JP2007231229A - Resin composition - Google Patents
Resin composition Download PDFInfo
- Publication number
- JP2007231229A JP2007231229A JP2006057882A JP2006057882A JP2007231229A JP 2007231229 A JP2007231229 A JP 2007231229A JP 2006057882 A JP2006057882 A JP 2006057882A JP 2006057882 A JP2006057882 A JP 2006057882A JP 2007231229 A JP2007231229 A JP 2007231229A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- epoxy
- resin
- resin composition
- weight
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 25
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 60
- 239000003822 epoxy resin Substances 0.000 claims abstract description 35
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229920000728 polyester Polymers 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- -1 polyethylene terephthalate Polymers 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229920003986 novolac Polymers 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims description 5
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 4
- 229930003836 cresol Natural products 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000203 mixture Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 239000000654 additive Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- MGAXYKDBRBNWKT-UHFFFAOYSA-N (5-oxooxolan-2-yl)methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1OC(=O)CC1 MGAXYKDBRBNWKT-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- USGYMDAUQBQWFU-UHFFFAOYSA-N 1,2,5,6-diepoxycyclooctane Chemical compound C1CC2OC2CCC2OC12 USGYMDAUQBQWFU-UHFFFAOYSA-N 0.000 description 1
- LFKLPJRVSHJZPL-UHFFFAOYSA-N 1,2:7,8-diepoxyoctane Chemical compound C1OC1CCCCC1CO1 LFKLPJRVSHJZPL-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-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
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HDHUBPBUIYXNSS-UHFFFAOYSA-N 2-methyl-6-(2-methylbutyl)phenol Chemical compound CCC(C)CC1=CC=CC(C)=C1O HDHUBPBUIYXNSS-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- GRXOKDOOUFYKLX-UHFFFAOYSA-N 3,5-dichloro-7-oxabicyclo[2.2.1]hepta-1(6),2,4-triene Chemical compound ClC1=C(O2)C(Cl)=CC2=C1 GRXOKDOOUFYKLX-UHFFFAOYSA-N 0.000 description 1
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- NGNBLQAYJAKWKR-UHFFFAOYSA-N 5-methyl-3-phenyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound O1C=2C(C)=CC1=CC=2C1=CC=CC=C1 NGNBLQAYJAKWKR-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ZFIVKAOQEXOYFY-UHFFFAOYSA-N Diepoxybutane Chemical compound C1OC1C1OC1 ZFIVKAOQEXOYFY-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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
本発明は機械特性に優れたポリフェニレンエーテル樹脂組成物に関する。 The present invention relates to a polyphenylene ether resin composition having excellent mechanical properties.
ポリフェニレンエーテルは高耐熱性、低吸水性、難燃性等の優れた特性を併せ持つ汎用エンジニアリングプラスチックとして知られているが成形加工時の流動性に劣ることが欠点である。流動性を改良するためにポリエステルを配合することが提案された（例えば、特許文献１参照。）が、一方でポリフェニレンエーテルとポリエステルの相容性と機械特性をより改善する要求もあった。相容性と機械特性を改良するためにエポキシ基を含有する共重合体を相容化剤として添加する方法（例えば、特許文献２。）、ポリフェニレンエーテル分子鎖末端とグリシドールを反応させることでエポキシ基を導入する方法（例えば、特許文献３参照。）等が提案されてきたが、より一層の改良が必要とされていた。
本発明の課題は、本発明は、耐熱性と機械特性が良好なポリフェニレンエーテル樹脂組成物を提供することである。 An object of the present invention is to provide a polyphenylene ether resin composition having good heat resistance and mechanical properties.
本発明者は前記課題を解決するためにポリフェニレンエーテルとポリエステルの組成物について鋭意検討を進めた結果、ポリフェニレンエーテル、ポリエステル、ポリフェニレンエーテルとエポキシ樹脂の反応によって得られるエポキシ変性ポリフェニレンエーテルの３成分を少なくとも含有する樹脂組成物は、機械特性が優れることを見出し本発明に至った。
即ち、本発明は
１．ポリフェニレンエーテル（Ａ）５〜９５重量部、ポリエステル（Ｂ）９５〜５重量部ならびにポリフェニレンエーテル（Ａ）およびエポキシ樹脂（Ｃ）の反応によって得られるエポキシ変性ポリフェニレンエーテル（Ｄ）１〜５０重量部、を含有することを特徴とする樹脂組成物、
２．成分（Ｄ）が、ポリエチレンテレフタレートであることを特徴とする上記１に記載の樹脂組成物、
３．成分（Ｃ）が、クレゾールノボラック型エポキシ樹脂および／またはビスフェノールＡ型エポキシ樹脂であることを特徴とする上記１または２に記載の樹脂組成物、
４．成分（Ｄ）が、ゲル化物を含有しないことを特徴とする上記１〜３のいずれかに記載の樹脂組成物、
５．成分（Ｄ）が、１分子鎖あたり平均２．１個以上のエポキシ基を有することを特徴とする上記１〜４のいずれかに記載の樹脂組成物、
６．成分（Ｂ）が、テレフタル酸を酸成分とし、エチレングリコールおよびシクロヘキサンジメタノールをグリコール成分とする共重合物であることを特徴とする上記１〜５のいずれかに記載の樹脂組成物、
である。
In order to solve the above-mentioned problems, the present inventor has intensively studied a composition of polyphenylene ether and polyester, and as a result, at least three components of epoxy-modified polyphenylene ether obtained by reaction of polyphenylene ether, polyester, polyphenylene ether and epoxy resin are included. The resin composition to be contained has been found to have excellent mechanical properties, leading to the present invention.
