JPH04311716A - Epoxy resin-modified product and epoxy resin composition - Google Patents
Epoxy resin-modified product and epoxy resin compositionInfo
- Publication number
- JPH04311716A JPH04311716A JP10516591A JP10516591A JPH04311716A JP H04311716 A JPH04311716 A JP H04311716A JP 10516591 A JP10516591 A JP 10516591A JP 10516591 A JP10516591 A JP 10516591A JP H04311716 A JPH04311716 A JP H04311716A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- polybutadiene
- phenolic hydroxyl
- integer
- block copolymer
- 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
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 67
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 67
- 239000000203 mixture Substances 0.000 title claims description 26
- 239000004593 Epoxy Substances 0.000 title abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 31
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 claims abstract description 26
- 229920001400 block copolymer Polymers 0.000 claims abstract description 21
- 229920003986 novolac Polymers 0.000 claims abstract description 19
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000004760 aramid Substances 0.000 description 9
- 229920003235 aromatic polyamide Polymers 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- -1 -CH2CH(CH3)2 Chemical group 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000013007 heat curing Methods 0.000 description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 2
- LFEWXDOYPCWFHR-UHFFFAOYSA-N 4-(4-carboxybenzoyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C=C1 LFEWXDOYPCWFHR-UHFFFAOYSA-N 0.000 description 2
- BCEQKAQCUWUNML-UHFFFAOYSA-N 4-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(O)C(C(O)=O)=C1 BCEQKAQCUWUNML-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920013646 Hycar Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000002560 nitrile group Chemical group 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
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001028 reflection method Methods 0.000 description 2
- 125000005591 trimellitate group Chemical group 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- BQIOTSCEOSMFOT-UHFFFAOYSA-N 1-hydroxycyclohexa-3,5-diene-1,2-dicarboxylic acid Chemical compound OC(=O)C1C=CC=CC1(O)C(O)=O BQIOTSCEOSMFOT-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- HQCHAOKWWKLXQH-UHFFFAOYSA-N 2,6-Dichloro-para-phenylenediamine Chemical compound NC1=CC(Cl)=C(N)C(Cl)=C1 HQCHAOKWWKLXQH-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- HVEAQFIZKONJJG-UHFFFAOYSA-N 3-(3-carboxybenzoyl)benzoic acid Chemical compound OC(=O)C1=CC=CC(C(=O)C=2C=C(C=CC=2)C(O)=O)=C1 HVEAQFIZKONJJG-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- FJXIPWRKSXGKSY-UHFFFAOYSA-N 4-(4-carboxyphenyl)sulfanylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1SC1=CC=C(C(O)=O)C=C1 FJXIPWRKSXGKSY-UHFFFAOYSA-N 0.000 description 1
- SQJQLYOMPSJVQS-UHFFFAOYSA-N 4-(4-carboxyphenyl)sulfonylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C=C1 SQJQLYOMPSJVQS-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- VTDMBRAUHKUOON-UHFFFAOYSA-N 4-[(4-carboxyphenyl)methyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C=C1 VTDMBRAUHKUOON-UHFFFAOYSA-N 0.000 description 1
- OAPDPORYXWQVJE-UHFFFAOYSA-N 4-propylaniline Chemical compound CCCC1=CC=C(N)C=C1 OAPDPORYXWQVJE-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Natural products CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005001 aminoaryl group Chemical group 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- OKBVMLGZPNDWJK-UHFFFAOYSA-N naphthalene-1,4-diamine Chemical compound C1=CC=C2C(N)=CC=C(N)C2=C1 OKBVMLGZPNDWJK-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
Landscapes
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、ノボラック型エポキシ
樹脂変性体及びこれを添加することにより強靱性を改善
したエポキシ樹脂組成物とその硬化物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified novolac type epoxy resin, an epoxy resin composition with improved toughness by adding the same, and a cured product thereof.
【０００２】0002
【従来の技術】エポキシ樹脂の改質は特に盛んに行われ
、その応用範囲の拡大が図られている。エポキシ樹脂は
電気的特性、接着性、熱特性等が優れているが、一般に
脆く、硬化時や使用時の応力歪み、熱や力学的衝撃によ
って容易にクラックが発生する問題がある。この問題に
対して、長鎖脂肪族基やゴム状性質を持つ硬化剤の使用
、エラストマー的性質を持つ化合物の添加、アスファル
ト物質、グリコール類等の可塑剤の添加、ガラス繊維、
アラミド繊維、炭素繊維等の繊維の添加、エポキシ化合
物自体のゴム弾性を示す分子基の導入等により、その強
靱化を図ることが行われている（越智 光一、高分子
３８（３）、２００（１９８９）。BACKGROUND OF THE INVENTION Modification of epoxy resins is particularly actively carried out, and efforts are being made to expand the range of their applications. Although epoxy resins have excellent electrical properties, adhesive properties, thermal properties, etc., they are generally brittle and have the problem of easily cracking due to stress distortion, heat, or mechanical shock during curing or use. To deal with this problem, the use of curing agents with long-chain aliphatic groups or rubber-like properties, the addition of compounds with elastomeric properties, the addition of asphalt materials, plasticizers such as glycols, glass fibers,
Efforts are being made to strengthen the epoxy compound by adding fibers such as aramid fibers and carbon fibers, and by introducing molecular groups that exhibit rubber elasticity into the epoxy compound itself (Koichi Ochi, Kobunshi 38 (3), 200 ( 1989).
