catalyst.
Examples of the alkali catalyst that can be used here include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. Of these, sodium hydroxide and potassium hydroxide are particularly preferred because they can be used in the form of an aqueous solution and the productivity is good.
前記反応は、具体的には有機溶媒の存在下、フェノール樹脂（ｂ’）と、アルキルエステル化剤又はアリールエステル化剤とを混合し、前記アルカリ触媒又はその水溶液を連続的乃至断続的に滴下しながら反応させる方法が挙げられる。その際、アルカリ触媒の水溶液の濃度は、３．０〜３０％の範囲であることが好ましい。また、ここで使用し得る有機溶媒としては、トルエン、ジクロロメタンなどが挙げられる。 Specifically, the reaction is performed by mixing the phenol resin (b ′) with an alkyl esterifying agent or an aryl esterifying agent in the presence of an organic solvent, and dropping the alkali catalyst or an aqueous solution thereof continuously or intermittently. The method of making it react is mentioned. At that time, the concentration of the aqueous solution of the alkali catalyst is preferably in the range of 3.0 to 30%. Examples of the organic solvent that can be used here include toluene and dichloromethane.
反応終了後は、アルカリ触媒の水溶液を用いている場合には、反応液を静置分液し、水層を取り除き、残った有機層を洗浄後の水層がほぼ中性になるまで繰り返し、目的とする樹脂を得ることができる。 After completion of the reaction, if an aqueous solution of an alkali catalyst is used, the reaction solution is allowed to stand for separation, the aqueous layer is removed, and the remaining organic layer is repeated until the aqueous layer after washing becomes almost neutral, The target resin can be obtained.
本発明のエポキシ樹脂組成物におけるエポキシ樹脂（Ａ）及び硬化剤（Ｂ）の配合量としては、特に制限されるものではないが、得られる硬化物特性が良好である点から、エポキシ樹脂のエポキシ基の合計１当量に対して、前記フェノール樹脂を含む硬化剤中の活性基が０．７〜１．２当量になる量が好ましい。 Although it does not restrict | limit especially as a compounding quantity of the epoxy resin (A) and the hardening | curing agent (B) in the epoxy resin composition of this invention, From the point that the hardened | cured material characteristic obtained is favorable, the epoxy of epoxy resin The amount of the active group in the curing agent containing the phenol resin is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the total group.
本発明のエポキシ樹脂組成物では、エポキシ樹脂用硬化剤として前記硬化剤（Ｂ）の他、本発明の効果を損なわない範囲でアミン系化合物、アミド系化合物、酸無水物系化合物、フェノ−ル系化合物など、その他のエポキシ樹脂用硬化剤（Ｂ’）を併用してもよい。この場合、硬化剤（Ｂ’）は、前記硬化剤（Ｂ）の一部を硬化剤（Ｂ’）に置き換えて使用することができる。即ち、硬化剤（Ｂ’）を併用する場合、該硬化剤（Ｂ’）中の活性水素と、硬化剤（Ｂ）中の活性水素及びエステル結合との合計が、エポキシ樹脂（Ａ）中のエポキシ基１モルに対して、０．３〜１．２となる割合であることが好ましい。また、硬化剤（Ｂ’）は、硬化剤（Ｂ）との合計質量に対して、５０質量％以下となる割合で使用することができる。或いは、当該他の硬化剤（Ｂ’）を主たる硬化剤として使用し、線膨張係数低減、誘電正接・誘電率の低減を目的に前記硬化剤（Ｂ）を改質剤として使用してもよく、この場合、硬化剤（Ｂ）と硬化剤（Ｂ’）との合計質量に対して、硬化剤（Ｂ）が２０〜５０質量％となる割合で用いることができる。 In the epoxy resin composition of the present invention, in addition to the curing agent (B) as an epoxy resin curing agent, an amine compound, an amide compound, an acid anhydride compound, phenol as long as the effects of the present invention are not impaired. You may use together other hardening | curing agents for epoxy resins (B '), such as a system compound. In this case, the curing agent (B ′) can be used by replacing a part of the curing agent (B) with the curing agent (B ′). That is, when the curing agent (B ′) is used in combination, the total of the active hydrogen in the curing agent (B ′) and the active hydrogen and ester bond in the curing agent (B) is in the epoxy resin (A). The ratio is preferably 0.3 to 1.2 with respect to 1 mol of the epoxy group. Moreover, a hardening | curing agent (B ') can be used in the ratio used as 50 mass% or less with respect to the total mass with a hardening | curing agent (B). Alternatively, the other curing agent (B ′) may be used as a main curing agent, and the curing agent (B) may be used as a modifier for the purpose of reducing linear expansion coefficient and dielectric loss tangent / dielectric constant. In this case, the curing agent (B) can be used at a ratio of 20 to 50% by mass with respect to the total mass of the curing agent (B) and the curing agent (B ′).
ここで使用し得る、アミン系化合物は、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、イミダゾ−ル、ＢＦ３−アミン錯体、グアニジン誘導体等が挙げられる。
アミド系化合物は、ジシアンジアミド、リノレン酸の２量体とエチレンジアミンとより合成されるポリアミド樹脂等が挙げられる。
Examples of amine compounds that can be used here include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF 3 -amine complex, and guanidine derivatives.
Examples of the amide compounds include polyamide resins synthesized from dimer of dicyandiamide and linolenic acid and ethylenediamine.
酸無水物系化合物は、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等が挙げられる。 Acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydroanhydride Examples include phthalic acid.
