JPS6333471A - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- JPS6333471A JPS6333471A JP17574186A JP17574186A JPS6333471A JP S6333471 A JPS6333471 A JP S6333471A JP 17574186 A JP17574186 A JP 17574186A JP 17574186 A JP17574186 A JP 17574186A JP S6333471 A JPS6333471 A JP S6333471A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- weight
- group
- carboxylic acid
- polyamide
- 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 description 20
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 7
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 51
- 239000004952 Polyamide Substances 0.000 claims abstract description 32
- 229920002647 polyamide Polymers 0.000 claims abstract description 32
- 229920000098 polyolefin Polymers 0.000 claims abstract description 21
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- 125000005462 imide group Chemical group 0.000 claims abstract description 7
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 6
- 150000002989 phenols Chemical class 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- -1 olefin compound Chemical class 0.000 claims description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000004018 acid anhydride group Chemical group 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 23
- 238000002156 mixing Methods 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 4
- 150000008064 anhydrides Chemical group 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 2
- 239000004677 Nylon Substances 0.000 abstract 1
- 150000007942 carboxylates Chemical group 0.000 abstract 1
- 229920001778 nylon Polymers 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 24
- 238000000034 method Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 229920002302 Nylon 6,6 Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 235000021388 linseed oil Nutrition 0.000 description 4
- 239000000944 linseed oil Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-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
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 2
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical class OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical class OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Chemical class OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical class OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 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
- GVJRTUUUJYMTNQ-UHFFFAOYSA-N 2-(2,5-dioxofuran-3-yl)acetic acid Chemical compound OC(=O)CC1=CC(=O)OC1=O GVJRTUUUJYMTNQ-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
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 description 1
- KUNNUNBSGQSGDY-UHFFFAOYSA-N 2-butyl-6-methylphenol Chemical compound CCCCC1=CC=CC(C)=C1O KUNNUNBSGQSGDY-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- TVOICAOPKRBXDY-UHFFFAOYSA-N 2-methyl-6-(2-methylphenyl)phenol Chemical compound CC1=CC=CC(C=2C(=CC=CC=2)C)=C1O TVOICAOPKRBXDY-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- SYIUWAVTBADRJG-UHFFFAOYSA-N 2H-pyran-2,6(3H)-dione Chemical compound O=C1CC=CC(=O)O1 SYIUWAVTBADRJG-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- USICVVZOKTZACS-UHFFFAOYSA-N 3-butylpyrrole-2,5-dione Chemical compound CCCCC1=CC(=O)NC1=O USICVVZOKTZACS-UHFFFAOYSA-N 0.000 description 1
- LBBVUHNMASXJAH-UHFFFAOYSA-N 3-ethylbicyclo[2.2.1]hepta-2,5-diene Chemical compound C1C2C(CC)=CC1C=C2 LBBVUHNMASXJAH-UHFFFAOYSA-N 0.000 description 1
- KBFJHOCTSIMQKL-UHFFFAOYSA-N 3-methoxycarbonylbut-3-enoic acid Chemical compound COC(=O)C(=C)CC(O)=O KBFJHOCTSIMQKL-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- OJOWICOBYCXEKR-UHFFFAOYSA-N 5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=CC)CC1C=C2 OJOWICOBYCXEKR-UHFFFAOYSA-N 0.000 description 1
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-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
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-BJUDXGSMSA-N carbon-11 Chemical compound [11C] OKTJSMMVPCPJKN-BJUDXGSMSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical class C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- OYOFUEDXAMRQBB-UHFFFAOYSA-N cyclohexylmethanediamine Chemical compound NC(N)C1CCCCC1 OYOFUEDXAMRQBB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- CATWEXRJGNBIJD-UHFFFAOYSA-N n-tert-butyl-2-methylpropan-2-amine Chemical compound CC(C)(C)NC(C)(C)C CATWEXRJGNBIJD-UHFFFAOYSA-N 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
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Chemical class CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は耐熱性、寸法安定性、耐衝撃性、溶融流動性な
どの諸特性の優れたブレンド系熱可塑性樹脂組成物に関
するものであり、さらに詳しくは、変性ポリフェニレン
エーテル、ポリアミドおよび特定の変性ポリオレフィン
からなる熱可塑性樹脂組成物に関するものである。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a blended thermoplastic resin composition having excellent properties such as heat resistance, dimensional stability, impact resistance, and melt flowability. More specifically, the present invention relates to a thermoplastic resin composition comprising a modified polyphenylene ether, a polyamide, and a specific modified polyolefin.
〈従来の技術〉
近年二種類以上のポリマをブレンドして新しい材料を生
み出そうとする検討が盛んに行われている。ポリマブレ
ンドは基本的には性質のことなるポリマを組合ぜて新た
な特徴を引き出そうとするものであり、成功すれば原料
成分ポリマの性質を相互に補完した有用な材料が得られ
るという点で価値の高い技術である。しかしただ単にこ
となるポリマを混ぜ合わせさえすればよい材料が得られ
るわけではなく、真に有用なポリマブレンド材料を設計
するためには、原料ポリマの構造、重合度、混合方法、
場合によっては相溶化剤などを高度に選択し、特定化し
なければならない。<Prior Art> In recent years, there has been much research into creating new materials by blending two or more types of polymers. Polymer blending is basically a combination of polymers with different properties to bring out new characteristics, and if successful, it is valuable in that it will yield a useful material that complements the properties of the raw material polymers. This is a highly advanced technology. However, it is not possible to obtain a good material simply by mixing different polymers; in order to design a truly useful polymer blend material, the structure of the raw material polymers, the degree of polymerization, the mixing method,
In some cases, compatibilizers and the like must be highly selected and specified.
ポリフェニレンエーテルは耐熱性、耐水性、寸法安定性
に優れた樹脂であるが、溶融粘性が高く成形性が悪いこ
と、あるいは耐衝撃性、耐薬品性が劣るなどの問題点も
ある。Although polyphenylene ether is a resin with excellent heat resistance, water resistance, and dimensional stability, it also has problems such as high melt viscosity and poor moldability, and poor impact resistance and chemical resistance.