That is, the present invention provides: 5 to 95 parts by weight of polyphenylene ether (A), 95 to 5 parts by weight of polyester (B) and 1 to 50 parts by weight of epoxy-modified polyphenylene ether (D) obtained by reaction of polyphenylene ether (A) and epoxy resin (C), Containing a resin composition,
2. The resin composition according to the above 1, wherein the component (D) is polyethylene terephthalate,
3. The resin composition according to the above 1 or 2, wherein the component (C) is a cresol novolak type epoxy resin and / or a bisphenol A type epoxy resin,
4). The resin composition according to any one of the above 1 to 3, wherein the component (D) does not contain a gelled product,
5). The resin composition according to any one of the above 1 to 4, wherein the component (D) has an average of 2.1 or more epoxy groups per molecular chain,
6). The resin composition according to any one of the above 1 to 5, wherein the component (B) is a copolymer having terephthalic acid as an acid component and ethylene glycol and cyclohexanedimethanol as a glycol component,
It is.
本発明は、流動性と機械特性が良好なポリフェニレンエーテル樹脂組成物を提供する The present invention provides a polyphenylene ether resin composition having good fluidity and mechanical properties.
本発明について、以下、具体的に説明する。
本発明のポリフェニレンエーテル（Ａ）は、下記式の繰り返しユニットから構成される。
The present invention will be specifically described below.
The polyphenylene ether (A) of the present invention is composed of repeating units of the following formula.
本発明のポリフェニレンエーテル（Ａ）の具体例は、ポリ（２，６−ジメチル−１，４−フェニレンエーテル）、ポリ（２−メチルー６−フェニルー１，４−フェニレンエーテル）、ポリ（２−メチル−６−フェニルー１，４−フェニレンエーテル）、ポリ（２，６−ジクロロ−１，４−フェニレンエーテル）、２，６−ジメチルフェノールと他の フェノール類（例えば２，３，６−トリメチルフェノールや２−メチル−６−メチルブチルフェノール）、テトラメチルビフェノールＡ，テトラメチルビスフェノールＡ、オルソクレゾールとの共重合体などが挙げられる。
本発明のポリフェニレンエーテル（Ａ）の数平均分子量は１万以上、３万未満であることが好ましく、より好ましくは１５，０００以上、２５，０００未満である。数平均分子量が１万未満では他樹脂と反応して得られるアロイ材料の機械特性や耐熱性が損なわれる場合があり、数平均分子量が３万以上では成形加工性が損なわれることがある。
Specific examples of the polyphenylene ether (A) of the present invention include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2-methyl). -6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol, 2-methyl-6-methylbutylphenol), tetramethylbiphenol A, tetramethylbisphenol A, and a copolymer with orthocresol.
The number average molecular weight of the polyphenylene ether (A) of the present invention is preferably 10,000 or more and less than 30,000, more preferably 15,000 or more and less than 25,000. If the number average molecular weight is less than 10,000, the mechanical properties and heat resistance of the alloy material obtained by reacting with other resins may be impaired, and if the number average molecular weight is 30,000 or more, molding processability may be impaired.
本発明のポリエステル樹脂（Ｂ）は、主として芳香族ジカルボン酸と脂肪族ジオールとからなるものである。
本発明における芳香族ジカルボン酸としては、テレフタル酸、イソフタル酸、５−ナトリウムスルホイソフタル酸、無水フタル酸、ナフタレンジカルボン酸等が挙げられるが、本発明の効果を損なわない範囲で、アジピン酸、セバシン酸、ドデカン二酸などの脂肪族ジカルボン酸、トリメリット酸、ピロメリット酸などの３価以上のカルボン酸を少量使用してもよい。
また、以上の酸のエステル形成性誘導体を使用してもよい。さらに、必要に応じて、４−ヒドロキシ安息香酸、ε−カプロラクトン等のオキシカルボン酸を併用してもよい。
The polyester resin (B) of the present invention is mainly composed of an aromatic dicarboxylic acid and an aliphatic diol.
Examples of the aromatic dicarboxylic acid in the present invention include terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, phthalic anhydride, naphthalenedicarboxylic acid, and the like, but adipic acid and sebacin are within the range not impairing the effects of the present invention. A small amount of an aliphatic dicarboxylic acid such as acid or dodecanedioic acid, or a trivalent or higher carboxylic acid such as trimellitic acid or pyromellitic acid may be used.
Further, ester-forming derivatives of the above acids may be used. Furthermore, you may use together oxycarboxylic acids, such as 4-hydroxybenzoic acid and (epsilon) -caprolactone, as needed.
本発明における脂肪族ジオールとしては、エチレングリコール、ネオペンチルグリコール、ジエチレングリコール、プロピレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール等が挙げられるが、本発明の効果を損なわない範囲で、１，４−シクロヘキサンジメタノール、１，４−シクロヘキサンジオール等の脂環族グリコール、トリメチロールプロパン、ペンタエリスリトール、グリセリン等の３価以上のアルコール、あるいはビスフェノールＡのエチレンオキサイド付加物、ビスフェノールＳのエチレンオキサイド付加物等の芳香族グリコールを併用してもよい。また、エチレングリコールおよびシクロヘキサンジメタノールの組み合わせが、特に推奨される。 Examples of the aliphatic diol in the present invention include ethylene glycol, neopentyl glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like, as long as the effects of the present invention are not impaired. Aliphatic glycols such as 1,4-cyclohexanedimethanol and 1,4-cyclohexanediol, trivalent or higher alcohols such as trimethylolpropane, pentaerythritol and glycerin, ethylene oxide adducts of bisphenol A, ethylene of bisphenol S Aromatic glycols such as oxide adducts may be used in combination. A combination of ethylene glycol and cyclohexanedimethanol is particularly recommended.