フェノール系化合物は、フェノールノボラック樹脂、クレゾールノボラック樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂、ジシクロペンタジエンフェノール付加型樹脂、フェノールアラルキル樹脂、α−ナフトールアラルキル樹脂、β−ナフトールアラルキル樹脂、ビフェニルアラルキル樹脂、トリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ナフトールノボラック樹脂、ナフトール−フェノール共縮ノボラック樹脂、ナフトール−クレゾール共縮ノボラック樹脂、アミノトリアジン変性フェノール樹脂等が挙げられる。また、前記アミノトリアジン変性フェノール樹脂は、具体的には、メラミンやベンゾグアナミン等のアミノ基含有トリアジン化合物と、フェノール、クレゾール等のフェノール類と、ホルムアルデヒドとの共重合体が挙げられる。 Phenol compounds include phenol novolak resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, α-naphthol aralkyl resin, β-naphthol aralkyl resin, biphenyl aralkyl resin. , Trimethylolmethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, aminotriazine-modified phenol resin, and the like. Specific examples of the aminotriazine-modified phenol resin include copolymers of formaldehyde and amino group-containing triazine compounds such as melamine and benzoguanamine, phenols such as phenol and cresol, and formaldehyde.
これらの中でも、特に、硬化物の線膨張係数がより低くなり、熱的衝撃及び物理的衝撃に強く靱性に優れる点から多価フェノール系化合物が好ましく、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、α−ナフトールアラルキル樹脂、β−ナフトールアラルキル樹脂、ビフェニルアラルキル樹脂、アミノトリアジン変性フェノール樹脂が好ましい。 Among these, polyhydric phenol compounds are particularly preferred because the linear expansion coefficient of the cured product is lower, and they are resistant to thermal and physical impacts and are excellent in toughness. Phenol novolac resins, cresol novolac resins, phenol aralkyl resins Α-naphthol aralkyl resin, β-naphthol aralkyl resin, biphenyl aralkyl resin, and aminotriazine-modified phenol resin are preferable.
本発明のエポキシ樹脂組成物は、上記した各成分に加え、更に、硬化促進剤（Ｃ）を併用してもよい。 The epoxy resin composition of the present invention may further contain a curing accelerator (C) in addition to the components described above.
ここで使用し得る硬化促進剤（Ｃ）は、イミダゾール類、三級アミン類、三級ホスフィン類等が挙げられる。 Examples of the curing accelerator (C) that can be used here include imidazoles, tertiary amines, and tertiary phosphines.
ここでイミダゾール類としては、具体的には２−エチル−４−メチルイミダゾール、２−メチルイミダゾール、２−エチルイミダゾール、２，４−ジメチルイミダゾール、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、１−ベンジル−２−メチルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾール、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、１−ビニル−２−メチルイミダゾール、１−プロピル−２−メチルイミダゾール、２−イソプロピルイミダゾール、１−シアノメチル−２−メチル−イミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾール、１−シアノエチル−２−ウンデシルイミダゾール、１−シアノエチル−２−フェニルイミダゾール等の他、マスク化イミダゾール類が挙げられる。 Specific examples of imidazoles include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2 -Phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1- Vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Undecyl Imi Tetrazole, another such 1-cyanoethyl-2-phenylimidazole, masking imidazoles and the like.
三級アミン類としては、具体的にはトリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、テトラメチルブタンジアミン、テトラメチルペンタンジアミン、テトラメチルヘキサジアミン、トリエチレンジアミン、Ｎ，Ｎ−ジメチルベンジルアミン、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジメチルトルイジン、Ｎ，Ｎ−ジメチルアニシジン、ピリジン、ピコリン、キノリン、Ｎ，Ｎ′−ジメチルアミノピリジン、Ｎ−メチルピペリジン、Ｎ，Ｎ′−ジメチルピペラジン、１，８−ジアザビシクロ−［５，４，０］−７−ウンデセン（ＤＢＵ）等が挙げられる。 Specific examples of the tertiary amines include trimethylamine, triethylamine, tripropylamine, tributylamine, tetramethylbutanediamine, tetramethylpentanediamine, tetramethylhexadiamine, triethylenediamine, N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N-dimethylanisidine, pyridine, picoline, quinoline, N, N'-dimethylaminopyridine, N-methylpiperidine, N, N'-dimethylpiperazine, 1, And 8-diazabicyclo- [5,4,0] -7-undecene (DBU).
三級ホスフィン類として具体的には、トリメチルホスフィン、トリエチルホスフィン、トリプロピルホスフィン、トリブチルホスフィン、トリフェニルホスフィン、ジメチルフェニルホスフィン、メチルジフェニルホスフィン等が挙げられる。これらの中でも、硬化物の耐熱性がより高くなる点から三級アミン類が好ましい。 Specific examples of the tertiary phosphines include trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, triphenylphosphine, dimethylphenylphosphine, and methyldiphenylphosphine. Among these, tertiary amines are preferable from the viewpoint of higher heat resistance of the cured product.
また、硬化促進剤（Ｃ）の添加量は、目標とする硬化時間等によって適宜調整することができるが、前記したエポキシ樹脂成分、硬化剤成分及び前記硬化促進剤（Ｃ）の総質量に対して０．１〜２質量％となる範囲であることが好ましい。 Moreover, although the addition amount of a hardening accelerator (C) can be suitably adjusted with the target hardening time etc., with respect to the total mass of an above-described epoxy resin component, a hardening | curing agent component, and the said hardening accelerator (C). It is preferable that it is the range used as 0.1-2 mass%.