一方、いわゆるナイロン６、ナイロン６６に代表される
ポリアミドは成形性、耐衝撃性、耐磨耗性などは優れて
いるが、耐熱性が若干低く、吸水時に剛性低下や寸法変
化を起こすなどの問題点がある。そこでポリフェニレン
エーテルとポリアミドを組合せて各々の長・短所を相互
に補完させることができれば新しい有用な材料が得られ
るものと考えられ、これまでにポリフェニレンエーテル
とポリアミドのブレンドについていくつか検討がなされ
ている。それらの例を挙げるとポリフェニレンエーテル
とポリアミドを単に配合するものくたとえば、特公昭４
５−９９７号公報、特公昭５９−４１６６３号公報など
）、ポリフェニレンエーテルとポリアミドを無水マレイ
ン酸、アマニ油や液状ポリブタジェンに代表される特定
の官能基を有する不飽和化合物や液状ジエン化合物の存
在下に混合するもの（たとえば特公昭６０−１１９６６
号公報、特公昭６１−１０４９４号公報など）、ポリフ
ェニレンエーテルを無水マレイン酸に代表される特定の
化合物で変性した後、ポリアミドと混合するもの（たと
えば、特開昭５９−６６４５２号公報）、ポリフェニレ
ンエーテル、ポリアミド、ゴム状物質を無水マレイン酸
、アマニ油ヤ液状ポリブタジェンに代表される特定の化
合物の存在下で混合するもの（たとえば、特開昭５６−
４９７５３号公報）などである。On the other hand, polyamides represented by so-called nylon 6 and nylon 66 have excellent moldability, impact resistance, and abrasion resistance, but have slightly low heat resistance and problems such as a decrease in rigidity and dimensional changes when water is absorbed. There is a point. Therefore, it is thought that if polyphenylene ether and polyamide can be combined to complement each other's strengths and weaknesses, a new and useful material can be obtained, and so far, several studies have been conducted on blends of polyphenylene ether and polyamide. . Examples of these include those that simply blend polyphenylene ether and polyamide;
5-997, Japanese Patent Publication No. 59-41663, etc.), polyphenylene ether and polyamide in the presence of maleic anhydride, unsaturated compounds having specific functional groups such as linseed oil and liquid polybutadiene, and liquid diene compounds. (e.g. Special Publication No. 60-11966)
(Japanese Patent Publication No. 61-10494, etc.), those in which polyphenylene ether is modified with a specific compound represented by maleic anhydride and then mixed with polyamide (for example, JP-A-59-66452), polyphenylene Those in which ether, polyamide, and rubbery substances are mixed in the presence of specific compounds such as maleic anhydride and linseed oil liquid polybutadiene (e.g.
49753).
〈発明が解決しようとする問題点〉
しかるに特公昭４５−９９７号公報および特公昭５９−
４１６６３号公報に記載されたポリフェニレンエーテル
とポリアミドの混合物はポリフェニレンエーテルの流動
性、耐薬品性の向上に効果はあるものの耐衝撃性は、た
かだか５醇・ｃ１１／ＣＩＩｔ・ノツチ程度でありまだ
不十分である。ポリフェニレンエーテルとポリアミドの
ブレンドに無水マレイン酸、アマニ油や変性ポリブタジ
ェンなどの特定化合物や液状ジエン化合物を添加した特
公昭６０−１１９６６号公報や特公昭６１−１０４９４
号公報に記された樹脂組成物もアイゾツト衝撃強度はた
かだか１０〜１３Ｋｇ・ｃｔａ／ａｘφノツチのレベル
であり、まだ十分とはいえず、耐熱性も不十分である。<Problems to be solved by the invention> However, Japanese Patent Publication No. 45-997 and Japanese Patent Publication No. 59-
Although the mixture of polyphenylene ether and polyamide described in Publication No. 41663 is effective in improving the fluidity and chemical resistance of polyphenylene ether, the impact resistance is still insufficient, at most 5 mm/c11/CIIt/notch. It is. Japanese Patent Publication No. 60-11966 and Japanese Patent Publication No. 61-10494, in which specific compounds such as maleic anhydride, linseed oil, modified polybutadiene, and liquid diene compounds are added to a blend of polyphenylene ether and polyamide.
The resin composition described in the publication also has an Izot impact strength of at most 10 to 13 kg·cta/axφ notch, which is still not sufficient, and the heat resistance is also insufficient.
また、特開昭５９−６６４５２号公報に記載の変性ポリ
フェニレンエーテルとポリアミドの混合物も耐衝撃性、
耐熱性の点でまだ満足できる水準に到っていない。特開
昭５６−４９７５３号公報に記載されたポリフェニレン
エーテル、ポリアミド、ゴム状物質の３者を無水マレイ
ン酸、アマニ油や液状ポリブタジェンに代表される特定
の不飽和化合物の存在下で配合して得られる組成物は耐
衝撃性、耐熱性の向上にある程度効果が認められるもの
のまだ不十分であり、また、樹脂組成物の溶融滞貿安定
性が悪く溶融射出成形などのおりにシリンダー内での滞
貿時間が長くなると分解発泡が起こりやすいという欠点
がある。In addition, the mixture of modified polyphenylene ether and polyamide described in JP-A No. 59-66452 also has impact resistance,
It has not yet reached a satisfactory level in terms of heat resistance. It is obtained by blending polyphenylene ether, polyamide, and rubbery substance described in JP-A No. 56-49753 in the presence of a specific unsaturated compound represented by maleic anhydride, linseed oil, and liquid polybutadiene. Although the resulting composition has some effect in improving impact resistance and heat resistance, it is still insufficient.Also, the resin composition has poor melting stability and is prone to stagnation in cylinders during melt injection molding. The drawback is that decomposition and foaming are more likely to occur if the trade time is long.
従って、ポリフェニレンエーテルとポリアミドの双方の
性質を相互に補完した耐熱性、寸法安定性、耐水性、耐
衝撃性、成形性のすべてを満足する材料はまだ得られて
いないのが現状であり、上記の特性すべてを満たす新し
い材料の出現が待望されている。Therefore, it is currently not possible to obtain a material that satisfies all of the heat resistance, dimensional stability, water resistance, impact resistance, and moldability that complement the properties of both polyphenylene ether and polyamide. The emergence of a new material that satisfies all of the properties is eagerly awaited.
よって、本発明は、上記の耐熱性、寸法安定性、耐水性
、耐衝撃性、成形性などのすべての特性に優れた熱可塑
性樹脂組成物を得ることを課題とする。Therefore, an object of the present invention is to obtain a thermoplastic resin composition that is excellent in all of the above properties such as heat resistance, dimensional stability, water resistance, impact resistance, and moldability.
く問題点を解決するための手段〉
本発明者らは、上記課題を解決すべく鋭意検討した結果
、特定の変性ポリフェニレンエーテル、ポリアミドおよ
び特定の変性ポリオレフィンの３者を特定の割合で配合
することにより一挙に目的が達成されることを見出し、
本発明に到達した。Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a specific modified polyphenylene ether, a polyamide, and a specific modified polyolefin are blended in a specific ratio. I discovered that the purpose could be achieved all at once by
We have arrived at the present invention.