【０００３】0003
【発明が解決しようとする課題】しかしながら、半導体
素子の封止剤として広く使用されているノボラック型エ
ポキシ樹脂は、多官能エポキシ樹脂で、架橋密度が高く
、硬くて脆いという問題がある。この問題に対して、前
記のゴム状物質を添加することで問題の解決を図る試み
がなされているが、充分な相溶性が得られないために充
分な効果が発揮できない、またエポキシ樹脂の優れた耐
熱性や接着性等の特性を損なう、非常にコスト高となる
等の問題を有している。本発明はこれらの問題点を鑑み
てなされたもので、ノボラック型エポキシ樹脂の耐熱性
の特徴を低減させることなく、改善された強靱性を与え
るノボラック型エポキシ樹脂組成物を提供することにあ
る。[Problems to be Solved by the Invention] However, the novolac type epoxy resin widely used as a sealant for semiconductor devices is a polyfunctional epoxy resin, and has a problem of having a high crosslinking density, being hard and brittle. Attempts have been made to solve this problem by adding the above-mentioned rubber-like substances, but they have not been able to achieve sufficient effects due to lack of sufficient compatibility, and the advantages of epoxy resins. However, there are problems such as impairing properties such as heat resistance and adhesiveness, and resulting in extremely high costs. The present invention was made in view of these problems, and it is an object of the present invention to provide a novolac-type epoxy resin composition that provides improved toughness without reducing the heat resistance characteristics of the novolac-type epoxy resin.
【０００４】0004
【課題を解決するための手段】本発明者らは、前記の問
題点を解決するために鋭意検討した結果、一般式（Ｉ）
で示すノボラック型エポキシ樹脂、硬化剤及び一般式（
ＩＩ）で示すフェノール性水酸基含有アラミド−ポリブ
タジエン−アクリロニトリルブロック共重合体とを主成
分として複合化することにより、エポキシ樹脂及びその
硬化物の特性を低減させることなく、エポキシ樹脂の強
靱性を向上できることを見いだし、本発明を完結した。[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors found that the general formula (I)
Novolac type epoxy resin, curing agent and general formula (
By compounding the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer shown in II) as the main component, the toughness of the epoxy resin can be improved without reducing the properties of the epoxy resin and its cured product. They discovered this and completed the present invention.
【化５】[C5]
【化６】[C6]
【化７】
（式中、Ｒは化６又は化７、Ｒ１ は水素原子、臭素原
子又はメチル基、Ｒ２ は−（ＣＨ２ ）３ ＣＨ３
、−ＣＨ２ ＣＨ（ＣＨ３ ）２ 、−Ｃ（ＣＨ３ ）
２ ＣＨ２ ＣＨ３ 、−ＣＨ＝ＣＨ２ 、−Ｃ６ Ｈ
６ 又は水素原子、ｎ＝１〜４０の整数を示す）[Formula 7] (wherein, R is Chemical formula 6 or Chemical formula 7, R1 is a hydrogen atom, bromine atom, or methyl group, R2 is -(CH2)3 CH3
, -CH2CH(CH3)2, -C(CH3)
2 CH2 CH3 , -CH=CH2 , -C6 H
6 or a hydrogen atom, n = an integer of 1 to 40)
【化８】
（式中、ｘ＝３〜７の整数、ｙ＝１〜４の整数、ｙ／（
ｘ＋ｙ）＝０．１〜０．３、ｚ＝５〜１５の整数、ｍ＝
１〜４００の整数、ｎ＝１〜４００の整数、ｎ／（ｍ＋
ｎ）＝０．０１〜０．５０、１＝１〜５０の整数、Ａｒ
１ 、Ａｒ３ は二価の芳香族基、Ａｒ２ はフェノー
ル性水酸基を含有する二価の芳香族基を示す）[Image Omitted]
x+y) = 0.1 to 0.3, z = integer of 5 to 15, m =
An integer from 1 to 400, n=an integer from 1 to 400, n/(m+
n) = 0.01 to 0.50, 1 = integer of 1 to 50, Ar
1, Ar3 represents a divalent aromatic group, Ar2 represents a divalent aromatic group containing a phenolic hydroxyl group)
【０００
５】本発明のエポキシ樹脂変性体は、ノボラック型エポ
キシ樹脂（Ｉ）とブロック共重合体（ＩＩ）をアミド系
溶媒中で反応させることにより得られる。アミド系溶媒
としては、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル
−２−ピロリドン等が用いられる。エポキシ樹脂（Ｉ）
の使用量は、ブロック共重合体（ＩＩ）に対して、１〜
２０倍当量、好ましくは５〜１５倍当量である。反応温
度は５０℃以上好ましくは７０℃以上である。000
5] The modified epoxy resin of the present invention can be obtained by reacting the novolac type epoxy resin (I) and the block copolymer (II) in an amide solvent. As the amide solvent, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. are used. Epoxy resin (I)
The amount used is 1 to 1 for block copolymer (II).
It is 20 times equivalent, preferably 5 to 15 times equivalent. The reaction temperature is 50°C or higher, preferably 70°C or higher.
【０００６】本発明のエポキシ樹脂組成物においては、
フェノール性水酸基含有アラミド−ポリブタジエン−ア
クリロニトリルブロック共重合体（ＩＩ）の使用量は、
ノボラック型エポキシ樹脂（Ｉ）に対して０．１から１
５１量％が好ましい。[0006] In the epoxy resin composition of the present invention,
The amount of the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer (II) used is:
0.1 to 1 for novolac type epoxy resin (I)
51% by weight is preferred.