本発明のエポキシ樹脂組成物は、用途に応じて、上記した各成分に加え、更に有機溶剤（Ｄ）を使用することができる。例えば、エポキシ樹脂組成物を積層板用ワニスとして用いる場合には基材への含浸性が改善される他、ビルドアップ用接着フィルムとして用いる場合には、基材シートへの塗工性が良好になる。ここで使用し得る有機溶剤（Ｄ）は、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等の酢酸エステル類、セロソルブ、ブチルカルビトール等のカルビトール類、トルエン、キシレン等の芳香族炭化水素類、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等が挙げられる。 The epoxy resin composition of the present invention can further use an organic solvent (D) in addition to the above-described components depending on the application. For example, when the epoxy resin composition is used as a varnish for a laminated board, the impregnation property to the base material is improved, and when used as an adhesive film for buildup, the coating property to the base material sheet is good. Become. Examples of the organic solvent (D) that can be used here include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. , Carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.
また、有機溶剤（Ｄ）の添加量は、目標とする粘度によって適宜調整することができるが、固形分濃度（［エポキシ樹脂（Ａ）及びその他エポキシ樹脂成分＋硬化剤（Ｂ）］／［エポキシ樹脂（Ａ）及びその他エポキシ樹脂成分＋硬化剤（Ｂ）＋有機溶剤（Ｄ）］で示される質量基準の濃度）が、５０〜８０質量％となる範囲であることが好ましい。 The addition amount of the organic solvent (D) can be appropriately adjusted according to the target viscosity, but the solid content concentration ([epoxy resin (A) and other epoxy resin component + curing agent (B)] / [epoxy It is preferable that the concentration of the resin (A) and the other epoxy resin component + curing agent (B) + organic solvent (D)] is 50 to 80% by mass.
本発明のエポキシ樹脂組成物は、上記した各成分に加え、更に、更に無機質充填材を使用することができる。この無機質充填材は、具体的には、溶融シリカ、結晶シリカ、アルミナ、窒化珪素、窒化アルミ等が挙げられる。無機質充填材の配合量を特に大きくする場合は、溶融シリカを用いることが好ましい。溶融シリカは、破砕状、球状のいずれでも使用可能であるが、溶融シリカの配合量を高め、且つ成形材料の溶融粘度の上昇を抑えるためには、球状のものを主に用いる方が好ましい。更に、球状シリカの配合量を高めるためには、球状シリカの粒度分布がより広くなるように調製することが好ましい。
ここで無機質充填材の使用量は、エポキシ樹脂組成物の用途に応じ適宜選択することができるが、例えばビルドアップフィルム絶縁層用途では、該無機質充填材の使用量を増加させた場合には、硬化物の線膨張係数はより低くなるものの、めっき層との接着性が低下する傾向にある。本発明のエポキシ樹脂組成物はその硬化物が顕著に低い線膨張係数を示すことから、ビルドアップフィルム絶縁層用途では無機質充填材の使用量を低く抑えることができ、例えば、エポキシ樹脂組成物中無機充填剤を８０質量％以下となる範囲で用いることができ、特に２０〜５０質量％の範囲、更に２０〜３０質量％の範囲で用いることができる。また、ビルドアップフィルム絶縁層用途では、その硬化物の線膨張係数が低くいことから無機充填剤を何等使用することなく、ビルドアップフィルムに供することができる。
The epoxy resin composition of the present invention can further use an inorganic filler in addition to the above-described components. Specific examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum nitride. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape, but in order to increase the blending amount of the fused silica and to suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. Furthermore, in order to increase the compounding amount of the spherical silica, it is preferable to prepare so that the particle size distribution of the spherical silica becomes wider.
Here, the amount of the inorganic filler used can be appropriately selected according to the use of the epoxy resin composition.For example, in a build-up film insulating layer application, when the amount of the inorganic filler used is increased, Although the linear expansion coefficient of the cured product is lower, the adhesion with the plating layer tends to be reduced. Since the cured product of the epoxy resin composition of the present invention exhibits a remarkably low linear expansion coefficient, the amount of the inorganic filler used in the build-up film insulating layer can be kept low. For example, in the epoxy resin composition An inorganic filler can be used in the range which becomes 80 mass% or less, and can be used in the range of 20-50 mass% especially 20-30 mass%. Moreover, in a buildup film insulation layer use, since the linear expansion coefficient of the hardened | cured material is low, it can use for a buildup film, without using any inorganic filler.
また、本発明のエポキシ樹脂組成物は、必要に応じて、難燃剤、シランカップリング剤、離型剤、顔料等の種々の配合剤を添加することができる。 Moreover, the epoxy resin composition of this invention can add various compounding agents, such as a flame retardant, a silane coupling agent, a mold release agent, and a pigment, as needed.
