JPH0319855B2 - - Google Patents
Info
- Publication number
- JPH0319855B2 JPH0319855B2 JP8469383A JP8469383A JPH0319855B2 JP H0319855 B2 JPH0319855 B2 JP H0319855B2 JP 8469383 A JP8469383 A JP 8469383A JP 8469383 A JP8469383 A JP 8469383A JP H0319855 B2 JPH0319855 B2 JP H0319855B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- epoxy resin
- epoxy
- component
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003822 epoxy resin Substances 0.000 claims description 49
- 229920000647 polyepoxide Polymers 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 19
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 229960003656 ricinoleic acid Drugs 0.000 claims description 11
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000003700 epoxy group Chemical group 0.000 claims description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- 150000008065 acid anhydrides Chemical class 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 description 41
- 239000011347 resin Substances 0.000 description 41
- 239000000463 material Substances 0.000 description 18
- 239000004593 Epoxy Substances 0.000 description 17
- 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 15
- -1 fatty acid glycidyl ester Chemical class 0.000 description 14
- 238000001723 curing Methods 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- 229920002857 polybutadiene Polymers 0.000 description 11
- 239000005062 Polybutadiene Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 238000010292 electrical insulation Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 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 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical class C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000011269 tar Substances 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- HGRZLIGHKHRTRE-UHFFFAOYSA-N 1,2,3,4-tetrabromobutane Chemical compound BrCC(Br)C(Br)CBr HGRZLIGHKHRTRE-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 2
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 2
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 2
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 2
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000019743 Choline chloride Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- IDSLNGDJQFVDPQ-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-yl) hexanedioate Chemical compound C1CC2OC2CC1OC(=O)CCCCC(=O)OC1CC2OC2CC1 IDSLNGDJQFVDPQ-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 2
- 229960003178 choline chloride Drugs 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- GVYLCNUFSHDAAW-UHFFFAOYSA-N mirex Chemical compound ClC12C(Cl)(Cl)C3(Cl)C4(Cl)C1(Cl)C1(Cl)C2(Cl)C3(Cl)C4(Cl)C1(Cl)Cl GVYLCNUFSHDAAW-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 2
- OFZRSOGEOFHZKS-UHFFFAOYSA-N (2,3,4,5,6-pentabromophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br OFZRSOGEOFHZKS-UHFFFAOYSA-N 0.000 description 1
- BKKVYNMMVYEBGR-UHFFFAOYSA-N (2,3,4,5,6-pentabromophenyl) prop-2-enoate Chemical compound BrC1=C(Br)C(Br)=C(OC(=O)C=C)C(Br)=C1Br BKKVYNMMVYEBGR-UHFFFAOYSA-N 0.000 description 1
- AYYISYPLHCSQGL-UHFFFAOYSA-N (2,3,4,5,6-pentachlorophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl AYYISYPLHCSQGL-UHFFFAOYSA-N 0.000 description 1
- KWQJKAHZHOILKK-UHFFFAOYSA-N (2,3,4,5,6-pentachlorophenyl) prop-2-enoate Chemical compound ClC1=C(Cl)C(Cl)=C(OC(=O)C=C)C(Cl)=C1Cl KWQJKAHZHOILKK-UHFFFAOYSA-N 0.000 description 1
- ZSVFYHKZQNDJEV-UHFFFAOYSA-N (2,3,4-tribromophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(Br)C(Br)=C1Br ZSVFYHKZQNDJEV-UHFFFAOYSA-N 0.000 description 1
- BUPRYTFTHBNSBD-UHFFFAOYSA-N (2,3,4-tribromophenyl) prop-2-enoate Chemical compound BrC1=CC=C(OC(=O)C=C)C(Br)=C1Br BUPRYTFTHBNSBD-UHFFFAOYSA-N 0.000 description 1
- IGWMFERXHIUPRD-UHFFFAOYSA-N (2,3,4-trichlorophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(Cl)C(Cl)=C1Cl IGWMFERXHIUPRD-UHFFFAOYSA-N 0.000 description 1
- JLOIRPJHPDQHHN-UHFFFAOYSA-N (2,3,4-trichlorophenyl) prop-2-enoate Chemical compound ClC1=CC=C(OC(=O)C=C)C(Cl)=C1Cl JLOIRPJHPDQHHN-UHFFFAOYSA-N 0.000 description 1
- BOOBDAVNHSOIDB-UHFFFAOYSA-N (2,3-dichlorobenzoyl) 2,3-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC(C(=O)OOC(=O)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl BOOBDAVNHSOIDB-UHFFFAOYSA-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
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
- CCBHUQDNJKGSHH-UHFFFAOYSA-N 1,1,1,2-tetrabromo-2,2-dichloroethane Chemical compound ClC(Cl)(Br)C(Br)(Br)Br CCBHUQDNJKGSHH-UHFFFAOYSA-N 0.000 description 1
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- QXSZNDIIPUOQMB-UHFFFAOYSA-N 1,1,2,2-tetrabromoethane Chemical group BrC(Br)C(Br)Br QXSZNDIIPUOQMB-UHFFFAOYSA-N 0.000 description 1
- DQYHBUIHXMLXFA-UHFFFAOYSA-N 1,1,4,7,10,10-hexabromododecane Chemical compound CCC(Br)(Br)CCC(Br)CCC(Br)CCC(Br)Br DQYHBUIHXMLXFA-UHFFFAOYSA-N 0.000 description 1
- GGMQZPIDPNAGFP-UHFFFAOYSA-N 1,1-dibromo-1,2,2,2-tetrachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Br)Br GGMQZPIDPNAGFP-UHFFFAOYSA-N 0.000 description 1