すなわち本発明は、
（＾）下記−投銭（Ｉ）で表わされるフェノール類の一
種または二種以上を酸化重合して得られるポリフェニレ
ンエーテルと該ポリフェニレンエーテル１００重母部に
対してカルボン酸基、カルボン酸無水物基、イミド基、
エポキシ基の内から選ばれた少なくとも一種の官能基を
分子内に有する置換オレフィン化合物０．０５〜２０重
發部をラジカル発生剤の共存下で反応させて得られる変
性ポリフェニレンエーテル５〜９０重」％、
（Ｂ）ポリアミド５〜９０重Ｑ％および（Ｃ）カルボン
酸基、カルボン酸金属塩基、カルボ酸エステル是、カル
ボン１！無水物基、イミド基の内から選ばれた少なくと
も一種の官能基を分子中に有する変性ポリオレフィン３
〜４０重量％よりなる熱可塑性樹脂組成物を提供するも
のである。That is, the present invention provides a polyphenylene ether obtained by oxidative polymerization of one or more phenols represented by (I) below, and a carboxylic acid group, a carbon Acid anhydride group, imide group,
Modified polyphenylene ether obtained by reacting 0.05 to 20 parts of a substituted olefin compound having at least one functional group selected from epoxy groups in the molecule in the coexistence of a radical generator. %, (B) polyamide 5 to 90% by weight and (C) carboxylic acid group, carboxylic acid metal base, carboxylic acid ester, carboxylic acid 1! Modified polyolefin 3 having at least one functional group selected from anhydride group and imide group in the molecule
to 40% by weight of a thermoplastic resin composition.
（ここでＲ１、Ｒ２、Ｒ３、Ｒ４は水素原子、炭素数１
〜１０のアルキル基およびハロアルキル基、アリール基
、ハロゲン原子の内から選ばれ、Ｒ１−Ｒ４は互いに同
じでも異なっていてもよい。）
本発明で用いられる（＾）成分の変性ポリフェニレンエ
ーテルの原料となるポリフェニレンエーテルは前記一般
式（Ｉ）で示されたフェノール類を酸化重合することに
よって得られる。(Here, R1, R2, R3, R4 are hydrogen atoms, carbon number 1
-10 alkyl groups, haloalkyl groups, aryl groups, and halogen atoms, and R1 to R4 may be the same or different from each other. ) Polyphenylene ether, which is a raw material for the modified polyphenylene ether component (^) used in the present invention, can be obtained by oxidative polymerization of the phenol represented by the general formula (I).
フェノール類の具体例としては、２．６−シメチルフエ
ノール、２．６−ジニチルフエノール、２゜６−シブチ
ルフェノール、２．６−ジプロピルフェノール、２．６
−ジフェニルフェノール、２−メチル−６−ニチルフエ
ノール、２−メチル−６−トリルフェノール、２−メチ
ル−６−メドキシフエノール、２−メチル−６−ブチル
フェノール、２．６−シメトキシフエノール、２．３．
６−ドリメチルフエノール、２．３．５．６−チトラメ
チルフエノールなどが挙げられる。これらフェノール類
を単独で重合せしめたホモポリマあるいは二種以上の混
合物を重合せしめたコポリマのいずれも本発明で使用可
能である。とりわけ２．６−シメチルフエノールを重合
して得られるホモポリマヤ２．６−シメチルフエノール
と２．３゜６−ドリメチルフエノールの混合物を共重合
して１ｑられるコポリマは好適に用いられる。Specific examples of phenols include 2.6-dimethylphenol, 2.6-dinitylphenol, 2.6-sibutylphenol, 2.6-dipropylphenol, and 2.6-dipropylphenol.
-diphenylphenol, 2-methyl-6-nitylphenol, 2-methyl-6-tolylphenol, 2-methyl-6-medoxyphenol, 2-methyl-6-butylphenol, 2.6-simethoxyphenol, 2. 3.
Examples include 6-dolimethylphenol and 2.3.5.6-titramethylphenol. Either a homopolymer made by polymerizing these phenols alone or a copolymer made by polymerizing a mixture of two or more of these phenols can be used in the present invention. In particular, a homopolymer obtained by polymerizing 2.6-dimethylphenol and a copolymer obtained by copolymerizing a mixture of 2.6-dimethylphenol and 2.3°6-dolimethylphenol are preferably used.
本発明で用いられる変性ポリフェニレンエーテルの変性
成分はカルボン酸基、カルボン１１！無水物基、イミド
基、エポキシ基の内から選ばれた少なくとも一種の官能
基を有する置換オレフィン化合物であり、具体例として
はアクリル酸、メタクリル酸、マレイン酸、フマル酸、
イタコン酸、無水マレイン酸、無水イタコン酸、無水グ
ルタコン酸、無水シトラコン酸、無水アコニット酸、マ
レイミド、Ｎ−フェニルマレイミド、Ｎ−メチルマレイ
ミド、Ｎ−エチルマレイミド、グリシジルアクリレート
、グリシジルメタクリレートなどを挙げることができる
。これら置換オレフィン化合物の使用量はポリフェニレ
ンエーテル１００重量部に対して０．０５〜２０重量部
、好ましくは０．１〜１０重口部の範囲内である。置換
オレフィン化合物の使用量が０．０５重組部に満たない
場合には変性ポリフェニレンエーテル、ポリアミド、変
性ポリオレフィンを混練して得られる組成物の耐衝撃性
、耐熱性が不足し、使用」が２０重量部を越えると組成
物の流動性が低下し、成形性が損なわれるので好ましく
ない。The modifying component of the modified polyphenylene ether used in the present invention is a carboxylic acid group, carbon 11! It is a substituted olefin compound having at least one functional group selected from anhydride group, imide group, and epoxy group, and specific examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid,
Itaconic acid, maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, maleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, glycidyl acrylate, glycidyl methacrylate, etc. can. The amount of these substituted olefin compounds used is within the range of 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of polyphenylene ether. If the amount of the substituted olefin compound used is less than 0.05 parts by weight, the impact resistance and heat resistance of the composition obtained by kneading the modified polyphenylene ether, polyamide, and modified polyolefin will be insufficient, and If the amount exceeds 50%, the fluidity of the composition will decrease and moldability will be impaired, which is not preferable.