本発明のポリエステル樹脂（Ｂ）の末端基構造は特に限定されないが、水酸基とカルボキシル基のいずれか、または両者を含む場合が好ましい。これらの官能基はエポキシ変性ポリフェニレンエーテル（Ｄ）との反応点となるため、本発明の樹脂組成物の相容性を改善する上で有用な（Ｂ）と（Ｄ）の共重合体を形成する上で有効に作用する。
本発明のポリエステル樹脂（Ｂ）１ｇあたりの酸価は１ｍｇＫＯＨ〜１０ｍｇＫＯＨであることが好ましい。
Although the terminal group structure of the polyester resin (B) of this invention is not specifically limited, The case where either a hydroxyl group and a carboxyl group or both are included is preferable. Since these functional groups serve as reaction points with the epoxy-modified polyphenylene ether (D), a copolymer of (B) and (D) that is useful in improving the compatibility of the resin composition of the present invention is formed. It works effectively in doing.
The acid value per 1 g of the polyester resin (B) of the present invention is preferably 1 mgKOH to 10 mgKOH.
本発明の樹脂組成物は、他の熱可塑性樹脂や熱硬化性樹脂を加えることができる。熱可塑性樹脂としては、エチレン、プロピレン、ブタジエン、イソプレン、スチレン、メタクリル酸、アクリル酸、メタクリル酸エステル、メタクリル酸グリシジルエステル、アクリル酸エステル、塩化ビニル、アクリロニトリル、無水マレイン酸、酢酸ビニルの群から選択される１種または２種以上のモノマーの重合体または共重合体、あるいはポリフェニレンエーテル、ポリアミド、ポリイミド、ポリカーボネート、ポリアセタール、ポリフェニレンスルフィド、ポリエチレングリコール、ポリエーテルイミド、ポリケトン、ポリエーテルエーテルケトン、ポリエーテルサルフォン、ポリアリレート等を例としてあげることができる。熱硬化性樹脂としては、フェノール樹脂、エポキシ樹脂、シアネートエステル、ポリイミド、ポリウレタン、ビスマレイミド樹脂、アルキド樹脂、不飽和ポリエステル、シリコーン樹脂、ベンゾシクロブテンを例として挙げることができる。上記熱可塑性樹脂や熱硬化性樹脂は官能基を有する化合物で変成されたものでもよい。官能基としてはビニル基、アリル基、カルボキシル基、酸無水基、エステル基、水酸基、アミノ基、アミド基、イミド基、エポキシ基から選ばれる１つ、または２つ以上を含むこともある。
本発明の樹脂組成物は、目的に応じ添加剤を加えても良い。添加剤としては、難燃剤、熱安定剤、酸化防止剤、ＵＶ吸収剤、界面活性剤、滑剤、充填剤、金属塩微粒子、金属微粒子等が挙げられる。
Other thermoplastic resins and thermosetting resins can be added to the resin composition of the present invention. The thermoplastic resin is selected from the group consisting of ethylene, propylene, butadiene, isoprene, styrene, methacrylic acid, acrylic acid, methacrylic ester, glycidyl methacrylate, acrylic ester, vinyl chloride, acrylonitrile, maleic anhydride, and vinyl acetate. Polymers or copolymers of one or more types of monomers, or polyphenylene ether, polyamide, polyimide, polycarbonate, polyacetal, polyphenylene sulfide, polyethylene glycol, polyether imide, polyketone, polyether ether ketone, polyether mon Examples include von and polyarylate. Examples of the thermosetting resin include phenol resin, epoxy resin, cyanate ester, polyimide, polyurethane, bismaleimide resin, alkyd resin, unsaturated polyester, silicone resin, and benzocyclobutene. The thermoplastic resin and thermosetting resin may be modified with a compound having a functional group. The functional group may include one or two or more selected from a vinyl group, an allyl group, a carboxyl group, an acid anhydride group, an ester group, a hydroxyl group, an amino group, an amide group, an imide group, and an epoxy group.
The resin composition of the present invention may contain an additive depending on the purpose. Examples of the additive include a flame retardant, a heat stabilizer, an antioxidant, a UV absorber, a surfactant, a lubricant, a filler, metal salt fine particles, and metal fine particles.
本発明のエポキシ樹脂（Ｃ）は分子内に平均２個以上のエポキシ基を有するものであればよく。具体例としては、トリグリシジルイソシアヌレート、１，３−ブタジエンジエポキシド、１，２，５，６−ジエポキシシクロオクタン、１，２，７，８−ジエポキシオクタン、ビニルシクロヘキセンジオキサイド、ジグリシジルエーテル、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ヒンダトイン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビスフェノール−ノボラック型エポキシ樹脂、脂環式エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、および、これらをハロゲン化したものの中から選ばれる１つ、または２つ以上を混合したものを用いることができ、中でもエポキシ樹脂が好ましく用いられ、特に好ましくは下記一般式（２）で表されるビスフェノールＡ型エポキシ樹脂、下記一般式（３）で表されるクレゾールノボラック型エポキシ樹脂を反応性や取り扱い性の観点から好ましく用いることができる。 The epoxy resin (C) of this invention should just have an average of 2 or more epoxy groups in a molecule | numerator. Specific examples include triglycidyl isocyanurate, 1,3-butadiene diepoxide, 1,2,5,6-diepoxycyclooctane, 1,2,7,8-diepoxyoctane, vinylcyclohexene dioxide, diglycidyl. Ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hindered-in type epoxy resin, biphenyl type epoxy resin, bisphenol-novolak type epoxy resin, alicyclic epoxy resin, triphenylmethane type epoxy resin, A phenol novolac type epoxy resin, an ortho cresol novolac type epoxy resin, and one obtained by halogenating these, or a mixture of two or more thereof can be used. Of these, an epoxy resin is preferred. In particular, a bisphenol A type epoxy resin represented by the following general formula (2) and a cresol novolac type epoxy resin represented by the following general formula (3) are preferably used from the viewpoints of reactivity and handleability. Can do.