- XQKQZOLAVMIQHZ-UHFFFAOYSA-N 1,1-dibromo-3-(3,3-dibromopropoxy)propane Chemical compound BrC(Br)CCOCCC(Br)Br XQKQZOLAVMIQHZ-UHFFFAOYSA-N 0.000 description 1
- ACRQLFSHISNWRY-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-phenoxybenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=CC=CC=C1 ACRQLFSHISNWRY-UHFFFAOYSA-N 0.000 description 1
- HHPUADFPUXGYTC-UHFFFAOYSA-N 1,2,3-tribromo-5-methylbenzene;1,2,5-tribromo-3-methylbenzene;1,3,5-tribromo-2-methylbenzene Chemical compound CC1=CC(Br)=C(Br)C(Br)=C1.CC1=CC(Br)=CC(Br)=C1Br.CC1=C(Br)C=C(Br)C=C1Br HHPUADFPUXGYTC-UHFFFAOYSA-N 0.000 description 1
- JHBKHLUZVFWLAG-UHFFFAOYSA-N 1,2,4,5-tetrachlorobenzene Chemical compound ClC1=CC(Cl)=C(Cl)C=C1Cl JHBKHLUZVFWLAG-UHFFFAOYSA-N 0.000 description 1
- WBEJYOJJBDISQU-UHFFFAOYSA-N 1,2-Dibromo-3-chloropropane Chemical compound ClCC(Br)CBr WBEJYOJJBDISQU-UHFFFAOYSA-N 0.000 description 1
- 229940100682 1,2-dibromo-3-chloropropane Drugs 0.000 description 1
- YAOMHRRYSRRRKP-UHFFFAOYSA-N 1,2-dichloropropyl 2,3-dichloropropyl 3,3-dichloropropyl phosphate Chemical compound ClC(Cl)CCOP(=O)(OC(Cl)C(Cl)C)OCC(Cl)CCl YAOMHRRYSRRRKP-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- PWXTUWQHMIFLKL-UHFFFAOYSA-N 1,3-dibromo-5-[2-(3,5-dibromo-4-prop-2-enoxyphenyl)propan-2-yl]-2-prop-2-enoxybenzene Chemical compound C=1C(Br)=C(OCC=C)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OCC=C)C(Br)=C1 PWXTUWQHMIFLKL-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- QEEPPWQOVJWUBC-UHFFFAOYSA-N 1-hydroperoxycyclohexene Chemical class OOC1=CCCCC1 QEEPPWQOVJWUBC-UHFFFAOYSA-N 0.000 description 1
- GQNOPVSQPBUJKQ-UHFFFAOYSA-N 1-hydroperoxyethylbenzene Chemical compound OOC(C)C1=CC=CC=C1 GQNOPVSQPBUJKQ-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- VFEXYZINKMLLAK-UHFFFAOYSA-N 2-(trichloromethyl)oxirane Chemical compound ClC(Cl)(Cl)C1CO1 VFEXYZINKMLLAK-UHFFFAOYSA-N 0.000 description 1
- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 description 1
- HJVAFZMYQQSPHF-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;boric acid Chemical compound OB(O)O.OCCN(CCO)CCO HJVAFZMYQQSPHF-UHFFFAOYSA-N 0.000 description 1
- ASLNDVUAZOHADR-UHFFFAOYSA-N 2-butyl-3-methylphenol Chemical compound CCCCC1=C(C)C=CC=C1O ASLNDVUAZOHADR-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
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- 239000000499 gel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
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- 238000013007 heat curing Methods 0.000 description 1
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- 229920001519 homopolymer Polymers 0.000 description 1
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- 239000011572 manganese Substances 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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- 238000006011 modification reaction Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
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- 229920006255 plastic film Polymers 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
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- 239000005060 rubber Substances 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 239000003566 sealing material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
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- 229910052623 talc Inorganic materials 0.000 description 1
- 230000003797 telogen phase Effects 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- PJNLXXROLSYGPE-UHFFFAOYSA-N tris(1-bromo-3-chloropropan-2-yl) phosphate Chemical compound ClCC(CBr)OP(=O)(OC(CCl)CBr)OC(CCl)CBr PJNLXXROLSYGPE-UHFFFAOYSA-N 0.000 description 1
- FFULTTXGZNPTQO-UHFFFAOYSA-N tris(2-bromoethyl) phosphate Chemical compound BrCCOP(=O)(OCCBr)OCCBr FFULTTXGZNPTQO-UHFFFAOYSA-N 0.000 description 1
- LKOCAGKMEUHYBV-UHFFFAOYSA-N tris(3-bromo-3-chloropropyl) phosphate Chemical compound ClC(Br)CCOP(=O)(OCCC(Cl)Br)OCCC(Cl)Br LKOCAGKMEUHYBV-UHFFFAOYSA-N 0.000 description 1
- DKWUPGWCPHICPJ-UHFFFAOYSA-N tris(4,4-dibromobutyl) phosphate Chemical compound BrC(Br)CCCOP(=O)(OCCCC(Br)Br)OCCCC(Br)Br DKWUPGWCPHICPJ-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
- 239000002383 tung oil Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Description
本発明は塗料用、含浸用、成形用、注型用又
は、積層用樹脂として有用な可撓性、耐熱衝撃性
及び電気特性に優れた変性エポキシ樹脂の製造方
法に関する。
エポキシ樹脂は、硬化の際に収縮が少なく金
属、プラスチツク、ガラス等に対するせん断接着
力に優れ、硬化樹脂の電気的、化学的、機械的性
質に卓越した特性を有している為、塗料、接着
剤、注型材、積層材等の分野で広く利用されてい
る。しかしエポキシ樹脂の硬化物は一般に剛性が
大きい反面、伸び変位が小さい為、可撓性、耐衝
撃性及び剥離強度に問題が有り、機械的衝撃や熱
衝撃を受けると亀裂や剥離を生じ易い欠点があつ
た。
かかるエポキシ樹脂の欠点を改良するために、
ポリエチレングリコール、コールタール、ジブチ
ルフタレート、ポリグリコールグリシジルエーテ
ル、有機脂肪酸グリシジルエステル、ポリエステ
ル、ポリアミド、ポリエーテル、ポリチオール等
を可撓性付与剤として併用することが行なわれて
いる。更にウレタン変性エポキシ樹脂、未端カル
ボキシニトリル変性ポリブタジエンをエポキシ樹
脂に混合して使用することが行なわれているが、
一般にエポキシ樹脂硬化物の電気的性質及び機械
的性質を低下させる欠点がある。
又、他の可撓性付与方法として分子の両末端に
カルボキシル基を有するポリブタジエンとエポキ
シ樹脂とを反応させて得られるポリブタジエン変
性エポキシ樹脂を用いる方法(特開昭53−144958
及び特開昭55−137125)等が提案されている。