ここで、難燃剤としては、例えば、ハロゲン化合物、燐原子含有化合物や窒素原子含有化合物や無機系難燃化合物などが挙げられる。具体的には、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ハロゲン化合物、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリ−２−エチルヘキシルホスフェート、トリブトキシエチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、キシレニルジフェニルホスフェート、２−エチルヘキシルジフェニルホスフェート、トリス（２，６ジメチルフェニル）ホスフェート、レゾルシンジフェニルホスフェートなどのリン酸エステル、ポリリン酸アンモニウム、ポリリン酸アミド、赤リン、リン酸グアニジン、ジアルキルヒドロキシメチルホスホネートなどの縮合リン酸エステル化合物、その他、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド、フェノキシフォスファゼンなどの燐原子含有化合物、メラミンなどの窒素原子含有化合物、水酸化アルミニウム、水酸化マグネシウム、硼酸亜鉛、硼酸カルシウムなどの無機系難燃化合物が挙げられる。 Here, examples of the flame retardant include halogen compounds, phosphorus atom-containing compounds, nitrogen atom-containing compounds, and inorganic flame retardant compounds. Specifically, halogen compounds such as tetrabromobisphenol A type epoxy resin and brominated phenol novolak type epoxy resin, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, Phosphate esters such as tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate, resorcin diphenyl phosphate, ammonium polyphosphate, Condensation of polyphosphate amide, red phosphorus, guanidine phosphate, dialkylhydroxymethylphosphonate, etc. Acid ester compounds, other, phosphorus atom-containing compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenoxyphosphazene, nitrogen atom-containing compounds such as melamine, aluminum hydroxide, Examples include inorganic flame retardant compounds such as magnesium hydroxide, zinc borate, and calcium borate.
本発明のエポキシ樹脂組成物は、上記した各成分を均一に混合することにより得られ、半導体封止材、回路基板材、複合材料、及びビルドアップフィルム等の各種の用途に適用できる。 The epoxy resin composition of the present invention is obtained by uniformly mixing the above-described components, and can be applied to various uses such as a semiconductor sealing material, a circuit board material, a composite material, and a build-up film.
例えば、無溶剤型の接着剤や塗料や封止材用エポキシ樹脂組成物を調整するには、当該エポキシ樹脂を含む、硬化剤及び、必要に応じて無機充填材などの成分を、予備混合した後に、撹拌混合機や押出機、ニ−ダ、ロ−ル等を用いて均一になるまで充分に混合して製造することができる。これらの用途において無機充填材の使用量は通常、充填率３０〜９５質量％となる範囲である。 For example, in order to prepare an epoxy resin composition for solvent-free adhesives, paints, and sealing materials, components such as a curing agent and an inorganic filler as necessary are premixed. Thereafter, the mixture can be sufficiently mixed using a stirring mixer, an extruder, a kneader, a roll or the like until uniform. In these applications, the amount of the inorganic filler used is usually in the range of 30 to 95% by mass.
また、銅張り積層板、ビルドアップ基板、繊維強化複合材料用のエポキシ樹脂組成物を調整するには、本発明のエポキシ樹脂成分、硬化剤成分、硬化促進剤、及び、必要により難燃剤等をトルエン、キシレン、アセトン、メチルエチルケトン、メチルイソブチルケトン等の有機溶剤に溶解させることにより製造することができる。この際の溶剤の使用量は、前記組成物ワニス中、１０〜７０質量％となる範囲であることが好ましい。 Moreover, in order to adjust the epoxy resin composition for copper-clad laminates, build-up substrates, and fiber reinforced composite materials, the epoxy resin component of the present invention, a curing agent component, a curing accelerator, and a flame retardant as necessary. It can be produced by dissolving in an organic solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone. The amount of the solvent used in this case is preferably in the range of 10 to 70% by mass in the composition varnish.
この様にして得られた本発明のエポキシ樹脂組成物を硬化させるには、通常、１２０℃以上２５０℃以下の温度で行うことができる。特に成形性が良好となる点から１７０〜２２０℃の温度範囲であることが好ましい。 The epoxy resin composition of the present invention thus obtained can be cured usually at a temperature of 120 ° C. or higher and 250 ° C. or lower. In particular, a temperature range of 170 to 220 ° C. is preferable from the viewpoint of good moldability.
以上の各種用途のなかでも、本発明のエポキシ樹脂組成物は、特に、ビルドアップフィルム絶縁材料、及び、積層板用プリプレグ用途に適するが、とりわけ優れた誘電特性と共に耐熱性に優れる点からビルドアップフィルム絶縁材料として有用である。 Among the above various applications, the epoxy resin composition of the present invention is particularly suitable for use as a buildup film insulating material and a prepreg for laminates, but it is particularly suitable for buildup because of its excellent dielectric properties and excellent heat resistance. It is useful as a film insulating material.
本発明のビルドアップフィルム絶縁材料からビルドアップフィルムを製造する方法は、例えば、本発明のエポキシ樹脂組成物を、支持フィルム上に塗布、乾燥させてフィルム状の絶縁層を形成する方法が挙げられる。このようにして形成させたフィルム状の絶縁層は、多層プリント配線板用のビルドアップフィルムとして使用できる。 Examples of the method for producing a build-up film from the build-up film insulating material of the present invention include a method in which the epoxy resin composition of the present invention is applied on a support film and dried to form a film-like insulating layer. . The film-like insulating layer thus formed can be used as a build-up film for a multilayer printed wiring board.
本発明のエポキシ樹脂組成物から製造されたビルドアップフィルムは、真空ラミネート法におけるラミネートの温度条件（通常７０℃〜１４０℃）で軟化し、回路基板のラミネートと同時に、回路基板に存在するビアホール或いはスルーホール内の樹脂充填が可能な流動性（樹脂流れ）を示すことが肝要であり、このような特性を発現するよう上記各成分を配合することが好ましい。 The build-up film produced from the epoxy resin composition of the present invention is softened under the lamination temperature conditions (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and simultaneously with the lamination of the circuit board, It is important to show fluidity (resin flow) capable of filling the resin in the through hole, and it is preferable to blend the above-described components so as to exhibit such characteristics.
