JPS63105051A - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- JPS63105051A JPS63105051A JP24848486A JP24848486A JPS63105051A JP S63105051 A JPS63105051 A JP S63105051A JP 24848486 A JP24848486 A JP 24848486A JP 24848486 A JP24848486 A JP 24848486A JP S63105051 A JPS63105051 A JP S63105051A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- copolymer
- unsaturated
- acid
- component
- 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 8
- 229920005992 thermoplastic resin Polymers 0.000 title description 2
- 229920001577 copolymer Polymers 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 32
- -1 unsaturated dicarboxylic acid imide Chemical class 0.000 claims abstract description 25
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 17
- 239000004952 Polyamide Substances 0.000 claims abstract description 15
- 229920002647 polyamide Polymers 0.000 claims abstract description 15
- 239000004711 α-olefin Substances 0.000 claims abstract description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 229920001971 elastomer Polymers 0.000 claims abstract description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 9
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 abstract description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 3
- 239000000470 constituent Substances 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229920002292 Nylon 6 Polymers 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000004018 acid anhydride group Chemical group 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 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
- 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
- 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
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012457 nonaqueous media Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000725 suspension Substances 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
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- SXTILEHINBCKSS-UHFFFAOYSA-N 1-chloro-3-phenylpyrrole-2,5-dione Chemical class O=C1N(Cl)C(=O)C=C1C1=CC=CC=C1 SXTILEHINBCKSS-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical class O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- QCOLXFOZKYRROA-UHFFFAOYSA-N 1-methoxy-3-phenylpyrrole-2,5-dione Chemical class O=C1N(OC)C(=O)C=C1C1=CC=CC=C1 QCOLXFOZKYRROA-UHFFFAOYSA-N 0.000 description 1
- QSWFISOPXPJUCT-UHFFFAOYSA-N 1-methyl-3-methylidenepyrrolidine-2,5-dione Chemical class CN1C(=O)CC(=C)C1=O QSWFISOPXPJUCT-UHFFFAOYSA-N 0.000 description 1
- IYBPIDAYDPNCTP-UHFFFAOYSA-N 1-methyl-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(C)C(=O)C=C1C1=CC=CC=C1 IYBPIDAYDPNCTP-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- PSKLSRMDQQEEGQ-UHFFFAOYSA-N 1-nitro-3-phenylpyrrole-2,5-dione Chemical class O=C1N([N+](=O)[O-])C(=O)C=C1C1=CC=CC=C1 PSKLSRMDQQEEGQ-UHFFFAOYSA-N 0.000 description 1
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical class CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 description 1
- WAXBZQUSTLNLPU-UHFFFAOYSA-N 2,5-dioxo-3-phenylpyrrole-1-carboxylic acid Chemical class O=C1N(C(=O)O)C(=O)C=C1C1=CC=CC=C1 WAXBZQUSTLNLPU-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- VISOTGQYFFULBK-UHFFFAOYSA-N 3-hydroxy-4-phenylpyrrole-2,5-dione Chemical class O=C1C(=O)NC(O)=C1C1=CC=CC=C1 VISOTGQYFFULBK-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-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
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-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
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical group 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 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
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229940066769 systemic antihistamines substituted alkylamines Drugs 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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、衝撃強度及び耐薬品性にすぐれた樹脂
組成物に関する。更に詳しくはイミド化共重合体、ポリ
アミドおよびα−オレフィンと不飽和カルボン酸又はα
、β−不飽和酸のグリシジルエステルとの共重合体から
なる熱可塑性樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a resin composition having excellent heat resistance, impact strength and chemical resistance. More specifically, imidized copolymers, polyamides, α-olefins and unsaturated carboxylic acids or α-olefins
, relates to a thermoplastic resin composition comprising a copolymer of a β-unsaturated acid with a glycidyl ester.
（従来の技術及び問題点）
ポリアミドはその耐薬品性、耐熱性、耐摩耗性のすぐれ
ていることから広く使用されている。しかしポリアミド
は成形時の収縮が大きく、成形品にヒケ、ソリが発生し
やすいと共に吸湿性が大であり、吸湿による機械的強度
の低下が大きく、また寸法変化が大であるという欠点が
ある。それらを改良するためにポリスチレンやスチレン
−アクリロニトリル共重合体を混合する方法が提案され
ている（特公昭４０−７３８０号）。しかしこれらの樹
脂はポリアミドとの相溶性が悪く、機械的強度が著しく
低下する欠点があった。またポリスチレン１スチレンー
アクリロニトリル共重合体に代えてスチレンとのα、β
−不飽和カルボン酸無水物を混合する方法（特開昭５６
−５０９３１号）やα、β−不飽和ジカルボン酸のイミ
ド化合物をポリアミドに混合する方法（特開昭５８−７
１９５２号）が提案されているが、ポリアミドとこれら
の樹脂との相溶性はまだ十分でなくしかも耐熱性も不十
分である。(Prior Art and Problems) Polyamide is widely used because of its excellent chemical resistance, heat resistance, and abrasion resistance. However, polyamides have the drawbacks of large shrinkage during molding, easy occurrence of sink marks and warpage in molded products, high hygroscopicity, large decrease in mechanical strength due to moisture absorption, and large dimensional changes. In order to improve these, a method of mixing polystyrene or a styrene-acrylonitrile copolymer has been proposed (Japanese Patent Publication No. 7380/1983). However, these resins have poor compatibility with polyamide and have the drawback of significantly lowering mechanical strength. Also, instead of polystyrene 1 styrene-acrylonitrile copolymer, α, β with styrene
- Method of mixing unsaturated carboxylic acid anhydrides (JP-A-56
-50931) and a method of mixing an imide compound of α,β-unsaturated dicarboxylic acid with polyamide (Japanese Unexamined Patent Publication No. 58-7
No. 1952) has been proposed, but the compatibility between polyamide and these resins is still insufficient, and the heat resistance is also insufficient.