特開昭53−144958に開示されている方法はポリ
ブタジエンで変性したエポキシ化合物を得る場合
変性樹脂が相溶性が悪く、硬化前に二層に分離し
たり加熱硬化中に二層に分離し、不均一な硬化物
を生成することをさける条件及びエステル反応中
の反応系のゲル化防止について何ら教示していな
い。
実際、上記公知の方法による変性エポキシ樹脂
は、変性反応中に反応系がゲル化し、安定性の良
い変性エポキシ樹脂を得ることが出来ない。
又、特開昭55−137125に開示されている方法
は、可撓性、耐衝撃性及び剥離強度においては改
良されているが、反面、変性樹脂の粘度が著るし
く高い為作業性に問題が有り、且つ、他のエポキ
シ樹脂との相溶性が極めて悪いため、実用上必ず
しも満足し得るものではなかつた。
本発明者らはこのような現状に鑑み、従来より
公知の可撓性エポキシ樹脂のもつ上記諸欠点を改
良し、機械的性質、電気絶縁性、接着性、特に可
撓性、耐クラツク性、耐熱衝撃性に優れ、低粘度
で、且つ、他のエポキシ樹脂との相溶性にも優れ
た変性エポキシ樹脂を提供することを目的に鋭意
検討を重ねた結果、リシノール酸及び/又はリシ
ノール酸誘導体と二塩基酸無水物とを反応せしめ
て得られるカルボキシル基を有する半エステル化
物とカルボキシル基を有するブタジエン系重合体
を用いてエポキシ樹脂を変性することにより上記
目的が達成されることを見い出し、本発明を完成
するに至つた。
すなわち、本発明は
(A) リシノール酸及び/又はリシノール酸誘導体
(イ)と二塩基酸無水物(ロ)とを反応せしめて得られ
るカルボキシル基を有する半エステル化物(ハ)と
カルボキシル基を有するブタジエン系重合体(ニ)
との混合物と
(B) 多官能性エポキシ樹脂
とを(A)のカルボキシル基1当量に対して(B)のエポ
キシ基1.8〜30当量の割合で加熱反応せしめて得
られることを特徴とする変性エポキシ樹脂の製造
方法である。
本発明における(イ)成分のリシノール酸はリシノ
レイン酸ともいわれ、分子中にヒドロキシル基、
カルボキシル基及び二重結合をそれぞれ1個づつ
有する下記の分子式で表わされる脂肪酸である。
又、リシノール酸誘導体としては例えばリシノ
ール酸とエチレングリコール、プロピレングリコ
ール等のグリコール類、ポリエチレングリコー
ル、ポリプロピレングリコール等のポリアルキレ
ングリコール類、トリメチロールプロパン、グリ
セリン、ペンタエリスリトール等のポリオール類
或はモノエポキシ化合物類の一種又は二種以上と
をエステル化反応せしめて得られる分子内に1個
以上のヒドロキシル基を有するものが用いられ
る。
本発明における(ロ)成分の二塩基酸無水物として
は、例えば無水マレイン酸、無水フタル酸、3−
メチルヘキサヒドロ無水フタル酸、4−メチルヘ
キサヒドロ無水フタル酸、4−メチルテトラヒド
ロ無水フタル酸、ヘキサヒドロ無水フタル酸とテ
トラヒドロ無水フタル酸の共融混合物、無水メチ
ルエンドメチレンテトラヒドロフタル酸、ドデセ
ニル無水コハク酸、エンドメチレンテトラヒドロ
無水フタル酸、無水トリメリツト酸、無水ピロメ
リツト酸等が挙げられる。
本発明における(ニ)成分の分子中にカルボキシル
基を有するブタジエン系重合体には両末端にカル
ボキシル基を有する分子量500〜10000のポリブタ
ジエン又はブタジエンと他のビニルモノマーとの
コポリマーで常温で液状のものが好ましく、市販
品としては日本曹達社の商品名Nisso−PBC−
1000、C−2000、グツドリツチ社の商品名Hycar
−CTB、CTBX、CTBN、ゼネラルタイヤ社の
商品名Telogen CT、S、フイリツプス社の商品
名Butarez CTL、HTPB等が挙げられる。
更に上記重合体の二重結合が水素添加によつて
部分的に、或は完全に飽和されたものも用いるこ
とが出来る。
本発明における多官能性エポキシ樹脂としては
2官能以上のエポキシ基を有するものであれば、
特に制限はないが、例えば、
a ビスフエノールA型エポキシ樹脂、例えば、
シエル化学(株)の商品名 エピコート827、同
828、同834、同836、同1001、同1004、同
1007;
チバガイギー(株)の商品名 アラルダイド
CY252、同CY250、同GY260、同GY280、同
6071、同6084、同6097;
ダウ・ケミカル(株)の商品名 DER330、同
331、同337、同661、同664;
大日本インキ化学工業(株)の商品名 エピクロ
ン1010、同1000、同3010、
b ノボラツク型エポキシ樹脂、例えば、シエル
化学(株)製の商品名 エピコート152、同154;
ダウ・ケミカル(株)の商品名 DEN−431、同
438、同439;
チバガイギー(株)の商品名 EPN−1138、
ECN1235;
大日本インキ化学(株)の商品名 エピクロンN
−740、同N−680、同N−695、同N−565、同
N−577、
c 水素添加ビスフエノールAジグリシジルエー
テル樹脂、例えば、
旭電化工業(株)の商品名 アデカレジンEP−
4080、
d ビスフエノールA側鎖型ジグリシジルエーテ
ル樹脂、例えば、
旭電化工業(株)の商品名 アデカレジンEP−
4000、
e ウレタン変性エポキシ樹脂、例えば、
旭電化工業(株)の商品名 アデカレンジEPU
−4、同EPU−6、同EPU−8、
f レゾルシンジグリシジルエーテルエポキシ樹
脂、例えば、住友化学工業(株)の商品名
SUMI−エポキシELR−130、同ELR−150、
g グリシジルエステル型エポキシ樹脂、例え
ば、
チバガイギー(株)の商品名 アラルダイトCY
−183、同CY−182、
シエル化学(株)の商品名 エピコートE−190、
同E−871、
昭和電工(株)の商品名 シヨウダインS−500、
同S−508、同S−509、同S−601X、同S−
603X、同S−607X、同S−609X、同S−729、
同S−540、同S−550;
大日本インキ化学工業(株)の商品名 エピクロ
ン200、同400、
h P−オキシ安息香酸ジグリシジルエーテルエ
ステル樹脂、例えば、住友化学工業(株)の商品名
SUMI−エポキシ樹脂 ELP−160、
i 脂環型エポキシ樹脂
UCCの商品名 ERL−4221、同4289、同
4206、同4234、同4205;
チバガイギー(株)の商品名 CY−179、同CY
−178、同CY−180、同CY−175、
j 臭素化ビスフエノールA型エポキシ樹脂
シエル化学(株)の商品名 エピコートDX−
245、同1045−B−80;
チバガイギー(株)の商品名 アラルダイド
8011、同8047;
大日本インキ化学工業(株)の商品名 エピクロ
ン152、同1120;
ダウ・ケミカル(株)の商品名 DER−542、同
511、同580、
k グリシジルアミンエポキシ樹脂、例えば、住
友化学工業(株)の商品名
SUMI−Epoxy ELM120、同ELM−125
等が挙げられる。
これらは単独又は混合系で使用することが出来
る。
次に本発明における変性エポキシ樹脂の変性に
おいてリシノール酸及び/又はリシノール酸誘導
体(イ)と二塩基酸無水物(ロ)との半エステル化反応
は、(イ)成分のヒドロキシル基1当量に対し(ロ)成分
を0.2〜1.0モルの割合で用い、反応温度50〜200
℃好ましくは80〜150℃で通常0.3〜5時間、好ま
しくは1〜3時間加熱反応せしめてカルボキシル
基を有する半エステル化物(ハ)が得られる。
ヒドロキシル基に対する二塩基酸無水物のモル
数が0.2モル以下では得られる変性エポキシ樹脂
の保存安定性、相溶性、電気絶縁性が劣り、1モ
ル以上では、未反応の二塩基酸無水物が残留する
為に、エポキシ樹脂との反応中にゲル化が起り好
ましくない。
又、半エステル化の際、必要に応じてテトラブ
チルチタネート、酢酸亜鉛、ナフテン酸マンガ
ン、トリフエニルアンチモン等のような通常用い
られるエステル化触媒を使用しても良い。
上記半エステル化反応によつて得られたカルボ
キシル基を有する半エステル化物(ハ)とカルボキシ
ル基を有するブタジエン系重合体(ニ)との配合割合
は(ハ)成分10〜90重量%、(ニ)成分90〜10重量%で用
いられ、好ましくは(ハ)成分20〜60重量%、(ニ)成分
80〜40重量%である。(ハ)成分が10重量%より少な
いと得られた変性エポキシ樹脂の粘度が著しく高
く、且つ、他のエポキシ樹脂との相溶性が著しく
悪くなり、一方90重量%より多いと耐衝撃性、耐
クラツク性、剥離強度等が劣るからである。
かくして得られた半エステル化物(ハ)とカルボキ
シル基を有するブタジエン系重合体(ニ)の混合物(A)
と前記の多官能性エポキシ樹脂(B)との反応は反応
温度80〜250℃、好ましくは100〜160℃であり、
反応時間は通常1〜20時間、好ましくは2〜10時
間が最適である。
又、多官能性エポキシ樹脂(B)の使用割合は、(A)
の混合物中のカルボキシル基1当量に対してエポ
キシ基を1.8〜30当量であり、好ましくは2.0〜20
当量用いられる。カルボキシル基に対するエポキ
シ基のモル数が1.8当量以下では反応物が高分子
量化し、著しく粘度が上昇し、時にはゲル化が起
きるので好ましくない。
一方上記最大限度の30当量をこえると未反応の
エポキシ樹脂の残存する量が多くなり、硬化物の
ハクリ強度、可撓性及び衝撃強度が著しく低下す
る。
カルボキシル基に対するエポキシ基の反応を促
進し、高温にさらされる時間を短縮してポリブタ
ジエン系ポリマーの熱重合による好ましくない粘
度上昇ないしはゲル化を防止する為に、反応系に
促進剤を添加することによつて反応を促進するこ
ともできる。この目的で使用される反応促進剤と
しては、例えば2−エチルイミダゾール、臭化テ
トラエチルアンモニウム、ベンジルジメチルアミ
ン、トリエチレンジアミン、トリエチルアミン、
ジエチルアミン、ブチルアミン、ベンジルジメチ
ルアミン、塩化コリン、カ性カリ、炭酸アルカリ
等があり、それらをエポキシ基に対して0.01〜5
モル%添加させる。又、熱重合の抑制をさらに完
全にするためには、例えばハイドロキノン、パラ
ベンゾキノン、アントラキノンなどのラジカル重
合禁止剤を全樹脂分に対して0.01〜5重量%添加
しておくと良い。又、不活性ガスの雰囲気下で反
応を行わせることによつて、炭素−炭素間の二重
結合部分の熱重合の抑制をいつそう確実にするこ
とができる。
また必要に応じて適当な溶媒を用いても良く、
この場合反応物の取扱い上効果的である。
本発明の最大の特徴は、変性エポキシ樹脂骨格
中にリシノール酸及び又はその誘導体を導入した
点にある。リシノール酸及びその誘導体は、一般
に常温で低粘度の液状物で他の樹脂類との相溶性
が極めて良好であり、前記エポキシ樹脂、ブタジ
エン重合体共ほとんど任意に相溶する。更に、リ
シノール酸及びその誘導体は、一般的なポリエス
テル系ポリオール、ポリエーテル系ポリオールと
くらべて柔軟性、耐衝撃性、電気絶縁性、耐加水
分解性等に優れている。
従つて本発明の変性エポキシ樹脂は、従来公知
のポリブタジエン単独からなる変性エポキシ樹脂
にくらべて、その優れた可撓性、耐衝撃性、剥離
強度、耐クラツク性及び電気絶縁性等を損なう事
なく粘度を著しく低下せしめ、且つ、他のエポキ
シ樹脂との相溶性を向上させ得た事は驚くべき優
れた効果である。
本発明の方法によつて得られる変性エポキシ樹
脂は少なくとも未反応のエポキシ基と、ヒドロキ
シル基を有する為、それ自体でも加熱硬化が可能
であるが、従来公知のエポキシ硬化剤を適当量配