ここで、多層プリント配線板のスルーホールの直径は通常０．１〜０．５ｍｍ、深さは通常０．１〜１．２ｍｍであり、通常この範囲で樹脂充填可能となるようエポキシ樹脂組成物中の各配合成分を調節することが好ましい。なお回路基板の両面をラミネートする場合はスルーホールの１／２程度充填されることが望ましい。 Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. Usually, the epoxy resin composition can be filled with resin in this range. It is preferable to adjust each compounding component. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.
上記ビルドアップフィルムの製造方法について、更に詳述すれば、具体的にはワニス状の本発明のエポキシ樹脂組成物を調製した後、支持フィルム（ｙ）の表面に、このワニス状の組成物を塗布し、更に加熱、あるいは熱風吹きつけ等の乾燥工程により有機溶剤を除去させることにより、絶縁層であるビルドアップフィルム樹脂組成物の層（ｘ）を形成させることにより製造することができる。 The manufacturing method of the build-up film will be described in more detail. Specifically, after preparing the varnish-like epoxy resin composition of the present invention, the varnish-like composition is applied to the surface of the support film (y). It can be manufactured by forming the layer (x) of the build-up film resin composition which is an insulating layer by applying and removing the organic solvent by a drying process such as heating or hot air blowing.
前記乾燥工程の条件は、ビルドアップフィルム樹脂組成物の層（ｘ）中の有機溶剤（Ｄ）の含有率が１０質量％以下、好ましくは５質量％以下となるように乾燥させることが好ましい。乾燥条件はワニス中の有機溶媒量によっても異なるが、例えば３０〜６０質量％の有機溶剤を含むワニスを５０〜１５０℃で３〜１０分程度乾燥させることができる。 The drying step is preferably performed so that the content of the organic solvent (D) in the layer (x) of the build-up film resin composition is 10% by mass or less, preferably 5% by mass or less. Although the drying conditions vary depending on the amount of organic solvent in the varnish, for example, a varnish containing 30 to 60% by mass of an organic solvent can be dried at 50 to 150 ° C. for about 3 to 10 minutes.
形成される層（ｘ）の厚さは、通常、導体層の厚さ以上とする。回路基板が有する導体層の厚さは通常５〜７０μｍの範囲であるので、樹脂組成物層の厚さは１０〜１００μｍの厚みを有するのが好ましい。 The thickness of the formed layer (x) is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.
なお、本発明における層（ｘ）は、保護フィルムで保護されることが、エポキシ樹脂組成物層表面へのゴミ等の付着やキズを防止することができる点から好ましい。 In addition, it is preferable that the layer (x) in this invention is protected by a protective film from the point which can prevent adhesion | attachment of a dust etc. to an epoxy resin composition layer surface, and a crack.
前記した支持フィルム及び保護フィルムは、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等のポリオレフィン、ポリエチレンテレフタレート（以下「ＰＥＴ」と略称することがある。）、ポリエチレンナフタレート等のポリエステル、ポリカーボネート、ポリイミド、更には離型紙や銅箔、アルミニウム箔等の金属箔などを挙げることができる。なお、支持フィルム及び保護フィルムはマッド処理、コロナ処理の他、離型処理を施してあってもよい。 The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.
支持フィルムの厚さは特に限定されないが、通常１０〜１５０μｍであり、好ましくは２５〜５０μｍの範囲で用いられる。また保護フィルムの厚さは１〜４０μｍとするのが好ましい。 Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.
上記した支持フィルム（ｙ）は、回路基板にラミネートした後に、或いは加熱硬化することにより絶縁層を形成した後に、剥離される。接着フィルムを加熱硬化した後に支持フィルム（ｙ）を剥離すれば、硬化工程でのゴミ等の付着を防ぐことができる。硬化後に剥離する場合、通常、支持フィルムには予め離型処理が施される。 The support film (y) described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (y) is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.
次に、上記のようして得られたビルドアップフィルムを用いて多層プリント配線板を製造する方法は、例えば、層（ｘ）が保護フィルムで保護されている場合はこれらを剥離した後、層（ｘ）を回路基板に直接接するように、回路基板の片面又は両面に、例えば真空ラミネート法によりラミネートする。ラミネートの方法はバッチ式であってもロールでの連続式であってもよい。またラミネートを行う前に接着フィルム及び回路基板を必要により加熱（プレヒート）しておいてもよい。 Next, the method of manufacturing a multilayer printed wiring board using the buildup film obtained as described above is, for example, when the layer (x) is protected with a protective film, (X) is laminated on one side or both sides of the circuit board by, for example, a vacuum laminating method so as to be in direct contact with the circuit board. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.
ラミネートの条件は、圧着温度（ラミネート温度）を好ましくは７０〜１４０℃、圧着圧力を好ましくは１〜１１ｋｇｆ／ｃｍ２（９．８×１０４〜１０７．９×１０４Ｎ／ｍ２）とし、空気圧２０ｍｍＨｇ（２６．７ｈＰａ）以下の減圧下でラミネートすることが好ましい。 The lamination conditions are such that the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 1 to 11 kgf / cm 2 (9.8 × 10 4 to 107.9 × 104 N / m 2), and the air pressure is 20 mmHg (26 It is preferable to laminate under a reduced pressure of 0.7 hPa or less.
ここで、回路基板とは、ガラスエポキシ、金属基板、ポリエステル基板、ポリイミド基板、ＢＴレジン基板、熱硬化型ポリフェニレンエーテル基板等の基板の片面又は両面にパターン加工された導体層（回路）が形成されたものが挙げられる。 Here, the circuit board has a conductive layer (circuit) patterned on one or both sides of a substrate such as a glass epoxy, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate or the like. Can be mentioned.
