JPH02132140A - Resin composition - Google Patents
Resin compositionInfo
- Publication number
- JPH02132140A JPH02132140A JP28372088A JP28372088A JPH02132140A JP H02132140 A JPH02132140 A JP H02132140A JP 28372088 A JP28372088 A JP 28372088A JP 28372088 A JP28372088 A JP 28372088A JP H02132140 A JPH02132140 A JP H02132140A
- Authority
- JP
- Japan
- Prior art keywords
- maleimide
- modified polyolefin
- polyamide
- mol
- polyolefin polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 66
- 229920001577 copolymer Polymers 0.000 claims abstract description 40
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 35
- 229920000098 polyolefin Polymers 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229920002647 polyamide Polymers 0.000 claims abstract description 28
- 239000004952 Polyamide Substances 0.000 claims abstract description 26
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 9
- 239000000194 fatty acid Substances 0.000 claims abstract description 9
- 229930195729 fatty acid Natural products 0.000 claims abstract description 9
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 2
- 150000008064 anhydrides Chemical class 0.000 claims description 19
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 229920005992 thermoplastic resin Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 229920002292 Nylon 6 Polymers 0.000 abstract description 8
- 150000001991 dicarboxylic acids Chemical class 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract 2
- 239000000047 product Substances 0.000 description 24
- -1 imide compound Chemical class 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 4
- 229920000299 Nylon 12 Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000004677 Nylon Substances 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- PFBWBEXCUGKYKO-UHFFFAOYSA-N ethene;n-octadecyloctadecan-1-amine Chemical compound C=C.CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC PFBWBEXCUGKYKO-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical class NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003334 secondary amides Chemical class 0.000 description 2
- 230000002889 sympathetic effect Effects 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- FBPVUBVZRPURIU-UHFFFAOYSA-N 1-hexylpyrrole-2,5-dione Chemical compound CCCCCCN1C(=O)C=CC1=O FBPVUBVZRPURIU-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
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-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
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 description 1
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 1
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-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
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- AXGOOCLYBPQWNG-UHFFFAOYSA-N 3-ethylfuran-2,5-dione Chemical compound CCC1=CC(=O)OC1=O AXGOOCLYBPQWNG-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- QZYCWJVSPFQUQC-UHFFFAOYSA-N 3-phenylfuran-2,5-dione Chemical compound O=C1OC(=O)C(C=2C=CC=CC=2)=C1 QZYCWJVSPFQUQC-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-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
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-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
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
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Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- 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81槻的特性、成型性および成型品の外観に優
れた熱可辺性樹詣耕成物に関する.更に詳しくは、ポリ
アミドと特定のマレイミド系共重合体とからなる、ポリ
アミドの吸湿性、耐熱性および成型加工性が改善された
、 しかも外観の優れた成型品を与える熱川私性樹脂!
6J1成物に関する.
〔従来の技術コ
ポリアミドは機械的特性、耐薬品性、耐摩耗性、電気的
特性等の性質に優れている反面、耐衝撃性(ノッチ付)
、耐熱性が低く、また、成型収縮率が大きく、成型品に
ヒケ、ソリ等の不具合が発生しやすい欠点を有している
.更に、吸湿性が高いため、成型加工時に成型品外観の
不良■1象が発生しやすいばかりでなく、成型品の寸法
あるいは形状の変化が大きく、成型品の機械的特性も変
化しやすいことが知られている.また、溶融樹脂の粘度
が低く、射出成型時に成型機のノズルから溶融樹脂が糸
を引くように流れ出すドルーイング■1象が起き易く、
成型操作が煩雑となる欠点を有している.
ポリアミドのこのような欠点を改良する目的で、ポリア
ミドに種々の高分子物質を混合あるいは反応させる試み
が行われてきた.例えば、ボリスチレンあるいはスチレ
ンーアクリロニトリル共重合体等のスチレン系樹脂を溶
融混合することが行われたが(特公昭3B−23476
号、同40−7380号、米国特許第3、243、47
8号、同3、 243、479号、西ドイツ公開特許第
2、403、8894!i、これら(Dm脂はポリアミ
ドとの相容性に劣るため、得られた紐成物からなる成型
品に層状の剥離現象が観察され、機械的性質にも劣って
いた.また、ポリアミドにスチレンと不飽和ジカルボン
酸無水物単量体との共重合体を混合する試みがなされた
が(特開昭56−50931号)、得られた組成物は熱
安定性に乏しかった.相容性の改善を目的として、スチ
レンと不飽和ジカルボン酸無水物単量体との共重合体を
スチレン系樹脂とポリアミドとの相容化剤として使用し
た、三成分からなる組成物が知られているが(特開昭6
0−195157号)、得られた組成物は相容性、熱安
定性の改良は果たされているものの、その効果は不十分
であった.不飽和ジカルボン酸のイミド化合物を含む共
重合体とポリアミドとを?a融混合して製造される、両
高分子鎖が結合した共1合体が知られているが(特開昭
57−577 19号、同57−141426号)、得
られた共重合体の性質は溶@混合機による製造条件の杉
響を受け易く、工業的に不利を来した.更には、゛得ら
れた共重合体のFj4p,性、耐衝撃性は必ずしも十分
ではなかった.不飽和ジカルボン酸無水物単量体と芳香
族ビニル共盪合体とポリアミドと変性ポリオレフィンか
らなる組成物も知られているが(特開昭+31−171
751号)、これらは耐熱性、熱安定性において不十分
である.この改良として、マレイミド系単量体の共重合
体とポリアミドおよび変性ポリオレフィンからなる三成
分系の組成物が知られているが(特開昭62−5964
7号、同62−179546号)、得られた組成物から
なる成型品はゲー1・近傍の表面に不良現象が認められ
、屠剥寓霞性があり、衝撃{直、伸び、剛性などのバラ
ンスの点で不十分であった.[発明が解決しようとする
問題点]
以上のように、ボリアミとの諸特性を改良する試みは数
多くなされてきたが、その効果はいずれも実用上不十分
であった.
本発明の意図するところは、耐熱性、耐衝撃性が良好で
、伸び、剛性などのバランスが良好で、 しかも美刑な
外観を与えるポリアミド系樹脂絹成物を提供することに
ある.
[問題点を解決するための手段]
即ち本発明では芳香族ビニル単量体基30〜70モル%
、マレイミド系単量体基30〜50モル%、不飽和ジカ
ルボン酸無水物単量体基3〜20モル%およびアクリル
系単量体基0〜50モル%からなるマレイミド系共道合
体10〜50ffi量%とポリアミド40〜80重量%
、不飽和ジカルボンII1!2無水物単量体基および/
または不飽和カルボン酸単量体基0. 1〜10ff
lffi%で変性された変性ポリオレフィン系重合体3
〜40重量%からなる却成物であり、マレイミド系共重
合体が分散粒子を形成する■成物であり、当該分散粒子
の粒子径が0.01〜L Oミクロンであることを特
徴とする熱可塑性樹脂紐成物にあっては、 得られたM
1成物は耐衝撃性、伸び、剛性、fA熱性などのバラン
スが良好で、成型加工性シこ侵れ、吸湿性が低く、しか
もその成型品は美麗な外観を与えることを見いだした.
更に本発明では、変性ポリオレフィン系重合体も分散粒
子として、数μ以下の独立した不定形で、ほぼ均一に分
散している事が好ましい.本発明で用いるマレイミド系
共重合体の製造方法については特に制限はなく、例えば
芳香族ビニル単量体、マレイミド系単量体、不飽和ジカ
ルボン酸無水物単量体およびアクリル系単量体のラジカ
ル共重合により製造することができる.
芳香族ビニル単量体の具体例としては、スチレン、α−
メチルスチレン、ビニルトルエン、t−プチルスチレン
等があり、マレイミド系単量体の具体例としては、マレ
イミド、N−メチルマレイミド、N一エチルマレイミド
、N−プロビルマレイミド、N−へキシルマレイミド、
N−シクロヘキシルマレイミド、N−フエニルマレイミ
ド、N−1リルマレイミド等があり、不飽和ジカルボン
酸無水物単量体の具体例としては、無水マレイン酸、無
水メチルマレイン酸、無水1,2−ジメチルマレイン酸
、無水エチルマレイン酸、無水フエニルマレイン酸等が
あり、アクリル系単量体の具体例としては、メチル(メ
タ)アクリレート、エチル(メタ)アクリレート、ブチ
ル(メタ)アクリレート、ヘキシル(メタ)アクリレー
ト、シクロヘキシル(メタ)アクリレート、デシル(メ
タ)アクリレート、オクタデシル(メタ)アクリレート
、 ヒドロキシエチル(メタ)アクリレート、 メトキ
シエチル(メタ)アクリレート、グリシジル(メタ)ア
クリレート等があり、これらを単独で、あるいは併用し
て用いることができる.ただし、ここでメチル(メタ)
アクリレートとはメチルアクリレートあるいはメチルメ
タクリレートを示すものとする.
これらの単同体の共重合方法については特に制限はなく
、公知のラジカル共重合方法を任意に採用できる.
本発明で用いるマレイミド系共重合体を製造する他の方
法として、芳香族ビニル単量体、不飽和ジカルボン酸無
水物単量体およびアクリル系単量体の井盾合体をアンモ
ニアあるいは第一級アミンと反応させて酸無水物基をイ
ミド化する方法を例示することができる.′ifIJ分
子鎖中に酸無水物基を有する高分子物質とアミン化合物
とのイミド化反応は公知であり、例えば、特公昭6 1
−26938号あるいは同82−8456号に間示され
ている方法に従って、高分子物質とアミン化合物とを反
応させて、目的とするイミド基を有するマレイミド系共
重合体を製造することができる.
イミド化反応に用いられる第一級アミンを例示すると、
メチルアミン、エチルアミン、プロビルアミン、ブチル
アミン、ヘキシルアミン、シクロヘキシルアミン、デシ
ルアミン、アニリン、 トルイジン、ナフチルアミン、
クロロフェニルアミン、ジクロ口フエニルアミン、プロ
モフエニルアミン、ジブロモフェニルアミン等があ る
.
イミド化反応は、オートクレープを用いて溶液状態、塊
状溶融状態あるいは懸濁状態で反応を行うことができる
.また、スクリュー押出機等の溶融混練Vi置を用いて
、溶融状態で反応を行うことも可能である.
溶液反応に用いられる溶媒は任意であり、例えば、アセ
トン、メチルエチルケトン、メチルイソブチルケトン、
シクロヘキサノン等のケトン類、テトラヒド口フラン
、1. 4−ジオキサン等のエーテル類、 トルエン
、キシレン等の芳香族炭化水素、ジメチルホルムアミド
、ジメチルスルホキシド、N−メチル−2−ビロリドン
等が例示される.
イミド化の反応温度は50〜350℃の仰囲が好ましく
、 100〜300℃の範囲が特に好ましい.
イミド化反応は触媒の存在を必ずしも必要としないが、
用いるならばトリメチルアミン、 トノエチルアミン、
トリブチルアミン、 N, N一ジメチルアニリン
、 N, N−ゾエチルアニリン等の第三級アミンが
好適である.
本発明で用いられるマレイミド系共重合体は、芳香族ビ
ニル単量体基30〜70モル%、マレイミド系単量体基
30〜50モル%、不飽和ジカルボン酸無水物単量体基
3〜20モル%およびアクリル系単量体基0〜50モル
%からなる.更に好ましい範囲は、芳香族ビニル単量体
基50〜60モル%、マレイミド系単量体基40〜50
モル%、不飽和ジカルボン酸無水物単量体基3〜10モ
ル%およびアクリル系単量体基0〜30モル%である.
芳香族ビニル単量体基が30モル%未満では、均質な絹
成を有する重合体を工業的に再現性よく製造することが
困難であり、当該マレイミド系共重合体をポリアミドと
混合して得られた絹成物の熱安定性、成型加工性、機槻
的強度等の性質が劣る.また、芳香族ビニルQlffi
体基が70モル%を越えるか、あるいはマレイミド系単
量体基が30モル%未溝であると得られた組成物の耐舶
性が劣り、マレイミド系単量体基が50モル%を越える
と得ろれた組成物の成型加工性が劣る.不飽和ジカルボ
ン酸無水物単量体基が3モル%未満であるとポリアミド
と混合して得られた朝成物の相容性が不良で、マレイミ
ド系共重合体分散粒子の粒子径が大きくなり、機槻的強
度が劣り、しかも当該朝成物の成型物に剥離現象が観察
される.また、不飽和ジカルボン酸無水物単量体基が2
0モル%を越えると当該紐成物のマレイミド系共重合体
分散粒子の粒子径が小さくなりすぎ、成型加工性が劣り
、また成型物の熱安定性が不良となり、表面が鮫肌状に
荒れることもある.本発明で用いられるポリアミドは特
に制限はなく、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
ルボン酸あるいは環状ラクタム類から得られるポリアミ
ド等であってよいが、具体例を挙げるとナイロン6、ナ
イロン6・6、ナイロン6l9、ナイロン6ゆ10、ナ
イロン6●12、ナイロン4争6、ナイロン11、ナイ
ロン12等の脂肪族ポリアミド、ポリ(ヘキサメテレン
テレフタラミド)、ボリ(ヘキサメチレンイソフタラミ
ド〉、ポリ(m−キシリレンアジバミド)等の芳香族環
を含むポリアミド等があり、これらを単独で、あるいは
併用して用いることができる.
本発明では、マレイミド系共重合体10〜50Mf!L
%とポリアミド40〜801i量%と変性ポリオレフィ
ン系重合体3〜40Il量%を混合して絹成物とするが
、マレイミド系共重合体が10fft量%未溝あるいは
ポリアミドが80ffi量%を越えて夷よ、得られた組
成物の耐熱性、成型加工性あるいは吸湿性の改良程度が
不十分であり、71ノイミド系共重合体が50重量%を
越えるか、あるいはポリアミドが4011ffi%未満
であっては当該絽成物の機械的強度、耐薬品性あるいは
耐摩耗性が劣る.
また、変性ポリオレフィン系重合体が3重量%未溝では
耐衡U値の改良効果が低く、40I1量%以上では剛性
の低下が大きすぎる.本発明で使用される変性ポリオレ
フィン系瓜合体は不飽和ジカルボン酸無水物単量体およ
び/または不飽和カルボン酸単量体により変性された変
性ポリオレフィン系重合体で、好ましくはゴム状弾性を
有する争
変性ポリオレフィン系重合体とは、オレフィン単量体の
1合体あるいは共i1i 合体の変性物を指し、用いら
れるオレフィン単量体の具体例としては、エチレン、ブ
ロビレン、 1−ブテン、イソブチレン、 2−ブテン
、シクロブテム 3一メチル−1−ブテン、4−メチル
ーI−ブテン、4−メチル−1−ペンテン、シクロベン
テン、1−ヘキセン、シクロヘキセン、 1−オクテン
、1−デセン、 1−ドデセン等がある。 また、当該
変性ポリオレフィン系重合体は必要に応じて、4−エチ
リデンノルボルネン、ジシクロペンタジェン等の非共役
ジェン11!. ffi体、マレイミド系共道合体を構
成しろる共扉合性単量体として既に例示ざれているアク
リル系単量体等が、ゴム吠弾性を示す範囲で共重合され
ていてよい。好ましい組成範囲を例示するならば、 エ
チレン20〜90モル%、α−オレフィン単量体10〜
80モル%およびその他の単量体O〜10モル%であり
、エチレン含有率が50〜86モル%であることが特に
好ましい.また、これら変性ポリオレフィン系重合体の
Tgは−10℃以下、特に好ましくは−30℃以下であ
る.変性ポリオレフィン系重合体を組成する不飽和ジカ
ルボン酸無水物単量体はマレイミド系共重合体を構成し
ろる単量体として既に例示されたものを使用できるが、
無水マレイン酸が特に好ましく、不飽和カルボン酸単量
体はアクリル酸、メタクリル酸等がある.
変性ポリオレフィン系重合体中の不飽和ジカルボン酸無
水物単量体基あるいは不飽和カルボン酸基の含有率は0
. 1〜101tffi%が好ましく、 0.1〜5
B!量%が特に好ましいが、 0.1mft%未満であ
っては得られた組成物の機械的強度が不十分であり、成
型品に屡状の剥離現象が観察されることがあり、 10
1L量%を越えると機械的強度あるいは熱安定性を損な
うことがある.
本発明でいう変性とは、ポリオレフィン系重合体の主鎖
あるいはI4鎖に変性に用いられた単量体基、例えば、
無水マレイン酸基が存在することを示しており、ランダ
ム共重合、グラフトm合等の公知技術で変性を行なうこ
とができる.変性方法は特に制限はなく、例えば、特公
昭39−6810号、特公昭52−43877号、特公
昭53−57 1 6号、特公昭56−9925号、特
公昭5B−445号等に開示された方法に従フて変性を
行うことができる.また、主鎖への導入よりグラフト体
として変性をしてあるものが、低温衝撃値などの点で好
ましい.更に、未反応の単量体残量は0.5ffif1
%以下少ない程好ましい.
変性ポリオレフィン系1合体の分子量は特に制限はない
が、耐衝撃性、成型性のバランスから5万〜50万、特
に好ましくは10万〜30万のものが好ましい.
市販のこれら変性ボリ才レフィン系重合体としては、タ
フマーM P O 8 2 0 (三井石油化学〉が
ある.
本発明の絹成物でよ、マレイミド系共重合体が分散粒子
を形成しハ しかも当該分散粒子の粒子径が0.01〜
1.0ミクロンであることが必要である.特に好ましい
粒子径は0.04〜飢 5ミクロンである.更に好まし
くは0.05〜0.3ミクロンである.ただし分散粒子
の粒子径は、ヒドラジンー水和物で処理した後にオスミ
ック酸で染色した試料から切削された超薄切片を透過型
電子顕微鎮で観察し゛C測定した値である.分散粒子径
が0.01ミクロン未満であると、ポリアミドと混合し
て得られた紐成物の溶融粘度が高く、成型物表面に鮫肌
状の不良現象が発生する。分散粒子径が1.0ミクロン
を越えると、当該組成物の機械的強度が劣る.また、変
性ポリオレフィン系重合体に間しても分散粒子を形成し
、独立した不定形で、ほぼ均一に分散していることが望
ましい.
本発明者らの知見によれば、同一のポリアミドを同量用
いる場合、当該絹成物中の分散泣子径を決定する因子と
して特にffl要であるものは、マレイミド系共重合体
中の不飽和ジカルボン酸無水物単量体基の含有率であり
、含有率が低い場合には粒子径は大きく、含有率が高い
場合には粒子径は小さくなる.また、変性ポリオレフィ
ン系重合体中の有機酸基の含有量も同様に重要であり、
イミド化樹脂共逍合体中の不飽和ジカルボン酸無水物単
量体基と同様の効果を示す.本発明の組成物は、有儂酸
金属塩および/または脂肪酸アミド化合物を含有するこ
とが好ましい.これらの化合物を含有すると得られた糾
成物の衝撃強度が向上する利点がある.本発明で用いら
れる有機酸金属塩とは、ラウリル酸、ミリスチル酸、バ
ルミチン酸、ステアノン故、ベヘニン酸、オレイン酸、
リノール故、リシノール酸、 ヒドロキシステアリン酸
等の脂肪酸、フタル酸等の芳香属カルボン酸と、ナ1リ
ウム、カリウム、 リチウム、マグネシウム、カルシウ
ム、ストロンチウム、バリウム、亜鉛.カドミウム、ア
ルミニウム、スズ、鉛等の金属との塩である.マグネシ
ウム、カルシウム、バリウム、亜鉛など、2価の金属塩
が好ましい.また、脂肪酸アミドとは、前記の脂肪酸の
第一アミド、第ニアミドであり、第ニアミドは、メチレ
ンビスステアリルアミド、エチレンビスステアリルアミ
ド等のビスアミドであってもよい.
本発明の朝成物中の有機酸金属塩および/または脂肪酸
アミドの含有率は0.01−5重量%、好ましくは0.
05〜2m量%の範囲で、更に好ましくは0.2〜1重
量%である.0.Ol重量%未溝であっては添加効果が
認められず、5!量%を越えると耐熱性、剛性等の性質
が低下、衝撃値の改良効果も小さいことがある.特に好
ましくは、これら有機酸金属塩と脂肪酸アミドの併用に
あり、有機酸金属塩と脂肪酸アミドの使用量は、前記添
加量内なら比率に特にこだわらないが、 1:l付近が
好ましい.また、酸化防止剤を含有することも可能であ
り・ フェノール系酸化防止剤の使用が変色などから好
ましい.フェノール系酸化防止剤として、オクタデシル
−3−(3.5−ジーt−ブチルー4−ヒドロキシフエ
ニル)プロビオネート(例えば、イルガノックス107
6)、N−N’へキサメチレンビス(3.6−ジーt−
ブチルー4−ヒドロキシシンナムアミド(例えば、イル
ガノックス1098)、 3.5−ジーt−ブチルー4
−ヒドロキシトルエン、2・2′−メチレンビスー(4
−メチル−6−t−プチルフェノール)、4・4′−メ
チレンビス(2・6ージーt−プチルフェノール)、4
◆4′−プチリデンビス−6−t−ブチルーm−クレゾ
ール、2・6−ビス(2’ −ヒドロキシ−3′t−ブ
チルー6′−メチルベンジル)−4−メチルフェノール
、 1・1・3−トリス(2’メチル−5’−t−ブチ
ルー4′−ヒドロキシフエニル)ブタン、 1・3・5
−トリメチルー2・4・6−トリス(3’ ・6゜−
ジーt−ブf− ル− 4 ’−ヒドロキシベンジル)
ベンゼン、4・4′−チオビス(2′−メチル−6’−
t−プチルフェノール)、2・2′−チオビス(4′−
メチル−6′一t−プチルフェノール)、4●4′−チ
オビス(3−メチル−6−t−プチルフェノール)、
1−1 1弓−テトラキス(メチル−3−(3.5−
ジーt−ブチルー4−ヒドロキシフエニル)プロビオネ
ート〕メタン、2・2′−チオジエチルビスー〔3−(
:3・5−ジーt−ブチルー4−ヒドロキシフエニル)
一ブロビオネート〕、N−ラウロイルーp−7ミノフェ
ノールおよびN−ステアロイルーp−アミノフェノール
などがあり、一般ナイロン用とオレフィン用を組合わせ
て使用したほうが好ましい. また、■キレート系のナ
,イロン川酸化防1ヒ剤の使用ももちろん可能である.
その他の要因として、分散粒子径はマレイミド系共重合
体とポリアミド、変性ポリオレフィン系重合体どの混合
方法にも依存する.マレイミド系共重合体とポリアミド
、変性ポリオレフィン系重合体の混合は、通常の溶融混
練装置を用いて行うことができるが、好適に使用できる
溶融混練装置としては、スクリュー押出機、バンバリー
ミキサー コニーダー 混合ロール等がある.
本発明の結成物は、用途に応じて他の添加剤あるいは改
質剤を加えて組成物とすることが可能であり、具体的に
は、ガラス繊維、カーボン繊維、アラミド繊維等の補強
繊維、タルク、シリカ、クレー マイカ、炭酸カルシウ
ム等の充填材、紫外線吸収剤、難燃剤、滑剤、着色剤等
がある.
[実施例]
以下に実施例をあげて本発明を更に詳細に説明するが、
実施例および比較例で用いた部お上び%はすべてffL
量基準である.また、これらはいずれも例示的なもので
あって、本発明の内容を限定するものではない.
尚、各種性質の測定方法は次の通りである.紐成物中の
分散粒子径: 予めトリミングした試料をヒドラジンー
水和物中に漫濱して、60℃で48時間放置した.水洗
後、この試料を1%才スミック酸水溶液中に浸漬し、室
温で24時間放置して染色した.染色した試料から超薄
切片を切り出し、透過型電子顕微鏡写真を撮影した.得
られた画像を解析して粒子径を求めた.耐熱性: A
STM D−648に従い、厚さ1/4#の射出成型
品を用いて、荷ffl18.6J/am2で加熱変形温
度( H D T )を測定した.くアニールなし)
衝撃強度: ASTM D−256に従い、厚さ1
/4#の剥出成型品によりノツチ付きアイゾ・ントを測
定した.雰囲気温度は23℃.流動性: ASTM
D−1238に準拠して、温度265℃、荷I!tl
okgでメルトフローレートを測定した.
外観: 5オンス射出成型機で裏面にボス、リブを有し
、かつ開口部を有する成型品を成型して成型品の外観を
目視判定した.成型温度は260℃.
(1)ポリアミド(B)
i’a Ta fi1合法によって得られた次のナイロ
ン6、ナイロン12、ナイロン66を使用.
b−1) ナイロン6: ε一カブロラクタムから得
られた瀾硫酸相対粘度2.65のナイロン6。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic tree-cultivated product that has excellent properties, moldability, and appearance of molded products. More specifically, Atagawa's proprietary resin is made of polyamide and a specific maleimide copolymer, and has improved hygroscopicity, heat resistance, and moldability of polyamide, and also provides molded products with excellent appearance!
Regarding the 6J1 product. [Conventional technology Copolyamides have excellent properties such as mechanical properties, chemical resistance, abrasion resistance, and electrical properties, but have poor impact resistance (notched)
, they have low heat resistance, high molding shrinkage, and are prone to problems such as sink marks and warpage in molded products. Furthermore, due to its high hygroscopicity, it not only tends to cause defects in the appearance of the molded product during the molding process, but also tends to cause large changes in the dimensions or shape of the molded product, as well as the mechanical properties of the molded product. Are known. In addition, the viscosity of the molten resin is low, and during injection molding, molten resin tends to flow out of the nozzle of the molding machine as if pulling a string, which is likely to occur.
The disadvantage is that the molding operation is complicated. In order to improve these drawbacks of polyamide, attempts have been made to mix or react various polymeric substances with polyamide. For example, styrene resins such as polystyrene or styrene-acrylonitrile copolymers were melt-blended (Japanese Patent Publication No. 3B-23476).
No. 40-7380, U.S. Patent No. 3,243,47
No. 8, No. 3, 243, 479, West German Published Patent No. 2, 403, 8894! i. These (Dm resins) have poor compatibility with polyamide, so a layered peeling phenomenon was observed in the molded product made from the obtained string composite, and the mechanical properties were also poor. An attempt was made to mix a copolymer of 100% and an unsaturated dicarboxylic anhydride monomer (JP-A-56-50931), but the resulting composition had poor thermal stability. For the purpose of improvement, a three-component composition is known in which a copolymer of styrene and an unsaturated dicarboxylic anhydride monomer is used as a compatibilizer between the styrenic resin and polyamide ( Tokukai Showa 6
No. 0-195157), the resulting composition was improved in compatibility and thermal stability, but its effects were insufficient. A copolymer containing an imide compound of unsaturated dicarboxylic acid and polyamide? A copolymer in which both polymer chains are bonded is known (Japanese Patent Application Laid-Open Nos. 57-577-19 and 57-141-426), which is produced by fusion mixing, but the properties of the obtained copolymer are was susceptible to the effects of manufacturing conditions using a melting machine and a mixer, which was an industrial disadvantage. Furthermore, the Fj4p properties and impact resistance of the obtained copolymer were not necessarily sufficient. A composition comprising an unsaturated dicarboxylic anhydride monomer, an aromatic vinyl copolymer, a polyamide, and a modified polyolefin is also known (Japanese Patent Application Laid-Open No. 2003-31-171).
No. 751), these are insufficient in heat resistance and thermal stability. As an improvement on this, a three-component composition consisting of a copolymer of a maleimide monomer, a polyamide, and a modified polyolefin is known (Japanese Patent Laid-Open No. 62-5964
No. 7, No. 62-179546), and the molded product made from the obtained composition showed defective phenomena on the surface in the vicinity of the gate, had peeling and hazy properties, and had poor impact properties such as straightness, elongation, and rigidity. It was inadequate in terms of balance. [Problems to be Solved by the Invention] As mentioned above, many attempts have been made to improve the various properties of polyamide, but the effects have not been sufficient for practical use. The purpose of the present invention is to provide a polyamide-based resin silk composition that has good heat resistance and impact resistance, a good balance of elongation and rigidity, and has a beautiful appearance. [Means for solving the problem] That is, in the present invention, 30 to 70 mol% of aromatic vinyl monomer groups
, 10 to 50 ffi, a maleimide co-modal polymer consisting of 30 to 50 mol% of maleimide monomer groups, 3 to 20 mol% of unsaturated dicarboxylic anhydride monomer groups, and 0 to 50 mol% of acrylic monomer groups Weight% and polyamide 40-80% by weight
, unsaturated dicarbon II1!2 anhydride monomer group and/
or unsaturated carboxylic acid monomer group 0. 1~10ff
Modified polyolefin polymer 3 modified with lffi%
-40% by weight, a composition in which a maleimide copolymer forms dispersed particles, characterized in that the particle size of the dispersed particles is 0.01 to LO microns. In the case of thermoplastic resin string composites, the obtained M
It has been found that the first product has a good balance of impact resistance, elongation, rigidity, fA thermal properties, etc., has low moldability and low moisture absorption, and gives molded products with a beautiful appearance.
Furthermore, in the present invention, it is preferable that the modified polyolefin polymer is also dispersed as dispersed particles in independent amorphous shapes of several microns or less and substantially uniformly dispersed. There are no particular limitations on the method for producing the maleimide copolymer used in the present invention, and for example, radicals of aromatic vinyl monomers, maleimide monomers, unsaturated dicarboxylic acid anhydride monomers, and acrylic monomers are used. It can be produced by copolymerization. Specific examples of aromatic vinyl monomers include styrene, α-
Examples of maleimide monomers include methylstyrene, vinyltoluene, t-butylstyrene, etc., and specific examples of maleimide monomers include maleimide, N-methylmaleimide, N-ethylmaleimide, N-probylmaleimide, N-hexylmaleimide,
Examples of unsaturated dicarboxylic anhydride monomers include N-cyclohexylmaleimide, N-phenylmaleimide, and N-1lylmaleimide. Specific examples of unsaturated dicarboxylic anhydride monomers include maleic anhydride, methylmaleic anhydride, and 1,2-dimethyl anhydride. Maleic acid, ethyl maleic anhydride, phenyl maleic anhydride, etc. Specific examples of acrylic monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, etc. Acrylate, cyclohexyl (meth)acrylate, decyl (meth)acrylate, octadecyl (meth)acrylate, hydroxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, glycidyl (meth)acrylate, etc., and these can be used alone or in combination. It can be used as However, here methyl (meta)
Acrylate refers to methyl acrylate or methyl methacrylate. There are no particular restrictions on the method of copolymerizing these monomers, and any known radical copolymerization method can be employed. Another method for producing the maleimide copolymer used in the present invention is to combine an aromatic vinyl monomer, an unsaturated dicarboxylic anhydride monomer, and an acrylic monomer with ammonia or a primary amine. An example of a method for imidizing an acid anhydride group by reacting with The imidization reaction between a polymeric substance having an acid anhydride group in its molecular chain and an amine compound is well known, for example, as described in Japanese Patent Publication No. 61, No.
According to the method disclosed in No. 26938 or No. 82-8456, a desired maleimide copolymer having an imide group can be produced by reacting a polymeric substance with an amine compound. Examples of primary amines used in imidization reactions are:
Methylamine, ethylamine, probylamine, butylamine, hexylamine, cyclohexylamine, decylamine, aniline, toluidine, naphthylamine,
These include chlorophenylamine, dichlorophenylamine, promophenylamine, and dibromophenylamine. The imidization reaction can be carried out in a solution state, bulk molten state, or suspension state using an autoclave. It is also possible to carry out the reaction in a molten state using a melt kneading device such as a screw extruder. Any solvent can be used in the solution reaction, such as acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as cyclohexanone, tetrahydrofuran, 1. Examples include ethers such as 4-dioxane, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone. The reaction temperature for imidization is preferably in the range of 50 to 350°C, particularly preferably in the range of 100 to 300°C. Although the imidization reaction does not necessarily require the presence of a catalyst,
If used, trimethylamine, tonoethylamine,
Tertiary amines such as tributylamine, N,N-dimethylaniline, N,N-zoethylaniline and the like are preferred. The maleimide copolymer used in the present invention contains 30 to 70 mol% of aromatic vinyl monomer groups, 30 to 50 mol% of maleimide monomer groups, and 3 to 20 mol% of unsaturated dicarboxylic anhydride monomer groups. mol% and 0 to 50 mol% of acrylic monomer groups. More preferred ranges are 50 to 60 mol% of aromatic vinyl monomer groups and 40 to 50 mol% of maleimide monomer groups.
mol%, unsaturated dicarboxylic anhydride monomer groups 3 to 10 mol%, and acrylic monomer groups 0 to 30 mol%.
If the aromatic vinyl monomer group is less than 30 mol %, it is difficult to industrially produce a polymer having a homogeneous silk composition with good reproducibility, and it is difficult to produce a polymer having a homogeneous silk composition industrially, and it is difficult to produce a polymer having a homogeneous silk composition by mixing the maleimide copolymer with a polyamide. The resulting silk products have poor properties such as thermal stability, moldability, and mechanical strength. Also, aromatic vinyl Qlffi
If the body group exceeds 70 mol% or if the maleimide monomer group is ungrooved by 30 mol%, the resulting composition will have poor ship resistance, and if the maleimide monomer group exceeds 50 mol%. The moldability of the resulting composition is poor. If the unsaturated dicarboxylic acid anhydride monomer group is less than 3 mol%, the compatibility of the morning product obtained by mixing with the polyamide will be poor, and the particle size of the maleimide copolymer dispersed particles will increase. , mechanical strength is poor, and peeling phenomenon is observed in the molded product. In addition, the unsaturated dicarboxylic anhydride monomer group has 2
If it exceeds 0 mol%, the particle size of the maleimide-based copolymer-dispersed particles in the strand becomes too small, resulting in poor molding processability, poor thermal stability of the molded product, and the surface becoming rough like a shark's skin. There is also. The polyamide used in the present invention is not particularly limited, and may be a polyamide obtained from an aliphatic, aromatic or alicyclic dicarboxylic acid and a diamine, a polyamide obtained from an aminocarboxylic acid or a cyclic lactam, etc. Specific examples include aliphatic polyamides such as nylon 6, nylon 6/6, nylon 6l9, nylon 6-10, nylon 6*12, nylon 4-6, nylon 11, and nylon 12, and poly(hexamethylene terephthalamide). ), poly(hexamethylene isophthalamide), poly(m-xylylene adivamide), and other polyamides containing aromatic rings, and these can be used alone or in combination.In the present invention, Maleimide copolymer 10-50Mf!L
% polyamide, 40-801i weight %, and modified polyolefin polymer 3-40 l weight % are mixed to make a silk composition. Unfortunately, the degree of improvement in heat resistance, moldability, or moisture absorption of the obtained composition is insufficient, and the 71-neumide copolymer content exceeds 50% by weight, or the polyamide content is less than 4011ffi%. The mechanical strength, chemical resistance, and abrasion resistance of the cast material are poor. Furthermore, if the modified polyolefin polymer contains 3% by weight of the ungrooved material, the effect of improving the equilibrium U value is low, and if the modified polyolefin polymer contains 1% by weight or more of 40I, the decrease in rigidity is too large. The modified polyolefin polymer used in the present invention is a modified polyolefin polymer modified with an unsaturated dicarboxylic anhydride monomer and/or an unsaturated carboxylic acid monomer, and preferably has rubber-like elasticity. The modified polyolefin polymer refers to a modified product of monomer or co-i1i polymer of olefin monomers, and specific examples of the olefin monomers used include ethylene, brobylene, 1-butene, isobutylene, and 2-butene. , cyclobutem, 3-methyl-1-butene, 4-methyl-1-butene, 4-methyl-1-pentene, cyclobentene, 1-hexene, cyclohexene, 1-octene, 1-decene, 1-dodecene, and the like. In addition, the modified polyolefin polymer may be used as a non-conjugated polymer such as 4-ethylidenenorbornene, dicyclopentadiene, etc., if necessary. .. Acrylic monomers, etc., which have already been exemplified as the co-doplexing monomers constituting the ffi-form and the maleimide-based copolymer, may be copolymerized within a range that exhibits rubber elasticity. Examples of preferred composition ranges include: 20 to 90 mol% ethylene, 10 to 90 mol% α-olefin monomer
It is particularly preferable that the ethylene content is 80 mol% and other monomers O to 10 mol%, and the ethylene content is 50 to 86 mol%. Further, the Tg of these modified polyolefin polymers is -10°C or lower, particularly preferably -30°C or lower. As the unsaturated dicarboxylic acid anhydride monomer constituting the modified polyolefin polymer, those already exemplified as monomers constituting the maleimide copolymer can be used, but
Maleic anhydride is particularly preferred, and unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, and the like. The content of unsaturated dicarboxylic anhydride monomer groups or unsaturated carboxylic acid groups in the modified polyolefin polymer is 0.
.. 1 to 101 tffi% is preferable, and 0.1 to 5
B! % is particularly preferable, but if it is less than 0.1 mft%, the mechanical strength of the resulting composition will be insufficient, and a peeling phenomenon may often be observed in molded products.
If the amount exceeds 1L, mechanical strength or thermal stability may be impaired. Modification in the present invention refers to monomer groups used for modification to the main chain or I4 chain of the polyolefin polymer, for example,
This indicates the presence of maleic anhydride groups, and modification can be carried out using known techniques such as random copolymerization and graft polymerization. The modification method is not particularly limited, and is disclosed in, for example, Japanese Patent Publication No. 39-6810, Japanese Patent Publication No. 52-43877, Japanese Patent Publication No. 53-57-16, Japanese Patent Publication No. 56-9925, Japanese Patent Publication No. 5B-445, etc. The denaturation can be carried out according to the method described above. In addition, it is preferable to use a graft that has been modified as a graft rather than introduced into the main chain in terms of low-temperature impact value. Furthermore, the amount of unreacted monomer remaining is 0.5ffif1
% or less, the better. There is no particular restriction on the molecular weight of the modified polyolefin 1 combination, but it is preferably 50,000 to 500,000, particularly preferably 100,000 to 300,000, in view of the balance between impact resistance and moldability. Examples of commercially available modified polyolefin-based polymers include Tafmer MPO 820 (Mitsui Petrochemical). In the silk composition of the present invention, the maleimide-based copolymer forms dispersed particles, and The particle diameter of the dispersed particles is 0.01~
It must be 1.0 micron. A particularly preferred particle size is 0.04 to 5 microns. More preferably, it is 0.05 to 0.3 micron. However, the particle diameter of the dispersed particles is the value determined by C measurement by observing an ultrathin section cut from a sample treated with hydrazine hydrate and stained with osmic acid using a transmission electron microscope. If the dispersed particle size is less than 0.01 micron, the melt viscosity of the string composite obtained by mixing with polyamide will be high, and a shark-skinned defective phenomenon will occur on the surface of the molded product. If the dispersed particle size exceeds 1.0 micron, the mechanical strength of the composition will be poor. It is also desirable to form dispersed particles in the modified polyolefin polymer, which are independent, amorphous, and almost uniformly dispersed. According to the findings of the present inventors, when the same amount of the same polyamide is used, the factors that are particularly important for determining the diameter of dispersed lachrymal particles in the silk composition are those in the maleimide copolymer. It is the content of saturated dicarboxylic anhydride monomer groups; when the content is low, the particle size is large, and when the content is high, the particle size is small. In addition, the content of organic acid groups in the modified polyolefin polymer is equally important.
It exhibits the same effect as the unsaturated dicarboxylic anhydride monomer group in the imidized resin copolymer. The composition of the present invention preferably contains a metal acid salt and/or a fatty acid amide compound. Containing these compounds has the advantage of improving the impact strength of the resulting cake. The organic acid metal salts used in the present invention include lauric acid, myristylic acid, valmitic acid, steanone acid, behenic acid, oleic acid,
Because of linole, fatty acids such as ricinoleic acid and hydroxystearic acid, aromatic carboxylic acids such as phthalic acid, and sodium, potassium, lithium, magnesium, calcium, strontium, barium, and zinc. It is a salt with metals such as cadmium, aluminum, tin, and lead. Divalent metal salts such as magnesium, calcium, barium, and zinc are preferred. Further, the fatty acid amide is a primary amide or a secondary amide of the aforementioned fatty acid, and the secondary amide may be a bisamide such as methylene bisstearylamide or ethylene bisstearylamide. The content of organic acid metal salt and/or fatty acid amide in the morning preparation of the present invention is 0.01-5% by weight, preferably 0.01-5% by weight.
The content is in the range of 0.05 to 2% by weight, more preferably 0.2 to 1% by weight. 0. No effect of addition was observed when the Ol weight% was not grooved, and 5! If the amount exceeds %, properties such as heat resistance and rigidity may deteriorate, and the effect of improving impact value may be small. Particularly preferably, these organic acid metal salts and fatty acid amide are used in combination, and the ratio of the organic acid metal salt and fatty acid amide to be used is not particularly limited as long as it is within the above-mentioned amounts, but it is preferably around 1:l. It is also possible to contain antioxidants, and the use of phenolic antioxidants is preferable because of discoloration. As a phenolic antioxidant, octadecyl-3-(3.5-di-t-butyl-4-hydroxyphenyl)probionate (for example, Irganox 107
6), N-N'hexamethylenebis(3.6-di-t-
Butyl-4-hydroxycinnamamide (e.g. Irganox 1098), 3,5-di-t-butyl-4
-Hydroxytoluene, 2,2'-methylenebis(4
-methyl-6-t-butylphenol), 4,4'-methylenebis(2,6-di-t-butylphenol), 4
◆4'-butylidenebis-6-t-butyl-m-cresol, 2,6-bis(2'-hydroxy-3't-butyl-6'-methylbenzyl)-4-methylphenol, 1,1,3-tris (2'methyl-5'-t-butyl-4'-hydroxyphenyl)butane, 1, 3, 5
-trimethyl-2,4,6-tris(3' 6゜-
(di-t-b-f-ru-4'-hydroxybenzyl)
Benzene, 4,4'-thiobis(2'-methyl-6'-
t-butylphenol), 2,2'-thiobis(4'-
Methyl-6'-t-butylphenol), 4●4'-thiobis(3-methyl-6-t-butylphenol),
1-1 1-tetrakis(methyl-3-(3.5-
di-t-butyl-4-hydroxyphenyl)probionate]methane, 2,2'-thiodiethylbis[3-(
:3,5-di-t-butyl-4-hydroxyphenyl)
monobrobionate], N-lauroyl p-7 mininophenol, and N-stearoyl p-aminophenol, and it is preferable to use a combination of those for general nylon and for olefin. In addition, it is of course also possible to use chelate-based antioxidants.
Another factor is that the dispersed particle size depends on the mixing method of the maleimide copolymer, polyamide, and modified polyolefin polymer. The maleimide copolymer, polyamide, and modified polyolefin polymer can be mixed using a normal melt kneading device, but suitable melt kneading devices include a screw extruder, a Banbury mixer, a co-kneader, and a mixing roll. etc. The composition of the present invention can be made into a composition by adding other additives or modifiers depending on the purpose. Specifically, reinforcing fibers such as glass fibers, carbon fibers, aramid fibers, etc. These include fillers such as talc, silica, clay mica, and calcium carbonate, ultraviolet absorbers, flame retardants, lubricants, and colorants. [Example] The present invention will be explained in more detail with reference to Examples below.
All parts and percentages used in Examples and Comparative Examples are ffL.
It is based on quantity. Furthermore, these are merely illustrative and do not limit the content of the present invention. The methods for measuring various properties are as follows. Dispersed particle size in the composite: A pre-trimmed sample was mixed in hydrazine hydrate and left at 60°C for 48 hours. After washing with water, this sample was immersed in a 1% aqueous Sumic acid solution and left at room temperature for 24 hours for staining. Ultrathin sections were cut from the stained samples and transmission electron micrographs were taken. The obtained images were analyzed to determine the particle size. Heat resistance: A
In accordance with STM D-648, the heat distortion temperature (H DT ) was measured using an injection molded product with a thickness of 1/4# at a load of 18.6 J/am2. Impact strength: According to ASTM D-256, thickness 1
/4# extrusion molded product was used to measure the notched iso-to. The ambient temperature is 23℃. Fluidity: ASTM
According to D-1238, temperature 265°C, load I! tl
The melt flow rate was measured using okg. Appearance: A molded product with bosses, ribs, and openings on the back side was molded using a 5-ounce injection molding machine, and the appearance of the molded product was visually evaluated. Molding temperature is 260℃. (1) Polyamide (B) The following nylon 6, nylon 12, and nylon 66 obtained by the i'a Ta fi 1 method were used. b-1) Nylon 6: Nylon 6 obtained from ε-cabrolactam with a sulfuric acid relative viscosity of 2.65.
b−2)ナイロン12;12−アミノドデカン酸から得
られた[[相対粘度2.40のナイロン12。b-2) Nylon 12; Nylon 12 obtained from 12-aminododecanoic acid with a relative viscosity of 2.40.
b−3)ナイロン66; ヘキサメチレンジアミンと
アジビン酸の等モル塩から得られた講硫酸相対粘度2.
55のナイロン66,(2)マレイミド系共重合体(
A)
マレイミド系共重合体は、攪拌器を{l1逢たオートク
レープ中にスチレン100部を仕込み、系内を望素ガス
で置換した後、温度80℃に加熱した.これに、無水マ
レイン酸67部、ペンゾインパーオキサイド0.2部を
メチルエチルケトン300部に溶解した溶液を8詩間で
添加した.添加後、更に4時間温廣を80℃に保つた.
上記共重合体に対し、 トリエチルアミン1.2部、ア
ニリン38. 1部を加え、 130℃で7時間反応を
行なった.反応溶液を室温まで冷却し、激しく攪拌した
メタノール300部に注ぎ、ろ別後92煙し、マレイミ
ド系共工合体くa一3)を得た.他のマレイミド系共重
合体も同様に作成した.これらを表−1に示す.(3)
変性ポリオレフィン系重合体
エチレン含量80モル%のエチレン参α−才レフィン共
重合体ベレッ}10kg、粉末状の無水マレイン!12
0g、2ψ5−ジメチルー2シェルミキサーに仕込み、
5分間攪拌して均一にブレンドし、これを40lφ押出
機(窒業を流通、L/T−28、ダルメージ型)にて、
ペレット状とする.シリンダー温度は、重合体温度が2
40℃になるように調節して、グラフト反応物(c−3
)を得た(無水マレイン酸の共重合体への導入量は0.
9!fit%).他の変性ポリオレフィン系重合体も同
様に作成した.これらを表−2に示す.
実施例−1〜1日および比較例−1〜5前記のナイロン
−6(b−1)10kgに、ステアリン酸バリウム0.
05ffi量%を2OLヘンシェルにてブレンドし、4
0Bφ1甲出機ζこて240゜Cで押出し、ベレット化
した物を560kg、20!ヘンシェルに投入、エチレ
ンビスステアリルアマイド0.5ffl重%をブレンド
後、マレイミド系共重合樹脂(a−2)3. 5kg
.変性ボリ才レフィン系重合体(c−3)1.5kg,
酸化防止剤(オクタデシル−3−(3・5ージーt
−ブチル)一ヒドロキシフェニルーブOヒt ネ− ト
0. 2 51fLm%オヨUN−N ’へキサメチ
レンビス(3・5−ジーし−ブチル)一ヒドロキシーヒ
ド口シンナマミド0.5ffiffi%)を投入、ブレ
ンド後、CTM(神戸製鋼社製)付40−φ押出機にて
290℃で押出し、べLノット化した.得られた組成物
中のマレイミド系共重合体の分散粒子径は、0.17t
rnであった.また、変.性ポリオレフィン系重合体の
分散粒子の状態も良好である.このペレットな使用し射
出成形機により、物性測定用の試験型を作成、各種物性
等を測定した.結果は表に示す.同様に、実施例−2〜
15、比較例−1〜5も行なった.比較例−1および2
は、マレイミド系共重合体中の無水マレイン酸含量が範
囲外.比較例−3は、変性ポリオレフィン系■合体中の
無水マレイン酸含量が範囲外.比較例−4および5は、
変性ポリオレフィン系重合体の含有量が範囲外.
尚、成形温度は270”Cを標準とし、成形品の状況に
よって、若干の修正を行なった。b-3) Nylon 66; Relative viscosity of sulfuric acid obtained from equimolar salts of hexamethylene diamine and adivic acid 2.
55 nylon 66, (2) maleimide copolymer (
A) The maleimide copolymer was prepared by placing 100 parts of styrene in an autoclave with a stirrer in place, purging the system with the desired gas, and then heating it to a temperature of 80°C. To this was added 8 parts of a solution of 67 parts of maleic anhydride and 0.2 parts of penzoin peroxide dissolved in 300 parts of methyl ethyl ketone. After the addition, the temperature was kept at 80°C for an additional 4 hours. To the above copolymer, 1.2 parts of triethylamine and 38 parts of aniline. 1 part was added and the reaction was carried out at 130°C for 7 hours. The reaction solution was cooled to room temperature, poured into 300 parts of vigorously stirred methanol, filtered and evaporated to obtain a maleimide-based copolymer (a-3). Other maleimide copolymers were prepared in the same way. These are shown in Table 1. (3)
Modified polyolefin polymer ethylene alpha-olefin copolymer Beret with ethylene content of 80 mol%} 10 kg, powdered anhydrous malein! 12
0g, 2ψ5-dimethyl - 2 Pour into a shell mixer,
Stir for 5 minutes to blend uniformly, and use a 40lφ extruder (L/T-28, Dalmage type, manufactured by Nitgyo wo Ryutsu).
Form into pellets. Cylinder temperature is polymer temperature 2
The temperature was adjusted to 40°C, and the graft reaction product (c-3
) was obtained (the amount of maleic anhydride introduced into the copolymer was 0.
9! fit%). Other modified polyolefin polymers were prepared in the same manner. These are shown in Table 2. Examples-1 to 1 day and Comparative Examples-1 to 5 0.0 kg of barium stearate was added to 10 kg of the above nylon-6 (b-1).
Blend 05ffi amount% in 2OL Henschel, 4
560kg of pelletized material extruded with a 0Bφ1 trowel at 240°C, 20! After adding 0.5 ffl weight % of ethylene bisstearylamide into Henschel and blending, maleimide copolymer resin (a-2) 3. 5kg
.. Modified polyolefin polymer (c-3) 1.5 kg,
Antioxidant (octadecyl-3-(3,5-T)
-butyl)monohydroxyphenyllube nate 0. 2 Add 51 fLm% OyoUN-N' hexamethylenebis(3,5-di-butyl)monohydroxyhydrocinnamamide 0.5ffiffi%), blend, and then add CTM (manufactured by Kobe Steel) to a 40-φ It was extruded using an extruder at 290°C and formed into an L knot. The dispersed particle size of the maleimide copolymer in the obtained composition was 0.17t.
It was rn. Also, weird. The condition of the dispersed particles of the polyolefin polymer is also good. Using this pellet, a test mold for measuring physical properties was created using an injection molding machine, and various physical properties were measured. The results are shown in the table. Similarly, Example-2~
15. Comparative Examples 1 to 5 were also conducted. Comparative example-1 and 2
The maleic anhydride content in the maleimide copolymer is out of range. In Comparative Example 3, the maleic anhydride content in the modified polyolefin compound was outside the range. Comparative Examples-4 and 5 are
The content of modified polyolefin polymer is out of range. The molding temperature was set at 270''C as a standard, and was slightly modified depending on the condition of the molded product.
実施例および比較例の結果から次のことが明らかである
.
実施例−2と比較例−1から、マレイミド系共道合体中
に不飽和ジカルボン酸無水物単量体2(を有していない
と衝撃値の改良効果が小さく、伸びも低く、実用的でな
い.また、この時のマレイミド系共重合体の分散も不良
で分散粒径が大きくなっている.
また、比較例−2のように不飽和ジカルボンlII無水
物量が多すぎても衝撃値は向上せず、外観不良、成形性
(流れ)の低下を生じる.実施例−2と比較例−3から
、ポリオレフィン系1合体中のジカルボン酸無水物の含
有が瓜要であり、含有していないと?gj撃値の改良効
果が小さく、外観も不良になることが判る.以上の様に
、両者が適性な不飽和カルボン酸無水物を含有(グラフ
ト、共重合)している時のみ、物性バランスが良好とな
ることが判る.また、実施例、比較例から判明するよう
に、マレイミド系共道合体の分散状態も物性にIi要で
あり、粒子径が大きくても、小さくても良くないことが
判る.
実施例−2並びに比較例−1および3で得られた樹脂絹
成物の電子顕微鏡写真を第1図並びに第2図および第3
図に示す.
第1図から判るように、本発明の樹脂胡成物はマレイミ
ド系共重合体の粒子径が0. 1μmで、しかも変性
ポリオレフィン系重合体もほぼ均一に半連続層とし分散
している.
比較例−1においては、マレイミド系共重合体の分散粒
子径が大きく、かつ変性ポリオレフィン系重合体の分散
粒子径も実施例−1と異なり不良である。The following is clear from the results of Examples and Comparative Examples. From Example 2 and Comparative Example 1, it is clear that if the maleimide-based sympathic polymer does not contain the unsaturated dicarboxylic anhydride monomer 2, the impact value improvement effect will be small and the elongation will be low, making it impractical. In addition, the dispersion of the maleimide copolymer at this time was poor and the dispersed particle size became large.Furthermore, as in Comparative Example 2, even if the amount of unsaturated dicarboxylic anhydride was too large, the impact value did not improve. However, it causes poor appearance and a decrease in moldability (flow).From Example 2 and Comparative Example 3, the presence of dicarboxylic acid anhydride in the polyolefin system 1 is essential, but is it not present? It can be seen that the effect of improving the gj impact value is small and the appearance becomes poor.As mentioned above, the physical property balance is achieved only when both contain suitable unsaturated carboxylic acid anhydrides (grafting, copolymerization). Furthermore, as is clear from the Examples and Comparative Examples, the dispersion state of the maleimide-based sympathic polymer is also important for the physical properties, and neither large nor small particle diameters are good. The electron micrographs of the resin silk compositions obtained in Example 2 and Comparative Examples 1 and 3 are shown in Figure 1, Figure 2, and Figure 3.
It is shown in the figure. As can be seen from FIG. 1, in the resin composite of the present invention, the particle size of the maleimide copolymer is 0. 1 μm, and the modified polyolefin polymer is almost uniformly dispersed in a semi-continuous layer. In Comparative Example-1, the dispersed particle size of the maleimide copolymer is large, and the dispersed particle size of the modified polyolefin polymer is also poor, unlike in Example-1.
比較例−3においては、マレイミド系共重合体の分散粒
子径が小さく、かつ変性ポリオレフィン系重合体の分散
が不均一である.
4,In Comparative Example 3, the dispersed particle size of the maleimide copolymer was small, and the modified polyolefin polymer was unevenly dispersed. 4,
第1図、第2図および第3図は、それぞれ実施例−2、
比較例−1および3で得られた樹脂組成物のマレイミド
系共重合体粒子の分散状態を示す電子[1鏡写真である
.
第2FIG. 1, FIG. 2, and FIG. 3 show Example-2, respectively.
This is an electron [1 mirror photograph] showing the dispersion state of the maleimide copolymer particles of the resin compositions obtained in Comparative Examples 1 and 3. Second
Claims (1)
レイミド系単量体基30〜50モル%、不飽和ジカルボ
ン酸無水物単量体基3〜20モル%およびその他の共重
合可能な単量体基0〜50モル%からなるマレイミド系
共重合体10〜50%重量%、(B)ポリアミド40〜
80重量%、および(C)不飽和ジカルボン酸無水物単
量体基および/または不飽和カルボン酸単量体基0.1
〜10重量%で変性された変性ポリオレフィン系重合体
3〜40重量%を有効成分とするマレイミド系共重合体
が0.01〜1.0ミクロンの分散粒子を形成したこと
を特徴とする熱可塑性樹脂組成物。 2、変性ポリオレフィン系重合体が不定形で、ほぼ均一
に分散していることを特徴とする請求項1記載の熱可塑
性樹脂組成物。 3、有機酸金属塩および/または脂肪酸アミドを含有す
る請求項1又は2記載の組成物。[Claims] 1. (A) 30 to 70 mol % of aromatic vinyl monomer groups, 30 to 50 mol % of maleimide monomer groups, 3 to 20 mol % of unsaturated dicarboxylic anhydride monomer groups. % and other copolymerizable monomer groups 10 to 50% by weight, (B) polyamide 40 to 50% by weight
80% by weight, and (C) unsaturated dicarboxylic anhydride monomer group and/or unsaturated carboxylic acid monomer group 0.1
Thermoplastic, characterized in that a maleimide copolymer containing 3 to 40% by weight of a modified polyolefin polymer modified at 10% by weight forms dispersed particles of 0.01 to 1.0 microns. Resin composition. 2. The thermoplastic resin composition according to claim 1, wherein the modified polyolefin polymer is amorphous and substantially uniformly dispersed. 3. The composition according to claim 1 or 2, containing an organic acid metal salt and/or a fatty acid amide.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63283720A JP2782518B2 (en) | 1988-11-11 | 1988-11-11 | Resin composition |
US07/310,903 US5049613A (en) | 1988-02-24 | 1989-02-16 | Thermoplastic resin composition |
DE89103107T DE68906292T2 (en) | 1988-02-24 | 1989-02-22 | Thermoplastic resin mixture. |
EP89103107A EP0331975B1 (en) | 1988-02-24 | 1989-02-22 | Thermoplastic resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63283720A JP2782518B2 (en) | 1988-11-11 | 1988-11-11 | Resin composition |
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Publication Number | Publication Date |
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JPH02132140A true JPH02132140A (en) | 1990-05-21 |
JP2782518B2 JP2782518B2 (en) | 1998-08-06 |
Family
ID=17669217
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100250699B1 (en) * | 1996-12-20 | 2000-04-01 | 기타가와 다이조 | Sprag type one-way clutch |
JP2009067868A (en) * | 2007-09-12 | 2009-04-02 | Daicel Polymer Ltd | Master batch for being added to resin |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5757719A (en) * | 1980-09-25 | 1982-04-07 | Asahi Chem Ind Co Ltd | High-molecular material, novel copolymer and their production |
JPS61171751A (en) * | 1985-01-28 | 1986-08-02 | Toray Ind Inc | Thermoplastic resin composition |
JPS6259647A (en) * | 1985-09-11 | 1987-03-16 | Toray Ind Inc | Thermoplastic resin composition |
JPS63105051A (en) * | 1986-10-21 | 1988-05-10 | Denki Kagaku Kogyo Kk | Thermoplastic resin composition |
-
1988
- 1988-11-11 JP JP63283720A patent/JP2782518B2/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5757719A (en) * | 1980-09-25 | 1982-04-07 | Asahi Chem Ind Co Ltd | High-molecular material, novel copolymer and their production |
JPS61171751A (en) * | 1985-01-28 | 1986-08-02 | Toray Ind Inc | Thermoplastic resin composition |
JPS6259647A (en) * | 1985-09-11 | 1987-03-16 | Toray Ind Inc | Thermoplastic resin composition |
JPS63105051A (en) * | 1986-10-21 | 1988-05-10 | Denki Kagaku Kogyo Kk | Thermoplastic resin composition |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100250699B1 (en) * | 1996-12-20 | 2000-04-01 | 기타가와 다이조 | Sprag type one-way clutch |
JP2009067868A (en) * | 2007-09-12 | 2009-04-02 | Daicel Polymer Ltd | Master batch for being added to resin |
Also Published As
Publication number | Publication date |
---|---|
JP2782518B2 (en) | 1998-08-06 |
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