合することによつて、常温から高温に至る所望の
条件下で容易に硬化架橋反応が進行し、可撓性と
耐衝撃性に富む優れた性能を有する硬化物を与え
るものである。この場合の公知のエポキシ硬化剤
として、ジエチレントリアミン、メタフエニレン
ジアミン等のアミン類、無水ドデセニル酸、無水
マレイン酸等のカルボン酸無水物、BF3のモノエ
チルアミン錯体やBF3のピリジン錯体等のBF3系
錯化合物、或はトリエタノールアミンボレート等
の錯化合物、チタニウムアルコキサイド、−SH
基、−NCO基、−NCS基、−CONH基を分子内に
1個以上有する化合物等が挙げられる。これらの
硬化剤の使用量としては、変性エポキシ樹脂のエ
ポキシ当量対官能基当量比0.8〜1.2相当量が使用
される。
本発明によつて得られた変性エポキシ樹脂に粘
度を低くする為に、ブチルグリシジルエーテル、
フエニルグリシジルエーテル、ビニルシクロヘキ
センジエポキサイド等のエポキシ樹脂用の反応性
希釈剤を配合することもできる。
本発明に係る樹脂を電気絶縁用の注型、含浸、
厚塗り、成形用樹脂として使用する場合、該樹脂
に反応性希釈剤、充填剤を混合し、要すれば難燃
剤、補強剤、顔料、可塑剤、酸化防止剤等を添加
し充分混和し樹脂組成物とする。その樹脂組成物
を加熱或は常温で硬化させるが、その硬化法とし
て上述の如く架橋剤としてエポキシ硬化剤を添
加して、エポキシ基と反応させて架橋反応を行な
う方法、架橋剤としてラジカル重合開始剤を添
加し、ポリブタジエン鎖の不飽和二重結合を架橋
反応に関与せしめる方法、エポキシ硬化剤及び
ラジカル重合開始剤の両者を添加して、エポキシ
基及び不飽和二重結合の両方で架橋反応を行い、
硬化物を得る方法、の三方法が可能である。
これらのうちのどの硬化方法を選ぶかは、目的
とする電気絶縁物の要求する、電気特性、機械的
特性、可撓性、耐熱性等を考慮して選択すること
が可能である。
ラジカル重合開始剤としては、ジアシルパーオ
キサイド類、例えば過酸化ベンゾイル、2・4−
ジクロル過酸化ベンゾイル、オクタノイルパーオ
キサイド、ラウロイルパーオキサイド等、ジアル
キルパーオキサイド類、例えばジ−第3ブチルパ
ーオキサイド、ジクミルパーオキサイド等、パー
オキシエステル類、例えば第3ブチルパーベンゾ
エート、第3ブチルパーアセテート、ジ−第3ブ
チルパーフタレート、2・5−ジメチル−2・5
−ジ(ベンゾイルパーオキシ)ヘキサン等、ケト
ンパーオキサイド類、例えばメチルエチルケトン
パーオキサイド、シクロヘキサノンパーオキサイ
ド等、ハイドロパーオキサイド類、例えば第3ブ
チルヒドロパーオキサイド、クメンハイドロパー
オキサイド、α−フエニルエチルヒドロパーオキ
サイド、シクロヘキセニルヒドロパーオキサイド
等およびこれらの混合物が適当であつて発泡性の
ないものが好ましく、その使用量は全樹脂分に対
し0.1〜10重量%、好ましくは0.5ないし5重量%
である。
又、上記硬化剤と併用される硬化促進剤として
は例えばジメチルアニリン、ジエチルアニリン等
のアミン化合物、ナフテン酸コバルト、オクテン
酸鉛、オクテン酸コバルト、ナフテン酸亜鉛、ロ
ジン酸マンガンのようなカルボン酸金属塩類があ
り、その添加量はアミン化合物の場合全樹脂分に
対し0.1ないし5重量%、カルボン酸金属塩の場
合金属として0.001ないし1重量%が好適である。
また充填材としては沈降性又は重質炭酸カルシ
ウム、シリカ、タルク、アルミナ、水酸化アルミ
ニウム、珪藻土、クレー、カオリン、マイカ、ガ
ラス粉、ガラスビーズ、硫酸バリウム等の無機
質、更には鉄、アルミ、銅等の金属粉及びこれら
の混合物が適当でその使用量は全樹脂分に対し50
〜500重量%である。
更に高温での粘度調整や沈降防止の目的で有機
ベントナイト例えばオルベン、微粉末シリカ例え
ばアエロジル等を混合することも出来る。その使
用量は全樹脂分に対し1〜10重量%である。
補強材としてはガラス繊維、ナイロン、テトロ
ン、ビニロン、アスベスト、ウイスカー等の繊維
物質が使用されその使用量は全樹脂分に対し2〜
100重量%である。可塑剤としては、一般公知の
ジブチルフタレート、ジオクチルフタレート、ト
リクレジルホスフエート、塩化パラフイン等の可
塑剤、石油系タール、石炭系タール等のタール
類、ナフテン系若しくはパラフイン系石油オイル
類(プロセスオイル類も含む)、アマニ油、ボデ
イ化アマニ油、大豆油、ボデイ化大豆油、桐油、
サフラワー油、ヒマシ油等の油脂類が用いられ
る。
反応性希釈剤としては、前述のエポキシ基を有
する反応性希釈剤の他にポリブタジエン樹脂用の
反応性希釈剤を使用することも可能で、この反応
性希釈剤として通常ビニルモノマーが使われる。
ビニルモノマーとしては、スチレン、メチルス
チレン、ビニルトルエン、メチルメタアクリレー
ト、ジビニルベンゼン、エチルフマレート、ジア
リルフタレート等が含まれ特にスチレン、ビニル
トルエンが好ましくその使用量は10〜100重量%
である。
更に本発明において耐熱性を向上させる為に使
用される酸化防止剤としてはアルキルフエノール
類、例えば4・4′−チオビス−(6−第3−ブチ
ル−3−メチルフエノール)、3・5−ジ−第3
−ブチル−ヒドロキシ−トルエン、2・2′−メチ
レン−ビス−(4−メチル−6−第3ブチルフエ
ノール)、4・4′−ブチリデン−ビス(6−第3
ブチル−3−クレゾール)等、アリルアミン類、
例えばフエニール−C−ナフチルアミン、N・
N′−ジ−β−ナフチル−P−フエニーレンジア
ミン等、チオン脂肪酸エステル類、例えばジラウ
リルチオジプロピオネート、ジステアリルチオジ
プロピオネート、ラウリルステアリルジプロピオ
ネート等及びこれらの混合物が適当であつてその
使用量は全樹脂分に対し0.01〜10重量%、好まし
くは0.1〜2重量%である。
又、本発明において絶縁樹脂組成物を高度に難
燃化する必要があるときは、一般公知の難燃剤を
使用することが出来る。例えば、無機系難燃剤と
しては水酸化アルミニウム(水和アルミナ)、硼
酸亜鉛等、有機ハロゲン化物としては、塩素化パ
ラフイン、四塩化ベンゼン、六塩化ベンゼン、塩
素化ジフエニル、塩素化トリフエニル、塩素ポリ
フエニル、3・3・3−トリクロロプロピレンオ
キサイドのポリマー、パークロロペンタシクロデ
カン、市販品としては、フツカー社のデクロラン
プラス、或はデクロランなど臭素化物としては例
えばテトラブロモエタン、テトラブロモブタン、
テトラブロモアセチレン、ヘキサブロモベンゼ
ン、トリブロモトルエン、ヘキサブロモドデカ
ン、トリブロモフエノールのアリルエステル、ト
リブロモフエノールのジブロモプロピルエーテ
ル、テトラブロモビスフエノールA、テトラブロ
モビスフエノールAのビスアリルエーテル、テト
ラブロモビスフエノールAのビスジブロモプロピ
ルエーテル、ペンタブロモジフエニルエーテル、
オクタブロモビスフエノール、帝人化成社の
HB、第一工業製薬社のピロカードSR−100等、
塩臭素化物としては例えば、ジクロロテトラブロ
モエタン、ジブロモテトラクロロエタン、1,2
−ジブロモ−3−クロロプロパン、2−クロロ−
1,2,3,4−テトラブロモブタン等、ハロゲ
ン含有リン酸塩としては、例えば、トリス(β−
クロロエチル)ホスフエート、トリス(クロロプ
ロピル)ホスフエート、トリス(ジクロロプロピ
ル)ホスフエート、トリス(2−ブロモエチル)
ホスフエート、トリス(2,3−ジブロモプロピ
ル)ホスフエート、トリス(ジブロモブチル)ホ
スフエート、トリス(ブロモクロロプロピル)ホ
スフエート、トリス(2−クロロエチル)ホスフ
エート、トリス(2−ブロモ−2−クロロイソプ
ロピル)ホスフエート、トリス(1−ブロモ−3
−クロロイソプロピル)ホスフエート、トリブロ
モフエノールメタアクリレート、トリブロモフエ
ノールアクリレート、ペンタブロモフエノールメ
タアクリレート、ペンタブロモフエノールアクリ
レート、トリクロロフエノールメタアクリレー
ト、トリクロロフエノールアクリレート、ペンタ
クロロフエノールメタアクリレート、ペンタクロ
ロフエノールアクリレート、三酸化アンチモン、
赤リン、リン化合物類等が用いられる。
本発明に係る変性エポキシ樹脂はその使用に際
し、目的とする電気絶縁物の要求する諸特性を満
足させる為ポリブタジエンホモポリマー、コポリ
マー、アクリル変性ポリブタジエン及び(又は)
その水素添加物等のポリブタジエン系樹脂や、エ
ポキシ化合物を適当量加える事も可能である。
かくして本発明の方法により製造された変性エ
ポキシ樹脂は、低粘度で、他のエポキシ樹脂との
相溶性が良好で、機械的性質、電気絶縁性、接着
性、可撓性、耐クラツク性及び耐熱衝撃性に優れ
ており、電気絶縁材料、成形材料、塗料、接着
剤、建材及び土木用途への有用な材料となる優れ
たものである。
本発明に係る変性エポキシ樹脂の電気絶縁材料
としての具体的用途の例としては塗料的使用形態
のものとしてコイル含浸ワニス、布管用ワニス、
電線用ワニス、表面仕上げ塗料、コアワニス等
に、又注形樹脂タイプとしてコンデンサー、フラ
イバツクトランス、ケーブル接続材、抵抗器、ト
ランジスタ、電動機、変圧器、発電機、碍子、プ
ツシング等の部品等に使われる。又成形樹脂の具
体的用途の例としてはコネクター、スイツチギ
ヤ、コンデンサー、トランジスタ、抵抗器、碍
子、プツシング、ブレーカ、ソケツト、コンセン
ト、スイツチケース等の電気部品、バルブ、コツ
ク、配管継手、インペラー、ポンプ等の化学装置
材料、ケーシング類、デイストリビユータ、キヤ
ツプ、ブレーキ、クラツチ等の自動車、二輪車、
船舶、ボートの部品及び車体等機械構造材料或は
コンテナのパレツト、食器、タイル、人工大理
石、人工庭石等の用途が含まれる。又、積層材と
しての具体的用途の例としてはFRPパイプ、プ
リント基板、電子レンジ用皿、レーダードーム、
マイクロウエーブ部品等の電気材料、配管用
FRPパイプ、反応槽等の化学装置材料、ロケツ
トエンジンアプレーダー、船舶部品等の機械構造
材料、その他FRP波板、浴槽、電解槽のフタ等
の広い用途を含むものである。
塗料として、水系塗料、無溶剤塗料、粉体塗料
分野への有用な材料として使用される。具体的用
途の例として複層厚塗り塗料、防蝕塗料、ノンタ
ールエポキシ塗料の形態で橋脚、フエンス、缶
用、港湾施設、橋梁、船舶、水処理施設、プレハ
ブ鉄骨等に対して用いられる。
接着剤としては金属、布、ゴム、木材、プラス
チツクフイルム及び樹脂等の接着に使用される。
また土木資材としてアスフアルト道路材、ノンス
リツプ道路材、トンネル止水材、伸縮目地材、滑
走路舗装材、モルタル打ち継き材等の用途が含ま
れる。さらに建材として、アスフアルト防水剤、
亀裂注入材、シーリング材、壁材等の用途にも使
用される。
次に本発明を実施例によつて更に詳細に説明す
るが、これは本発明を限定するものでない。以下
実施例中、部とあるのはことわりのない限り重量
部を意味するものとする。
実施例 1
リシノール酸(伊藤製油社製)50部と4−メチ
ルヘキサヒドロ無水フタル酸22部とを窒素を吹き
こみながら100℃で1時間反応させた後、NISSO
−PBC−1000(M-n=1450、酸価60.1)100部及び
ビスフエノールAジグリシジルエーテル(エポキ
シ当量190)258部を加えて130℃で8時間反応せ
しめて酸価0.1以下の淡黄色透明な樹脂(樹脂)
を得た。
次いで得られた樹脂100部に対してヘキサヒ
ドロ無水フタル酸(以下HHPAと記す)34部、