このように接着フィルムを回路基板にラミネートした後、支持フィルム（ｙ）を剥離する場合は剥離し、熱硬化することにより回路基板に絶縁層が形成される。加熱硬化の条件は１５０℃〜２２０℃で２０分〜１８０分の範囲で選択され、より好ましくは１６０℃〜２００℃で３０〜１２０分である。 After laminating the adhesive film on the circuit board in this way, when the support film (y) is peeled off, the support film (y) is peeled off and thermally cured to form an insulating layer on the circuit board. The conditions of heat curing are selected in the range of 20 to 180 minutes at 150 to 220 ° C, more preferably 30 to 120 minutes at 160 to 200 ° C.
絶縁層を形成した後、硬化前に支持フィルム（ｙ）を剥離しなかった場合は、ここで剥離する。次に回路基板上に形成された絶縁層に、ドリル、レーザー、プラズマ等の方法により、穴開けを行いビアホール、スルーホールを形成する。 If the support film (y) is not peeled off after the insulating layer is formed, it is peeled off here. Next, holes are formed in the insulating layer formed on the circuit board by a method such as drilling, laser, or plasma to form via holes and through holes.
次いで、絶縁層表面を酸化剤より粗化処理を行う。酸化剤としては、過マンガン酸カリウム、過マンガン酸ナトリウム等の過マンガン酸塩、重クロム酸塩、オゾン、及び硝酸等が挙げられる。 Next, the surface of the insulating layer is roughened with an oxidizing agent. Examples of the oxidizing agent include permanganates such as potassium permanganate and sodium permanganate, dichromates, ozone, and nitric acid.
次に、粗化処理により凸凹のアンカーが形成された樹脂組成物層表面に、無電解めっきと電解めっきを組み合わせた方法で導体層を形成する。また導体層とは逆パターンのめっきレジストを形成し、無電解めっきのみで導体層を形成してもよい。なお導体層形成後、１５０〜２００℃で２０〜９０分アニール処理することにより、導体層のピール強度をさらに向上、安定化させることができる。本発明では、前記したとおり、無機充填材の使用量を低く抑えることができる点から、優れたピール強度を発現させることができる。 Next, a conductor layer is formed on the surface of the resin composition layer on which uneven anchors are formed by the roughening treatment by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. After forming the conductor layer, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes. In the present invention, as described above, an excellent peel strength can be exhibited because the amount of the inorganic filler used can be kept low.
また、導体層をパターン加工し回路形成する方法としては、例えばサブトラクティブ法、セミアディディブ法などを用いることができる。 Moreover, as a method of patterning the conductor layer to form a circuit, for example, a subtractive method, a semi-additive method, or the like can be used.
次に、繊維からなるシート状補強基材に本発明のエポキシ該樹脂組成物を含浸させて多層プリント配線板の層間絶縁層用のプリプレグを製造する方法は、例えば、本発明のエポキシ樹脂組成物を繊維からなるシート状補強基材にホットメルト法又はソルベント法により含浸させ、加熱により半硬化させることにより製造する方法が挙げられる。ここで使用し得る繊維からなるシート状補強基材としては、例えばガラスクロスやアラミド繊維等が挙げられる。 Next, a method for producing a prepreg for an interlayer insulating layer of a multilayer printed wiring board by impregnating a sheet-like reinforcing substrate made of fibers with the epoxy resin composition of the present invention includes, for example, the epoxy resin composition of the present invention. There is a method in which a sheet-like reinforcing substrate made of fiber is impregnated by a hot melt method or a solvent method and semi-cured by heating. Examples of the sheet-like reinforcing substrate made of fibers that can be used here include glass cloth and aramid fibers.
次に上記プリプレグを用いて多層プリント配線板を製造する方法は、例えば回路基板に本発明のプリプレグを１枚あるいは必要により数枚重ね、離型フィルムを介して金属プレートを挟み加圧・加熱条件下でプレス積層する方法が挙げられる。圧力条件は具体的には５〜４０ｋｇｆ／ｃｍ２、温度は１２０〜２５０℃で２０〜１２０分の範囲であることが好ましい。また接着フィルムと同様に真空ラミネート法により回路基板にラミネートした後、加熱硬化することによっても製造可能である。その後、前に記載した方法と同様、酸化剤により硬化したプリプレグ表面を粗化した後、導体層をめっきにより形成して多層プリント配線板を製造することができる。 Next, a method for producing a multilayer printed wiring board using the above prepreg includes, for example, one or several prepregs of the present invention on a circuit board, and a metal plate sandwiched between release films and pressurizing / heating conditions. The method of carrying out press lamination below is mentioned. Specifically, the pressure condition is preferably 5 to 40 kgf / cm 2 , and the temperature is preferably 120 to 250 ° C. and 20 to 120 minutes. Moreover, it can also be manufactured by laminating on a circuit board by a vacuum laminating method as in the case of an adhesive film, and then curing by heating. Thereafter, similar to the method described above, the surface of the prepreg cured with an oxidizing agent is roughened, and then a conductor layer is formed by plating to produce a multilayer printed wiring board.
以下、実施例及び比較例において本発明を詳細に説明する。なお、以下の実施例及び比較例中のエポキシ樹脂の性状値の測定方法は下記の通りである。 Hereinafter, the present invention will be described in detail in Examples and Comparative Examples. In addition, the measuring method of the property value of the epoxy resin in a following example and a comparative example is as follows.