ポリフェニレンエーテルと置換オレフィン化合物の反応
はラジカル発生剤の存在下に行われ、好適なラジカル発
生剤の例としてはベンゾイルパーオキシド、ジクミルパ
ーオキシド、ジ−ｔ−ブチルパーオキシド、ｔ−ブチル
クミルパーオキシド、クメンハイドロパーオキシド、２
，５−ジメチル−２，５−ジ−ｔ−ブチルパーオキシヘ
キサン、２，５−ジメチル−２，５−ジ−ｔ−ブチルパ
ーオキシヘキシン−３、アゾビスイソブチロニトリルな
どを挙げることができ、ラジカル発生剤は好適には置換
オレフィン化合物１００重量部に対して５〜３０重吊部
の範囲内で使用されるがラジカル発生剤の種類、使用量
ともこれに限定されるものではない。The reaction between the polyphenylene ether and the substituted olefin compound is carried out in the presence of a radical generator, and examples of suitable radical generators include benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, and t-butyl cumyl peroxide. oxide, cumene hydroperoxide, 2
, 5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butylperoxyhexane-3, azobisisobutyronitrile, etc. The radical generator is preferably used in an amount of 5 to 30 parts by weight per 100 parts by weight of the substituted olefin compound, but the type and amount of the radical generator is not limited to this. .
ポリフェニレンエーテルと置換オレフィン化合物を反応
させる方法については適当な溶媒を用いて溶液中で反応
せしめる方法や溶媒の非存在下に２００〜３５０℃の高
温でポリフェニレンエーテル、置換オレフィン化合物、
ラジカル発生剤の混合物を１０秒〜３０分間溶融混合し
ながら反応せしめる方法などがあり、いずれの方法を用
いてもよい。Regarding the method of reacting polyphenylene ether with a substituted olefin compound, there is a method of reacting it in a solution using an appropriate solvent, or a method of reacting polyphenylene ether with a substituted olefin compound at a high temperature of 200 to 350°C in the absence of a solvent.
There is a method in which a mixture of radical generators is reacted while being melt-mixed for 10 seconds to 30 minutes, and any method may be used.
このようにして得られた変性ポリフェニレンエーテルの
最終樹脂組成物中に占める割合は５〜９０重Ｄ％、好ま
しくは１０〜８０重量％である。変性ポリフェニレンエ
ーテルが５重量％に満だないと樹脂組成物の耐熱性、寸
法安定性が不足し、９０重辺％を越えると樹脂組成物の
成形性が損なわれるので好ましくない。The proportion of the modified polyphenylene ether thus obtained in the final resin composition is 5 to 90% by weight, preferably 10 to 80% by weight. If the amount of modified polyphenylene ether is less than 5% by weight, the resin composition will lack heat resistance and dimensional stability, and if it exceeds 90% by weight, the moldability of the resin composition will be impaired, which is not preferred.
本発明で用いられる（Ｂ）成分のポリアミドは、アミノ
酸、ラクタム、あるいはジアミンとジカルボン酸を主た
る構成成分とするポリアミドである。構成成分の具体例
を挙げるとε−カプロラクタム、エナントラクタム、ω
−ラウロラクタムなどのラクタム、ε−アミノカプロン
酸、１１−アミノウンデカン酸、１２−アミノドデカン
酸などのアミノ酸、テトラメチレンジアミン、ヘキサメ
チレンジアミン、ウンデカメチレンジアミン、ドデカメ
チレンジアミン、２．２．４−／２．４．４−トリメチ
ルへキサメチレンジアミン、５−メチルノナメチレンジ
アミン、ｍ−キシリレンジアミン、ｐ−キシリレンジア
ミン、１．３−ビスアミノメチルシクロヘキサン、１，
４−ビスアミノメチルシクロヘキサン、ビス−ｐ−アミ
ノシクロヘキシルメタン、ビス−ｐ−アミノシクロヘキ
シルプロパン、イソホロンジアミンなどのジアミン、ア
ジピン酸、スペリン酸、アゼライン酸、セバシン酸、ド
デカンニ酸、１゜４−シクロヘキサンジカルボン酸、１
，３−シクロヘキサンジカルボン酸、テレフタル酸、イ
ソフタル酸、ナフタレンジカルボン酸、ダイマー酸など
のジカルボン酸がある。これらの構成成分は単独あるい
は二種以上の混合物の形で重合に供され、そうして得ら
れるポリアミドホモポリマ、コポリマいずれも本発明で
用いることができる。特に本発明で有用に用いられるポ
リアミドはポリカプロアミド（ナイロン６）、ポリヘキ
サメチレンアジパミド（ナイロン６６）、ポリへキサメ
チレンジアミン（ナイロン６１０）、ポリウンデカンア
ミド（ナイロン１１）、ポリドデカンアミド（ナイロン
１２）、そしてこれらポリアミドの共重合体および混合
物である。ここで用いられるポリアミドの重合度につい
ては特に制限なく、１％濃硫酸溶液の２５℃における相
対粘度が１．５〜５．０の範囲内にあるものを任意に用
いることができる。The polyamide component (B) used in the present invention is a polyamide whose main components are an amino acid, a lactam, or a diamine and a dicarboxylic acid. Specific examples of constituent components include ε-caprolactam, enantlactam, ω
- Lactams such as laurolactam, amino acids such as ε-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2.2.4- /2.4.4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m-xylylenediamine, p-xylylenediamine, 1.3-bisaminomethylcyclohexane, 1,
Diamines such as 4-bis-aminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-p-aminocyclohexylpropane, isophoronediamine, adipic acid, superric acid, azelaic acid, sebacic acid, dodecanoic acid, 1°4-cyclohexanedicarboxylic acid acid, 1
, 3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and dimer acid. These components are subjected to polymerization either alone or in the form of a mixture of two or more, and both the polyamide homopolymer and copolymer thus obtained can be used in the present invention. Polyamides particularly useful in the present invention include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene diamine (nylon 610), polyundecaneamide (nylon 11), and polydodecanamide. (nylon 12), and copolymers and mixtures of these polyamides. The degree of polymerization of the polyamide used here is not particularly limited, and any polyamide having a relative viscosity of 1% concentrated sulfuric acid solution at 25° C. within the range of 1.5 to 5.0 can be used.
本発明の樹脂組成物中に占めるポリアミドの割合は５〜
９０重串％、好ましくは１０〜８０重量％である。ポリ
アミドが５重量％に満たないと樹脂組成物の溶融流動性
、耐薬品性が不十分であり、ポリアミドが９０重迅％を
越えると耐水性、寸法安定性が不足するので好ましくな
い。The proportion of polyamide in the resin composition of the present invention is 5 to 5.
It is 90% by weight, preferably 10 to 80% by weight. If the polyamide content is less than 5% by weight, the melt flowability and chemical resistance of the resin composition will be insufficient, and if the polyamide content exceeds 90% by weight, the water resistance and dimensional stability will be insufficient.