ベンジルジメチルアミン(以下BDMAと記す)
1部を加えて混合し、100℃で4時間、更に150℃
で3時間加熱硬化せしめて硬化物(硬化物)を
得た。
実施例 2
リシノール酸誘導体(伊藤製油社製、URICH
−53ヒドロキシル価110)100部とエンドメチレン
テトラヒドロ無水フタル酸24部とを窒素を吹き込
みながら120℃で1時間反応させた後、NISSO−
PBC−1000(M-n=1560、酸価58.2)70部及びビ
スフエノールAジグリシジルエーテル(エポキシ
当量190)291部を加えて140℃で5時間反応せし
めて酸価0.1以下の淡黄色透明な樹脂(樹脂)
を得た。
次いで得られた樹脂100部に対してHHPA37
部、BDMA1部を加えて混合し、実施例1と同様
にして加熱硬化せしめて硬化物(硬化物)を得
た。
実施例 3
実施例2と同様にして得られたリシノール酸誘
導体の半エステル化物124部に対し、NISSO−
PBC−2000(M-n=1980、酸価51.2)62部及びビ
ス−3,4−エポキシシクロヘキシルアジペート
(ユニオンカーバイド社製、ERL−4299、エポキ
シ当量195)160部を加えて120℃で2時間反応せ
しめて酸価0.1以下の褐色透明な樹脂(樹脂)
を得た。
次いで得られた樹脂100部に対してHHPA40
部、BDMA1部を加えて混合し、実施例1と同様
にして加熱硬化せしめて硬化物(硬化物)を得
た。
実施例 4
実施例2と同様にして得られたリシノール酸誘
導体の半エステル化物124部に対して、NISSO−
PBC−1000(M-n=1560、酸価58.2)124部、水添
ビスフエノールA型エポキシ樹脂(旭電化工業社
製、EP−4080、エポキシ当量240)300部及び塩
化コリン0.3部を加えて130℃で3.5時間反応せし
めて酸価0.1以下の淡黄色透明な樹脂(樹脂)
を得た。
次いで得られた樹脂100部に対してHHPA38
部、BDMA1部を加えて混合し、実施例1と同様
にして加熱硬化せしめて硬化物(硬化物)を得
た。
比較例 1
実施例1におけると同一のNISSO−PBC−
1000 100部とビスフエノールAジグリシジルエー
テル(エポキシ当量190)150部とを窒素を吹き込
みながら、130℃で8時間反応せしめて酸価0.1以
下の淡黄色透明な樹脂(樹脂)を得た。
次いで得られた樹脂100部に対して、
HHPA38部、BDMA1部を加えて混合し、実施
例1と同様にして加熱硬化せしめて硬化物(硬化
物)を得た。
比較例 2
実施例3で用いたと同一のNISSO−PBC−
2000 100部とビス−3,4−エポキシシクロヘキ
シルアジペート100部とを窒素を吹き込みながら
120℃で2時間反応せしめて酸価0.1以下の淡黄色
透明な樹脂(樹脂)を得た。
次いで得られた樹脂100部に対してHHPA31
部、BDMA1部を加えて混合し実施例1と同様に
して加熱硬化せしめて硬化物(硬化物)を得
た。
以上のようにして得られた実施例及び比較例に
おける樹脂(樹脂〜)の性状を表1に示し、
又、硬化物(硬化物〜)について諸試験を行
いその特性値を表2に示した。
The present invention relates to a method for producing a modified epoxy resin that is useful as a resin for coating, impregnation, molding, casting, or lamination, and has excellent flexibility, thermal shock resistance, and electrical properties. Epoxy resin has little shrinkage during curing and has excellent shear adhesion to metals, plastics, glass, etc., and the cured resin has excellent electrical, chemical, and mechanical properties, so it can be used for paints, adhesives, etc. It is widely used in fields such as additives, casting materials, and laminated materials. However, although cured epoxy resins generally have high rigidity, they have small elongation displacement, so they have problems with flexibility, impact resistance, and peel strength, and are prone to cracking and peeling when subjected to mechanical or thermal shock. It was hot. In order to improve the drawbacks of such epoxy resins,
Polyethylene glycol, coal tar, dibutyl phthalate, polyglycol glycidyl ether, organic fatty acid glycidyl ester, polyester, polyamide, polyether, polythiol, etc. are used in combination as flexibility imparting agents. Furthermore, urethane-modified epoxy resins and unterminated carboxynitrile-modified polybutadienes have been mixed with epoxy resins.
Generally, there is a drawback that the electrical properties and mechanical properties of the cured epoxy resin are deteriorated. Another method for imparting flexibility is a method using a polybutadiene-modified epoxy resin obtained by reacting polybutadiene having carboxyl groups at both ends of the molecule with an epoxy resin (Japanese Patent Application Laid-Open No. 144958/1983).
and Japanese Unexamined Patent Publication No. 55-137125) have been proposed. In the method disclosed in JP-A-53-144958, when an epoxy compound modified with polybutadiene is obtained, the modified resin has poor compatibility, and it separates into two layers before curing or separates into two layers during heat curing. There is nothing taught about conditions to avoid producing a uniform cured product and about prevention of gelation of the reaction system during the ester reaction. In fact, in modified epoxy resins produced by the above-mentioned known methods, the reaction system gels during the modification reaction, making it impossible to obtain modified epoxy resins with good stability. Furthermore, the method disclosed in JP-A No. 55-137125 has improved flexibility, impact resistance, and peel strength, but on the other hand, the viscosity of the modified resin is extremely high, resulting in problems in workability. In addition, the compatibility with other epoxy resins is extremely poor, so it is not necessarily satisfactory in practical use. In view of the current situation, the present inventors improved the above-mentioned drawbacks of conventionally known flexible epoxy resins, and improved mechanical properties, electrical insulation properties, adhesive properties, especially flexibility, crack resistance, As a result of extensive research aimed at providing a modified epoxy resin with excellent thermal shock resistance, low viscosity, and excellent compatibility with other epoxy resins, we found that ricinoleic acid and/or ricinoleic acid derivatives It has been discovered that the above object can be achieved by modifying an epoxy resin using a half-esterified product having a carboxyl group obtained by reacting a dibasic acid anhydride with a butadiene polymer having a carboxyl group, and the present invention I was able to complete it. That is, the present invention provides (A) ricinoleic acid and/or ricinoleic acid derivatives.