本発明のエポキシ変性ポリフェニレンエーテル（Ｄ）はポリフェニレンエーテル（Ａ）のエポキシ変性に用いるエポキシ樹脂（Ｃ）が残渣として含まれることも有り、その好ましい組成は（Ａ）１００重量部に対し３０重量部未満、さらに好ましくは２０重量部未満、特に好ましくは１０重量部未満である。（Ｄ）に（Ｃ）が全く含まれない場合が最もよい。
該エポキシ樹脂（Ｃ）残渣は他樹脂と（Ｄ）との反応性およびそのポリマーアロイの機械特性の観点から（Ａ）１００重量部に対して３０重量部未満である。
本発明においてゲル化物とは、３０℃においてエポキシ変性ポリフェニレンエーテル（Ｄ）０.１ｇをクロロホルム２５ｍｌと混合したときに不溶分として現れる。本発明の樹脂組成物は、射出成形品の機械特性や外観の観点からゲル化物を含まない。
In the epoxy-modified polyphenylene ether (D) of the present invention, the epoxy resin (C) used for the epoxy modification of the polyphenylene ether (A) may be contained as a residue, and its preferred composition is 30 parts by weight with respect to 100 parts by weight of (A). Less than, more preferably less than 20 parts by weight, particularly preferably less than 10 parts by weight. It is best if (C) is not included in (D).
The epoxy resin (C) residue is less than 30 parts by weight with respect to (A) 100 parts by weight from the viewpoint of the reactivity between the other resin and (D) and the mechanical properties of the polymer alloy.
In the present invention, the gelled product appears as an insoluble matter when 0.1 g of epoxy-modified polyphenylene ether (D) is mixed with 25 ml of chloroform at 30 ° C. The resin composition of the present invention does not contain a gelled product from the viewpoint of mechanical properties and appearance of the injection molded product.
本発明のエポキシ変性ポリフェニレンエーテル（Ｄ）はポリフェニレンエーテル（Ａ）とエポキシ樹脂（Ｃ）を混合、反応させることにより得られる。反応方法としては、ポリフェニレンエーテル（Ａ）の良溶剤に（Ａ）とエポキシ樹脂（Ｃ）を均一に溶解させ、反応させる溶液反応方法、（Ａ）のスラリー液に（Ｃ）を混合させ反応させるスラリー反応方法、溶剤を用いずに（Ａ）と（Ｃ）の混合物を加熱、溶融させる溶融反応方法、粉末状の（Ａ）と（Ｃ）を（Ａ）が粉末状態を維持したまま反応させる方法が挙げられるが、中でも溶液反応方法が好ましく用いられる。
溶液反応方法に用いられる溶剤としてはベンゼン、トルエン、キシレン、塩化メチレン、クロロホルム、トリクロロエタン、クロロベンゼンを用いることができるが、沸点や取り扱い性の観点からトルエンが好ましく用いられる。ポリフェニレンエーテル（Ａ）が析出しない程度に（Ａ）の貧溶剤を混合することもできる。この貧溶剤としては、メタノール、ブタノール、アセトン、水が例として挙げられ、中でもメタノールが好ましい。
The epoxy-modified polyphenylene ether (D) of the present invention can be obtained by mixing and reacting the polyphenylene ether (A) and the epoxy resin (C). As a reaction method, (A) and the epoxy resin (C) are uniformly dissolved in a good solvent of polyphenylene ether (A) and reacted, and (C) is mixed and reacted in the slurry liquid of (A). A slurry reaction method, a melt reaction method in which a mixture of (A) and (C) is heated and melted without using a solvent, and powdery (A) and (C) are reacted while (A) maintains the powder state. Among them, a solution reaction method is preferably used.
As the solvent used in the solution reaction method, benzene, toluene, xylene, methylene chloride, chloroform, trichloroethane, and chlorobenzene can be used, and toluene is preferably used from the viewpoint of boiling point and handleability. The poor solvent (A) can be mixed to such an extent that the polyphenylene ether (A) does not precipitate. Examples of the poor solvent include methanol, butanol, acetone, and water, and methanol is preferable.
本発明のエポキシ変性ポリフェニレンエーテル（Ｄ）の製造方法は室温以上、１７０℃未満であることが好ましく、より好ましくは８０℃以上、１５０℃未満、さらに好ましくは１００℃以上、１３０℃未満である。ここで室温とは１５〜２５℃である。該反応温度は反応速度や溶液中におけるポリフェニレンエーテル（Ａ）の濃度の観点から室温以上であり、エポキシ樹脂（Ｃ）の副反応抑制の観点から１７０℃未満である。
本発明のエポキシ変性ポリフェニレンエーテル（Ｄ）を製造する場合のポリフェニレンエーテル（Ａ）１００重量部に対するエポキシ樹脂（Ｃ）の組成は、１０〜９００重量部が好ましく、より好ましくは２０〜６００重量部、さらに好ましくは４０〜３００重量部、特に好ましくは６０〜１００重量部である。該エポキシ樹脂（Ｃ）の（Ａ）１００重量部に対する組成は反応速度の観点から１０重量部以上であり、（Ｄ）と他樹脂の反応性の観点から９００重量部以下である。
The method for producing the epoxy-modified polyphenylene ether (D) of the present invention is preferably room temperature or higher and lower than 170 ° C., more preferably 80 ° C. or higher and lower than 150 ° C., further preferably 100 ° C. or higher and lower than 130 ° C. Here, room temperature is 15 to 25 ° C. The reaction temperature is room temperature or higher from the viewpoint of reaction rate and the concentration of polyphenylene ether (A) in the solution, and is lower than 170 ° C. from the viewpoint of suppressing side reactions of the epoxy resin (C).
The composition of the epoxy resin (C) with respect to 100 parts by weight of the polyphenylene ether (A) when producing the epoxy-modified polyphenylene ether (D) of the present invention is preferably 10 to 900 parts by weight, more preferably 20 to 600 parts by weight, More preferably, it is 40-300 weight part, Most preferably, it is 60-100 weight part. The composition of the epoxy resin (C) with respect to 100 parts by weight of (A) is 10 parts by weight or more from the viewpoint of reaction rate, and 900 parts by weight or less from the viewpoint of the reactivity of (D) with other resins.