本発明の（Ｃ）変性ポリオレフィンとはエチレン、プロ
ピレン、ブテン−１、ペンテン−１，４−メチルペンテ
ン−１、イソブチレン、１，４−へキサジエン、ジシク
ロペンタジェン、２，５−ノルボルナジェン、５−エチ
リデンノルボルネン、５−エチル−２，５−ノルボルナ
ジェン、５− Ｍ−−プロペニル）−２−ノルボルネン
、スチレンの内から選ばれた少なくとも一種のオレフイ
ンをラジカル手合して得られるポリオレフィンにカルボ
ンｌｌ、カルボン酸エステル基、カルボン酸金属塩基、
カルボン酸無水物事、イミド基の内から選ばれた少なく
とも一種の官能基を有する単量体成分（以下、官能基含
有成分と称する）を導入して１りられる変性ポリオレフ
ィンである。(C) modified polyolefin of the present invention is ethylene, propylene, butene-1, pentene-1,4-methylpentene-1, isobutylene, 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5 - ethylidenenorbornene, 5-ethyl-2,5-norbornadiene, 5-M--propenyl)-2-norbornene, and a polyolefin obtained by radical reaction of at least one olefin selected from styrene. acid ester group, carboxylic acid metal base,
This is a modified polyolefin obtained by introducing a monomer component having at least one functional group selected from carboxylic acid anhydrides and imide groups (hereinafter referred to as a functional group-containing component).
官能基含有成分の例を挙げると、アクリル酸、メタアク
リル酸、マレイン酸、フマル酸、イタコン酸、クロトン
酸、メチルマレイン酸、メチルフマル酸、メサコン酸、
シトラコン酸、グルタコン酸およびこれらカルボン酸の
金属塩、マレイン酸水素メチル、イタコン酸水素メチル
、アクリル酸メチル、アクリル酸エチル、アクリル酸ブ
チル、アクリル！２−エチルヘキシル、アクリル酸ヒド
ロキシエチル、メタアクリル酸メチル、イタアクリル酸
２−エチルヘキシル、メタアクリル酸ヒドロキシエチル
、メタアクリル酸アミノエチル、マレイン酸ジメチル、
イタコン酸ジメチル、無水マレイン酸、無水イタコン酸
、無水シトラコン酸、エンドビシクロー（２・２・１）
−５−へブテン−２・３−ジカルボン酸、エンドビシク
ロ−（２・２・１）−５−ヘプテン−２・３−ジカルボ
ン酸無水物、マレイミド、Ｎ−エチルマレイミド、Ｎ−
ブチルマレイミド、Ｎ−フェニルマレイミドなどがある
。Examples of functional group-containing components include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid, mesaconic acid,
Citraconic acid, glutaconic acid and metal salts of these carboxylic acids, methyl hydrogen maleate, methyl hydrogen itaconate, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic! 2-ethylhexyl, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl itaacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate,
Dimethyl itaconate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo (2.2.1)
-5-hebutene-2,3-dicarboxylic acid, endobicyclo-(2,2,1)-5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-
Examples include butylmaleimide and N-phenylmaleimide.
これらの官能基含有成分を導入する方法は、特に制限な
く、主成分のオレフィン類と混合して共重合せしめたり
、ポリオレフィンにラジカル開始剤を用いてグラフト導
入するなどの方法を用いることができる。官能基含有成
分の導人足は変性ポリオレフィン全体に対して０．００
１〜４０モル％、好ましくは０．０１〜３５モル％の範
囲内であるのが適当である。The method for introducing these functional group-containing components is not particularly limited, and methods such as mixing with the main component olefins and copolymerizing them, or grafting them into polyolefins using a radical initiator can be used. The guide foot of the functional group-containing component is 0.00 relative to the entire modified polyolefin.
A suitable range is 1 to 40 mol%, preferably 0.01 to 35 mol%.
本発明で特に有用な変性ポリオレフィンの具体例として
はエチレン／アクリル酸共申合体、エチレン／メタクリ
ル酸共重合体およびこれら共重合体中のカルボン酸部分
の一部またはすべてをナトリウム、リチウム、カリウム
、亜鉛、カルシウムとの塩としたもの、エチレン／アク
リル酸メチル共重合体、エチレン／アクリル酸エチル共
重合体、エチレン／メタクリル酸メチル共重合体、エチ
レン／メタクリル酸エチル共重合体、エチレン／アクリ
ル酸エチル−９−無水マレイン酸共重合体、（ｔｔ ｇ
；ｔはグラフトを表わす、以下同じ）、エチレン／メ
タクリル酸メチル−３−無水マレイン酸共重合体、エチ
レン／アクリル酸エチル−９−マレイミド共重合体、エ
チレン／アクリル酸エチル−９−Ｎ−フェニルマレイミ
ド共重合体およびこれら共重合体の部分ケン化物、エチ
レン／プロピレン−９−無水マレイン酸共重合体、エチ
レン／ブテン−１−９−無水マレイン酸共重合体、エチ
レン／プロピレン／１．４−へキサジエン−び−無水マ
レイン酸共重合体、エチレン／プロピレン／ジシクロペ
ンタジェン−３−無水マレイン酸共重合体、エチレン／
プロピレン／２，５−ノルボルナジエン−９−無水マレ
イン酸共重合体、エチレン／プロピレン−７−Ｎ−フェ
ニルマレイミド共重合体、エチレン／ブテン−１−フー
Ｎ−フエニルマレイミド共重合体、スチレン／無水マレ
イン酸共重合体などが挙げることができ、これらは各々
単独あるいは混合物の形で用いることができる。Specific examples of modified polyolefins particularly useful in the present invention include ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, and some or all of the carboxylic acid moieties in these copolymers including sodium, lithium, potassium, Zinc, salts with calcium, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/methyl methacrylate copolymer, ethylene/ethyl methacrylate copolymer, ethylene/acrylic acid Ethyl-9-maleic anhydride copolymer, (tt g
; t represents a graft; the same applies hereinafter), ethylene/methyl methacrylate-3-maleic anhydride copolymer, ethylene/ethyl acrylate-9-maleimide copolymer, ethylene/ethyl acrylate-9-N-phenyl Maleimide copolymer and partially saponified products of these copolymers, ethylene/propylene-9-maleic anhydride copolymer, ethylene/butene-1-9-maleic anhydride copolymer, ethylene/propylene/1.4- Hexadiene-maleic anhydride copolymer, ethylene/propylene/dicyclopentadiene-3-maleic anhydride copolymer, ethylene/
Propylene/2,5-norbornadiene-9-maleic anhydride copolymer, ethylene/propylene-7-N-phenylmaleimide copolymer, ethylene/butene-1-fu-N-phenylmaleimide copolymer, styrene/anhydride Examples include maleic acid copolymers, and these can be used alone or in the form of a mixture.