Half-esterified product (c) having a carboxyl group obtained by reacting (a) with a dibasic acid anhydride (b) and a butadiene polymer (d) having a carboxyl group
and (B) a polyfunctional epoxy resin in a ratio of 1.8 to 30 equivalents of epoxy groups in (B) per 1 equivalent of carboxyl groups in (A). This is a method for producing epoxy resin. The component (a) in the present invention, ricinoleic acid, is also called ricinoleic acid, and has a hydroxyl group in the molecule.
It is a fatty acid represented by the following molecular formula having one carboxyl group and one double bond. Examples of ricinoleic acid derivatives include ricinoleic acid and glycols such as ethylene glycol and propylene glycol, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyols such as trimethylolpropane, glycerin, and pentaerythritol, or monoepoxy compounds. A compound having one or more hydroxyl groups in the molecule obtained by subjecting one or two or more of the above to an esterification reaction is used. Examples of the dibasic acid anhydride as component (b) in the present invention include maleic anhydride, phthalic anhydride, 3-
Methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, eutectic mixture of hexahydrophthalic anhydride and tetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride , endomethylenetetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. In the present invention, the butadiene-based polymer having a carboxyl group in the molecule of component (2) is a polybutadiene having a molecular weight of 500 to 10,000 and having a carboxyl group at both ends, or a copolymer of butadiene and other vinyl monomer that is liquid at room temperature. is preferable, and a commercially available product is Nisso-PBC- manufactured by Nippon Soda Co., Ltd.
1000, C-2000, Gutsudoritsuchi's product name Hycar
- CTB, CTBX, CTBN, General Tire Co.'s product name Telogen CT, S, Philips Co.'s product name Butarez CTL, HTPB, etc. Furthermore, it is also possible to use the above-mentioned polymers whose double bonds are partially or completely saturated by hydrogenation. As the polyfunctional epoxy resin in the present invention, as long as it has two or more functional epoxy groups,
Although there are no particular limitations, for example, a bisphenol A type epoxy resin, for example,
Product name of Ciel Chemical Co., Ltd. Epicote 827
828, 834, 836, 1001, 1004,
1007; Product name of Ciba Geigy Co., Ltd. Araldide
CY252, CY250, GY260, GY280,
6071, 6084, 6097; Dow Chemical Co., Ltd. product name DER330, 6097;
331, 337, 661, 664; Dainippon Ink & Chemicals Co., Ltd. product name Epicron 1010, 1000, 3010, b Novolac type epoxy resin, for example, Ciel Chemical Co., Ltd. product name Epicort 152 , 154; Product name of Dow Chemical Co., Ltd. DEN-431, 154;
438, 439; Ciba Geigy Co., Ltd. product name EPN-1138,
ECN1235; Trade name of Dainippon Ink Chemical Co., Ltd. Epicron N
-740, N-680, N-695, N-565, N-577, c Hydrogenated bisphenol A diglycidyl ether resin, for example, Asahi Denka Kogyo Co., Ltd. trade name Adekal Resin EP-
4080, d Bisphenol A side chain type diglycidyl ether resin, for example, Asahi Denka Kogyo Co., Ltd. trade name Adekal Resin EP-
4000, e Urethane-modified epoxy resin, for example, Asahi Denka Kogyo Co., Ltd.'s product name ADEKA RANGE EPU
-4, EPU-6, EPU-8, f Resorcin diglycidyl ether epoxy resin, for example, Sumitomo Chemical Co., Ltd. product name SUMI-Epoxy ELR-130, ELR-150, g Glycidyl ester type epoxy resin For example, Ciba Geigy's product name Araldite CY
-183, CY-182, Ciel Chemical Co., Ltd. trade name Epicote E-190,
E-871, Showa Denko Co., Ltd.'s product name S-500,
Same S-508, Same S-509, Same S-601X, Same S-
603X, S-607X, S-609X, S-729,
Same S-540, Same S-550; Trade names of Dainippon Ink and Chemicals Co., Ltd. Epiclon 200, Same 400, h P-oxybenzoic acid diglycidyl ether ester resins, for example, trade names of Sumitomo Chemical Industries, Ltd. SUMI-Epoxy resin ELP-160, i Alicyclic epoxy resin UCC product name ERL-4221, ERL-4289, ERL-4221, ERL-4289,
4206, 4234, 4205; Product name of Ciba Geigy Co., Ltd. CY-179, CY-179
-178, CY-180, CY-175, j Brominated bisphenol A type epoxy resin Product name of Ciel Chemical Co., Ltd. Epicote DX-
245, 1045-B-80; Product name of Ciba Geigy Co., Ltd. Araldide
8011, 8047; Dainippon Ink & Chemicals Co., Ltd.'s product name Epicron 152, 1120; Dow Chemical Co., Ltd.'s product name DER-542,
511, 580, k Glycidylamine epoxy resins, such as SUMI-Epoxy ELM120 and SUMI-Epoxy ELM-125 manufactured by Sumitomo Chemical Co., Ltd. These can be used alone or in a mixed system. Next, in the modification of the modified epoxy resin in the present invention, the half-esterification reaction between ricinoleic acid and/or ricinoleic acid derivative (a) and dibasic acid anhydride (b) is carried out per equivalent of hydroxyl group of component (a). (b) Component is used in a proportion of 0.2 to 1.0 mol, and the reaction temperature is 50 to 200.
The reaction is carried out by heating at a temperature of preferably 80 to 150°C for usually 0.3 to 5 hours, preferably 1 to 3 hours to obtain a half-esterified product (c) having a carboxyl group. If the number of moles of dibasic acid anhydride relative to the hydroxyl group is less than 0.2 mole, the storage stability, compatibility, and electrical insulation properties of the resulting modified epoxy resin will be poor, and if it is more than 1 mole, unreacted dibasic acid anhydride will remain. Therefore, gelation occurs during the reaction with the epoxy resin, which is undesirable. Further, during the half-esterification, a commonly used esterification catalyst such as tetrabutyl titanate, zinc acetate, manganese naphthenate, triphenylantimony, etc. may be used as necessary. The blending ratio of the half-esterified product (c) having a carboxyl group obtained by the above half-esterification reaction and the butadiene-based polymer (d) having a carboxyl group is 10 to 90% by weight of the component (c); ) component is used at 90 to 10% by weight, preferably component (c) is used at 20 to 60% by weight, and component (d) is used at 90 to 10% by weight.
It is 80-40% by weight. If the component (c) is less than 10% by weight, the viscosity of the resulting modified epoxy resin will be extremely high and the compatibility with other epoxy resins will be extremely poor, while if it is more than 90% by weight, the impact resistance and This is because crack resistance, peel strength, etc. are inferior. A mixture (A) of the thus obtained semi-esterified product (c) and a butadiene polymer having a carboxyl group (d)
and the polyfunctional epoxy resin (B) at a reaction temperature of 80 to 250°C, preferably 100 to 160°C,
The optimal reaction time is usually 1 to 20 hours, preferably 2 to 10 hours. In addition, the proportion of polyfunctional epoxy resin (B) used is (A)
The amount of epoxy group is 1.8 to 30 equivalents, preferably 2.0 to 20 equivalents per equivalent of carboxyl group in the mixture.
Equivalent amounts are used. If the number of moles of epoxy group to carboxyl group is less than 1.8 equivalents, the molecular weight of the reactant increases, the viscosity increases significantly, and gelation sometimes occurs, which is not preferable. On the other hand, if the above-mentioned maximum limit of 30 equivalents is exceeded, the amount of unreacted epoxy resin remaining increases, and the peeling strength, flexibility and impact strength of the cured product are significantly reduced. In order to accelerate the reaction of epoxy groups to carboxyl groups, shorten the time of exposure to high temperatures, and prevent undesirable increases in viscosity or gelation due to thermal polymerization of polybutadiene-based polymers, an accelerator is added to the reaction system. It is also possible to accelerate the reaction. Reaction promoters used for this purpose include, for example, 2-ethylimidazole, tetraethylammonium bromide, benzyldimethylamine, triethylenediamine, triethylamine,
Diethylamine, butylamine, benzyldimethylamine, choline chloride, caustic potash, alkali carbonate, etc.
Add mole%. Further, in order to further completely suppress thermal polymerization, it is preferable to add a radical polymerization inhibitor such as hydroquinone, parabenzoquinone, anthraquinone, etc. in an amount of 0.01 to 5% by weight based on the total resin content. Furthermore, by carrying out the reaction in an inert gas atmosphere, thermal polymerization of the carbon-carbon double bond can be suppressed more reliably. In addition, an appropriate solvent may be used as necessary.