本発明のエポキシ変性ポリフェニレンエーテル（Ｄ）を製造する場合、ポリフェニレンエーテル（Ａ）とエポキシ樹脂（Ｃ）の他に反応の促進を目的に触媒を添加することもできる。触媒の具体例としてはリチウム、ナトリウム、カリウム、ナトリウムメチラート、ナトリウムエチラート、トリエチルアミンやトリブチルアミン等の３級アミン、イミダゾール、ナトリウムフェノキシド、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、炭酸カリウム、炭酸ナトリウム等が挙げられるが、中でもナトリウムメチラート、トリエチルアミン、トリブチルアミン、水酸化ナトリウム等が好ましい。上記塩基性化合物の他にも４級アンモニウム塩も用いることができる。 When producing the epoxy-modified polyphenylene ether (D) of the present invention, a catalyst may be added for the purpose of promoting the reaction in addition to the polyphenylene ether (A) and the epoxy resin (C). Specific examples of the catalyst include lithium, sodium, potassium, sodium methylate, sodium ethylate, tertiary amines such as triethylamine and tributylamine, imidazole, sodium phenoxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium carbonate, Examples include sodium carbonate, among which sodium methylate, triethylamine, tributylamine, sodium hydroxide and the like are preferable. In addition to the above basic compounds, quaternary ammonium salts can also be used.
本発明のエポキシ変性ポリフェニレンエーテル（Ｄ）は連続反応プロセス、バッチ反応プロセスのいずれのプロセス形態でも製造可能である。
本発明でポリフェニレンエーテル（Ａ）とエポキシ樹脂（Ｃ）を反応させた後、反応物を溶液状態とし、ポリフェニレンエーテルの貧溶剤を混合攪拌し、エポキシ変性ポリフェニレンエーテル（Ｄ）を析出、スラリー化することができる。このスラリーを固液分離し、固形分を乾燥させることにより、エポキシ変性ポリフェニレンエーテル（Ｄ）の粉末を得ることができる。
本発明のエポキシ変性ポリフェニレンエーテル（Ｄ）を製造する際、混合、反応系に熱可塑性樹脂やエポキシ化合物以外の熱硬化性樹脂を添加することもできる。
The epoxy-modified polyphenylene ether (D) of the present invention can be produced by either a continuous reaction process or a batch reaction process.
After the polyphenylene ether (A) and the epoxy resin (C) are reacted in the present invention, the reaction product is put into a solution state, a poor solvent of the polyphenylene ether is mixed and stirred, and the epoxy-modified polyphenylene ether (D) is precipitated and slurried. be able to. The slurry is subjected to solid-liquid separation, and the solid content is dried to obtain an epoxy-modified polyphenylene ether (D) powder.
When producing the epoxy-modified polyphenylene ether (D) of the present invention, a thermosetting resin other than a thermoplastic resin or an epoxy compound can be added to the mixing and reaction system.
＜評価方法＞
１．エポキシ変性ポリフェニレンエーテルの精製
反応後、エポキシ変性ポリフェニレンエーテル（Ｄ）に含まれる未反応のエポキシ樹脂（Ｃ）を除去するために、反応生成物２ｇを２０ｍｌのトルエンに溶解し後、大過剰のメタノールを加えてエポキシ変性ポリフェニレンエーテル（Ｄ）を沈殿させた。沈殿したエポキシ変性ポリフェニレンエーテル（Ｄ）をろ過して単離した後、８０℃、０．１ｍｍＨｇの条件で１時間、減圧乾燥させた。
２．エポキシ変性ポリフェニレンエーテル（Ｄ）の分子量分布測定
クロロホルムを溶剤としたＧＰＣ測定を行った。予め作成したポリスチレンの分子量と溶出量の関係を表すグラフから数平均分子量、重量平均分子量を算出した。
３．ポリフェニレンエーテル分子鎖末端フェノール性水酸基数の定量
高分子論文集，ｖｏｌ．５１，Ｎｏ．７（１９９４）、４８０頁記載の方法に従い、ポリマーの塩化メチレン溶液にテトラメチルアンモニウムハイドロオキシド溶液を加えたときの３１８ｎｍにおける吸光度変化を紫外可視吸光光度計で測定した値、及び数平均分子量の値から算出した。
<Evaluation method>
1. Purification of epoxy-modified polyphenylene ether After the reaction, in order to remove unreacted epoxy resin (C) contained in epoxy-modified polyphenylene ether (D), 2 g of the reaction product was dissolved in 20 ml of toluene, and then a large excess of methanol. Was added to precipitate the epoxy-modified polyphenylene ether (D). The precipitated epoxy-modified polyphenylene ether (D) was isolated by filtration, and then dried under reduced pressure for 1 hour at 80 ° C. and 0.1 mmHg.
2. Measurement of molecular weight distribution of epoxy-modified polyphenylene ether (D) GPC measurement using chloroform as a solvent was performed. The number average molecular weight and the weight average molecular weight were calculated from a graph showing the relationship between the molecular weight and elution amount of polystyrene prepared in advance.