本発明の樹脂組成物中に占める変性ポリオレフィンの割
合は３〜４０重量％、好ましくは５〜３０重量％の範囲
内である。変性ポリオレフィンの量が３重間％に満たな
いと、変性ポリフェニレンエーテル、ポリアミド、変性
ポリオレフィンからなる樹脂組成物の耐衝撃性が不足す
るので好ましくなく、逆に４０重間％を越えると樹脂組
成物の耐熱性、剛性が損なわれるので好ましくない。The proportion of the modified polyolefin in the resin composition of the present invention is in the range of 3 to 40% by weight, preferably 5 to 30% by weight. If the amount of modified polyolefin is less than 3% by weight, the resin composition consisting of modified polyphenylene ether, polyamide, and modified polyolefin will not have sufficient impact resistance, which is undesirable.On the other hand, if it exceeds 40% by weight, the resin composition will deteriorate. This is not preferable because it impairs the heat resistance and rigidity of the material.
変性ポリフェニレンエーテル、ポリアミドおよび変性ポ
リオレフィンの混合方法については特に限定はなく、各
樹脂の粉末、細片、ペレットの混合物を単軸または二軸
の押出機、バンバリーミキナー、ニーダ−、ミキシング
ロールなど通常公知の溶融混合機に供給して２２０〜３
５０℃の温度で混練する方法などを例として挙げること
ができる。また、３種の樹脂の混合順序にも特に限定は
なく、３種の樹脂を一括して混合してもよく、２種の樹
脂を予め混合してその債に残る他の樹脂との混合を実施
する方法をとってもよい。There are no particular limitations on the method of mixing modified polyphenylene ether, polyamide, and modified polyolefin, and the mixture of powders, pieces, and pellets of each resin may be mixed using a single-screw or twin-screw extruder, a Banbury mixer, a kneader, a mixing roll, etc. 220-3 by supplying it to a known melt mixer
Examples include a method of kneading at a temperature of 50°C. Furthermore, there is no particular limitation on the order in which the three types of resins are mixed, and the three types of resins may be mixed together, or two types of resins may be mixed in advance and then mixed with other resins remaining in the bond. You may also take the method of implementing it.
本発明の樹脂組成物にはその物性を損なわない限りにお
いて樹脂の混合時、成形時に他の添加剤、たとえば顔料
、染料、補強剤、充填剤、耐熱剤、酸化劣化防止剤、耐
候剤、滑剤、離型剤、結晶核剤、可塑剤、難燃剤、流動
性改良剤、帯電防止剤などを添加導入することができる
。The resin composition of the present invention may contain other additives such as pigments, dyes, reinforcing agents, fillers, heat resistant agents, oxidative deterioration inhibitors, weathering agents, and lubricants during resin mixing and molding as long as the physical properties are not impaired. , a mold release agent, a crystal nucleating agent, a plasticizer, a flame retardant, a fluidity improver, an antistatic agent, etc. can be added and introduced.
本発明の樹脂組成物を射出成形、ブロー成形、押出し成
形などの方法で成形した成形品は耐熱性、耐水性、寸法
安定性、耐衝撃性の優れたものであり、これらは特に自
動車の７エーダー、ドアパネル、クォーターパネル、バ
ンバ、スポイラ、オイールキャップ、フエーエルリツド
、サイトシールドなどの外装部品あるいはその他一般機
械部品として極めて有用である。Molded products made from the resin composition of the present invention by methods such as injection molding, blow molding, and extrusion molding have excellent heat resistance, water resistance, dimensional stability, and impact resistance. It is extremely useful as exterior parts such as edders, door panels, quarter panels, bumpers, spoilers, oil caps, fuel lids, sight shields, and other general mechanical parts.
〈実施例〉 以下に実施例を挙げて本発明をざらに詳しく説明する。<Example> EXAMPLES The present invention will be explained in more detail with reference to Examples below.
なお、実施例および比較例に記した諸特性は次の方法に
より評価した。The various properties described in the Examples and Comparative Examples were evaluated by the following methods.
（１）メルトインデックス：ＪＩＳ Ｋ７２１０（２
）引 張 特 性：ＡＳＴＭ Ｄ６３８（３）
曲 げ 特 性：ＡＳＴＭ Ｄ７９０（４）ア
イゾツト衝撃強度：ＡＳＴＭ Ｄ２５６（５）熱変形
温度：ＡＳＴＭ Ｄ６４８（６）耐水性、寸法安定性：
引張試験片を２３℃水中に２４時間浸漬し、この間の吸
水最および吸水前後の試験片タテ方向の寸法変化を測定
した。(1) Melt index: JIS K7210 (2
) Tensile properties: ASTM D638 (3)
Bending properties: ASTM D790 (4) Izot impact strength: ASTM D256 (5) Heat distortion temperature: ASTM D648 (6) Water resistance, dimensional stability:
A tensile test piece was immersed in water at 23° C. for 24 hours, and the dimensional change in the longitudinal direction of the test piece before and after water absorption was measured.
ｆｊＪ考例１（ポリフェニレンエーテルの製造〉無水塩
化第１銅７．６ｇとジ−ｔ−ブチルアミン１０ｇを溶か
したトルエン溶液１１を重合槽に仕込み、次いで５５重
量％２，６−シメチルフエノールのトルエン溶液４１を
添加し、３０℃の温度に保持し、この混合溶液に酸素を
吹き込みながら攪拌し、酸化重合を行った。重合後、酢
酸水溶液を加えて触媒を失活させ、反応を停止し、反応
溶液を濃縮した後多量のメタノールを加えてポリマを析
出させた。析出したポリマを濾過、洗浄、乾燥すること
によりポリフェニレンエーテルを得た。fjJ Example 1 (Manufacture of polyphenylene ether) Toluene solution 11 in which 7.6 g of anhydrous cuprous chloride and 10 g of di-t-butylamine were dissolved was charged into a polymerization tank, and then 55% by weight of 2,6-dimethylphenol in toluene was added. Solution 41 was added, the temperature was maintained at 30°C, and the mixed solution was stirred while blowing oxygen to perform oxidative polymerization. After polymerization, an acetic acid aqueous solution was added to deactivate the catalyst to stop the reaction. After concentrating the reaction solution, a large amount of methanol was added to precipitate a polymer.The precipitated polymer was filtered, washed, and dried to obtain polyphenylene ether.
参考例２（変性ポリフェニレンエーテルの製造）
参考例１の得られたポリフェニレンエーテル１００型組
部、無水マレイン！！１重量部および２．５−ジメチル
−２，５−ジ−ｔ−ブチルパーオキシヘキサン０．１重
量部の混合物を押出機のホッパーに供給し、シリンダ一
温度３２０℃で溶融混練することにより無水マレイン酸
変性ポリフェニレンエーテル（Ａ−１）を得た。Reference Example 2 (Manufacture of modified polyphenylene ether) Polyphenylene ether 100 type assembly obtained in Reference Example 1, anhydrous maleic! ! A mixture of 1 part by weight of 2.5-dimethyl-2,5-di-t-butylperoxyhexane and 0.1 part by weight of peroxyhexane is supplied to the hopper of an extruder and melt-kneaded at a cylinder temperature of 320°C to obtain anhydrous Maleic acid-modified polyphenylene ether (A-1) was obtained.