以下、実施例及び比較例において本発明を詳細に説明する。なお、以下の実施例及び比較例中のエポキシ樹脂の性状値の測定方法は下記の通りである。
［エポキシ当量］ 「ＪＩＳ Ｋ７２３６（２００１）」に準拠して測定した。
［軟化点］ 「ＪＩＳ Ｋ７２３４」に準拠して測定した。
［ＩＣＩ粘度］ 「ＡＳＴＭ Ｄ４２８７」に準拠して測定し、１５０℃における溶融粘度を測定した。
［ＧＰＣ］
測定装置 ：東ソー株式会社製「ＨＬＣ−８２２０ ＧＰＣ」、
カラム ：東ソー株式会社製ガードカラム「ＨＸＬ−Ｌ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ３０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ４０００ＨＸＬ」
検出器： ＲＩ（示差屈折径） データ処理：東ソー株式会社製「ＧＰＣ−８０２０モデルIIバージョン４．１０」
測定条件： カラム温度 ４０℃
展開溶媒 テトラヒドロフラン
流速 １．０ｍｌ／分
標準 ： 前記「ＧＰＣ−８０２０モデルIIバージョン４．１０」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
（使用ポリスチレン）
東ソー株式会社製「Ａ−５００」
東ソー株式会社製「Ａ−１０００」
東ソー株式会社製「Ａ−２５００」
東ソー株式会社製「Ａ−５０００」
東ソー株式会社製「Ｆ−１」
東ソー株式会社製「Ｆ−２」
東ソー株式会社製「Ｆ−４」
東ソー株式会社製「Ｆ−１０」
東ソー株式会社製「Ｆ−２０」
東ソー株式会社製「Ｆ−４０」
東ソー株式会社製「Ｆ−８０」
東ソー株式会社製「Ｆ−１２８」
試料 ： 樹脂固形分換算で１．０質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（５０μｌ）。
Hereinafter, the present invention will be described in detail in Examples and Comparative Examples. In addition, the measuring method of the property value of the epoxy resin in a following example and a comparative example is as follows.
[Epoxy equivalent] Measured according to "JIS K7236 (2001)".
[Softening point] Measured according to "JIS K7234".
[ICI Viscosity] Measured according to “ASTM D4287”, the melt viscosity at 150 ° C. was measured.
[GPC]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column "H XL- L" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (differential refractive diameter) Data processing: “GPC-8020 model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
［ＦＴ−ＩＲ］ 良くすりつぶした試料をＫＢrの脱水粉末と均一に混合（メノウ乳鉢）して成型器にいれ、真空加圧して透明な錠剤を作り、日本分光(株)製「ＦＴ／ＩＲ−５５０」を用いて測定した。 [FT-IR] A well-ground sample is uniformly mixed with KBr dehydrated powder (agate mortar), placed in a molder, vacuum-pressed to make a transparent tablet, and "FT / IR-" manufactured by JASCO Corporation. 550 ".
［合成例1］
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコに下記構造式
[Synthesis Example 1]
The following structural formula is attached to a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer.
で表されるビフェニルアラルキル樹脂（明和化成製「ＭＥＨＣ−７８５１ＳＳ」水酸基当量：２０２（固形分値）、軟化点６５℃（固形分値）、上記構造式中のｎの平均２）１７９ｇとメチルイソブチルケトン［以下ＭＩＢＫと記す。］８１８ｇを仕込み系内を減圧窒素置換し溶解させた。次いで、塩化ベンゾイル１２６．５ｇ（０．９０モル）を仕込み、系内を減圧窒素置換し溶解させた。その後、テトラブチルアンモニウムブロマイドを０．５４ｇを溶解させ、窒素ガスパージを施しながら、系内を６０℃以下に制御して、２０％水酸化ナトリウム水溶液１８１．８ｇを３時間かけて滴下した。次いでこの条件下で１．０時間撹拌を続けた。反応終了後、静置分液し、水層を取り除いた。更に反応物が溶解しているＭＩＢＫ相に水を投入して約１５分間撹拌混合し、静置分液して水層を取り除いた。水槽のＰＨが７になるまでこの操作を繰り返した。その後、デカンタ脱水で水分を除去し、続いて減圧脱水でＭＩＢＫを除去し、活性エステル樹脂（Ａ−１）を合成した。この樹脂（Ａ−１）の官能基当量２９６、軟化点は８０℃であった。
179 g of biphenyl aralkyl resin (Maywa Kasei "MEHC-7851SS" hydroxyl equivalent: 202 (solid content value), softening point 65 ° C. (solid content value), average 2 of n in the above structural formula) and methyl isobutyl Ketone [hereinafter referred to as MIBK. 818 g was charged and the inside of the system was purged with nitrogen under reduced pressure to dissolve. Next, 126.5 g (0.90 mol) of benzoyl chloride was charged, and the inside of the system was purged with nitrogen under reduced pressure to dissolve. Thereafter, 0.54 g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60 ° C. or lower while performing a nitrogen gas purge, and 181.8 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hour under these conditions. After completion of the reaction, the solution was allowed to stand for separation, and the aqueous layer was removed. Further, water was added to the MIBK phase in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes. This operation was repeated until the pH of the water tank reached 7. Thereafter, water was removed by decanter dehydration, and subsequently MIBK was removed by vacuum dehydration to synthesize an active ester resin (A-1). This resin (A-1) had a functional group equivalent of 296 and a softening point of 80 ° C.