【０００７】本発明において、一般式（ＩＩ）で示すフ
ェノール性水酸基含有アラミド−ポリブタジエン−アク
リロニトリル共重合体が一般式（Ｉ）で示すエポキシ樹
脂の強靱化を促す理由は定かではないが、これらフェノ
ール性水酸基含有アラミド−ポリブタジエン−アクリロ
ニトリル共重合体の水酸基とエポキシ樹脂とを反応させ
ることにより、エポキシ樹脂への相溶化を促し、アラミ
ド成分がエポキシ樹脂と均一に分子分散したエポキシ樹
脂組成物が得られる。更に、このエポキシ樹脂組成物の
加熱硬化によって、ポリブタジエン−アクリロニトリル
成分がミクロ相分離を起こすと共に、アラミド成分がエ
ポキシ成分中に分子分散した状態で固定化される。この
機構により、剛直性とガラス転移点が高いアラミド鎖が
エポキシ樹脂中に分子分散され、エポキシ樹脂の耐熱性
と靱性が改善されるばかりでなく、均一に分散したポリ
ブタジエン−アクリロニトリル成分も応力暖和作用を果
たすので、エポキシ樹脂硬化物の耐熱性を低下させるこ
となしに強靱化が効率良く行われると推定される。この
フェノール性水酸基含有アラミド−ポリブタジエン−ア
クリロニトリルブロック共重合体の強靱化の改質効果が
、これら共重合体の少ない添加量で達成される。その結
果、エポキシ樹脂組成物及びその硬化物が持つ優れた特
性を損なうことがなく、その耐熱性を向上させることが
できる。In the present invention, although it is not clear why the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile copolymer represented by the general formula (II) promotes toughening of the epoxy resin represented by the general formula (I), these phenols By reacting the hydroxyl groups of the hydroxyl group-containing aramid-polybutadiene-acrylonitrile copolymer with the epoxy resin, compatibilization with the epoxy resin is promoted, and an epoxy resin composition in which the aramid component is uniformly molecularly dispersed with the epoxy resin can be obtained. . Furthermore, by heating and curing the epoxy resin composition, the polybutadiene-acrylonitrile component undergoes microphase separation, and the aramid component is immobilized in a molecularly dispersed state in the epoxy component. Through this mechanism, aramid chains with high rigidity and glass transition temperature are molecularly dispersed in the epoxy resin, improving the heat resistance and toughness of the epoxy resin, and the evenly dispersed polybutadiene-acrylonitrile component also has a stress-relaxing effect. Therefore, it is presumed that toughening can be efficiently performed without reducing the heat resistance of the cured epoxy resin product. The effect of toughening the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer can be achieved by adding a small amount of these copolymers. As a result, the heat resistance of the epoxy resin composition and its cured product can be improved without impairing the excellent properties of the epoxy resin composition and its cured product.
【０００８】本発明に用いられるブロック共重合体（Ｉ
Ｉ）は、下記の方法で合成できる。一般式（Ｉ）中のフ
ェノール性水酸基を含有する二価の芳香族基Ａｒ２ を
持つジカルボン酸と一般式（Ｉ）中の二価の芳香族基Ａ
ｒ１ 持つジカルボン酸に対して過剰量の一般式（Ｉ）
中の二価の芳香族基Ａｒ３ を持つジアミンを加え、こ
れらを例えば亜リン酸エステルとピリジン誘導体等の存
在でＮ−メチル−２−ピロリドンによって代表される有
機溶媒中で、窒素等の不活性雰囲気下にて、加熱攪拌す
る。この結果、得られる両末端がアミノアリール基とな
ったフェノール性水酸基含有ポリアラミドオリゴマー溶
液に、両末端にカルボキシル基をもつポリブタジエン−
アクリロニトリル共重合体を添加し、重縮合することに
よりブロック共重合体（ＩＩ）が得られる。Block copolymer (I) used in the present invention
I) can be synthesized by the following method. A dicarboxylic acid having a divalent aromatic group Ar2 containing a phenolic hydroxyl group in general formula (I) and a divalent aromatic group A in general formula (I)
Excess amount of general formula (I) with respect to the dicarboxylic acid having r1
Diamines having divalent aromatic groups Ar3 in Heat and stir under atmosphere. As a result, the resulting phenolic hydroxyl group-containing polyaramid oligomer solution with aminoaryl groups at both ends was mixed with polybutadiene having carboxyl groups at both ends.
A block copolymer (II) is obtained by adding an acrylonitrile copolymer and performing polycondensation.
【０００９】フェノール性水酸基を有するＡｒ２ 含有
ジカルボン酸としては、４−ヒドロキシイソフタル酸、
５−ヒドロキシイソフタル酸、２−ヒドロキシフタル酸
、２−ヒドロキシテレフタル酸、フェノール性水酸基を
有しないＡｒ１ 含有ジカルボン酸としては、フタル酸
、イソフタル酸、テレフタル酸、４，４′−ビフェニル
ジカルボン酸、３，３′−メチレン二安息香酸、４，４
′−メチレン二安息香酸、４，４′−オキシ二安息香酸
、４，４′−チオ二安息香酸、３，３′−カルボニル二
安息香酸、４，４′−カルボニル二安息香酸、４，４′
−カルボニル二安息香酸、４，４′−スルフホニル二安
息香酸、１，４−ナフタレンジカルボン酸、１，５−ナ
フタレンジカルボン酸、２，６−ナフタレンジカルボン
酸等があげられるが、これらに限定されるものではない
。
これらの芳香族ジカルボン酸を又は混合して使用するこ
ともできる。Examples of the Ar2-containing dicarboxylic acid having a phenolic hydroxyl group include 4-hydroxyisophthalic acid,
Examples of 5-hydroxyisophthalic acid, 2-hydroxyphthalic acid, 2-hydroxyterephthalic acid, and Ar1-containing dicarboxylic acids having no phenolic hydroxyl group include phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, , 3'-methylene dibenzoic acid, 4,4
'-Methylene dibenzoic acid, 4,4'-oxydibenzoic acid, 4,4'-thiodibenzoic acid, 3,3'-carbonyl dibenzoic acid, 4,4'-carbonyl dibenzoic acid, 4,4 ′
- Carbonyl dibenzoic acid, 4,4'-sulfonyl dibenzoic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, etc., but are limited to these. It's not a thing. These aromatic dicarboxylic acids can also be used or in combination.
【００１０】前記のＡｒ３ 含有ジアミンとしては、例
えばｍ−フェニレンジアミン、ｐ−フェニレンジアミン
、３，３′−オキシジアニリン、３，４′−オキシジア
ニリン、４，４′−オキシジアニリン、３，３′−ジア
ミノベンゾフェノン、ビス（４−アミノフェニル）スル
ホン、ビス（３−アミノフェニル）スルホン、ビス（４
−アミノフェニル）スルフィド、１，４−ナフタレンジ
アミン、２，６−ナフタレンジアミン、４，４′−ビス
（４−フェノキシ）ジフェニルスルホン、４，４′−ビ
ス（３−フェノキシ）ジフェニルスルホン、２，２′−
（４−アミノフェニル）プロパン、ビス（４−アミノフ
ェニル）メタン、ｏ−トリジン、ｏ−ジアニリジン等が
あげられるが、これらに限定されるものではない。これ
らの芳香族ジアミンは混合して使用することもできる。Examples of the above-mentioned Ar3-containing diamine include m-phenylenediamine, p-phenylenediamine, 3,3'-oxydianiline, 3,4'-oxydianiline, 4,4'-oxydianiline, , 3'-diaminobenzophenone, bis(4-aminophenyl)sulfone, bis(3-aminophenyl)sulfone, bis(4-aminophenyl)sulfone,
-aminophenyl) sulfide, 1,4-naphthalenediamine, 2,6-naphthalenediamine, 4,4'-bis(4-phenoxy)diphenylsulfone, 4,4'-bis(3-phenoxy)diphenylsulfone, 2, 2'-
Examples include (4-aminophenyl)propane, bis(4-aminophenyl)methane, o-tolidine, o-dianilidine, etc., but are not limited to these. These aromatic diamines can also be used in combination.