ポリフェニレンエーテルと無水マレイン酸が反応したこ
とは、変性ポリフェニレンエーテルをメタノール溶媒と
して浴比３０：１で４８時間抽出をした優、変性ポリフ
ェニレンエーテルのＩＲを観測し、１．６００〜１．８
００ａ−１の領域のνＣ＝Ｏの吸収ピークを解析するこ
とにより確認した。The reaction between polyphenylene ether and maleic anhydride was confirmed by extracting the modified polyphenylene ether using methanol as a solvent for 48 hours at a bath ratio of 30:1.The IR of the modified polyphenylene ether was observed to be 1.600 to 1.8.
This was confirmed by analyzing the absorption peak of νC=O in the region of 00a-1.
参考例３
オレフィン化合物の種類と量を変えた以外は参考例２に
示したのと全く同様の操作を行い変性ポリフェニレンエ
ーテルＡ−２およびＡ−３を得た。Reference Example 3 Modified polyphenylene ethers A-2 and A-3 were obtained by carrying out exactly the same operation as shown in Reference Example 2, except that the type and amount of the olefin compound were changed.
オレフィン化合物 添 加 量
（重量部ＶＳポリフ
ェニレンエーテル
１００重量部）
Ａ−２Ｎ−フェニル ３．０
マレイミド
Ａ−３無水イタコン酸 ０．５
実施例１
参考例２に記した方法で調製した変性ポリフェニレンエ
ーテル（Ａ−１＞３０重量部、ナイロン６６樹脂（東し
■製ＣＭ３００１Ｎ＞６０重足部および無水マレイン酸
を１モル％含有し、メルトインデックス０．４ｇ／１０
分のエチレンプロピレン共重合体（Ｃ−１＞１０重足部
を予備混合した後、３０ｍφ口径の二軸押出機のホッパ
ーに供給し、シリンダ一温度２８０℃で溶融混練しベレ
ット化した。このペレットを真空乾燥した後、シリンダ
一温度２８０℃、金型温度８０℃の条件で射出し、各種
物性評価用試験片を得た。試験片の特性は第１表に示し
た。ここで得られた樹脂組成物は熱変形温度に代表され
る耐熱性、吸水時寸法変化に代表される寸法安定性、吸
水率に代表される耐水性、アイゾツト衝撃強度に代表さ
れる耐衝撃性のすべてが良好であり、極めてバランスの
取れた実用価値の高い材料であることが判明した。Olefin compound addition amount (parts by weight VS polyphenylene ether 100 parts by weight) A-2N-phenyl 3.0 Maleimide A-3 itaconic anhydride 0.5 Example 1 Modified polyphenylene ether prepared by the method described in Reference Example 2 ( A-1>30 parts by weight, nylon 66 resin (CM3001N>60 manufactured by Toshi ■) containing 1 mol% of heavy foot parts and maleic anhydride, melt index 0.4 g/10
After premixing the ethylene propylene copolymer (C-1>10 parts), it was supplied to the hopper of a twin screw extruder with a diameter of 30 mφ, and was melt-kneaded at a cylinder temperature of 280°C to form pellets. After drying in vacuum, it was injected under the conditions of a cylinder temperature of 280°C and a mold temperature of 80°C to obtain test pieces for evaluating various physical properties.The properties of the test pieces are shown in Table 1. The resin composition has good heat resistance as represented by heat distortion temperature, dimensional stability as represented by dimensional change upon water absorption, water resistance as represented by water absorption rate, and impact resistance as represented by Izotsu impact strength. It turned out to be an extremely well-balanced material with high practical value.
比較例１
変性ポリフェニレンエーテル（Ａ−１＞の代りに参考例
１に示した方法で重合したポリフェニレンエーテルを用
いた以外は実施例１と全く同様に混線、射出成形を実施
して各種試験片を得た。これらの特性は第１表に示した
とおりであり衝撃強度、耐熱性ともに不足であった。Comparative Example 1 Various test pieces were prepared by cross-crossing and injection molding in exactly the same manner as in Example 1, except that polyphenylene ether polymerized by the method shown in Reference Example 1 was used instead of modified polyphenylene ether (A-1>). These properties were as shown in Table 1, and both impact strength and heat resistance were insufficient.
比較例２
変性ポリオレフィンを添加せず、変性ポリフェニレンエ
ーテル（Ａ−１＞４０重量部および実施例１で用いたナ
イロン６６樹脂６０重母部を予備混合した債、以下実施
例１に記したのと全く同じ手順で混練、射出成形を行い
各種試験片を得た。ここで得られた試験片の特性は第１
表に示すとおりであり衝撃強度が不十分であった。Comparative Example 2 A bond prepared by premixing modified polyphenylene ether (A-1>40 parts by weight and 60 parts by weight of the nylon 66 resin used in Example 1, without adding modified polyolefin, as described in Example 1 below) Various test pieces were obtained by kneading and injection molding in exactly the same procedure.The characteristics of the test pieces obtained here were as follows.
As shown in the table, the impact strength was insufficient.
比較例３
未変性のポリフェニレンエーテル３０重囲部、ナイロン
６６樹脂６０重量部、実施例１で用いた変性ポリオレフ
ィン（Ｃ−１＞１０重量部および無水マレイン酸２重量
部を混合し、以下実施例１に記したのと全く同じ操作で
混線、射出成形を実施した。ここで得られた試験片の物
性は第１表に示したとおりであり、このものも衝撃強度
が不満足なレベルであった。また、この組成物は成形中
にシリンダー内で発泡が認められ溶融安定性が悪い。Comparative Example 3 30 parts by weight of unmodified polyphenylene ether, 60 parts by weight of nylon 66 resin, the modified polyolefin (C-1>10 parts by weight used in Example 1) and 2 parts by weight of maleic anhydride were mixed, and the following Example Cross-crossing and injection molding were carried out in exactly the same manner as described in 1.The physical properties of the test specimens obtained here are as shown in Table 1, and the impact strength of this specimen was also at an unsatisfactory level. In addition, this composition showed foaming within the cylinder during molding and had poor melt stability.