実施例１及び比較例１〜２（エポキシ樹脂組成物の調整及び物性評価）
下記表１記載の配合に従い、エポキシ樹脂及びエステル化合物を配合し、更に、硬化触媒としてジメチルアミノピリジン０．５ｐｈｒを加え、最終的に各組成物の不揮発分（Ｎ．Ｖ．）が５８質量％となるようにメチルエチルケトンを配合して調整した。これをアルミシャーレに移し、１２０℃で乾燥させてメチルエチルケトンを除去して半硬化物とした。次いで、１５ｃｍ×１５ｃｍ×２ｍｍの型枠に該半硬化物を入れ真空プレス成形（温度条件：２００℃、圧力：４０ｋｇ／ｃｍ２、成形時間：１．５時間）して板状の硬化物を得た。これを試験片として用い、以下の各種の評価を行った。結果を表１に示す。
Example 1 and Comparative Examples 1 and 2 (Adjustment of epoxy resin composition and evaluation of physical properties)
In accordance with the formulation shown in Table 1 below, an epoxy resin and an ester compound were blended, and 0.5 phr of dimethylaminopyridine was further added as a curing catalyst. Finally, the nonvolatile content (NV) of each composition was 58% by mass. It adjusted by mix | blending methyl ethyl ketone so that it might become. This was transferred to an aluminum petri dish and dried at 120 ° C. to remove methyl ethyl ketone to obtain a semi-cured product. Next, the semi-cured product is put into a 15 cm × 15 cm × 2 mm mold and vacuum press-molded (temperature conditions: 200 ° C., pressure: 40 kg / cm 2 , molding time: 1.5 hours) to obtain a plate-shaped cured product. Obtained. Using this as a test piece, the following various evaluations were performed. The results are shown in Table 1.
［難燃性試験］
１×１０ｃｍに成形した試験片の片端に１０秒間着火。自然消火後の試験片状態を目視にて観察
○： 炭化するが試験片形状を維持
×： 完全燃焼。若しくは、完全消失
［耐熱性試験］
ガラス転移温度： 試験片をＤＭＡ法にて測定。昇温スピード３℃／分。
［誘電率及び誘電正接の測定］
ＪＩＳ−Ｃ−６４８１に準拠し、アジレント・テクノロジー株式会社製インピーダンス・マテリアル・アナライザ「ＨＰ４２９１Ｂ」により、絶乾後２３℃、湿度５０％の室内に２４時間保管した後の試験片の１ＧＨｚでの誘電率および誘電正接を測定した。
[Flame retardance test]
Ignition for 10 seconds at one end of a test piece molded to 1 × 10 cm. Visual observation of specimen state after natural fire extinguishing ○: Carbonized but maintained specimen shape ×: Complete combustion. Or complete disappearance [heat resistance test]
Glass transition temperature: The test piece was measured by the DMA method. Temperature rising speed 3 ° C / min.
[Measurement of dielectric constant and dissipation factor]
In accordance with JIS-C-6481, the dielectric material at 1 GHz of the test piece after being stored in an indoor room at 23 ° C. and 50% humidity for 24 hours after absolutely dry using an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, Inc. The rate and dielectric loss tangent were measured.
表１中の各成分は、以下の通りである。
「ＴＤ−２０９０」：フェノールノボラック樹脂（水酸基当量：１０５ｇ／ｅｑ．、軟化点１２０℃、平均核体数８）
ビフェニルアラルキル樹脂：前記合成例１で用いたビフェニルアラルキル樹脂
Each component in Table 1 is as follows.
“TD-2090”: phenol novolak resin (hydroxyl equivalent: 105 g / eq., Softening point 120 ° C., average number of nuclei 8)
Biphenyl aralkyl resin: biphenyl aralkyl resin used in Synthesis Example 1
Claims (8)
（式中、Ｘは水素原子、アルキルカルボニル基、又は、アリールカルボニル基を表し、Ｒ１〜Ｒ３は、水素原子、炭素原子数１〜４のアルキル基、又はフェニル基を表し、Ｒ４は水素原子又はメチル基を表し、ｎは繰り返し単位の平均で０〜１０である。但し、Ｘのうち少なくとも１つはアルキルカルボニル基又はアリールカルボニル基である。）
で表される活性エステル樹脂（ｂ）を含有することを特徴とするエポキシ樹脂組成物。 An epoxy resin composition comprising an epoxy resin (A) and a curing agent (B) as essential components, wherein the curing agent (B) is represented by the following general formula 1
(In the formula, X represents a hydrogen atom, an alkylcarbonyl group, or an arylcarbonyl group, R 1 to R 3 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R 4 represents Represents a hydrogen atom or a methyl group, and n is an average of repeating units of 0 to 10, provided that at least one of X is an alkylcarbonyl group or an arylcarbonyl group.
The epoxy resin composition characterized by including the active ester resin (b) represented by these.
（式中、Ｒ１〜Ｒ３は、水素原子、炭素原子数１〜４のアルキル基、又はフェニル基を表し、Ｒ４は水素原子又はメチル基を表し、ｎは繰り返し単位の平均で０〜１０である。）
で表されるフェノール樹脂（ｂ’）のフェノール性水酸基の８０〜９８％をアルキルエステル化又はアリールエステル化した分子構造を有するものである請求項１記載のエポキシ樹脂組成物。 The active ester resin (b) is represented by the following general formula 1 ′
(Wherein R 1 to R 3 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, R 4 represents a hydrogen atom or a methyl group, and n represents an average of 0 to 0 repeating units. 10)
The epoxy resin composition according to claim 1, which has a molecular structure obtained by alkylesterifying or arylesterifying 80 to 98% of the phenolic hydroxyl group of the phenolic resin (b ') represented by formula (1).
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