【００１１】また両末端にカルボキシル基を持つポリブ
タジエン−アクリロニトリル共重合体は、Ｇｏｏｄｒｉ
ｃｈ社からＨｙｃａｒ ＣＴＢＮとして市販されており
、これらを使用することができる。[0011] Furthermore, a polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends is produced by Goodri.
It is commercially available as Hycar CTBN from ch company, and these can be used.
【００１２】ノボラック型エポキシ樹脂としては、オル
トクレゾールノボラック型、フェノールノボラック型、
ノボラック型ナフトール及びこれらのメチル化又は臭素
化したものがあげられる。本発明においては、これらの
エポキシ樹脂を混合して使用することもできる。[0012] Examples of the novolac type epoxy resin include orthocresol novolac type, phenol novolac type,
Examples include novolak-type naphthol and methylated or brominated versions thereof. In the present invention, a mixture of these epoxy resins can also be used.
【００１３】本発明で使用する硬化剤として、例えばビ
ス（４−アミノフェニル）スルホン、ビス（４−アミノ
フェニル）メタン、１，５−ジアミノナフタレン、ｐ−
フェニレンジアミン、ｍ−フェニレンジアミン、ｏ−フ
ェニレンジアミン、２，６−ジクロロ−１，４−ベンゼ
ンジアミン、１，３−（ｐ−アミノフェニル）ブロパン
、ｍ−キシレンジアミン等の芳香族アミン系化合物、エ
チレンジアミン、ジエチレントリアミン、テトラエチレ
ンペンタミン、ジエチルアミノプロピルアミン、ヘキサ
メチレンジアミン、メンセンジアミン、イソフォロンジ
アミン、ビス（４−アミノ−３−メチルジシクロヘキシ
ル）メタン、ポリメチレンジアミン、ポリエーテルジア
ミン等の脂肪族アミン系化合物、ポリアミノアミド系化
合物、ドデシル無水コハク酸、ポリアジピン酸無水物、
ポリアゼライン酸無水物等の脂肪族酸無水物、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
の脂環式酸無水物、無水フタル酸、無水トリメリット酸
、ベンゾフェノンテトラカルボン酸無水物、エチレング
リコールビストリメリテート、グリセロールトリストリ
メリテート等の芳香族酸無水物、ジシアンジアミド、有
機酸ジヒドラジド等の塩基性活性水素化合物類、イミダ
ゾール化合物類、ルイス酸及びブレステッド酸塩類、ポ
リメルカプタン化合物類、フェノール樹脂類、ユリア樹
脂類、メラミン樹脂類、イソシアネート及びブロックイ
ソシアネート化合物類等があげられるが、これらに限定
されるものではない。Examples of the curing agent used in the present invention include bis(4-aminophenyl)sulfone, bis(4-aminophenyl)methane, 1,5-diaminonaphthalene, p-
Aromatic amine compounds such as phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,6-dichloro-1,4-benzenediamine, 1,3-(p-aminophenyl)propane, m-xylenediamine, Aliphatic amines such as ethylenediamine, diethylenetriamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, menzendiamine, isophoronediamine, bis(4-amino-3-methyldicyclohexyl)methane, polymethylenediamine, polyetherdiamine, etc. based compounds, polyaminoamide based compounds, dodecyl succinic anhydride, polyadipic anhydride,
Aliphatic acid anhydrides such as polyazelaic anhydride, alicyclic acid anhydrides such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene Aromatic acid anhydrides such as glycol bis trimellitate and glycerol tris trimellitate, basic active hydrogen compounds such as dicyandiamide and organic acid dihydrazide, imidazole compounds, Lewis acids and brested acid salts, polymercaptan compounds, phenol Examples include, but are not limited to, resins, urea resins, melamine resins, isocyanates and blocked isocyanate compounds.
【００１４】本発明のエポキシ樹脂組成物は、必要に応
じて硬化促進剤、エポキシ樹脂用反応希釈剤、染料、酸
化安定剤、カップリング剤、他の樹脂等を配合すること
ができる。硬化促進剤としては、燐系例えばトリフェニ
ルホスフィン、３級アミン系例えばトリエタノールアミ
ン、テトラエチルアミン、１，８−ジアザ−ビシクロ〔
５，４，０〕−７−ウンデセン（ＤＢＵ）、Ｎ，Ｎ−ジ
メチルベンジルアミン、１，１，３，３−テトラメチル
グアニジン、２−エチル−４−メチルイミダゾール、Ｎ
−メチルピペラジン等、ホウ素系例えば１，８−ジアザ
−ビシクロ〔５，４，０〕−７−ウンデセニウムテトラ
フェニルボレート等が用いられる。The epoxy resin composition of the present invention may contain a curing accelerator, a reaction diluent for epoxy resin, a dye, an oxidation stabilizer, a coupling agent, other resins, and the like, if necessary. Examples of curing accelerators include phosphorus-based agents such as triphenylphosphine, tertiary amine-based agents such as triethanolamine, tetraethylamine, and 1,8-diaza-bicyclo[
5,4,0]-7-undecene (DBU), N,N-dimethylbenzylamine, 1,1,3,3-tetramethylguanidine, 2-ethyl-4-methylimidazole, N
-Methylpiperazine and the like, boron compounds such as 1,8-diaza-bicyclo[5,4,0]-7-undecenium tetraphenylborate and the like are used.