実施例２
実施例１で用いて変性ポリフェニレンエーテル（Ａ−１
）４５重量部、ナイロン６６樹脂４５重団部およびＮ−
フェニルマレイミドを１モル％含有し、メルトインデッ
クス０．５ｇ／１０分のエチレン／プロピレン共重合体
（Ｃ−２＞１０重量部を混合し、以下実施例１に記した
のと同様の操作、手順で混線、成形を行い、各種試験片
を得た。これらの試験片の特性は第１表に示すとおりで
あり、本組成物も耐熱性、寸法安定性、耐衝撃性に優れ
た極めて実用価値の高いものであることが判明した。Example 2 Modified polyphenylene ether (A-1
) 45 parts by weight, 45 parts by weight of nylon 66 resin and N-
An ethylene/propylene copolymer (C-2>10 parts by weight) containing 1 mol% of phenylmaleimide and a melt index of 0.5 g/10 min was mixed, and the same operations and procedures as described in Example 1 were carried out. The composition was cross-wired and molded to obtain various test pieces.The properties of these test pieces are shown in Table 1, and this composition also has excellent heat resistance, dimensional stability, and impact resistance, and has extremely practical value. It turned out that it was a high value.
実施例３〜６
変性ポリフェニレンエーテル、ポリアミド樹脂および変
性ポリオレフィンの種類、混合比を種々に変えて、混練
、成形を行って得られた成形片の物性を第１表にまとめ
て示した。ここで得られた組成物はいずれも耐熱性、耐
水性、寸法安定性、耐衝撃性に優れ、実用価値の高いも
のであることが判明した。Examples 3 to 6 Table 1 summarizes the physical properties of molded pieces obtained by kneading and molding with various types and mixing ratios of modified polyphenylene ether, polyamide resin, and modified polyolefin. It was found that all of the compositions obtained here have excellent heat resistance, water resistance, dimensional stability, and impact resistance, and are of high practical value.
〈発明の効果〉
本発明の特徴は特定の化合物で変性した変性ポリフェニ
レンエーテル、ポリアミド樹脂および特定の変性ポリオ
レフィンを特定の組成比で組合せた点におる。これによ
りポリフェニレンエーテルとポリアミドの双方の長所を
バランスよく結合させることが可能になり、耐熱性、寸
法安定性、耐水性、耐衝撃性、成形性などの緒特性の優
れた新規な熱可塑性樹脂組成物が得られるようになった
。<Effects of the Invention> A feature of the present invention is that a modified polyphenylene ether modified with a specific compound, a polyamide resin, and a specific modified polyolefin are combined in a specific composition ratio. This makes it possible to combine the advantages of both polyphenylene ether and polyamide in a well-balanced manner, creating a new thermoplastic resin composition with excellent properties such as heat resistance, dimensional stability, water resistance, impact resistance, and moldability. I can now get things.
特許出願大東し株式会社Patent application Daitoshi Co., Ltd.
Claims (1)
一種または二種以上を酸化重合して得られるポリフェニ
レンエーテルと該ポリフェニレンエーテル１００重量部
に対してカルボン酸基、カルボン酸無水物基、イミド基
、エポキシ基の内から選ばれる少なくとも一種の官能基
を分子内に有する置換オレフィン化合物０．０５〜２０
重量部をラジカル発生剤の共存下で反応させて得られる
変性ポリフェニレンエーテル５〜９０重量％、 （Ｂ）ポリアミド５〜９０重量％および、 （Ｃ）カルボン酸基、カルボン酸金属塩基、カルボン酸
エステル基、カルボン酸無水物基、イミド基の内から選
ばれた少なくとも一種の官能基を分子中に有する変性ポ
リオレフィン３〜４０重量％よりなる熱可塑性樹脂組成
物。 ▲数式、化学式、表等があります▼・・・（ I ） （ここでＲ＾１、Ｒ＾２、Ｒ＾３、Ｒ＾４は水素原子、
炭素数１〜１０のアルキル基およびハロアルキル基、ア
リール基、ハロゲン原子の内から選ばれ、Ｒ＾１〜Ｒ＾
４は互いに同じでも異なつていてもよい。）[Scope of Claims] (A) A polyphenylene ether obtained by oxidative polymerization of one or more phenols represented by the following general formula (I), and a carboxylic acid group, a carbon Substituted olefin compound having at least one functional group selected from acid anhydride group, imide group, and epoxy group in the molecule 0.05 to 20
5 to 90% by weight of modified polyphenylene ether obtained by reacting parts by weight in the presence of a radical generator, (B) 5 to 90% by weight of polyamide, and (C) carboxylic acid group, carboxylic acid metal base, carboxylic acid ester 1. A thermoplastic resin composition comprising 3 to 40% by weight of a modified polyolefin having in its molecule at least one functional group selected from a group consisting of a carboxylic acid anhydride group and an imide group. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (Here, R^1, R^2, R^3, R^4 are hydrogen atoms,
selected from alkyl groups having 1 to 10 carbon atoms, haloalkyl groups, aryl groups, and halogen atoms, R^1 to R^
4 may be the same or different. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61175741A JPH0737564B2 (en) | 1986-07-28 | 1986-07-28 | Thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61175741A JPH0737564B2 (en) | 1986-07-28 | 1986-07-28 | Thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6333471A true JPS6333471A (en) | 1988-02-13 |
| JPH0737564B2 JPH0737564B2 (en) | 1995-04-26 |
Family
ID=16001438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61175741A Expired - Fee Related JPH0737564B2 (en) | 1986-07-28 | 1986-07-28 | Thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0737564B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01149852A (en) * | 1987-12-04 | 1989-06-12 | Toray Ind Inc | Thermoplastic resin composition |
| JPH02115263A (en) * | 1988-10-25 | 1990-04-27 | Mitsubishi Gas Chem Co Inc | Solvent-resistant polyphenylene ether resin composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5966452A (en) * | 1982-10-08 | 1984-04-14 | Unitika Ltd | Resin composition |
| JPS63503392A (en) * | 1986-05-27 | 1988-12-08 | ゼネラル・エレクトリック・カンパニイ | Functionalized polyphenylene ethers, processes for their preparation and polyphenylene ether-polyamide compositions made therefrom |
-
1986
- 1986-07-28 JP JP61175741A patent/JPH0737564B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5966452A (en) * | 1982-10-08 | 1984-04-14 | Unitika Ltd | Resin composition |
| JPS63503392A (en) * | 1986-05-27 | 1988-12-08 | ゼネラル・エレクトリック・カンパニイ | Functionalized polyphenylene ethers, processes for their preparation and polyphenylene ether-polyamide compositions made therefrom |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01149852A (en) * | 1987-12-04 | 1989-06-12 | Toray Ind Inc | Thermoplastic resin composition |
| JPH02115263A (en) * | 1988-10-25 | 1990-04-27 | Mitsubishi Gas Chem Co Inc | Solvent-resistant polyphenylene ether resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0737564B2 (en) | 1995-04-26 |
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