3. Quantification of the number of phenolic hydroxyl groups at the end of polyphenylene ether molecular chain. 51, no. 7 (1994), 480, 480, the value of the number-average molecular weight and the number average molecular weight measured by measuring the change in absorbance at 318 nm when a tetramethylammonium hydroxide solution was added to the methylene chloride solution of the polymer. Calculated from
［エポキシ変性ポリフェニレンエーテルの製造例１]
ポリフェニレンエーテル（旭化成プラスチックスシンガポール株式会社製Ｓ２０２Ａ）（Ａ−１）１，６００ｇ、ビスフェノールＡ型エポキシ樹脂（旭化成ケミカルズ株式会社製ＡＥＲ２５０）（Ｃ−１）２００ｇ、クレゾールノボラック型エポキシ樹脂（大日本インキ株式会社製ＥＰＩＣＬＯＮ Ｎ−６６０）（Ｃ−２）２００ｇ、トリ−ｎ−ブチルアミン３０ｇを内容積２０Ｌのヘンシェルミキサーを使い、室温下、攪拌数２，０００ｒｐｍ、３分間攪拌、混合した。（Ｃ−１）と（Ｃ−２）の混合物は１分子あたり平均３．２個のエポキシ基を有する。この混合物（Ｄ−１）を内容積１０Ｌのジャケット型バッチ反応器に入れ、さらにトルエン３，０００ｇを入れた。この状態で反応器のジャケットに１３０℃の加熱オイルを流し、反応器のパドル型攪拌翼を３００ｒｐｍで回転させ、さらに気相部に流量毎分１Ｌで乾燥窒素ガスを送り続けた。この状態を維持したまま、およそ２０分後には反応器内部の樹脂固形物は完全に溶解し、均一溶液となった。揮発した溶剤分は反応器上部に設置したジムロート型冷却管で液化し、反応器に還流された。加熱、攪拌を開始して３時間経過した時点で反応器内部の溶液を抜き出し、この溶液にポリマー固化防止のためにトルエン３，０００ｇを加えて希釈し、室温にて放冷しポリマー溶液（Ｅ−１）を得た。予めトルエン５０重量％、メタノール５０重量％の混合溶媒をいれた容器に攪拌しながら、（Ｅ−１）を少量ずつ加えると同時に容器中のトルエンとメタノールの組成比が変わらないようにメタノールも同時に加えていくと容器内でポリマー固形分が析出しスラリー液（Ｆ−１）が得られる。（Ｆ−１）をガラスフィルターでろ過しポリマー固形分（Ｇ−１）を単離する。（Ｇ−１）を１２０℃、２時間減圧乾燥し、乾燥したポリマー粉末（Ｈ−１）を得た。（Ｈ−１）０．１ｇは３０℃のクロロホルム２５ｍｌに完全に溶解し、不溶分は見られなかった。（Ｈ−１）のＧＰＣ測定を行った結果、（Ｈ−１）のエポキシ変性ポリフェニレンエーテル（Ｃ−１）に相当するメインピークの分子量分布は（Ａ−１）のピーク形状を維持したまま、わずかに高分子量側に平行移動していた。（Ｈ−１）ＧＰＣ曲線の（Ｃ−１）、（Ｃ−２）に相当するピークの積分値は（Ｅ−１）の時の８％に低減し、仕込み原料の（Ｃ−１）、（Ｃ−２）の９０％以上が固液分離により（Ｃ−１）、（Ｃ−２）がろ液側に移動していることがわかった。よって、（Ｈ−１）中の（Ｃ−１）、（Ｃ−２）の残渣は変性ポリフェニレンエーテルに対し３重量％未満であることが確認された。（Ｈ−１）を上記、＜評価方法．１＞に従って処理して得られたポリマー（Ｉ−１）を５００ＭＨｚプロトンＮＭＲで測定した結果、（Ｉ−１）は１分子鎖あたりエポキシ基を平均３．２個有している事がわかった。
[Production Example 1 of Epoxy-Modified Polyphenylene Ether]
Polyphenylene ether (A202) manufactured by Asahi Kasei Plastics Singapore Co., Ltd. (A-1) 1,600 g, bisphenol A type epoxy resin (AER250 manufactured by Asahi Kasei Chemicals Co., Ltd.) 200 g, cresol novolak type epoxy resin (Dainippon Ink) EPICLON N-660) (C-2) (200 g) and tri-n-butylamine (30 g) were mixed using a Henschel mixer having an internal volume of 20 L at room temperature with stirring at 2,000 rpm for 3 minutes. The mixture of (C-1) and (C-2) has an average of 3.2 epoxy groups per molecule. This mixture (D-1) was put into a jacket type batch reactor having an internal volume of 10 L, and 3,000 g of toluene was further added. In this state, 130 ° C. heating oil was poured into the reactor jacket, the paddle type stirring blade of the reactor was rotated at 300 rpm, and dry nitrogen gas was continuously fed to the gas phase part at a flow rate of 1 L / min. While maintaining this state, the resin solids inside the reactor were completely dissolved after about 20 minutes, and became a uniform solution. The volatilized solvent was liquefied with a Dimroth type condenser installed in the upper part of the reactor and refluxed to the reactor. When 3 hours have passed since the start of heating and stirring, the solution inside the reactor was withdrawn, and 3,000 g of toluene was added to this solution to dilute it to prevent solidification of the polymer, and it was allowed to cool at room temperature. -1) was obtained. While stirring (E-1) in small portions while stirring in a container containing 50% by weight of toluene and 50% by weight of methanol in advance, methanol is simultaneously added so that the composition ratio of toluene and methanol in the container does not change. As it is added, polymer solids precipitate in the container, and a slurry liquid (F-1) is obtained. (F-1) is filtered through a glass filter to isolate the polymer solid (G-1). (G-1) was dried under reduced pressure at 120 ° C. for 2 hours to obtain a dried polymer powder (H-1). 0.1 g of (H-1) was completely dissolved in 25 ml of chloroform at 30 ° C., and no insoluble matter was observed. As a result of performing the GPC measurement of (H-1), the molecular weight distribution of the main peak corresponding to the epoxy-modified polyphenylene ether (C-1) of (H-1) is maintained while maintaining the peak shape of (A-1). It moved slightly to the high molecular weight side. (H-1) The integrated value of the peaks corresponding to (C-1) and (C-2) of the GPC curve is reduced to 8% in the case of (E-1), and (C-1), It was found that 90% or more of (C-2) moved (C-1) and (C-2) to the filtrate side by solid-liquid separation. Therefore, it was confirmed that the residue of (C-1) and (C-2) in (H-1) was less than 3% by weight based on the modified polyphenylene ether. (H-1) above, <evaluation method. As a result of measuring the polymer (I-1) obtained by treatment according to 1> by 500 MHz proton NMR, it was found that (I-1) had an average of 3.2 epoxy groups per molecular chain. .