【００１５】本発明のエポキシ樹脂組成物は、好ましく
は式（Ｉ）のノボラック型エポキシ樹脂に対して、式（
ＩＩ）の共重合体を０．１〜１０重量％及び硬化剤を２
〜６０重量％好ましくは５〜４０重量％を加え、混合す
ることにより得られる。本発明のエポキシ樹脂組成物は
、エポキシ樹脂変性体とノボラック型エポキシ樹脂と硬
化剤から成る組成物の加熱硬化前の状態と加熱硬化後の
硬化物を包含するものである。この場合における加熱硬
化後の組成物は各種の形成体として供給することができ
る。この加熱硬化は一般に２５０℃以下で数時間の条件
で行われるが、本発明においては、この条件に左右され
るものではない。The epoxy resin composition of the present invention preferably has a novolak type epoxy resin of the formula (I), and a novolac type epoxy resin of the formula (I).
0.1 to 10% by weight of the copolymer II) and 2% of the curing agent.
It is obtained by adding and mixing up to 60% by weight, preferably 5 to 40% by weight. The epoxy resin composition of the present invention includes a state of a composition comprising a modified epoxy resin, a novolac type epoxy resin, and a curing agent before heat curing, and a cured product after heat curing. In this case, the composition after heat curing can be supplied as various formed bodies. This heat curing is generally carried out at 250° C. or lower for several hours, but the present invention is not dependent on these conditions.
【００１６】[0016]
【実施例】以下、本発明を実施例により説明するが、本
発明はこれらに限定されるものではない。
合成例１
フェノール性水酸基含有アラミド−ポリブタジエン−ア
クリロニトリルブロック共重合体（アラミド部に含有す
るフェノール性す水酸基が２モル％）の合成：イソフタ
ル酸１９．６０ｇ（１１８ｍｍｏ１）、３，４′−オキ
シジアニリン２６．４ｇ（１３２ｍｍｏ１）、５−ヒド
キシイソフタル酸０．４１ｇ（２．３ｍｍｏ１）、塩化
リチウム３．９ｇ、塩化カルシウム１２．１ｇ、Ｎ−メ
チル−２−ピロリドン２４０ｍｌ、ピリジン５４ｍｌを
１１の４ツロ丸底フラスコの中に入れ、攪拌溶解させた
後、亜リン酸トリフェニル７４ｇを加えて、９０℃で４
時間反応させて、フェノール性水酸基含有アラミドオリ
ゴマ一体を生成させた。これに両末端にカルボキシル基
を持つポリブタジエン−アクリロニトリル共重合体（Ｈ
ｙｃａｒ ＣＴＢＮ、ＢＦ Ｇｏｏｄｒｉｃｈ 社製。
ポリブタジエンアクリロニトリル部に含有するアクリロ
ニトリル成分が１７モル％で、分子量が約３６００）４
８ｇを２４０ｍｌのピリジンに溶かした液を加えて、更
に４時間反応させた後、室温に冷却、この反応液をメタ
ノール２０１に投入して本発明に使用するポリブタジエ
ン−アクリロニトリル共重合体部の含有量が５０ｗｔ％
であるフェノール性水酸基を約２モル％含有するアラミ
ド−ポリブタジエン−アクリロニトリルブロック共重合
体を析出させた。この析出ポリマーを更にメタノールで
洗浄及びメタノール還流して精製した。このポリマーの
固有粘度は０．８５ｄｌ／ｇ（ジメチルアセトアミド、
３０℃）であった。ポリマー粉末を拡散反射法により赤
外スペクトルを測定したところ、１６７４ｃｍ−１にア
ミドカルボニル基、２８５６−２９７５ｃｍ−１にブタ
ジエン部分のＣ−Ｈ結合に基づく吸収を、２２４５ｃｍ
−１にニトリル基に基づく吸収を認めた。[Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. Synthesis Example 1 Synthesis of phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer (2 mol% of phenolic hydroxyl groups contained in the aramid part): 19.60 g (118 mmol) of isophthalic acid, 3,4'-oxydi 26.4 g (132 mmol) of aniline, 0.41 g (2.3 mmol) of 5-hydroxyisophthalic acid, 3.9 g of lithium chloride, 12.1 g of calcium chloride, 240 ml of N-methyl-2-pyrrolidone, and 54 ml of pyridine in 4 parts of 11. Pour into a Turo round-bottomed flask, stir to dissolve, add 74 g of triphenyl phosphite, and incubate at 90°C for 4 hours.
The reaction was carried out for a period of time to produce an integrated aramid oligomer containing a phenolic hydroxyl group. This is combined with a polybutadiene-acrylonitrile copolymer (H
ycar CTBN, manufactured by BF Goodrich. The acrylonitrile component contained in the polybutadiene acrylonitrile portion is 17 mol%, and the molecular weight is approximately 3600)4
A solution of 8 g dissolved in 240 ml of pyridine was added, and the reaction was further carried out for 4 hours, then cooled to room temperature, and the reaction solution was poured into methanol 201 to determine the content of the polybutadiene-acrylonitrile copolymer used in the present invention. is 50wt%
An aramid-polybutadiene-acrylonitrile block copolymer containing about 2 mol% of phenolic hydroxyl groups was precipitated. This precipitated polymer was further purified by washing with methanol and refluxing the methanol. The intrinsic viscosity of this polymer is 0.85 dl/g (dimethylacetamide,
30°C). When the infrared spectrum of the polymer powder was measured by the diffuse reflection method, it was found that the absorption based on the amide carbonyl group at 1674 cm-1, the absorption based on the C-H bond of the butadiene moiety at 2856-2975 cm-1, and the absorption based on the C-H bond of the butadiene moiety at 2245 cm-1.
Absorption based on nitrile groups was observed in -1.