一部α−オレフィンと不飽和カルボン酸又はα。Some α-olefins and unsaturated carboxylic acids or α.
β−不飽和酸のグリシジルエステルとの共重合体をＡＢ
Ｓ樹脂と飽和ポリエステルあるいはポリカーボネートと
の混合物に添加しウェルド強度を改良する方法（特開昭
５８−１５７８４８号、６〇−６３２５０号）が提案さ
れているが耐熱性が不十分であった。AB copolymer with glycidyl ester of β-unsaturated acid
A method of improving weld strength by adding it to a mixture of S resin and saturated polyester or polycarbonate has been proposed (Japanese Patent Application Laid-open Nos. 157848-1982 and 63250-60), but the heat resistance was insufficient.
（問題点を解決するための手段）
本発明者は上記問題点を解決することを目的として検討
した結果、イミド化共重合体とポリアミドに更にα−オ
レフィンの共重合体をブレンドすることによりイミド化
共重合体とポリアミドとの相溶性を向上させ耐熱性及び
衝撃強度に優れた組成物を得ることができた。更に衝撃
強度耐熱性のみならず耐薬品性、成形性にも優れた樹脂
組成物を得ることができた。すなわち本発明は、（Ａ）
成分：ゴム状重合体０〜４０重足％、芳香族ビニル単量
体残基３０〜６９重量％、
不飽和ジカルボン酸イミド誘導体残基
３０〜６０重量％、不飽和ジカルボン
酸無水物単量体残基１〜１０重量％お
よびこれら以外のビニル単量体残基０
〜４０重量％からなるイミド化共重合
体１０〜９０重量％と
（Ｂ）成分：ポリアミド１０〜９０重量％からなる樹脂
組成物９９〜８０重世％と
（Ｃ）成分：α−オレフィンと不飽和カルボン酸又はα
、β−不飽和酸のグリシジルエス
テルとの共重合体１〜２０重量％
を含有することを特徴とする熱可塑性樹脂組成物である
。(Means for Solving the Problems) As a result of studies aimed at solving the above problems, the present inventor has developed an imidized copolymer and a polyamide by further blending an α-olefin copolymer. The compatibility between the chemical copolymer and the polyamide was improved, and a composition excellent in heat resistance and impact strength could be obtained. Furthermore, it was possible to obtain a resin composition that was excellent not only in impact strength and heat resistance but also in chemical resistance and moldability. That is, the present invention provides (A)
Ingredients: 0 to 40% by weight of rubbery polymer, 30 to 69% by weight of aromatic vinyl monomer residue, 30 to 60% by weight of unsaturated dicarboxylic acid imide derivative residue, unsaturated dicarboxylic anhydride monomer A resin composition consisting of 10 to 90% by weight of an imidized copolymer consisting of 1 to 10% by weight of residues and 0 to 40% by weight of vinyl monomer residues other than these, and 10 to 90% by weight of component (B): polyamide. Component (C): α-olefin and unsaturated carboxylic acid or α
, a copolymer of β-unsaturated acid with glycidyl ester, in an amount of 1 to 20% by weight.
まず（Ａ）成分のイミド化共重合体およびその製法を説
明する。First, the imidized copolymer of component (A) and its production method will be explained.
（Ａ）成分共重合体の製法としては、第１の製法として
必要ならゴム状重合体の存在下、芳香族ビニル単量体不
飽和ジカルボン酸イミド誘導体、不飽和ジカルボン酸無
水物単量体、及びこれらと共重合可能なビニル単量体混
合物を共重合させる・ 方法、第２の製法として必要な
らゴム状重合体の存在下、芳香族ビニル単量体、不飽和
ジカルボン酸無水物及びこれらと共重合可能なビニル単
量体混合物を共重合させた重合体に該重合体中の酸無水
物基に対しアンモニア及び／又は第１級アミンを反応さ
せて酸無水物基の一部をイミド基に変換させる方法が挙
げられ、いずれの方法によってもイミド化共重合体を得
ることができる。(A) As a method for producing the component copolymer, in the first production method, if necessary, in the presence of a rubbery polymer, an aromatic vinyl monomer, an unsaturated dicarboxylic acid imide derivative, an unsaturated dicarboxylic anhydride monomer, and copolymerizing a vinyl monomer mixture copolymerizable with these, as a second production method, aromatic vinyl monomers, unsaturated dicarboxylic acid anhydrides, and these in the presence of a rubbery polymer if necessary. A polymer obtained by copolymerizing a copolymerizable vinyl monomer mixture is reacted with ammonia and/or a primary amine on the acid anhydride groups in the polymer to convert some of the acid anhydride groups into imide groups. The imidized copolymer can be obtained by any of the methods.
（Ａ）成分共重合体第１の製法に使用される芳香族ビニ
ル単量体としてはスチレン、α−メチルスチレン、ビニ
ルトルエン、ｔ−ブチルスチレン、クロロスチレン等の
スチレン単量体およびその置換単量体であり、これらの
中でスチレンが特に好ましい。(A) The aromatic vinyl monomers used in the first production method include styrene monomers and substituted monomers thereof such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene. Among these, styrene is particularly preferred.
不飽和ジカルボン酸イミド＝ｉ体としてはマレイミド、
Ｎ−メチルマレイミド、Ｎ−ブチルマレイミド、Ｎ−フ
ェニルマレイミド、Ｎ−メチルフェニルマレイミド、Ｎ
−ヒドロキシフェニルマレイミド、Ｎ−メトキシフェニ
ルマレイミド、Ｎ−クロロフェニルマレイミド、Ｎ−カ
ルボキシフェニルマレイミド、Ｎ−ニトロフェニルマレ
イミド、Ｎ−シクロへキシルマレイミド、Ｎ−イソプロ
ピルマレイミド等のマレイミド誘導体、Ｎ−メチルイタ
コン酸イミド、Ｎ−フェニルイタコン酸イミド等のイタ
コン酸イミド誘導体等が挙げられ、これらの中でＮ−フ
ェニルマレイミドが特に好ましい。Unsaturated dicarboxylic acid imide = i-form maleimide,
N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N
-Maleimide derivatives such as hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-chlorophenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-cyclohexylmaleimide, N-isopropylmaleimide, N-methylitaconimide , and itaconic acid imide derivatives such as N-phenyl itaconic acid imide. Among these, N-phenyl maleimide is particularly preferred.
不飽和ジカルボン酸無水物としては、マレイン酸、イタ
コン酸、シトラコン酸、アコニット酸等の無水物があり
、マレイン酸無水物が特に好ましい。Examples of the unsaturated dicarboxylic anhydride include anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, with maleic anhydride being particularly preferred.
またこれらと共重合可能なビニル単量体としては、アク
リロニトリル、メタクリロニトリル、α−クロロアクリ
ロニトリル等のシアン化ビニル単量体、メチルアクリル
酸エステル、エチルアクリル酸エステル等のアクリル酸
エステル単量体、メチルメタクリル酸エステル、エチル
メタクリル酸エステル等のメタクリル酸エステルＱＪｔ
体、アクリル酸、メタクリル酸等のビニルカルボン酸単
晴体、アクリル酸アミド、メタクリル酸アミド等があっ
てこれらの中でアクリロニトリル、メタクリル酸エステ
ル、アクリル酸、メタクリル酸などの単量体が好ましい
。Vinyl monomers that can be copolymerized with these include vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, and acrylic ester monomers such as methyl acrylate and ethyl acrylate. , methyl methacrylate, ethyl methacrylate etc. QJt
Among these, monomers such as acrylonitrile, methacrylic ester, acrylic acid, and methacrylic acid are preferred.
また第２の製法に使用される芳香族ビニル単量体、不飽
和ジカルボン酸無水物及びこれらと共重合可能なビニル
単量体は前記の第１の製法に使用されるものが使用でき
る。Further, as the aromatic vinyl monomer, unsaturated dicarboxylic acid anhydride, and vinyl monomer copolymerizable with these used in the second production method, those used in the first production method can be used.
また、イミド化反応に用いるアンモニアや第１級アミン
は無水又は水溶液のいずれの状態であってもよく、また
第１級アミンの例としてメチルアミン、エチルアミン、
ブチルアミン、シクロヘキシルアミン等のアルキルアミ
ン、およびこれらのクロル又はブロム置換アルキルアミ
ン、アニリン、トリルアミン、ナフチルアミン等の芳香
族アミンおよびクロル又はブロム置換アニリン等のハロ
ゲン置換芳香族アミンがあげられる。In addition, ammonia and primary amines used in the imidization reaction may be in either an anhydrous or aqueous solution state, and examples of primary amines include methylamine, ethylamine,
Examples include alkyl amines such as butylamine and cyclohexylamine, and aromatic amines such as chloro- or bromine-substituted alkyl amines, aniline, tolylamine, naphthylamine, and halogen-substituted aromatic amines such as chloro- or bromine-substituted aniline.
さらに、イミド化反応を溶液状態又は）懸濁状態で行な
う場合は、通常の反応容器、例えばオートクレーブなど
を用いるのが好ましく、塊状溶融状態で行なう場合は脱
揮装置の付いた押出機を用いてもよい。またイミド化す
る際に触媒を存在させてもよく、例えば第３級アミン等
が好ましく用いられる。Furthermore, when the imidization reaction is carried out in a solution or suspension state, it is preferable to use an ordinary reaction vessel, such as an autoclave, and when it is carried out in a bulk molten state, an extruder equipped with a devolatilization device is used. Good too. Further, a catalyst may be present during imidization, and for example, a tertiary amine or the like is preferably used.
イミド化反応の温度は、約８０〜３５０℃であり、好ま
しくは１００〜３００℃である。８０℃未満の場合には
反応速度が遅く、反応に長時間を要し実用的でない。一
方３５０℃を越える場合には重合体の熱分解による物性
低下をきたす。The temperature of the imidization reaction is about 80 to 350°C, preferably 100 to 300°C. If the temperature is lower than 80°C, the reaction rate is slow and the reaction takes a long time, which is not practical. On the other hand, if the temperature exceeds 350°C, the physical properties will deteriorate due to thermal decomposition of the polymer.
酸無水物残基量の調整は酸無水物基に対して添加するア
ンモニア及び／又は第１級アミンのモル当量によって行
なわれる。The amount of acid anhydride residue is adjusted by adjusting the molar equivalent of ammonia and/or primary amine added to the acid anhydride group.
溶液状態でイミド化する場合の溶剤としては、アセトン
、メチルエチルケトン、メチルイソブチルケトン、アセ
トフェノン、テトラヒドロフラン、ジメチルホルムアミ
ド等がありこれらの中でメチルエチルケトン、メチルイ
ソブチルケトンが好ましい。非水性媒体中での懸濁状態
でイミド化する時の非水性媒体にはへブタン、ヘキサン
、ペンタン、オクタン、２−メチルペンタン、シクロペ
ンタン、シクロヘキサン等の脂肪族炭化水素がある。Solvents for imidization in a solution state include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, tetrahydrofuran, dimethyl formamide, etc. Among these, methyl ethyl ketone and methyl isobutyl ketone are preferred. Non-aqueous media used for imidization in suspension in non-aqueous media include aliphatic hydrocarbons such as hebutane, hexane, pentane, octane, 2-methylpentane, cyclopentane, and cyclohexane.
（Ａ）成分共重合体は、ゴム状重合体０〜４０重量％、
好ましくは０〜３０重量％、芳香族ビニル単量体残基３
０〜６９重量％、好ましくは４０〜６４重量％、不飽和
ジカルボン酸イミド誘導体残基３０〜６０重量％、好ま
しくは３５〜５５重量％、不飽和ジカルボン酸無水物単
量体残基１〜１０重量％、好ましくは１〜５重景重量お
よびこれら以外のビニル単量体残基０〜４０重量％、好
ましくは０〜３０重景％重量なるイミド化共重合体であ
り、ゴム状重合体の量が４０重量％を越えると組成物の
耐熱性、成形性及び寸法安定性が損われる。(A) component copolymer is a rubbery polymer 0 to 40% by weight,
Preferably 0 to 30% by weight, aromatic vinyl monomer residue 3
0-69% by weight, preferably 40-64% by weight, unsaturated dicarboxylic acid imide derivative residues 30-60% by weight, preferably 35-55% by weight, unsaturated dicarboxylic anhydride monomer residues 1-10 It is an imidized copolymer containing 1 to 5% by weight, preferably 1 to 5% by weight and 0 to 40% by weight, preferably 0 to 30% by weight of vinyl monomer residues other than these, and is a rubber-like polymer. If the amount exceeds 40% by weight, the heat resistance, moldability and dimensional stability of the composition will be impaired.
芳香族ビニル単量体残基の量が３０重量％未満であると
成形性及び寸法安定性が損われ、６９重量％を越えると
衝撃強度及び耐熱性が損われる。If the amount of aromatic vinyl monomer residue is less than 30% by weight, moldability and dimensional stability will be impaired, and if it exceeds 69% by weight, impact strength and heat resistance will be impaired.
不飽和ジカルボン酸イミド誘導体残基の量が３０重単量
未満の場合は耐熱性改良の効果が不十分てあり、一方６
０重量％を越えると樹脂組成物が脆くなり成形性も悪く
なる。When the amount of unsaturated dicarboxylic acid imide derivative residue is less than 30 monomers, the effect of improving heat resistance is insufficient;
If it exceeds 0% by weight, the resin composition will become brittle and its moldability will deteriorate.
不飽和ジカルボン酸無水物単量体残基の量が１０重量％
を越えると組成物の熱安定性及び耐熱水性が低下し好ま
しくない。１重量％未満の場合は成形性が劣る。The amount of unsaturated dicarboxylic anhydride monomer residue is 10% by weight
Exceeding this is not preferable because the thermal stability and hot water resistance of the composition decrease. If it is less than 1% by weight, moldability will be poor.
本発明において（Ｂ）成分として用いられるポリアミド
は、脂肪族、芳香族あるいは脂環族のジカルボン酸とジ
アミンとから得られるポリアミド、アミノカルボン酸や
環状のラクタム類から得られるポリアミドなどが挙げら
れるが、具体例としてはナイロン６、ナイロン６．６、
ナイロン６゜１０、ナイロン１１、ナイロン１２、ナイ
ロン６゜１２のような脂肪族ポリアミド、ポリへキサメ
チレンジアミンテレフタルアミド、ポリへキサメチレン
ジアミンイソフタルアミドのような芳香族ポリアミド等
が挙げられ、これら２種以上の混合物または共重合体と
して用いることもできる。Examples of the polyamide used as component (B) in the present invention include polyamides obtained from aliphatic, aromatic, or alicyclic dicarboxylic acids and diamines, and polyamides obtained from aminocarboxylic acids and cyclic lactams. , Specific examples include nylon 6, nylon 6.6,
Examples include aliphatic polyamides such as nylon 6゜10, nylon 11, nylon 12, and nylon 6゜12, aromatic polyamides such as polyhexamethylene diamine terephthalamide, polyhexamethylene diamine isophthalamide, etc. It can also be used as a mixture or copolymer of more than one species.
本発明において（Ｃ）成分として用いられるα−オレフ
ィンと不飽和カルボン酸又はα、β−不飽和酸のグリシ
ジルエステルとの共重合体について説明する。α−オレ
フィンとしてはエチレン、プロピレン、ブテン−１，４
−メチルペンテン−１などが挙げられ特にエチレン、プ
ロピレンが好ましい。The copolymer of α-olefin and unsaturated carboxylic acid or glycidyl ester of α,β-unsaturated acid used as component (C) in the present invention will be explained. α-olefins include ethylene, propylene, butene-1,4
-Methylpentene-1, etc., and ethylene and propylene are particularly preferred.
不飽和カルボン酸としてはアクリル酸、メタクリル酸等
のモノカルボン酸、マレイン酸、フマル酸、イタコン酸
等のジカルボン酸、無水マレイン酸、無水イタコン酸等
のジカルボン酸無水物、アクリル酸メチル、メタアクリ
ル酸メチル、アクリル酸エチル、メタアクリル酸エチル
等のカルボン酸アルキルエステル等が挙げられる。Examples of unsaturated carboxylic acids include monocarboxylic acids such as acrylic acid and methacrylic acid, dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, methyl acrylate, and methacrylic acid. Examples include carboxylic acid alkyl esters such as methyl acid, ethyl acrylate, and ethyl methacrylate.
また、α、β−不飽和酸のグリシジルエステルとは一般
式
（式中Ｒは水素原子又は低級アルキル基）で示される化
合物であり、具体的にはアクリル酸グリシジルメタクリ
ル酸グリシジルなどである。Further, the glycidyl ester of an α,β-unsaturated acid is a compound represented by the general formula (in the formula, R is a hydrogen atom or a lower alkyl group), and specific examples include glycidyl acrylate and glycidyl methacrylate.
さらに上記の共重合体と共重合可能である不飽和モノマ
ーとして具体的にはビニルエーテル類、酢酸ビニル、プ
ロピオン酸ビニルなどのビニルエステル類、メチル、エ
チル、プロピルなどのアクリル酸およびメタクリル酸の
エステル類などを１種以上共重合せしめてもよい。Furthermore, unsaturated monomers that can be copolymerized with the above copolymers include vinyl ethers, vinyl esters such as vinyl acetate and vinyl propionate, and esters of acrylic acid and methacrylic acid such as methyl, ethyl, and propyl. One or more of these may be copolymerized.
本発明において（Ａ）成分、（Ｂ）成分及び（Ｃ）成分
の割合は（Ａ）成分１０〜９０重景％、重量しくは２０
〜８０重量％と（Ｂ）成分１０〜９０重量％、好ましく
は２０〜８０重量％とからなる樹脂組成物９９〜８０重
量％に対しくＣ）成分１〜２０重景％重量ましくは３〜
１５重量％の範囲が採られる。In the present invention, the ratio of component (A), component (B), and component (C) is 10 to 90% by weight, or 20% by weight of component (A).
-80% by weight of component C) and 10-90% by weight, preferably 20-80% by weight of component (B), and 1-20% by weight of component C) or 3% by weight. ~
A range of 15% by weight is taken.
（Ａ）成分の割合が１０重量％未満であると耐熱性向上
の効果が十分でない。If the proportion of component (A) is less than 10% by weight, the effect of improving heat resistance will not be sufficient.
一方（Ａ）成分と（Ｂ）成分の合計量中、（Ａ）成分が
９０重量％を越えると組成物の衝撃強度が低下し成形性
も悪くなり、（Ｂ）成分の割合がＩＯ重重量未満である
と本発明の組成物の衝撃に対する補強効果が不足し満足
な衝撃強度が得られない。また、耐薬品性も劣る。一方
（Ｂ）成分のの組成物中（Ｃ）成分の割合が１重量％未
満であると衝撃性改良の効果が乏しく （Ａ）成分と（
Ｂ）成分との相溶性向上の効果も十分でなく、一方２０
重量％を越えると耐熱性の低下が著しく好ましくない。On the other hand, if component (A) exceeds 90% by weight of the total amount of components (A) and (B), the impact strength of the composition will decrease and the moldability will deteriorate, and the proportion of component (B) will be lower than IO weight. If it is less than that, the impact reinforcing effect of the composition of the present invention will be insufficient and satisfactory impact strength will not be obtained. It also has poor chemical resistance. On the other hand, if the proportion of component (C) in the composition of component (B) is less than 1% by weight, the effect of improving impact properties will be poor, and component (A) and (
The effect of improving compatibility with component B) is also not sufficient; on the other hand, 20
If it exceeds % by weight, the heat resistance will drop significantly, which is undesirable.
本発明の樹脂組成物の混合方法は特に制限がなく、公知
の手段を使用することができる。その手段として例えば
バンバリーミキサ−、タンブラ−ミキサー、混合ロール
、１軸又は２軸押比機等があげられる。The method of mixing the resin composition of the present invention is not particularly limited, and known means can be used. Examples of the means include a Banbury mixer, a tumbler mixer, a mixing roll, a single-screw or twin-screw press ratio machine, and the like.
混合形態としては通常の溶融混合、マスターペレット等
を用いる多段階溶融混練、溶液中でのブレンド等により
組成物を得る方法がある。As for the mixing form, there are methods of obtaining the composition by ordinary melt mixing, multi-stage melt kneading using master pellets, etc., blending in a solution, and the like.
また本発明の組成物にさらにガラス繊維、カーボン繊維
、アラミド繊維、安定剤、難燃剤、可塑剤、滑剤、紫外
線吸収剤、着色剤およびタルク、シリカ、クレー、マイ
カ、炭酸カルシウム等の充てん剤などを添加することも
可能である。The composition of the present invention may further include glass fibers, carbon fibers, aramid fibers, stabilizers, flame retardants, plasticizers, lubricants, ultraviolet absorbers, colorants, and fillers such as talc, silica, clay, mica, and calcium carbonate. It is also possible to add.
（実施例） 以下本発明を実施例によって説明する。(Example) The present invention will be explained below with reference to Examples.
なお実施例中の部、％はいずれも重量基準で表わした。Note that all parts and percentages in the examples are expressed on a weight basis.
実験例（１）
攪拌機を備えてオートクレーブ中にスチレン１００部、
及びメチルエチルケトン５０部、小片状に切断したポリ
ブタジェン２４部を仕込み、系内を窒素ガスで置換した
後、室温で一昼夜攪拌しゴムを溶解させた。温度を８３
°Ｃに昇温後熱水マレイン酸６７部とベンゾイルパーオ
キサイド０．２部、アゾビスイソブチロニトリル０．２
部をメチルエチルケトン４００部に溶解した溶液を８時
間で添加した。添加後さらに３時間８３℃に保つ重合を
完了させた。ここで得られた共重合体溶液に含まれてい
る無水マレイン酸に対し０．８５モル当量のアニリン５
４．０部およびトリエチルアミン２部を加え１４０℃で
７時間反応させた。脱気処理し得られたイミド化共重合
体中の無水マレイン酸単量体残基は４．３重量％であっ
た。これを重合体（Ａ） とした。Experimental example (1) 100 parts of styrene was placed in an autoclave equipped with a stirrer.
Then, 50 parts of methyl ethyl ketone and 24 parts of polybutadiene cut into small pieces were charged, and after purging the system with nitrogen gas, the mixture was stirred at room temperature all day and night to dissolve the rubber. Temperature 83
After raising the temperature to °C, 67 parts of hydrothermal maleic acid, 0.2 parts of benzoyl peroxide, and 0.2 parts of azobisisobutyronitrile were added.
A solution of 400 parts of methyl ethyl ketone was added over 8 hours. After the addition, the polymerization was maintained at 83° C. for an additional 3 hours to complete the polymerization. 0.85 molar equivalent of aniline 5 to maleic anhydride contained in the copolymer solution obtained here.
4.0 parts and 2 parts of triethylamine were added and reacted at 140°C for 7 hours. The maleic anhydride monomer residue in the imidized copolymer obtained by degassing was 4.3% by weight. This was designated as Polymer (A).
実験例（２）
実施例（１）のスチレン１００部の代りにスチレン１０
０部とアクリロニトリル１０部を用い、無水マレイン酸
６７部を５７部にし、アニリン５４部に代え４６部を用
いた以外は実験例（１）と全く同じ操作を行ないイミド
化重合体を得た。Experimental example (2) 10 parts of styrene instead of 100 parts of styrene in Example (1)
An imidized polymer was obtained by carrying out exactly the same operation as in Experimental Example (1) except that 0 parts and 10 parts of acrylonitrile were used, 67 parts of maleic anhydride was changed to 57 parts, and 46 parts of aniline was used instead of 54 parts.
これを重合体（Ｂ）とした。This was designated as polymer (B).
実験例（３）
芳３己−ビニル二′科 と無ツマレインう７を乗入さ攪
拌機を備えたオートクレーブ中にスチレン６０部、メチ
ルエチルケトン５０部を仕込み、系内を窒素ガスで置換
した後温度を８５℃に昇温し、無水マレイン酸４０部と
ベンゾイルパーオキサイド０．１５部をメチルエチルケ
トン２５０部に溶解した溶液を８時間で連続的に添加し
た。添加後さらに３時間温度を８５℃に保った。精鋼な
反応液の一部とサンプリングしてガスクロマトグラフィ
ーにより重合率の定量を行った結果、スチレン９９％、
無水マレイン酸９９％であった。ここで得られた共重合
体溶液に無水マレイン酸に対して０．９０モル当最のア
ニリン３４部、トリエチルアミン０．３部を加え、１４
０℃で７時間反応させた。Experimental Example (3) 60 parts of styrene and 50 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, and the system was replaced with nitrogen gas, and then the temperature was lowered. The temperature was raised to 85°C, and a solution of 40 parts of maleic anhydride and 0.15 parts of benzoyl peroxide dissolved in 250 parts of methyl ethyl ketone was continuously added over 8 hours. The temperature was maintained at 85° C. for an additional 3 hours after the addition. As a result of sampling a part of the steel reaction solution and quantifying the polymerization rate by gas chromatography, it was found that styrene was 99%,
The maleic anhydride content was 99%. To the copolymer solution obtained here were added 34 parts of aniline and 0.3 parts of triethylamine equivalent to 0.90 mol based on maleic anhydride.
The reaction was carried out at 0°C for 7 hours.
反応溶液にメチルエチルケトン２００部を加え、室温ま
で冷却し、激しく攪拌したメタノール１５００部に注ぎ
、析出、濾別、乾燥しイミド化共重合体を得た。Ｃ−Ｃ
−１３部分析より無水マレイン酸単量体残基は３．１重
量％であった。これを重合体（Ｃ）とした。200 parts of methyl ethyl ketone was added to the reaction solution, cooled to room temperature, poured into 1500 parts of vigorously stirred methanol, precipitated, filtered, and dried to obtain an imidized copolymer. C-C
-13 parts Analysis revealed that the maleic anhydride monomer residue was 3.1% by weight. This was designated as Polymer (C).
実施例１〜３
実験例（１）で得られた重合体（Ａ）、ナイロン−６（
宇部興産製、１０１３Ｂ）およびエチレン−グリシジル
メタクリレート共重合体（住友化学工業製、ボンドファ
ーストＥ）を表−１の割合で混合し２７０℃にてベント
付押出機で押出しベレット化後、２７０℃で射出成形を
行ない試験片を成形した。結果を表−１に示した。Examples 1 to 3 Polymer (A) obtained in Experimental Example (1), nylon-6 (
(manufactured by Ube Industries, Ltd., 1013B) and ethylene-glycidyl methacrylate copolymer (manufactured by Sumitomo Chemical Industries, Ltd., Bond Fast E) were mixed in the proportions shown in Table 1 and extruded at 270°C using a vented extruder to form pellets, and then at 270°C. A test piece was formed by injection molding. The results are shown in Table-1.
実施例４
実施例１においてナイロン−６に代えナイロン−１２（
宇部興産製、３０２４Ｕ）を用いた以外は実施例１と同
様に行なった。結果を表−１に示した。Example 4 In Example 1, nylon-12 (
The same procedure as in Example 1 was conducted except that 3024U (manufactured by Ube Industries, Ltd.) was used. The results are shown in Table-1.
実施例５〜６−
実験例（２）および（３）で得られた重合体（Ｂ）、（
Ｃ）を表−１の割合で混合し実施例１と同様に物性を測
定した。結果を表−１に示した。Examples 5-6 - Polymers (B) obtained in Experimental Examples (2) and (3), (
C) were mixed in the proportions shown in Table 1, and the physical properties were measured in the same manner as in Example 1. The results are shown in Table-1.
実施例７〜８
実施例１においてエチレン−グリシジルメタクリレート
共重合体に代えエチレン−酢酸ビニル−グリシジルメタ
クリレート共重合体（住友化学工業製、ボンドファース
ト７Ｂ）、エチレン−エチルアクリレート−無水マレイ
ン酸共重合体（住友化学工業製、ボンダイン ＡＸ−８
０６０）を用いた以外は実施例１と同様に行なった。結
果を表−１に示した。Examples 7 to 8 In Example 1, ethylene-vinyl acetate-glycidyl methacrylate copolymer (manufactured by Sumitomo Chemical, Bond First 7B), ethylene-ethyl acrylate-maleic anhydride copolymer were used instead of ethylene-glycidyl methacrylate copolymer. (Sumitomo Chemical, Bondine AX-8
The same procedure as in Example 1 was conducted except that 060) was used. The results are shown in Table-1.
比較例１〜４
実施例１で用いたイミド化共重合体、ナイロン−６、エ
チレン−グリシジルメタクリレート共重合体を表−１の
割合で混合し実施例１と同様に物製を測定した。結果を
表−１に示した。Comparative Examples 1 to 4 The imidized copolymer used in Example 1, nylon-6, and ethylene-glycidyl methacrylate copolymer were mixed in the proportions shown in Table 1, and the product properties were measured in the same manner as in Example 1. The results are shown in Table-1.
（註）（１）エチレン−グリシジルメタクリレート共重
合体
（２）エチレン−酢酸ビニル−グリシジルメタイン酸共
重合体
生性血定跋狂１広
■）熱変形温度（ＨＤＴ）
荷重１８．６ｋｇ／ｃＪ、 ＡＳＴＭ Ｄ−６４８に
準じた。(Note) (1) Ethylene-glycidyl methacrylate copolymer (2) Ethylene-vinyl acetate-glycidyl methacrylate copolymer According to ASTM D-648.
２）アイゾツト衝撃強度
幅１／４インチのノツチなし、ＡＳＴＭＤ−２５６に準
じた。2) Izot impact strength: 1/4 inch width, no notch, in accordance with ASTM D-256.
３）耐ガソリン性
ガソリンが接触している時にクラックが発生する臨界歪
％で示す。3) Gasoline resistance Indicates the critical strain percentage at which cracks occur when gasoline is in contact.
Claims (1)
ル単量体残基３０〜６９重量％、 不飽和ジカルボン酸イミド誘導体残基 ３０〜６０重量％、不飽和ジカルボン 酸無水物単量体残基１〜１０重量％お よびこれら以外のビニル単量体残基０ 〜４０重量％からなるイミド化共重合 体１０〜９０重量％と （Ｂ）成分：ポリアミド１０〜９０重量％からなる樹脂
組成物９９〜８０重量％と （Ｃ）成分：α−オレフィンと不飽和カルボン酸又はα
，β−不飽和酸のグリシジルエス テルとの共重合体１〜２０重量％ を含有することを特徴とする熱可塑性樹脂組成物。[Scope of Claims] Component (A): 0 to 40% by weight of rubbery polymer, 30 to 69% by weight of aromatic vinyl monomer residues, 30 to 60% by weight of unsaturated dicarboxylic acid imide derivative residues, 10 to 90% by weight of an imidized copolymer consisting of 1 to 10% by weight of saturated dicarboxylic anhydride monomer residues and 0 to 40% by weight of vinyl monomer residues other than these, and component (B): Polyamide 10 99 to 80% by weight of a resin composition consisting of ~90% by weight and component (C): α-olefin and unsaturated carboxylic acid or α
, a copolymer of a β-unsaturated acid with a glycidyl ester in an amount of 1 to 20% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61248484A JPH083018B2 (en) | 1986-10-21 | 1986-10-21 | Thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61248484A JPH083018B2 (en) | 1986-10-21 | 1986-10-21 | Thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63105051A true JPS63105051A (en) | 1988-05-10 |
| JPH083018B2 JPH083018B2 (en) | 1996-01-17 |
Family
ID=17178843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61248484A Expired - Fee Related JPH083018B2 (en) | 1986-10-21 | 1986-10-21 | Thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH083018B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63193947A (en) * | 1987-02-06 | 1988-08-11 | Japan Synthetic Rubber Co Ltd | Thermoplastic resin composition |
| JPH02132140A (en) * | 1988-11-11 | 1990-05-21 | Denki Kagaku Kogyo Kk | Resin composition |
| JPH02251557A (en) * | 1989-03-24 | 1990-10-09 | Denki Kagaku Kogyo Kk | Fiber-reinforced resin composition |
| US5049613A (en) * | 1988-02-24 | 1991-09-17 | Denki Kagaku Kogyo Kabushiki Kaisha | Thermoplastic resin composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6259647A (en) * | 1985-09-11 | 1987-03-16 | Toray Ind Inc | Thermoplastic resin composition |
-
1986
- 1986-10-21 JP JP61248484A patent/JPH083018B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6259647A (en) * | 1985-09-11 | 1987-03-16 | Toray Ind Inc | Thermoplastic resin composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63193947A (en) * | 1987-02-06 | 1988-08-11 | Japan Synthetic Rubber Co Ltd | Thermoplastic resin composition |
| US5049613A (en) * | 1988-02-24 | 1991-09-17 | Denki Kagaku Kogyo Kabushiki Kaisha | Thermoplastic resin composition |
| JPH02132140A (en) * | 1988-11-11 | 1990-05-21 | Denki Kagaku Kogyo Kk | Resin composition |
| JPH02251557A (en) * | 1989-03-24 | 1990-10-09 | Denki Kagaku Kogyo Kk | Fiber-reinforced resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH083018B2 (en) | 1996-01-17 |
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