［エポキシ変性ポリフェニレンエーテルの製造例２]
トルエン３Ｌ、ポリフェニレンエーテル（Ａ−１）４００ｇ、テレフタル酸クロライド１５ｇを４０℃で８時間混合攪拌し、その後、トリエチルアミン１５ｇを加え、さらに３時間攪拌した。その後、グリシドール１５ｇを加え、４８時間攪拌した後メタノールを加え、沈殿物（Ｈ−２）を得た。（Ｈ−２）を上記、＜評価方法．１＞に従って処理して得られたポリマー（Ｉ−２）を５００ＭＨｚプロトンＮＭＲで測定した結果、（Ｉ−２）は１分子鎖あたりエポキシ基を平均１.２個有している事がわかった。
〔ポリフェニレンエーテル／ポリエステルを含む配合物の溶融混練の製造例〕
ポリフェニレンエーテルとポリエステルと添加剤を所定の組成で配合する。この配合物をＺＳＫ−２６二軸回転押出機［ウェルナー＆フライデラー社製］を用いて、加熱シリンダーの設定温度を２９０℃に設定し、供給口より上記配合物を１５Ｋｇ／時間で供給し、スクリュー回転数３００ｒｐｍで溶融混練し、ノズルから押出される溶融ポリマーのストランドを冷却裁断して樹脂組成物ペレットを得た。上記組成物に用いた原料を以下に示す。
[Production Example 2 of Epoxy-Modified Polyphenylene Ether]
3 L of toluene, 400 g of polyphenylene ether (A-1), and 15 g of terephthalic acid chloride were mixed and stirred at 40 ° C. for 8 hours, and then 15 g of triethylamine was added and further stirred for 3 hours. Thereafter, 15 g of glycidol was added, and after stirring for 48 hours, methanol was added to obtain a precipitate (H-2). (H-2) above, <Evaluation method. As a result of measuring the polymer (I-2) obtained by treatment according to 1> by 500 MHz proton NMR, it was found that (I-2) had an average of 1.2 epoxy groups per molecular chain. .
[Production example of melt kneading of blend containing polyphenylene ether / polyester]
Polyphenylene ether, polyester and additives are blended in a predetermined composition. Using the ZSK-26 twin-screw rotary extruder (manufactured by Werner & Frederer), the temperature of the heating cylinder was set to 290 ° C., and the formulation was fed from the feed port at a rate of 15 kg / hour. Melt kneading was performed at a rotation speed of 300 rpm, and the strand of the molten polymer extruded from the nozzle was cooled and cut to obtain a resin composition pellet. The raw materials used for the composition are shown below.
［原料］
・ポリフェニレンエーテル（Ａ−１）：
旭化成プラスチックスシンガポール株式会社製Ｓ２０２Ａ
・ポリエステル：
ポリエチレンテレフタレート（Ｂ−１）日本ユニペット株式会社製ＲＴ５５３、
テレフタル酸とエチレングリコールとシクロヘキサンジメタノールの共重合体であるポリエチレンテレフタレート（Ｂ−２）ＳＫケミカルズ社製ＰＥＴＧ（Ｓ２００８）
・ＳＥＢＳ：
スチレン−エチレン／ブチレン−スチレンのトリブロック共重合体（クレイトンポリマージャパン社製Ｇ−１６５１）
[material]
-Polyphenylene ether (A-1):
Asahi Kasei Plastics Singapore Co., Ltd. S202A
·polyester:
Polyethylene terephthalate (B-1) Nippon Unipet Co., Ltd. RT553,
Polyethylene terephthalate which is a copolymer of terephthalic acid, ethylene glycol and cyclohexanedimethanol (B-2) PETG manufactured by SK Chemicals (S2008)
・ SEBS:
Styrene-ethylene / butylene-styrene triblock copolymer (G-1651 manufactured by Kraton Polymer Japan)
［実施例１〜４および比較例１〜５］
〔溶融混練されて得られたペレットの評価試験用射出成形品の製造例〕
（Ｂ−１）を含む組成物は樹脂温度２９０℃、金型温度２０℃として射出成形した。（Ｂ−２）を含む組成物は実施例１〜３、比較例１〜３および比較例５の場合は樹脂温度２９０℃、金型温度３０℃で、また実施例４および比較例４の場合は樹脂温度２６０℃、金型温度３０℃として射出成形した。
〔射出成形品の評価〕
上記射出成形品の評価結果を表１に示す。
[Examples 1 to 4 and Comparative Examples 1 to 5]
[Production example of injection molded product for evaluation test of pellets obtained by melt-kneading]
The composition containing (B-1) was injection molded at a resin temperature of 290 ° C and a mold temperature of 20 ° C. In the case of Examples 1-3, Comparative Examples 1-3, and Comparative Example 5, the composition containing (B-2) has a resin temperature of 290 ° C. and a mold temperature of 30 ° C., and in the case of Example 4 and Comparative Example 4 Was injection molded at a resin temperature of 260 ° C. and a mold temperature of 30 ° C.
[Evaluation of injection molded products]
The evaluation results of the injection molded product are shown in Table 1.