【００１７】合成例２
フェノール性水酸基含有アラミド−ポリブタジエン−ア
クリロニトリルブロック共重合体（アラミド部に含有す
るフェノール性水酸基が１４モル％）の合成：合成例１
のイソフタル酸１９．６０ｇ（１１８ｍｍｏ１）、３，
４′−オキシジアニン２６．４ｇ（１３２ｍｍｏ１）、
５−ヒドキシイソフタル酸０．４１ｇ（２．３ｍｍｏ１
）と両末端にカルボキシル基を持つポリブタジエン−ア
クリロニトリル共重合体４８ｇの仕込み量をイソフタル
酸１９．９３ｇ（１２０ｍｍｏ１）、３，４′−オキシ
ジアニリン３０．６３ｇ（１５３ｍｍｏ１）と５−ヒド
キシイソフタル酸３．６４（２０ｍｍｏ１）と両末端に
カルボキシル基を持つポリブタジエン−アクリロニトリ
ル共重合体（Ｈｙｃａｒ ＣＴＢＮ、ＢＦ Ｇｏｏｄｒ
ｉｃｈ 社製。ポリブタジエンアクリロニトリル部に含
有するアクリロニトリルが１７モル％で、分子量が約３
６００）５５．５ｇに変えた以外は同様の操作の重合を
行い、同様の後処理をして、本発明に使用するフェノー
ル性水酸基を約１４モル％含有するアラミド−ポリブタ
ジエン−アクリロニトリルブロック共重合体を析出させ
た。このポリマーの固有粘度は０．８２ｄｌ／ｇ（ジメ
チルアセトアミド、３０℃）であった。ポリマー粉末を
拡散反射法により赤外スペクトルを測定したところ、１
６７５ｃｍ−１にアミドカルボニル基、２８５４−２９
７１ｃｍ−１にブタジエン部分のＣ−Ｈ結合に基づく吸
収を、２２４３ｃｍ−１にニトリル基に基づく吸収を認
めた。Synthesis Example 2 Synthesis of phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer (14 mol% of phenolic hydroxyl groups contained in the aramid part): Synthesis Example 1
of isophthalic acid 19.60 g (118 mmol), 3,
26.4 g (132 mmol) of 4'-oxydianine,
5-Hydoxyisophthalic acid 0.41g (2.3mmol
) and 48 g of polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends, 19.93 g (120 mmol) of isophthalic acid, 30.63 g (153 mmol) of 3,4'-oxydianiline, and 5-hydroxyisophthalic acid. 3.64 (20 mmol) and polybutadiene-acrylonitrile copolymer with carboxyl groups at both ends (Hycar CTBN, BF Goodr
Manufactured by ich company. The acrylonitrile contained in the polybutadiene acrylonitrile portion is 17 mol%, and the molecular weight is approximately 3.
600) Aramid-polybutadiene-acrylonitrile block copolymer containing about 14 mol% of phenolic hydroxyl groups used in the present invention was obtained by carrying out polymerization in the same manner except that the amount was changed to 55.5 g, and by performing the same post-treatment. was precipitated. The intrinsic viscosity of this polymer was 0.82 dl/g (dimethylacetamide, 30°C). When the infrared spectrum of the polymer powder was measured using the diffuse reflection method, it was found that 1
Amidocarbonyl group at 675 cm-1, 2854-29
Absorption based on the C--H bond of the butadiene moiety was observed at 71 cm-1, and absorption based on the nitrile group was observed at 2243 cm-1.
【００１８】実施例１
ジメチルホルムアミド２００ｇ中に合成例１で得られた
フェノール性水酸基が２モル％含有したフェノール性水
酸基含有アラミド−ポリブタジエン−アクリロニトリル
ブロック共重合体２４ｇを溶解させた後、オルトクレゾ
ールノボラック型エポキシ樹脂（ＥＯＣＮ−１０３Ｓ、
平均重合度：５〜７、エポキシ当量：２１０〜２３０、
日本化学薬品社製）４．５ｇ、反応促進剤であるトリフ
ェニルホスフィン０．０８ｇを加えて、９０℃で２時間
反応させた。これを水に添加して樹脂を析出させ、温水
で洗浄を繰り返し、更にテトラハイドロフランを加えて
減圧下でこれらの溶媒を共沸させた後、真空乾燥させ、
アラミド部にエポキシ樹脂が反応した樹脂組成物を得た
。この生成物１ｍｇを約３０ｍｌのピリジンに溶解した
溶液に、フェノール性水酸基の呈色指示液（無水塩化鉄
（ＩＩＩ）１ｇをクロロホルム１００ｍｌに溶かし、更
にピリジン８ｍｌを加えた後、析出物をろ過して赤色溶
液を調製して得られた）を数滴加えて攪拌したが、全く
変色は認められず、この樹脂にはフェノール性水酸基が
全てグリシジル基と反応し、含有されていないことを確
認した。Example 1 After dissolving 24 g of the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer containing 2 mol% of phenolic hydroxyl groups obtained in Synthesis Example 1 in 200 g of dimethylformamide, ortho-cresol novolac was dissolved. Type epoxy resin (EOCN-103S,
Average degree of polymerization: 5-7, epoxy equivalent: 210-230,
4.5 g (manufactured by Nippon Kagaku Yakuhin Co., Ltd.) and 0.08 g of triphenylphosphine as a reaction accelerator were added, and the mixture was reacted at 90° C. for 2 hours. Add this to water to precipitate the resin, repeat washing with warm water, further add tetrahydrofuran to azeotrope these solvents under reduced pressure, and then vacuum dry.
A resin composition in which the epoxy resin reacted with the aramid portion was obtained. To a solution of 1 mg of this product dissolved in about 30 ml of pyridine, 1 g of an anhydrous iron chloride (III) chloride indicator solution for phenolic hydroxyl groups was dissolved in 100 ml of chloroform, and 8 ml of pyridine was added, and the precipitate was filtered. (obtained by preparing a red solution) was added and stirred, but no discoloration was observed, confirming that all phenolic hydroxyl groups in this resin had reacted with glycidyl groups and were not contained. .
【００１９】比較例１
オルトクレゾールノボラック型エポキシ樹脂（ＥＯＣＮ
−１０３Ｓ、平均重合度：５〜７、エポキシ当量：２１
０〜２３０、日本化学薬品社製）１００ｇ、硬化促進剤
であるトリエタノールアミン１．０ｇ、硬化剤であるビ
ス（４−アミノフェニル）メタン２２ｇを加えて攪拌、
均一混合させた後、真空乾燥させ、比較用エポキシ樹脂
試料を得た。Comparative Example 1 Orthocresol novolac type epoxy resin (EOCN
-103S, average degree of polymerization: 5-7, epoxy equivalent: 21
0-230, manufactured by Nippon Kagaku Yakuhin Co., Ltd.), 1.0 g of triethanolamine as a curing accelerator, and 22 g of bis(4-aminophenyl)methane as a curing agent, and stirred.
After uniformly mixing, the mixture was vacuum dried to obtain an epoxy resin sample for comparison.
【００２０】実施例２
実施例１で得た生成物３．６ｇ、前記エポキシ樹脂９６
．４ｇ、硬化剤であるビス（４−アミノフェニル）メタ
ン２１．３ｇ、硬化促進剤であるテトラエチルアミン１
ｇを溶融させて加えて攪拌、均一混合させて本発明のエ
ポキシ樹脂組成物を得た。Example 2 3.6 g of the product obtained in Example 1, the epoxy resin 96
．． 4g, bis(4-aminophenyl)methane as a curing agent, 21.3g, and tetraethylamine as a curing accelerator, 1
The epoxy resin composition of the present invention was obtained by melting and adding g and stirring to mix uniformly.
【００２１】実施例３
実施例１で得た生成物５．９ｇ、前記エポキシ樹脂９４
．１ｇ、硬化剤であるビス（４−アミノフェニル）メタ
ン２０．９ｇ、硬化促進剤であるトリエタノールアミン
１ｇを溶融させて加えて攪拌、均一混合させて本発明の
エポキシ樹脂組成物を得た。Example 3 5.9 g of the product obtained in Example 1, the epoxy resin 94
．． 1 g of bis(4-aminophenyl)methane as a curing agent, and 1 g of triethanolamine as a curing accelerator were melted and added and stirred to uniformly mix to obtain an epoxy resin composition of the present invention.
【００２２】実施例４
合成例２で得られたフェノール性水酸基が約１４モル％
含有したアラミド−ポリブタジエンアクリロニトリルブ
ロック共重合体２４ｇ、エポキシ樹脂１１．４ｇ、反応
促進剤であるトリフェニルホスフィン０．６４ｇをジメ
チルホルムアミド２００ｇに溶解させて実施例１と同様
な操作を行って、アラミド−ポリブタジエンアクリロニ
トリルブロック共重合体とエポキシ樹脂との反応生成物
を得た。この生成物１ｍｇを約３０ｍｌのピリジンに溶
解した溶液に、フェノール性水酸基の呈色指示液（無水
塩化鉄（ＩＩＩ）１ｇをクロロホルム１００ｍｌに溶か
し、更にピリジン８ｍｌを加えた後、析出物をろ過して
赤色溶液を調製して得られた）を数滴加えて攪拌したが
、全く変色は認められず、この樹脂にはフェノール性水
酸基が全てグリシジル基と反応し、含有されていないこ
とを確認した。Example 4 Approximately 14 mol% of the phenolic hydroxyl group obtained in Synthesis Example 2
24 g of the contained aramid-polybutadiene acrylonitrile block copolymer, 11.4 g of epoxy resin, and 0.64 g of triphenylphosphine as a reaction accelerator were dissolved in 200 g of dimethylformamide, and the same operation as in Example 1 was performed to obtain aramid-polybutadiene acrylonitrile block copolymer. A reaction product of a polybutadiene acrylonitrile block copolymer and an epoxy resin was obtained. To a solution of 1 mg of this product dissolved in about 30 ml of pyridine, 1 g of an anhydrous iron chloride (III) chloride indicator solution for phenolic hydroxyl groups was dissolved in 100 ml of chloroform, and 8 ml of pyridine was added, and the precipitate was filtered. (obtained by preparing a red solution) was added and stirred, but no discoloration was observed, confirming that all phenolic hydroxyl groups in this resin had reacted with glycidyl groups and were not contained. .
【００２３】実施例５
実施例４で得られた生成物４．４ｇ、前記エポキシ樹脂
９５．６ｇ、硬化剤であるビス（４−アミノフェニル）
メタン２１．３ｇ、硬化促進剤であるテトラエチルアミ
ン１ｇを溶融させて加えて攪拌、均一混合させて本発明
のエポキシ樹脂組成物を得た。Example 5 4.4 g of the product obtained in Example 4, 95.6 g of the epoxy resin, and bis(4-aminophenyl) as a curing agent.
21.3 g of methane and 1 g of tetraethylamine, which is a curing accelerator, were melted and added, stirred, and mixed uniformly to obtain an epoxy resin composition of the present invention.
【００２４】実施例６
実施例４で得た生成物７．４ｇ、前記エポキシ樹脂９２
．６ｇ、硬化剤であるビス（４−アミノフェニル）メタ
ン２０．９ｇ、硬化促進剤であるテトラエチルアミン１
ｇを溶融させて加えて攪拌、均一混合させて本発明のエ
ポキシ樹脂組成物を得た。Example 6 7.4 g of the product obtained in Example 4, the epoxy resin 92
．． 6g, 20.9g of bis(4-aminophenyl)methane as a curing agent, 1 of tetraethylamine as a curing accelerator
The epoxy resin composition of the present invention was obtained by melting and adding g and stirring to mix uniformly.
【００２５】比較例１と実施例２、３、５、６のエポキ
シ樹脂組成物を成形後、１２０℃で２時間及び２００℃
で５時間加熱し、試験片を作成した。この試験片を用い
て衝撃靱性を下記の方法で測定し、得られた結果を表１
にまとめた。
衝撃強度の測定 ：ダインシュタッド（Ｄｙｎｅｓｔ
ｓｔ Ｆｅｉｎｍｅｃｈａｎｉｃ Ｒａｌｆ Ｋｏｇｅ
ｌ）を使用して、ＤＩＮ−５３４５３に準じて行った。
試験片は１５×１０×２（ｍｍ）とした。After molding the epoxy resin compositions of Comparative Example 1 and Examples 2, 3, 5, and 6, the epoxy resin compositions were heated at 120°C for 2 hours and at 200°C.
A test piece was prepared by heating for 5 hours. The impact toughness of this test piece was measured using the following method, and the results are shown in Table 1.
summarized in. Measurement of impact strength: Dynest
st Feinmechanic Ralph Koge
l) according to DIN-53453. The test piece was 15×10×2 (mm).
【００２６】[0026]
【表１】
ａ）ブロック共重合体のエポキシ樹脂に対する添加量ｂ
）ブロック共重合体において、アラミド部分に含有する
水酸基のモル％を示す。[Table 1] a) Addition amount b of block copolymer to epoxy resin
) Indicates the mol% of hydroxyl groups contained in the aramid moiety in the block copolymer.
【００２７】本発明のエポキシ樹脂組成物は、ノボラッ
ク型エポキシ樹脂硬化物の耐熱性を損なうことなしに、
改善された強靱性を有する成形体を製造できる。[0027] The epoxy resin composition of the present invention can improve the heat resistance of the cured novolac type epoxy resin without impairing the heat resistance.
Molded bodies with improved toughness can be produced.
Claims (1)
キシ樹脂と一般式（ＩＩ）で示すフェノール性水酸基含
有アラミド−ポリブタジエン−アクリロニトリルブロッ
ク共重合体とを反応させることにより得られるエポキシ
樹脂変性体。 【化１】 （式中、Ｒは化２又は化３、Ｒ１ は水素原子、臭素原
子又はメチル基、Ｒ２ は−（ＣＨ２ ）３ ＣＨ３
、−ＣＨ２ ＣＨ（ＣＨ３ ）２ 、−Ｃ（ＣＨ３ ）
２ ＣＨ２ ＣＨ３ 、−ＣＨ＝ＣＨ２ 、−Ｃ６ Ｈ
６ 又は水素原子、ｎ＝１〜４０の整数を示す） 【化２】 【化３】 【化４】 （式中、ｘ＝３〜７の整数、ｙ＝１〜４の整数、ｙ／（
ｘ＋ｙ）＝０．１〜０．３、ｚ＝５〜１５の整数、ｍ＝
１〜４００の整数、ｎ＝１〜４００の整数、ｎ／（ｍ＋
ｎ）＝０．０１〜０．５０、１＝１〜５０の整数、Ａｒ
１ 、Ａｒ３ は二価の芳香族基、Ａｒ２ はフェノー
ル性水酸基を含有する二価の芳香族基を示す）【請求項
２】 請求項１記載のエポキシ樹脂変性体、ノボラッ
ク型エポキシ樹脂及び硬化剤を含有するエポキシ樹脂組
成物。 【請求項３】 一般式（ＩＩ）で示すフェノール性水
酸基含有アラミド−ポリブタジエン−アクリロニトリル
ブロック共重合体を、一般式（Ｉ）で示すノボラック型
エポキシ樹脂に対して０．１から１５重量％含有してい
ることを特徴とする請求項２のエポキシ樹脂組成物。[Scope of Claims] [Claim 1] Obtained by reacting a novolac type epoxy resin represented by general formula (I) with a phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer represented by general formula (II). modified epoxy resin. Formula 1
, -CH2CH(CH3)2, -C(CH3)
2 CH2 CH3 , -CH=CH2 , -C6 H
6 or a hydrogen atom, n = an integer of 1 to 40) [Formula 2] [Chemical 3] [Chemical 4] (where x = an integer of 3 to 7, y = an integer of 1 to 4, y/(
x+y) = 0.1 to 0.3, z = integer of 5 to 15, m =
An integer from 1 to 400, n=an integer from 1 to 400, n/(m+
n) = 0.01 to 0.50, 1 = integer of 1 to 50, Ar
1, Ar3 represents a divalent aromatic group, and Ar2 represents a divalent aromatic group containing a phenolic hydroxyl group) [Claim 2] The modified epoxy resin, novolac type epoxy resin, and curing agent according to claim 1. An epoxy resin composition containing. 3. The phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer represented by the general formula (II) is contained in an amount of 0.1 to 15% by weight based on the novolac type epoxy resin represented by the general formula (I). The epoxy resin composition according to claim 2, characterized in that:
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03105165A JP3100662B2 (en) | 1991-04-11 | 1991-04-11 | Modified epoxy resin and epoxy resin composition |
| DE19924208134 DE4208134A1 (en) | 1991-03-15 | 1992-03-13 | Epoxy] resin compsns. with improved toughness - contain material prepd. by reaction of epoxy] resin with phenolic hydroxyl gp.-contg. aramid-polybutadiene-acrylonitrile] block copolymer |
| US07/851,801 US5258456A (en) | 1991-03-15 | 1992-03-16 | Epoxy resin with phenolic OH-aramide/ban block copolymer |
| US08/097,890 US5334661A (en) | 1991-03-15 | 1993-07-28 | Epoxy resin reacted with phenolic OH-aramide/ban |
| US08/149,371 US5334662A (en) | 1991-03-15 | 1993-11-09 | Epoxy resin/phenolic OH-aramid/ban block copolymer product with CTBN |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03105165A JP3100662B2 (en) | 1991-04-11 | 1991-04-11 | Modified epoxy resin and epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04311716A true JPH04311716A (en) | 1992-11-04 |
| JP3100662B2 JP3100662B2 (en) | 2000-10-16 |
Family
ID=14400078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03105165A Expired - Fee Related JP3100662B2 (en) | 1991-03-15 | 1991-04-11 | Modified epoxy resin and epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3100662B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06299133A (en) * | 1993-04-14 | 1994-10-25 | Tomoegawa Paper Co Ltd | Epoxy resin adhesive composition |
| JP2008163330A (en) * | 2000-10-20 | 2008-07-17 | Nippon Kayaku Co Ltd | Polyamide resin-containing varnish |
-
1991
- 1991-04-11 JP JP03105165A patent/JP3100662B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06299133A (en) * | 1993-04-14 | 1994-10-25 | Tomoegawa Paper Co Ltd | Epoxy resin adhesive composition |
| JP2008163330A (en) * | 2000-10-20 | 2008-07-17 | Nippon Kayaku Co Ltd | Polyamide resin-containing varnish |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3100662B2 (en) | 2000-10-16 |
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