In this case, it is effective in handling the reactants. The greatest feature of the present invention is that ricinoleic acid and/or its derivatives are introduced into the modified epoxy resin skeleton. Ricinoleic acid and its derivatives are generally liquid substances with low viscosity at room temperature and have extremely good compatibility with other resins, and are almost freely compatible with the epoxy resins and butadiene polymers. Furthermore, ricinoleic acid and its derivatives are superior in flexibility, impact resistance, electrical insulation, hydrolysis resistance, etc. compared to general polyester polyols and polyether polyols. Therefore, the modified epoxy resin of the present invention has excellent flexibility, impact resistance, peel strength, crack resistance, electrical insulation properties, etc., compared to conventionally known modified epoxy resins made of polybutadiene alone. It is a surprising and excellent effect that the viscosity can be significantly lowered and the compatibility with other epoxy resins can be improved. Since the modified epoxy resin obtained by the method of the present invention has at least unreacted epoxy groups and hydroxyl groups, it can be heat-cured by itself, but it is necessary to mix an appropriate amount of a conventionally known epoxy curing agent. Accordingly, the curing and crosslinking reaction easily proceeds under desired conditions ranging from room temperature to high temperature, and a cured product having excellent performance with high flexibility and impact resistance is obtained. Known epoxy curing agents in this case include amines such as diethylenetriamine and metaphenylenediamine, carboxylic acid anhydrides such as dodecenyl anhydride and maleic anhydride, and BFs such as monoethylamine complexes of BF3 and pyridine complexes of BF3 . Tri -complex compounds, complex compounds such as triethanolamine borate, titanium alkoxide, -SH
Examples include compounds having one or more groups, -NCO group, -NCS group, -CONH group in the molecule. The amount of these curing agents used is equivalent to the epoxy equivalent to functional group equivalent ratio of 0.8 to 1.2 in the modified epoxy resin. In order to lower the viscosity of the modified epoxy resin obtained by the present invention, butyl glycidyl ether,
Reactive diluents for epoxy resins such as phenyl glycidyl ether and vinyl cyclohexene diepoxide can also be blended. Casting, impregnating the resin according to the present invention for electrical insulation,
When using as a resin for thick coating or molding, mix reactive diluents and fillers with the resin, add flame retardants, reinforcing agents, pigments, plasticizers, antioxidants, etc. if necessary, and thoroughly mix the resin. A composition. The resin composition is cured by heating or at room temperature, and the curing method is to add an epoxy curing agent as a crosslinking agent as described above and react with the epoxy group to perform a crosslinking reaction, or to initiate radical polymerization as a crosslinking agent. A method in which the unsaturated double bonds of the polybutadiene chain are involved in the crosslinking reaction by adding an epoxy curing agent and a radical polymerization initiator, and a crosslinking reaction is performed at both the epoxy group and the unsaturated double bond by adding both an epoxy curing agent and a radical polymerization initiator. conduct,
There are three possible methods for obtaining a cured product. Which of these curing methods should be selected can be selected by considering the electrical properties, mechanical properties, flexibility, heat resistance, etc. required of the intended electrical insulator. As the radical polymerization initiator, diacyl peroxides such as benzoyl peroxide, 2,4-
Dialkyl peroxides such as dichlorobenzoyl peroxide, octanoyl peroxide, lauroyl peroxide, etc., such as di-tert-butyl peroxide, dicumyl peroxide, etc., peroxy esters, such as tert-butyl perbenzoate, tert-butyl peroxide, etc. Peracetate, di-tert-butyl perphthalate, 2,5-dimethyl-2,5
-Di(benzoylperoxy)hexane, etc., ketone peroxides, e.g. methyl ethyl ketone peroxide, cyclohexanone peroxide, etc., hydroperoxides, e.g. tert-butyl hydroperoxide, cumene hydroperoxide, α-phenylethyl hydroperoxide; Suitable oxides, cyclohexenyl hydroperoxides, etc., and mixtures thereof are preferred, and non-foaming ones are used, and the amount used is 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the total resin content.
It is. Examples of curing accelerators used in combination with the above curing agents include amine compounds such as dimethylaniline and diethylaniline, metal carboxylates such as cobalt naphthenate, lead octenoate, cobalt octenoate, zinc naphthenate, and manganese rosinate. There are salts, and the amount of addition thereof is preferably 0.1 to 5% by weight based on the total resin content in the case of an amine compound, and 0.001 to 1% by weight based on the metal in the case of a metal carboxylic acid salt. In addition, fillers include sedimentary or heavy calcium carbonate, silica, talc, alumina, aluminum hydroxide, diatomaceous earth, clay, kaolin, mica, glass powder, glass beads, barium sulfate, and other inorganic materials, as well as iron, aluminum, and copper. Metal powders such as and mixtures thereof are suitable, and the amount used is 50
~500% by weight. Further, for the purpose of adjusting viscosity at high temperatures and preventing sedimentation, organic bentonite such as olben, finely powdered silica such as Aerosil, etc. may be mixed. The amount used is 1 to 10% by weight based on the total resin content. Fiber materials such as glass fiber, nylon, Tetoron, vinylon, asbestos, and whiskers are used as reinforcing materials, and the amount used is 2 to 2 to 30% of the total resin content.
It is 100% by weight. Examples of plasticizers include generally known plasticizers such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and chlorinated paraffin, tars such as petroleum tar and coal tar, naphthenic or paraffinic petroleum oils (process oils), etc. ), linseed oil, bodied linseed oil, soybean oil, bodied soybean oil, tung oil,
Fats and oils such as safflower oil and castor oil are used. As the reactive diluent, in addition to the above-mentioned reactive diluent having an epoxy group, it is also possible to use a reactive diluent for polybutadiene resin, and a vinyl monomer is usually used as this reactive diluent. Vinyl monomers include styrene, methylstyrene, vinyltoluene, methylmethacrylate, divinylbenzene, ethyl fumarate, diallyl phthalate, etc. Styrene and vinyltoluene are particularly preferred, and the amount used is 10 to 100% by weight.
It is. Furthermore, the antioxidants used in the present invention to improve heat resistance include alkylphenols, such as 4,4'-thiobis-(6-tert-butyl-3-methylphenol), 3,5-di -Third
-Butyl-hydroxy-toluene, 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis(6-tert-butylphenol),
butyl-3-cresol), allylamines,
For example, phenyl-C-naphthylamine, N.
Thione fatty acid esters such as N'-di-β-naphthyl-P-phenylenediamine, such as dilaurylthiodipropionate, distearylthiodipropionate, laurylstearyldipropionate, etc., and mixtures thereof are suitable. The amount used is 0.01 to 10% by weight, preferably 0.1 to 2% by weight based on the total resin content. Further, in the present invention, when it is necessary to make the insulating resin composition highly flame retardant, generally known flame retardants can be used. For example, inorganic flame retardants include aluminum hydroxide (hydrated alumina), zinc borate, etc., and organic halides include chlorinated paraffin, benzene tetrachloride, benzene hexachloride, chlorinated diphenyl, chlorinated triphenyl, chlorinated polyphenyl, Polymer of 3,3,3-trichloropropylene oxide, perchloropentacyclodecane, commercially available products include Futsker's Dechlorane Plus, dechlorane, etc. Brominated products include, for example, tetrabromoethane, tetrabromobutane,
Tetrabromoacetylene, hexabromobenzene, tribromotoluene, hexabromododecane, allyl ester of tribromophenol, dibromopropyl ether of tribromophenol, tetrabromobisphenol A, bisallyl ether of tetrabromobisphenol A, tetrabromobis Bisdibromopropyl ether of phenol A, pentabromodiphenyl ether,
Octabromobisphenol, Teijin Kasei Co., Ltd.
HB, Daiichi Kogyo Seiyaku Co., Ltd.'s Pirocard SR-100, etc.
Examples of chlorobrominated compounds include dichlorotetrabromoethane, dibromotetrachloroethane, 1,2
-dibromo-3-chloropropane, 2-chloro-
Examples of halogen-containing phosphates such as 1,2,3,4-tetrabromobutane include tris(β-
chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloropropyl) phosphate, tris(2-bromoethyl)
Phosphate, Tris(2,3-dibromopropyl)phosphate, Tris(dibromobutyl)phosphate, Tris(bromochloropropyl)phosphate, Tris(2-chloroethyl)phosphate, Tris(2-bromo-2-chloroisopropyl)phosphate, Tris (1-bromo-3
-chloroisopropyl) phosphate, tribromophenol methacrylate, tribromophenol acrylate, pentabromophenol methacrylate, pentabromophenol acrylate, trichlorophenol methacrylate, trichlorophenol acrylate, pentachlorophenol methacrylate, pentachlorophenol acrylate, trioxide antimony,
Red phosphorus, phosphorus compounds, etc. are used. When the modified epoxy resin according to the present invention is used, polybutadiene homopolymer, copolymer, acrylic modified polybutadiene and/or
It is also possible to add an appropriate amount of a polybutadiene resin such as a hydrogenated product or an epoxy compound. Thus, the modified epoxy resin produced by the method of the present invention has low viscosity, good compatibility with other epoxy resins, and has good mechanical properties, electrical insulation, adhesiveness, flexibility, crack resistance, and heat resistance. It has excellent impact resistance and is an excellent material useful for electrical insulation materials, molding materials, paints, adhesives, building materials, and civil engineering applications. Examples of specific uses of the modified epoxy resin according to the present invention as electrical insulating materials include coil impregnation varnish, cloth pipe varnish,
Can be used as varnish for electric wires, surface finishing paints, core varnishes, etc., and as a molded resin type for parts such as capacitors, flyback transformers, cable connection materials, resistors, transistors, motors, transformers, generators, insulators, and pushing. be exposed. Examples of specific uses for molded resin include electrical parts such as connectors, switch gears, capacitors, transistors, resistors, insulators, pushers, breakers, sockets, outlets, switch cases, valves, sockets, piping joints, impellers, pumps, etc. Chemical equipment materials, casings, distributors, caps, brakes, clutches, etc. for automobiles, motorcycles,
Applications include mechanical structural materials such as ship and boat parts and car bodies, container pallets, tableware, tiles, artificial marble, artificial garden stones, etc. In addition, examples of specific uses for laminated materials include FRP pipes, printed circuit boards, microwave oven dishes, radar domes,
Electrical materials such as microwave parts, piping
It has a wide range of uses, including FRP pipes, chemical equipment materials such as reaction tanks, mechanical structural materials such as rocket engine appraders and ship parts, and other FRP corrugated sheets, bathtubs, and electrolytic tank lids. It is used as a useful material in the fields of water-based paints, solvent-free paints, and powder paints. As examples of specific applications, it is used in the form of multi-layer thick paint, anti-corrosion paint, and non-tar epoxy paint for bridge piers, fences, cans, port facilities, bridges, ships, water treatment facilities, prefabricated steel frames, etc. As an adhesive, it is used to bond metal, cloth, rubber, wood, plastic film, resin, etc.
Civil engineering materials include asphalt road materials, non-slip road materials, tunnel water stop materials, expansion joint materials, runway paving materials, and mortar joint materials. Furthermore, asphalt waterproofing agent,
It is also used for applications such as crack filling materials, sealing materials, and wall materials. EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. In the following examples, parts mean parts by weight unless otherwise specified. Example 1 After reacting 50 parts of ricinoleic acid (manufactured by Ito Oil Co., Ltd.) and 22 parts of 4-methylhexahydrophthalic anhydride at 100°C for 1 hour while blowing nitrogen, NISSO
- 100 parts of PBC-1000 (M - n = 1450, acid value 60.1) and 258 parts of bisphenol A diglycidyl ether (epoxy equivalent 190) were added and reacted at 130°C for 8 hours to produce a pale yellow transparent color with an acid value of 0.1 or less. resin (resin)
I got it. Next, 34 parts of hexahydrophthalic anhydride (hereinafter referred to as HHPA) for 100 parts of the obtained resin,
Benzyldimethylamine (hereinafter referred to as BDMA)
Add 1 part, mix and heat at 100°C for 4 hours, then at 150°C.
The mixture was heated and cured for 3 hours to obtain a cured product. Example 2 Ricinoleic acid derivative (manufactured by Ito Oil Co., Ltd., URICH
-53 Hydroxyl number 110) and 24 parts of endomethylenetetrahydrophthalic anhydride were reacted at 120°C for 1 hour while blowing nitrogen, and then NISSO-
70 parts of PBC-1000 (M - n = 1560, acid value 58.2) and 291 parts of bisphenol A diglycidyl ether (epoxy equivalent 190) were added and reacted at 140°C for 5 hours to form a pale yellow transparent product with an acid value of 0.1 or less. resin (resin)
I got it. Then HHPA37 for 100 parts of the resin obtained
1 part of BDMA were added and mixed, and the mixture was heated and cured in the same manner as in Example 1 to obtain a cured product. Example 3 NISSO-
Add 62 parts of PBC-2000 (M - n = 1980, acid value 51.2) and 160 parts of bis-3,4-epoxycyclohexyl adipate (manufactured by Union Carbide, ERL-4299, epoxy equivalent 195) and heat at 120°C for 2 hours. Transparent brown resin (resin) with an acid value of 0.1 or less after reaction
I got it. Then HHPA40 for 100 parts of the resin obtained
1 part of BDMA were added and mixed, and the mixture was heated and cured in the same manner as in Example 1 to obtain a cured product. Example 4 NISSO-
Add 124 parts of PBC-1000 (M - n = 1560, acid value 58.2), 300 parts of hydrogenated bisphenol A type epoxy resin (manufactured by Asahi Denka Kogyo Co., Ltd., EP-4080, epoxy equivalent 240) and 0.3 parts of choline chloride. A pale yellow transparent resin (resin) with an acid value of 0.1 or less after reacting at 130℃ for 3.5 hours
I got it. Then HHPA38 for 100 parts of the resin obtained
1 part of BDMA were added and mixed, and the mixture was heated and cured in the same manner as in Example 1 to obtain a cured product. Comparative Example 1 Same NISSO-PBC- as in Example 1
1000 and 150 parts of bisphenol A diglycidyl ether (epoxy equivalent: 190) were reacted at 130° C. for 8 hours while blowing nitrogen to obtain a pale yellow transparent resin having an acid value of 0.1 or less. Then, for 100 parts of the obtained resin,
38 parts of HHPA and 1 part of BDMA were added and mixed, and heated and cured in the same manner as in Example 1 to obtain a cured product. Comparative Example 2 Same NISSO-PBC- as used in Example 3
2000 and 100 parts of bis-3,4-epoxycyclohexyl adipate while blowing nitrogen.
The reaction was carried out at 120°C for 2 hours to obtain a pale yellow transparent resin with an acid value of 0.1 or less. Then HHPA31 for 100 parts of the resin obtained
1 part of BDMA were added and mixed, and the mixture was heated and cured in the same manner as in Example 1 to obtain a cured product. Table 1 shows the properties of the resins (resin ~) in the Examples and Comparative Examples obtained as above,
In addition, various tests were conducted on the cured product (cured product ~), and the characteristic values are shown in Table 2.
【表】【table】
【表】【table】
【表】【table】
Claims (1)
導体(イ)と二塩基酸無水物(ロ)とを反応せしめて得
られるカルボキシル基を有する半エステル化物
(ハ)とカルボキシル基を有するブタジエン系共重
合体(ニ)との混合物と (B) 多官能性エポキシ樹脂とを(A)のカルボキシル
基1当量に対して(B)のエポキシ基1.8〜30当量
の割合で加熱反応せしめることを特徴とする変
性エポキシ樹脂の製造方法。 2 (イ)成分のヒドロキシル基1当量に対して(ロ)成
分を0.2〜1.0モルの割合で反応せしめて得られる
特許請求の範囲第1項記載の変性エポキシ樹脂の
製造方法。 3 (ハ)成分と(ニ)成分との配合割合が(ハ)成分が10〜
90重量%、(ニ)成分が90〜10重量%である特許請求
の範囲第1項記載の変性エポキシ樹脂の製造方
法。[Scope of Claims] 1 (A) A half-esterified product having a carboxyl group obtained by reacting ricinoleic acid and/or a ricinoleic acid derivative (a) with a dibasic acid anhydride (b)
A mixture of (c) and a butadiene-based copolymer (d) having a carboxyl group, and (B) a polyfunctional epoxy resin, with 1.8 to 30 epoxy groups of (B) per equivalent of carboxyl group of (A). A method for producing a modified epoxy resin characterized by carrying out a heating reaction at an equivalent ratio. 2. The method for producing a modified epoxy resin according to claim 1, which is obtained by reacting component (b) at a ratio of 0.2 to 1.0 mole per equivalent of the hydroxyl group of component (a). 3 The blending ratio of component (c) and component (d) is 10 to 10%.
90% by weight, and the method for producing a modified epoxy resin according to claim 1, wherein component (ii) is 90 to 10% by weight.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8469383A JPS59210929A (en) | 1983-05-14 | 1983-05-14 | Modified epoxy resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8469383A JPS59210929A (en) | 1983-05-14 | 1983-05-14 | Modified epoxy resin |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59210929A JPS59210929A (en) | 1984-11-29 |
JPH0319855B2 true JPH0319855B2 (en) | 1991-03-18 |
Family
ID=13837743
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8469383A Granted JPS59210929A (en) | 1983-05-14 | 1983-05-14 | Modified epoxy resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59210929A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003201375A (en) * | 2002-01-08 | 2003-07-18 | Sumitomo Seika Chem Co Ltd | Polyolefin composition |
-
1983
- 1983-05-14 JP JP8469383A patent/JPS59210929A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS59210929A (en) | 1984-11-29 |
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