本発明は機械特性が良好なポリフェニレンエーテル樹脂組成物を提供すること。 The present invention provides a polyphenylene ether resin composition having good mechanical properties.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006057882A JP5252780B2 (en) | 2006-03-03 | 2006-03-03 | Resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006057882A JP5252780B2 (en) | 2006-03-03 | 2006-03-03 | Resin composition |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2007231229A true JP2007231229A (en) | 2007-09-13 |
| JP2007231229A5 JP2007231229A5 (en) | 2009-04-16 |
| JP5252780B2 JP5252780B2 (en) | 2013-07-31 |
Family
ID=38552142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006057882A Expired - Fee Related JP5252780B2 (en) | 2006-03-03 | 2006-03-03 | Resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5252780B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951961A (en) * | 2014-04-18 | 2014-07-30 | 安徽省中日农业环保科技有限公司 | Temperature-resistant polyvinyl chloride modified polyphenyl ether material for automobile plastic component |
| JP2015512982A (en) * | 2012-03-08 | 2015-04-30 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | Compatibilizing composition, method for forming the same, and article containing the same |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04239029A (en) * | 1991-01-14 | 1992-08-26 | Mitsubishi Kasei Corp | Production of thermoplastic polyester/polyphenylene ether resin composition |
| JPH05117387A (en) * | 1991-10-25 | 1993-05-14 | Mitsubishi Petrochem Co Ltd | Production of hydroxylated polyphenylene ether |
| JPH05320498A (en) * | 1992-05-21 | 1993-12-03 | Kanegafuchi Chem Ind Co Ltd | Thermoplastic resin composition |
| JP2000001606A (en) * | 1998-04-15 | 2000-01-07 | Mitsubishi Eng Plast Corp | Flame-retardant polyester resin composition |
| JP2000212411A (en) * | 1999-01-21 | 2000-08-02 | Mitsubishi Engineering Plastics Corp | Flame-retarded polyester resin composition |
| JP2003138010A (en) * | 2001-11-06 | 2003-05-14 | Asahi Kasei Corp | Epoxy-containing low molecular weight polyphenylene ether and method for producing the same |
| JP2005226006A (en) * | 2004-02-13 | 2005-08-25 | Asahi Kasei Chemicals Corp | Method for producing epoxy-modified polyphenylene ether with improved solubility |
| JP2005290124A (en) * | 2004-03-31 | 2005-10-20 | Asahi Kasei Chemicals Corp | Polyphenylene ether resin composition |
| JP2006057037A (en) * | 2004-08-23 | 2006-03-02 | Mitsubishi Engineering Plastics Corp | Flame retardant polyester resin composition |
-
2006
- 2006-03-03 JP JP2006057882A patent/JP5252780B2/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04239029A (en) * | 1991-01-14 | 1992-08-26 | Mitsubishi Kasei Corp | Production of thermoplastic polyester/polyphenylene ether resin composition |
| JPH05117387A (en) * | 1991-10-25 | 1993-05-14 | Mitsubishi Petrochem Co Ltd | Production of hydroxylated polyphenylene ether |
| JPH05320498A (en) * | 1992-05-21 | 1993-12-03 | Kanegafuchi Chem Ind Co Ltd | Thermoplastic resin composition |
| JP2000001606A (en) * | 1998-04-15 | 2000-01-07 | Mitsubishi Eng Plast Corp | Flame-retardant polyester resin composition |
| JP2000212411A (en) * | 1999-01-21 | 2000-08-02 | Mitsubishi Engineering Plastics Corp | Flame-retarded polyester resin composition |
| JP2003138010A (en) * | 2001-11-06 | 2003-05-14 | Asahi Kasei Corp | Epoxy-containing low molecular weight polyphenylene ether and method for producing the same |
| JP2005226006A (en) * | 2004-02-13 | 2005-08-25 | Asahi Kasei Chemicals Corp | Method for producing epoxy-modified polyphenylene ether with improved solubility |
| JP2005290124A (en) * | 2004-03-31 | 2005-10-20 | Asahi Kasei Chemicals Corp | Polyphenylene ether resin composition |
| JP2006057037A (en) * | 2004-08-23 | 2006-03-02 | Mitsubishi Engineering Plastics Corp | Flame retardant polyester resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015512982A (en) * | 2012-03-08 | 2015-04-30 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | Compatibilizing composition, method for forming the same, and article containing the same |
| CN103951961A (en) * | 2014-04-18 | 2014-07-30 | 安徽省中日农业环保科技有限公司 | Temperature-resistant polyvinyl chloride modified polyphenyl ether material for automobile plastic component |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5252780B2 (en) | 2013-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5488084A (en) | Polyphenylene sulfide resin composition | |
| JPH07736B2 (en) | Solvent resistant compatible blend of polyphenylene ether and linear polyester | |
| JPH0264127A (en) | Polyphenylene ether capped with epoxytriazine and manufacture thereof | |
| JPH02225560A (en) | Thermoplastic resin composition | |
| JP2010077185A (en) | Aromatic polyethersulfone having hydroxyphenyl terminal group, and method for producing the same | |
| EP0530442B1 (en) | Process for producing a hydroxy-substituted poly (phenylene ether) resin | |
| JP5252780B2 (en) | Resin composition | |
| JPH09137056A (en) | Compatibilized composition of poly(phenylene ether) resin and semicrystalline resin | |
| JPH02283760A (en) | Thermoplastic resin composition | |
| JP2010001446A (en) | Aromatic polyether sulfone having hydroxyphenyl end group, and its manufacturing method | |
| JP2007231228A (en) | Epoxy-modified polyphenylene ether | |
| JP2837163B2 (en) | Solvent-resistant, compatible polyphenylene ether-linear polyester blend | |
| JP2010001447A (en) | Manufacturing method for aromatic polyether sulfone having hydroxyphenyl terminal end group | |
| JP2009019135A (en) | Polyester resin composition for laser welding and molded product using the same | |
| JPH02218737A (en) | Solvent-resistant,compatible polyphenylene ether/thermoplastic polyester composition | |
| JP3049778B2 (en) | Method for producing thermoplastic polyester-polyphenylene ether resin composition | |
| JP2606333B2 (en) | Resin composition | |
| JP4426332B2 (en) | Process for producing epoxy-modified polyphenylene ether with improved solubility | |
| JPH09324113A (en) | Thermoplastic polyester resin composition | |
| JPS6242941B2 (en) | ||
| JPH06122762A (en) | Modified polyphenylene ether, its production and thermoplastic resin composition | |
| JPH02222452A (en) | Resin composition | |
| JPH05339493A (en) | Flame-retardant resin composition | |
| JP2755339B2 (en) | Thermoplastic resin composition | |
| JPH04136065A (en) | Resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090227 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090227 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100701 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120619 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120808 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130416 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130416 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160426 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |