JPH02208359A - Polyamide resin composition - Google Patents
Polyamide resin compositionInfo
- Publication number
- JPH02208359A JPH02208359A JP2865189A JP2865189A JPH02208359A JP H02208359 A JPH02208359 A JP H02208359A JP 2865189 A JP2865189 A JP 2865189A JP 2865189 A JP2865189 A JP 2865189A JP H02208359 A JPH02208359 A JP H02208359A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- propylene
- copolymer
- nylon
- resin composition
- 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.)
- Pending
Links
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 31
- 239000011342 resin composition Substances 0.000 title claims description 28
- 239000004952 Polyamide Substances 0.000 claims abstract description 28
- 229920002647 polyamide Polymers 0.000 claims abstract description 28
- 229920001155 polypropylene Polymers 0.000 claims abstract description 27
- 229920000098 polyolefin Polymers 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 16
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 9
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 27
- 239000005749 Copper compound Substances 0.000 claims description 10
- 150000001880 copper compounds Chemical class 0.000 claims description 10
- 229920005989 resin Polymers 0.000 abstract description 19
- 239000011347 resin Substances 0.000 abstract description 19
- 230000032683 aging Effects 0.000 abstract description 11
- 229920002302 Nylon 6,6 Polymers 0.000 abstract description 7
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 abstract description 6
- MZZYGYNZAOVRTG-UHFFFAOYSA-N 2-hydroxy-n-(1h-1,2,4-triazol-5-yl)benzamide Chemical compound OC1=CC=CC=C1C(=O)NC1=NC=NN1 MZZYGYNZAOVRTG-UHFFFAOYSA-N 0.000 abstract description 3
- 229940076286 cupric acetate Drugs 0.000 abstract description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 abstract description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 abstract 1
- 239000002574 poison Substances 0.000 abstract 1
- 231100000614 poison Toxicity 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 29
- -1 polypropylene Polymers 0.000 description 29
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 16
- 239000005977 Ethylene Substances 0.000 description 16
- 239000004743 Polypropylene Substances 0.000 description 12
- 239000008188 pellet Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 230000006866 deterioration Effects 0.000 description 8
- 229920002292 Nylon 6 Polymers 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N fumaric acid group Chemical group C(\C=C\C(=O)O)(=O)O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 229920000577 Nylon 6/66 Polymers 0.000 description 5
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920001384 propylene homopolymer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 150000003254 radicals Chemical group 0.000 description 4
- 239000000126 substance Substances 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000156978 Erebia Species 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-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
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 2
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 2
- 229920000572 Nylon 6/12 Polymers 0.000 description 2
- 229920000393 Nylon 6/6T Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000012765 fibrous filler Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-UHFFFAOYSA-N 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 1
- ZOMWPAHEBIICIQ-UHFFFAOYSA-N 2,4-dimethyl-6-(4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl)phenol Chemical compound CC1=CC(C)=C(O)C(C2C3(C)CCC(C3(C)C)C2)=C1 ZOMWPAHEBIICIQ-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- ANJHKVLUGKEZJB-UHFFFAOYSA-N 2,4-ditert-butyl-6-(3,5-ditert-butyl-2-hydroxyphenyl)sulfanylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(SC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O ANJHKVLUGKEZJB-UHFFFAOYSA-N 0.000 description 1
- LZFZQYNTEZSWCP-UHFFFAOYSA-N 2,6-dibutyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC(CCCC)=C1O LZFZQYNTEZSWCP-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- XZNHGJHMFKJIIV-UHFFFAOYSA-N 2-[(3-octadecoxy-3-oxopropyl)sulfanylmethyl]tetradecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCC(CCCCCCCCCCCC)C(=O)O XZNHGJHMFKJIIV-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-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
- JTTMYKSFKOOQLP-UHFFFAOYSA-N 4-hydroxydiphenylamine Chemical compound C1=CC(O)=CC=C1NC1=CC=CC=C1 JTTMYKSFKOOQLP-UHFFFAOYSA-N 0.000 description 1
- LZAIWKMQABZIDI-UHFFFAOYSA-N 4-methyl-2,6-dioctadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC(C)=CC(CCCCCCCCCCCCCCCCCC)=C1O LZAIWKMQABZIDI-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- 229920012753 Ethylene Ionomers Polymers 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical group CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- XBJJRSFLZVLCSE-UHFFFAOYSA-N barium(2+);diborate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]B([O-])[O-].[O-]B([O-])[O-] XBJJRSFLZVLCSE-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- OMCYEZUIYGPHDJ-OQLLNIDSSA-N chembl354261 Chemical compound OC1=CC=CC=C1\C=N\NC(=O)C1=CC=CC=C1O OMCYEZUIYGPHDJ-OQLLNIDSSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- CMRVDFLZXRTMTH-UHFFFAOYSA-L copper;2-carboxyphenolate Chemical compound [Cu+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O CMRVDFLZXRTMTH-UHFFFAOYSA-L 0.000 description 1
- SVOAENZIOKPANY-UHFFFAOYSA-L copper;octadec-9-enoate Chemical compound [Cu+2].CCCCCCCCC=CCCCCCCCC([O-])=O.CCCCCCCCC=CCCCCCCCC([O-])=O SVOAENZIOKPANY-UHFFFAOYSA-L 0.000 description 1
- PEVZEFCZINKUCG-UHFFFAOYSA-L copper;octadecanoate Chemical compound [Cu+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O PEVZEFCZINKUCG-UHFFFAOYSA-L 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- NMAKPIATXQEXBT-UHFFFAOYSA-N didecyl phenyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OC1=CC=CC=C1 NMAKPIATXQEXBT-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical group OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000004492 methyl ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 229960000990 monobenzone Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002912 oxalic acid derivatives Chemical class 0.000 description 1
- GGROONUBGIWGGS-UHFFFAOYSA-N oxygen(2-);zirconium(4+);hydrate Chemical class O.[O-2].[O-2].[Zr+4] GGROONUBGIWGGS-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229940058287 salicylic acid derivative anticestodals Drugs 0.000 description 1
- 150000003872 salicylic acid derivatives Chemical class 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- JZNDMMGBXUYFNQ-UHFFFAOYSA-N tris(dodecylsulfanyl)phosphane Chemical compound CCCCCCCCCCCCSP(SCCCCCCCCCCCC)SCCCCCCCCCCCC JZNDMMGBXUYFNQ-UHFFFAOYSA-N 0.000 description 1
- GNFABDZKXNKQKN-UHFFFAOYSA-N tris(prop-2-enyl)phosphane Chemical compound C=CCP(CC=C)CC=C GNFABDZKXNKQKN-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Chemical group 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- KMNUDJAXRXUZQS-UHFFFAOYSA-L zinc;n-ethyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCN(C([S-])=S)C1=CC=CC=C1.CCN(C([S-])=S)C1=CC=CC=C1 KMNUDJAXRXUZQS-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はポリアミド樹脂組成物に関し、詳しくはポリア
ミドとプロピレン重合体のそれぞれの優れた特性を併せ
有し、特に耐熱老化性に優れたポリアミド樹脂組成物に
関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a polyamide resin composition, and more specifically to a polyamide resin that has both the excellent properties of polyamide and propylene polymer, and has particularly excellent heat aging resistance. Regarding the composition.
〔従来の技術及び発明が解決しようとする課題〕一般に
、ポリアミド樹脂は、物理的、化学的性質に優れている
ことから合成繊維などとして幅広く利用されているが、
近年成形材料としても利用されるようになっている。こ
れは、ポリアミド樹脂が熱可塑性樹脂の中にあって、高
い機械的強度。[Prior art and problems to be solved by the invention] In general, polyamide resins are widely used as synthetic fibers due to their excellent physical and chemical properties.
In recent years, it has come to be used as a molding material. This is because polyamide resin is contained within thermoplastic resin and has high mechanical strength.
優れた耐摩耗性、耐薬品性、耐熱性及び比較的価れた電
気的性質を有し、エンジニアリングプラスチックとして
の性能を充分有していることによる。This is because it has excellent wear resistance, chemical resistance, heat resistance, and relatively good electrical properties, and has sufficient performance as an engineering plastic.
しかし、その反面、アミド基（−ＣＯＮＨ−）に起因し
て吸水による寸法変化や機械的強度の低下が生ずるなど
の好ましからざる性能を有しており、それが故に、成形
材料としての市場性が限定されている。However, on the other hand, it has undesirable properties such as dimensional changes due to water absorption and a decrease in mechanical strength due to the amide group (-CONH-), which makes it less marketable as a molding material. Limited.
一方、プロピレン重合体は安価で、かつ吸水性はほとん
ど示さないが、軟質であり、高温時の物性が劣るなどの
欠点がある。On the other hand, propylene polymer is inexpensive and exhibits almost no water absorption, but has drawbacks such as being soft and having poor physical properties at high temperatures.
したがって、ポリアミド樹脂およびポリプロピレン樹脂
のそれぞれの欠点を改善するために、これらの樹脂を併
用することは当然考えられるが、ポリアミド樹脂とポリ
プロピレン樹脂を通常の方法で混合して得た樹脂混合物
、あるいはそれらを単に溶融混練して得た樹脂組成物で
は相溶性が劣り、目的とする優れた物性を持つ組成物と
はなりえない。Therefore, in order to improve the respective disadvantages of polyamide resin and polypropylene resin, it is natural to think of using these resins together, but it is possible to use a resin mixture obtained by mixing polyamide resin and polypropylene resin in the usual way, or a mixture of them. A resin composition obtained by simply melting and kneading the materials has poor compatibility and cannot provide a composition with the desired excellent physical properties.
そのため、従来からポリアミド樹脂とポリプロピレン樹
脂のそれぞれの優れた特性を併せ有する樹脂組成物、す
なわちポリアミド樹脂が存する優れた耐摩耗性、電気特
性、耐熱性２機械的強度。Therefore, resin compositions that combine the excellent properties of polyamide resins and polypropylene resins have been developed, that is, polyamide resins have excellent abrasion resistance, electrical properties, heat resistance, and mechanical strength.
耐油性、さらにポリプロピレン樹脂が有する低吸水性、
耐熱水性、耐ハロゲン化金属性、低温耐衝撃性を併せ有
する樹脂組成物を得ることを目的として、ポリアミド樹
脂、オレフィン重合体及び不飽和カルボン酸またはその
誘導体をグラフトした変性オレフィン重合体の三成分を
溶融混合して、強度、耐熱変形性、外観、成形加工性の
バランスが優れた組成物を得ることについては、すでに
特公昭４２−１２５４６号公報、特公昭４５３０９４５
号公報、特公報５０−７６３６号公報などに示されてい
る。また、このような優れた性質を利用して、自動車部
品、電機器具２機械部品。Oil resistance, low water absorption of polypropylene resin,
In order to obtain a resin composition that has hot water resistance, resistance to metal halides, and low-temperature impact resistance, three components are made: a polyamide resin, an olefin polymer, and a modified olefin polymer grafted with an unsaturated carboxylic acid or a derivative thereof. Regarding obtaining a composition with an excellent balance of strength, heat deformation resistance, appearance, and moldability by melt-mixing the
This method is disclosed in Japanese Patent Publication No. 50-7636 and the like. We also use these excellent properties to manufacture automobile parts, electrical appliances, and 2 mechanical parts.
工業部品などの強度や耐熱変形性の要求される用途で実
用化が検討されたり、一部では実用化がなされている。Practical use is being considered for industrial parts and other uses that require strength and heat deformation resistance, and in some cases it has been put into practical use.
しかしながら、このような多くの特徴を有するポリマー
組成物であっても、長期的な熱劣化に対する抵抗性、す
なわち耐熱老化性が未だ充分でないという問題がある。However, even with polymer compositions having many of these characteristics, there is a problem that resistance to long-term thermal deterioration, that is, heat aging resistance is still insufficient.
この問題解決の手段としては、例えば特公昭５９２７９
４８号公報に、ヒンダードフェノール芳香族アミン及び
銅化合物を配合する方法が提案されている。しかし、こ
の方法をオレイン重合体としてプロピレン重合体を用い
たものに適用しても、完全には熱劣化を防止することが
できずに、むしろ劣化が促進される場合がある。この原
因として考えられるのは、ポリアミドの安定剤として配
合された銅化合物中の銅が、三級炭素を含んで構造的に
不安定なプロピレン重合体に対して、熱劣化を促進させ
る、いわゆる調書のためであると推定される。As a means of solving this problem, for example,
No. 48 proposes a method of blending a hindered phenol aromatic amine and a copper compound. However, even if this method is applied to a product using a propylene polymer as the oleic polymer, thermal deterioration cannot be completely prevented and the deterioration may be accelerated. A possible cause of this is that the copper in the copper compound blended as a stabilizer for polyamide accelerates thermal deterioration of the structurally unstable propylene polymer, which contains tertiary carbon. It is estimated that this is because of
かかる推定から、本発明者らは、プロピレン重合体を使
用する場合に、銅害防止剤を配合することが、銅による
プロピレン重合体の劣化を抑制する上で有効であるとの
知見を得た。この知見に基いて更に様々な検討を重ねた
ところ、これらを含む各種の添加剤、すなわち銅化合物
、ラジカル連鎖禁止剤、過酸化分解剤などの耐熱安定剤
及び銅害防止剤の配合方法を工夫することにより、耐熱
老化性に優れたポリアミド樹脂組成物が得られることを
見出した。本発明はこのような研究過程を経て完成した
ものである。Based on this estimation, the present inventors have found that when using a propylene polymer, blending a copper damage inhibitor is effective in suppressing the deterioration of the propylene polymer due to copper. . Based on this knowledge, we conducted a variety of further studies and devised a method for blending various additives, including copper compounds, radical chain inhibitors, heat stabilizers such as peroxide decomposers, and copper damage inhibitors. It has been found that by doing so, a polyamide resin composition with excellent heat aging resistance can be obtained. The present invention was completed through such a research process.
すなわち本発明は、ポリアミド樹脂（Ａ）に銅化合物（
Ｂ）を添加したポリアミド組成物と、プロピレン重合体
（Ｃ）に耐熱安定剤（Ｄ）と銅害防止剤（Ｅ）とを添加
したプロピレン樹脂組成物と、
変性ポリオレフィン（Ｆ）
の三者を溶融混合することを特徴とするポリアミド樹脂
組成物を提供するものであり、また、このようにして該
ポリアミド樹脂組成物を製造する方法を提供するもので
ある。That is, the present invention provides polyamide resin (A) with a copper compound (
A polyamide composition containing B), a propylene resin composition containing a heat stabilizer (D) and a copper damage inhibitor (E) added to a propylene polymer (C), and a modified polyolefin (F). The present invention provides a polyamide resin composition that is characterized by being melt-mixed, and also provides a method for producing the polyamide resin composition in this manner.
本発明に用いるポリアミド樹脂（Ａ）としては各種のも
のが使用可能であるが、具体的にはナイロン６、ナイロ
ン１１．ナイロン１２などのポリラクタム類；ナイロン
６６、ナイロン６１０．ナイロン６１２．ナイロン４６
等のジカルボン酸とジアミンとから得られるポリアミド
類；ナイロン６／６６、ナイロン６／１２．ナイロン６
／６６／６１０等の共重合体ポリアミド類；ナイロン６
／６Ｔ（Ｔ：テレフタル酸成分）、イソフタル酸のよう
な芳香族ジカルボン酸とメタキシレンジアミンあるいは
脂環族ジアミンから得られる半芳香族ポリアミド類；ポ
リエステルアミド、ポリエーテルアミド及びポリエステ
ルエーテルアミドを挙げることができる。なお、（Ａ）
成分のポリアミド樹脂としては、上記各種のポリアミド
を単独で用いてもよく、また二種以上のポリアミドを併
用することもできる。Various types of polyamide resin (A) can be used in the present invention, and specifically, nylon 6, nylon 11. Polylactams such as nylon 12; nylon 66, nylon 610. Nylon 612. nylon 46
Polyamides obtained from dicarboxylic acids and diamines such as nylon 6/66, nylon 6/12. nylon 6
Copolymer polyamides such as /66/610; nylon 6
/6T (T: terephthalic acid component), semi-aromatic polyamides obtained from aromatic dicarboxylic acids such as isophthalic acid and metaxylene diamine or alicyclic diamine; include polyesteramide, polyetheramide and polyesteretheramide Can be done. In addition, (A)
As the component polyamide resin, the above-mentioned various polyamides may be used alone, or two or more types of polyamides may be used in combination.
さらに、本発明において使用できるポリアミド樹脂は、
上述のポリアミドより選択されたものであれば、これら
のポリアミドの末端基の種類や濃度および分子量などに
より制限されることなく種々のものを使用することがで
きるが、とりわけ高アミノ末端ポリアミドが好ましい。Furthermore, the polyamide resin that can be used in the present invention is
As long as it is selected from the above-mentioned polyamides, various polyamides can be used without being limited by the type, concentration, molecular weight, etc. of the terminal groups of these polyamides, but highly amino-terminated polyamides are particularly preferred.
また、ポリアミドの重合時に残存または生成するモノマ
ー、オリゴマー等の低分子量物が混在しているポリアミ
ドも用いることが可能である。Furthermore, it is also possible to use polyamide in which low molecular weight substances such as monomers and oligomers that remain or are generated during polymerization of polyamide are mixed.
このポリアミド樹脂に添加される銅化合物（Ｂ）として
は、ポリアミドの安定剤とし周知のものであり、様々な
ものを使用することができるが、具体的には、塩化第１
銅、塩化第２銅、臭化第１銅臭化第２銅、コラ化第１銅
などの無機ハロゲン化銅、硫酸第２銅、硝酸第２銅、リ
ン酸銅などの無機酸の銅塩、酢酸第２銅、サリチル酸第
２銅、ステアリン酸第２銅、オレイン酸第２銅、安息香
酸第２銅などの有機酸の銅塩、あるいは無機ハロゲン化
銅とキシレンジアミン、ベンズイミダゾール２−メルカ
プトベンズイミダゾールなどとの錯化合物などを例示す
ることができる。The copper compound (B) added to this polyamide resin is a well-known stabilizer for polyamide, and various compounds can be used.
Copper, inorganic copper halides such as cupric chloride, cupric bromide, cupric bromide, cupric chloride, copper salts of inorganic acids such as cupric sulfate, cupric nitrate, copper phosphate, Copper salts of organic acids such as cupric acetate, cupric salicylate, cupric stearate, cupric oleate, cupric benzoate, or inorganic copper halides and xylene diamine, benzimidazole 2-mercaptobenz Examples include complex compounds with imidazole and the like.
次にプロピレン重合体（Ｃ）としては、プロピレン単独
重合体および／あるいはプロピレン共重合体が用いられ
る。ここでプロピレン共重合体としては、プロピレン−
エチレン共重合体、プロピレン−ブテン−１共重合体な
どがあり、これらのブロック共重合体やランダム共重合
体が用いられる。なお、このポリプロピレン樹脂は、プ
ロピレン単独重合体やプロピレン共重合体を一種類で使
用してもよく、あるいは二種類以上併用することもでき
る。この際プロピレン単独重合体、プロピレン共重合体
の分子量は、特に制限されないが、一般にはＭＦＲが１
〜５０ ｇ／ｌ ０分のものが好適に使用される。Next, as the propylene polymer (C), a propylene homopolymer and/or a propylene copolymer is used. Here, as the propylene copolymer, propylene-
Examples include ethylene copolymer and propylene-butene-1 copolymer, and block copolymers and random copolymers of these are used. In addition, for this polypropylene resin, a propylene homopolymer or a propylene copolymer may be used alone, or two or more types may be used in combination. At this time, the molecular weight of the propylene homopolymer and propylene copolymer is not particularly limited, but generally the MFR is 1.
~50 g/l 0 minutes is preferably used.
このプロピレン重合体（Ｃ）に添加される耐熱安定剤（
Ｄ）としては、各種のものがあるが、特に有機系耐熱安
定剤を用いることが好ましい。この有機系耐熱安定剤と
しては、ラジカル連鎖禁止剤、過酸化物分解剤などがあ
り、これらを単独であるいは組み合わせて用いればよい
。ここでラジカル連鎖禁止剤としては、ヒンダードフェ
ノール系化合物、芳香族アミン化合物があり、また、過
酸化物分解剤としては、メルカプタンおよびサルファイ
ド化合物、ジチオ酸化合物、ホスファイト化合物などが
ある。より具体的には、ヒンダードフェノール系化合物
としては、２，６−ジーもブチル−４−メチルフェノー
ル；２，４−ジメチル−６−ｔ−ブチルフェノール；３
−ｔ−ブチル−４−ヒドロキシアニソール；２，６−ジ
オクタデシル−ｐ−クレゾール；２．４−ジメチル−６
イソボルニルフエノール；２．６−ジイソボルニル−ｐ
−クレゾール；ｎ−オクタデシル−β−（４′−ヒドロ
キシ−３’、５’ −ジ−ｔ−ブチルフェニル）プロピ
オネート；スチレン化フェノール；２．４−ジメチル−
６−α−メチルシクロヘキシル−フェノ−ルミ４，４’
−ブチリデンビス−（３−メチル−６−ｔ−ブチルフェ
ノール）；４．４′−メチレン−ビス−（２，６−ジー
ｔブチルフエノール）；２，２’ −メチレン−ビス−
（６−１−ブチル−ｐ−クレゾール）ｉ２，２’−メチ
レン−ビス−（６−ｔ−ブチル−４−エチルフェノール
）；アルキル化ビスフェノール；２゜６−ビス−（２′
−ヒドロキシ−３′−も−ブチル−５′−メチルベンジ
ル）−４−メチルフェノール；トリス（２−メチル−４
−ヒドロキシ−５−１−ブチルフェニル）ブタン；テト
ラキス−〔メチレン−（３，５−ジ−ｔ−ブチル−４−
ヒドロキシ−ヒドロシンナメート）〕〕メタン；ヒドロ
キノンーモノベンジルエーテル４．４’−チオビス（６
−も−ブチル−ｍ−クレゾール）；２゜２′−チオビス
（４−メチル−６−ｔ−ブチルフェノール）；ビス（２
−ヒドロキシ−３，５−ジ−ｔ−ブチルフェニル）サル
ファイド；２，２’メチレン−ビス−（４−メチル−６
−α−メチルシクロヘキシルフェノール）ｉｔ、３．５
−）ジメチル−２，４，６−）リス（３，５−ジーＬ−
フチルー４−ヒドロキシベンジル）ベンゼン；２．４−
ビス−（４−ヒドロキシ−３，５−ジ−ｔ−ブチルフェ
ノキシ）−６−（ｎ−オクチルチオ）−１，３，５−ト
リアジン１６−（４−ヒドロキシ−３，５−ジーＬ−ブ
チルアニリノ）−２゜４−ビス−（ｎ−オクチルチオ）
−１，３，５−トリアジン； （４−ヒドロキシ−３５
−ジーＬブチル−ベンジル）−ジオクタデシルリン酸エ
ステル；リン−アルキル化フェノール縮合体などがある
。また、芳香族アミン化合物としてはフェニル−α−ナ
フチルアミン；フェニル−β−ナフチルアミン；ジフェ
ニルアミン、Ｎ、Ｎ’ −ジフェニル−ｐ−フェニレン
ジアミン、Ｎ、Ｎ’−ジβ−ナフチルーｐ−フェニレン
ジアミン；ＮＮ′−フェニルシクロへキシル−Ｐ−フェ
ニレンジアミン；ｐ−ヒドロキシジフェニルアミン；ｐ
−ヒドロキシジフェニル−β−ナフチルアミン；２．２
．ｌｌ−リンチルヒドロキノリンなどがある。A heat-resistant stabilizer (
Although there are various types of D), it is particularly preferable to use an organic heat-resistant stabilizer. Examples of the organic heat-resistant stabilizer include radical chain inhibitors and peroxide decomposers, and these may be used alone or in combination. Examples of radical chain inhibitors include hindered phenol compounds and aromatic amine compounds, and examples of peroxide decomposers include mercaptans, sulfide compounds, dithioic acid compounds, and phosphite compounds. More specifically, the hindered phenol compounds include 2,6-dibutyl-4-methylphenol; 2,4-dimethyl-6-t-butylphenol;
-t-butyl-4-hydroxyanisole; 2,6-dioctadecyl-p-cresol; 2,4-dimethyl-6
Isobornylphenol; 2,6-diisobornyl-p
-Cresol; n-octadecyl-β-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate; styrenated phenol; 2,4-dimethyl-
6-α-Methylcyclohexyl-phenolumi 4,4'
-Butylidenebis-(3-methyl-6-t-butylphenol); 4,4'-methylene-bis-(2,6-di-t-butylphenol);2,2'-methylene-bis-
(6-1-butyl-p-cresol)i2,2'-methylene-bis-(6-t-butyl-4-ethylphenol); alkylated bisphenol; 2゜6-bis-(2'
-hydroxy-3'-butyl-5'-methylbenzyl)-4-methylphenol; tris(2-methyl-4
-hydroxy-5-1-butylphenyl)butane; tetrakis-[methylene-(3,5-di-t-butyl-4-
Hydroxy-hydrocinnamate)]]methane; Hydroquinone-monobenzyl ether 4.
-Mo-butyl-m-cresol); 2゜2'-thiobis(4-methyl-6-t-butylphenol); bis(2
-Hydroxy-3,5-di-t-butylphenyl) sulfide; 2,2'methylene-bis-(4-methyl-6
-α-methylcyclohexylphenol) it, 3.5
-)dimethyl-2,4,6-)lis(3,5-di-L-
phthyl-4-hydroxybenzyl)benzene; 2.4-
Bis-(4-hydroxy-3,5-di-t-butylphenoxy)-6-(n-octylthio)-1,3,5-triazine 16-(4-hydroxy-3,5-di-L-butylanilino) -2゜4-bis-(n-octylthio)
-1,3,5-triazine; (4-hydroxy-35
-di-L-butyl-benzyl)-dioctadecyl phosphate; phosphorus-alkylated phenol condensates, and the like. In addition, aromatic amine compounds include phenyl-α-naphthylamine; phenyl-β-naphthylamine; diphenylamine, N,N'-diphenyl-p-phenylenediamine, N,N'-diβ-naphthyl-p-phenylenediamine;NN'-Phenylcyclohexyl-P-phenylenediamine;p-hydroxydiphenylamine; p
-Hydroxydiphenyl-β-naphthylamine; 2.2
．． Examples include ll-lyntylhydroquinoline.
過酸化物分解剤の具体例としては、ジラウリルチオジプ
ロピオネート：ジステアリルチオジプロピオネート；ス
テアリル−ラウリルチオジプロピオネート；ジラウリル
チオジイソブチレート；ジステアリル−エチリデンジチ
オグリコレート；ジβ−ナフチル−エチリデンジチオグ
リコレ−１・；トリフェニルホスファイト；トリスノニ
ルフェニルホスファイト；ジフェニルデシルボスファイ
ト；フエニルジデシルホスファイト；トリデシルホスフ
ァイト；トリラウリルトリチオホスファイト；トリオク
タデシルホスファイト；メルカプトヘンヅイミダゾール
；メルカプトベンゾチアゾール；エチル−フエニルジチ
オカルバミン酸亜鉛；ドデシルメルカプタン；チオビス
（β−ナフトール）；チオビス（Ｎ−フェニル−β−ナ
フチルアミン）；フェノチアジン；トリアリルホスフィ
ン、４．４’チオビス（３−メチル−５＝ｊ−ブチルフ
ェノール）；テトラメチルチウラムダイサルファイドな
どがある。Specific examples of peroxide decomposers include dilaurylthiodipropionate: distearylthiodipropionate; stearyl-laurylthiodipropionate; dilaurylthiodiisobutyrate; distearyl-ethylidene dithioglycolate; diβ -naphthyl-ethylidene dithioglycole-1; triphenyl phosphite; trisnonylphenyl phosphite; diphenyldecyl bosphite; phenyl didecyl phosphite; tridecyl phosphite; trilauryl trithiophosphite; triotadecyl phosphite; Mercaptohenzimidazole; Mercaptobenzothiazole; Zinc ethyl-phenyldithiocarbamate; Dodecyl mercaptan; Thiobis(β-naphthol); Thiobis(N-phenyl-β-naphthylamine); Phenothiazine; Triallylphosphine, 4.4' Thiobis( 3-methyl-5=j-butylphenol); tetramethylthiuram disulfide, etc.
また、前記耐熱安定剤（Ｄ）とともにプロピレン重合体
（Ｃ）に添加する銅害防止剤（Ｅ）としては、周知のも
のであれば基本的に如何なるものでもよく、シュウ酸誘
導体、ザリチル酸誘導体。The copper damage inhibitor (E) to be added to the propylene polymer (C) together with the heat stabilizer (D) may be basically any known agent, including oxalic acid derivatives and salicylic acid derivatives. .
ヒドラジド誘導体などがあり、より具体的には、商品名
Ｅａｓｔｍａｎ ＩｎｈｉｂｉｔｏｒＯＡＢ Ｈ（イー
ストマンコダソク社製） 、 ＮａｕｇａｒｏｌＸ Ｌ
１ （ユニロイヤルケミカル社製） 、 Ｍａｒｋ
ＣＤＡ−１，ＭａｒｋＣＤＡ−６Ｍａｒｋ ＺＳ２７
（以上アデカ・アーガス社製）、Ｃｈｅｌ−１８０、Ｉ
ｎｇａｎｏｘ ＭＤ １０２４（以上チバ・ガイギー
社製）、Ｑｕｎｏｘ （三井東圧ファイン社製）などが
例示でき、更に特公昭３７１４４８４号公報、特公昭３
９−．９０７２号公報。There are hydrazide derivatives, etc., and more specifically, the product names are Eastman Inhibitor OAB H (manufactured by Eastman Kodasoku), Naugarol X L
1 (manufactured by Uniroyal Chemical Co., Ltd.), Mark
CDA-1, MarkCDA-6Mark ZS27
(manufactured by Adeca Argus), Chel-180, I
Examples include nganox MD 1024 (manufactured by Ciba-Geigy) and Qunox (manufactured by Mitsui Toatsu Fine Co., Ltd.).
9-. Publication No. 9072.
特公昭３９−１２−４５４号公報、特公昭３９１９５４
１号公報、特公昭４０−１２２９３号公報、特公昭４０
−１８８５．２号公報、特公昭４２４３５６号公報、特
公昭４２−４５９６号公報。Special Publication No. 39-12-454, Special Publication No. 391954
Publication No. 1, Special Publication No. 12293, Special Publication No. 1973
-1885.2, Japanese Patent Publication No. 424356, and Japanese Patent Publication No. 42-4596.
特公昭４２−１３’２４７号公報、特公昭４３６５３８
号公報、特公昭４３−１８６０６号公報。Special Publication No. 42-13'247, Special Publication No. 436538
No. 43-18606.
特公昭４７−２７６２４号公報、特公昭４８−３６８３
７号公報、特公昭４９−１５４６６号公報、特公昭５２
−２２８３４号公報、特公昭５４４３５３７号公報、特
公昭５４−９０１４３号公報、米国特許第３３５７９４
４号明細書、米国特許第３３６７９０７号明細書、仏国
特許第１４８１１０５号明細書、仏国特許第１４９５８
３０号明細書などに例示されているものでもよい。Special Publication No. Sho 47-27624, Special Publication No. Sho 48-3683
Publication No. 7, Special Publication No. 15466/1983, Special Publication No. 15466/1973
-22834, Japanese Patent Publication No. 5443537, Japanese Patent Publication No. 54-90143, U.S. Patent No. 335794
4 specification, US Patent No. 3367907 specification, French Patent No. 1481105 specification, French Patent No. 14958
It may be exemplified in the specification of No. 30.
さらに変性ポリオレフィン（Ｆ）としては、カルボン酸
基（酢酸基、アクリル酸基、メタクリル酸基、フマル酸
基、イタコン酸基など）、カルボン酸金属塩基（ナトリ
ウム塩、カルシウム塩、マグネシウム塩、亜鉛塩など）
、カルボン酸エステル基（メチルエステル基、エチルエ
ステル基、プロピルエステルＬ ブチルエステル基、ビ
ニルエステル基など）、酸無水物基（無水マレイン酸基
など）およびエポキシ基から選ばれた少なくとも一種の
官能基を有するポリオレフィンである。またこのポリオ
レフィンとしては、ポリエチレン。Furthermore, the modified polyolefin (F) includes carboxylic acid groups (acetic acid group, acrylic acid group, methacrylic acid group, fumaric acid group, itaconic acid group, etc.), carboxylic acid metal bases (sodium salt, calcium salt, magnesium salt, zinc salt, etc.). Such)
, at least one functional group selected from carboxylic acid ester groups (methyl ester group, ethyl ester group, propyl ester group, butyl ester group, vinyl ester group, etc.), acid anhydride groups (maleic anhydride group, etc.), and epoxy groups. It is a polyolefin having Also, this polyolefin is polyethylene.
ポリプロピレン、ポリブテン、エチレン／プロピレン共
重合体、エチレン／ブテン共重合体、エチレン／ヘキセ
ン共重合体さらにはこれらに少量のジエンを含む共重合
体などをあげることができる。Examples include polypropylene, polybutene, ethylene/propylene copolymers, ethylene/butene copolymers, ethylene/hexene copolymers, and copolymers containing a small amount of diene.
このような変性ポリオレフィンの具体例としては、エチ
レン／アクリル酸共重合体、エチレン／メタクリル酸共
重合体、エチレン／フマル酸共重合体、エチレン／メタ
クリル酸／メタクリル酸亜鉛共重合体３エチレン／アク
リル酸／メタクリル酸ナトリウム共重合体、エチレン／
アクリル酸イソブチル／メタクリル酸／メタクリル酸亜
鉛共重合体、エチレン／ヌククリル酸メチル／メタクリ
ル酸／メタクリル酸マグネシウム共重合体１エチレン／
アクリル酸エチル共重合体、エチレン／酢酸ビニル共重
合体、エチレン／メタクリル酸グリシジル共重合体、エ
チレン／酢酸ビニル／メタクリル酸グリシジル共重合体
、無水マレイン酸クラフトポリエチレン、アクリル酸グ
ラフトポリエチレン、無水マレイン酸グラフトポリプロ
ピレン無水マレイン酸グラフトエチレン／プロピレン共
重合体、アクリル酸グラフトエチレン／プロピレン共重
合体、フマル酸グラフトエチレン／１−ブデン共重合体
、エチレン／１−へギセンーイタコン酸共重合体、エチ
レン／プロピレン−エンドビシクロ（２，２，１）−５
−へブテン−２，３無水ジ力ルボン酸共重合体、エチレ
ン／プロピレン−メタクリル酸グラフトグリシジル共重
合体無水マレイン酸グラフトエチレン／プロピレン／１
．４−へキサジエン共重合体、フマル酸グラフトエチレ
ン／プロピレン／ジシクロペンクジエン共重合体、マレ
イン酸グラフトエチレン／プロピレン／ノルボルナジェ
ン共重合体およびアクリル酸グラフトエチレン／酢酸ビ
ニル共重合体などであり、これらの変性ポリオレフィン
を単独で使用してもよく、また二種以上を併用すること
も可能である。Specific examples of such modified polyolefins include ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/fumaric acid copolymer, ethylene/methacrylic acid/zinc methacrylate copolymer, and ethylene/acrylic acid copolymer. Acid/sodium methacrylate copolymer, ethylene/
Isobutyl acrylate/methacrylic acid/zinc methacrylate copolymer, ethylene/methyl nuccrylate/methacrylic acid/magnesium methacrylate copolymer 1 ethylene/
Ethyl acrylate copolymer, ethylene/vinyl acetate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, maleic anhydride kraft polyethylene, acrylic acid graft polyethylene, maleic anhydride Grafted polypropylene Maleic anhydride grafted ethylene/propylene copolymer, acrylic acid grafted ethylene/propylene copolymer, fumaric acid grafted ethylene/1-butene copolymer, ethylene/1-hegycene-itaconic acid copolymer, ethylene/propylene- endobicyclo(2,2,1)-5
-hebutene-2,3 dicarboxylic anhydride copolymer, ethylene/propylene-methacrylic acid grafted glycidyl copolymer, maleic anhydride grafted ethylene/propylene/1
．． These include 4-hexadiene copolymer, fumaric acid grafted ethylene/propylene/dicyclopencdiene copolymer, maleic acid grafted ethylene/propylene/norbornadiene copolymer, and acrylic acid grafted ethylene/vinyl acetate copolymer. These modified polyolefins may be used alone, or two or more types may be used in combination.
上記変性ポリオレフィンの製造は公知の方法、例えば特
公昭３９−６８１０号公報、特公昭４６２７５２７号公
報、特公昭５０−２６３０号公報、特公昭５２−４３６
７７号公報、特公昭５３５７１６号公報、特公昭５３−
１９０３７号公報、特公昭５３−４１１７３号公報、特
公昭５６９９２５号公報などに示された方法に従って製
造することができる。なお、エチレン系アイオノマーに
ついては一般に゛′サーリン°”、 “°ハイミラン″
′、“コーボレン”なる商品名で市販されている各種グ
レードを用いることができる。また、本発明で用いられ
る変性ポリオレフィンの重合度は特に制限はないが、通
常メルトインデックスが０．０１〜１００ｇ／１０分の
範囲内にあるものを任意に選択できる。The above-mentioned modified polyolefin can be produced by known methods, for example, Japanese Patent Publication No. 39-6810, Japanese Patent Publication No. 4627527, Japanese Patent Publication No. 50-2630, Japanese Patent Publication No. 52-436.
Publication No. 77, Special Publication No. 535716, Special Publication No. 53-
It can be produced according to the methods disclosed in Japanese Patent Publication No. 19037, Japanese Patent Publication No. 53-41173, Japanese Patent Publication No. 569925, etc. Regarding ethylene ionomers, generally ``Surlyn'' and ``Himilan'' are used.
', various grades commercially available under the trade name "Kobolene" can be used. Further, the degree of polymerization of the modified polyolefin used in the present invention is not particularly limited, but it can be selected arbitrarily from one having a melt index usually in the range of 0.01 to 100 g/10 minutes.
本発明の組成物において、耐熱老化性に優れたポリアミ
ド樹脂組成物を製造するための各成分の配合割合は、得
られる樹脂の使用目的などにより、適宜定めればよい。In the composition of the present invention, the blending ratio of each component for producing a polyamide resin composition with excellent heat aging resistance may be determined as appropriate depending on the intended use of the resulting resin.
−船釣には、樹脂の主要成分であるポリアミド（Ａ）が
９０〜１０重量％、好ましくは７０〜３０重量％、同じ
くプロピレン重合体（Ｃ）が１０〜９０Ｍ量％、好まし
くは３０〜７０重量％であり、これらの成分の合計量、
すなわち（Ａ） ＋ （ｃ） ＝１００重量部に対して
、変性ポリオレフィン（Ｆ）が０．２〜５０重量部、好
ましくは０．５〜３０重量部である。さらにこれらの樹
脂成分に対する各添加物の配合割合は、（Ａ） ＋ （
Ｃ） ＋ （Ｆ） ＝１００重量部に対して、銅化合物
（Ｂ）が ０．００５〜３重量部、好ましくは０．０１
〜１重量部であり、同じ＜ （Ａ）＋（Ｃ） ＋ （Ｆ
） −１００重量部に対して、耐熱安定剤（Ｄ）が０．
００５〜５重量部、好ましくは０．０１〜３重量部であ
り、同じ＜ （Ａ）＋ （Ｃ）十（Ｆ）＝１００重量部
に対して、銅害防止剤（Ｅ）が０．００５〜５重量部、
好ましくは０．０１〜３重量部である。- For boat fishing, the main component of the resin, polyamide (A), is 90 to 10% by weight, preferably 70 to 30% by weight, and the propylene polymer (C) is 10 to 90M%, preferably 30 to 70% by weight. % by weight, the total amount of these ingredients,
That is, for (A) + (c) = 100 parts by weight, the modified polyolefin (F) is 0.2 to 50 parts by weight, preferably 0.5 to 30 parts by weight. Furthermore, the blending ratio of each additive to these resin components is (A) + (
C) + (F) = 0.005 to 3 parts by weight, preferably 0.01 parts by weight of the copper compound (B)
~1 part by weight, the same < (A) + (C) + (F
) -100 parts by weight, the heat stabilizer (D) is 0.
005 to 5 parts by weight, preferably 0.01 to 3 parts by weight, and for the same < (A) + (C) 10 (F) = 100 parts by weight, the copper damage inhibitor (E) is 0.005 parts by weight. ~5 parts by weight,
Preferably it is 0.01 to 3 parts by weight.
ここで、ポリアミド（Ａ）が１０重量％未満では、得ら
れる樹脂組成物が耐熱性、機械的強度の特性において満
足できないものとなることがあり、逆にプロピレン重合
体（Ｃ）が１０重量％未満では、得られる樹脂組成物に
ポリプロピレンが本来有する低吸水性などの優れた特性
を充分に付与することができないことがある。また、変
性ポリオレフィン（Ｆ）が０．２重量部未満では、（Ａ
）成分であるポリアミドと（Ｃ）成分であるプロピレン
重合体との相溶性を改善することがむずかしいため、得
られる組成物に所望する物性を付与することができない
場合がある。一方、変性ポリオレフィン（Ｆ）が５０重
量部を超えても、配合量に相当する効果は少なく、むし
ろ得られる樹脂組成物の諸物性を低下させるおそれがあ
る。Here, if the polyamide (A) is less than 10% by weight, the resulting resin composition may not be satisfactory in terms of heat resistance and mechanical strength; conversely, if the polyamide (C) is less than 10% by weight, If the amount is less than that, it may not be possible to sufficiently impart the excellent properties inherent to polypropylene, such as low water absorption, to the resulting resin composition. Furthermore, if the modified polyolefin (F) is less than 0.2 parts by weight, (A
Since it is difficult to improve the compatibility between the polyamide (component) and the propylene polymer (component (C)), it may not be possible to impart desired physical properties to the resulting composition. On the other hand, even if the modified polyolefin (F) exceeds 50 parts by weight, the effect corresponding to the amount blended is small, and there is a risk that the various physical properties of the resulting resin composition may be deteriorated.
また添加物としての銅化合物（Ｂ）、耐熱安定剤（Ｄ）
及び銅害防止剤（Ｅ）が前記の各範囲未満では耐熱老化
性が低下する傾向にあり、前記範囲を超えても、それに
相当する効果はなく、むしＢ
ろ得られる樹脂組成物の耐熱老化性が低下することがあ
る。Also, copper compounds (B) and heat stabilizers (D) as additives.
If the copper damage inhibitor (E) is less than the above ranges, the heat aging resistance tends to decrease, and even if it exceeds the above ranges, there is no corresponding effect, and the heat aging resistance of the resulting resin composition is rather reduced. Sexuality may decrease.
前記の配合割合で各成分を混合して耐熱老化性に優れた
樹脂組成物を製造するには、ポリアミド（Ａ）に銅化合
物（Ｂ）を添加したポリアミド組成物と、プロピレン重
合体（Ｃ）に耐熱安定剤（Ｄ）と銅害防止剤（Ｅ）とを
添加したプロピレン樹脂組成物、及び変性ポリオレフィ
ン（Ｆ）の王者をそれぞれ用意し、これらを溶融混合す
る必要がある。このような操作をすることによって、は
じめて耐熱老化性に優れたポリアミド樹脂組成物を製造
することができる。In order to produce a resin composition with excellent heat aging resistance by mixing each component in the above blending ratio, a polyamide composition in which a copper compound (B) is added to a polyamide (A), and a propylene polymer (C) are used. It is necessary to prepare a propylene resin composition containing a heat stabilizer (D) and a copper damage inhibitor (E) and a modified polyolefin (F), respectively, and melt and mix them. By performing such an operation, a polyamide resin composition having excellent heat aging resistance can be produced for the first time.
その他の手法、たとえば全ての成分をそれぞれ単独で用
意し、これらを同時に溶融混合したとしても充分な耐熱
老化性を発現させることは困難であり、また発現したと
しても、その効果は小さく、本発明の目的を達成するこ
とはできない。Even if other methods, such as preparing all the components individually and melting and mixing them at the same time, it is difficult to develop sufficient heat aging resistance, and even if they are developed, the effect is small, and the present invention cannot achieve its purpose.
このような耐熱老化性に優れたポリアミド樹脂組成物を
製造する方法は、銅化合物を含む市販のポリアミド樹脂
と、耐熱安定剤と銅害防止剤とを含む市販のポリプロピ
レン樹脂、及び変性ポリオレフィンを熔融混合あるいは
混練することにより行うこともでき、また重合反応終了
後、未だ溶融状態にあるポリアミド樹脂及びポリプロピ
レン樹脂にそれぞれの添加剤を加え、それらに変性ポリ
オレフィンを加えて溶融混合あるいは混練することも可
能である。A method for producing such a polyamide resin composition with excellent heat aging resistance involves melting a commercially available polyamide resin containing a copper compound, a commercially available polypropylene resin containing a heat resistant stabilizer and a copper damage inhibitor, and a modified polyolefin. This can be done by mixing or kneading, or after the completion of the polymerization reaction, it is also possible to add the respective additives to the polyamide resin and polypropylene resin that are still in a molten state, add the modified polyolefin to them, and then melt mix or knead. It is.
各成分を溶融混合する際の温度は、適宜選定すればよい
が、通常は１８０°Ｃ〜３５０°Ｃ１好ましくは２００
〜３００ ’Ｃの範囲から選定される。温度が低すぎる
と、各成分の溶融が不充分であるため、完全な溶融混合
が困難となり、また高すぎると分解反応が進行するおそ
れがあり、好ましくない。The temperature at which each component is melted and mixed may be selected as appropriate, but is usually 180°C to 350°C, preferably 200°C.
~300'C. If the temperature is too low, each component will be insufficiently melted, making complete melt mixing difficult, and if the temperature is too high, there is a risk that decomposition reaction will proceed, which is not preferable.
なお、上記溶融混合の操作は、単軸、二軸押出機など公
知の溶融混合装置を用いて行えばよい。The above-mentioned melt-mixing operation may be performed using a known melt-mixing device such as a single-screw or twin-screw extruder.
さらに本発明の方法において、得られるポリアミド樹脂
組成物の剛性、耐熱性、引張強度などを改善するために
、各種の無機充填剤や繊維状充填剤その他のものを適宜
配合することができる。Furthermore, in the method of the present invention, in order to improve the rigidity, heat resistance, tensile strength, etc. of the resulting polyamide resin composition, various inorganic fillers, fibrous fillers, and other substances may be appropriately blended.
上記無機充填剤としては、粉末状充填剤、例えば酸化鉄
、アルミナ、酸化マグネシウム、酸化カルシウム、亜鉛
華などの酸化物、水酸化アルミニウム、水酸化マグネシ
ウム、塩基性炭酸マグネシウム、水酸化カルシウム、酸
化スズ水和物、酸化ジルコニウム水和物などのような水
和金属酸化物、炭酸カルシウム、炭酸マグネシウムなど
のような炭酸塩、タルク、クレー、ベントナイト、アタ
パルジャイトなどのようなケイ酸塩、ホウ酸バリウム、
ホウ酸亜鉛などのようなホウ酸塩、リン酸アルミニウム
、トリポリリン酸ナトリウムなどのようなリン酸塩、石
コウなどのような硫酸塩あるいは亜硫酸塩などを挙げる
ことができる。また繊維状充填剤としては、例えばガラ
ス繊維、チタン酸カリウム繊維、金属被覆ガラス繊維、
セラミックス繊維、ウオラストナイト、炭素繊維、アラ
ミド繊維、金属炭化物繊維、超高弾性ポリエチレン繊維
などを挙げることができる。その他のものとしては、ガ
ラスピーズ、ガラスバルーン、シラスバルーンなどの球
状物、ガラス粉末、ガラスフレーク、マイカなどを用い
ることができる。The above-mentioned inorganic fillers include powder fillers, such as oxides such as iron oxide, alumina, magnesium oxide, calcium oxide, and zinc white, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium hydroxide, and tin oxide. hydrates, hydrated metal oxides such as zirconium oxide hydrates, carbonates such as calcium carbonate, magnesium carbonate etc., silicates such as talc, clay, bentonite, attapulgite etc., barium borate,
Examples include borates such as zinc borate, phosphates such as aluminum phosphate, sodium tripolyphosphate, and sulfates or sulfites such as gypsum. Examples of fibrous fillers include glass fibers, potassium titanate fibers, metal-coated glass fibers,
Examples include ceramic fibers, wollastonite, carbon fibers, aramid fibers, metal carbide fibers, and ultra-high elastic polyethylene fibers. Other materials that can be used include spherical objects such as glass peas, glass balloons, and glass balloons, glass powder, glass flakes, and mica.
これらの充填剤の種類及び配合量は、目的に応じて適宜
選定することができ、各種充填剤を単独で用いてもよく
、また二種以上の充填剤を混合して使用することもでき
る。その配合量は、一般には前記樹脂成分、すなわち（
Ａ）＋ （Ｃ）＋ （Ｆ）−１００重量部に対して５〜
２００重量部、好ましくは１０〜１５０重量部である。The types and amounts of these fillers can be appropriately selected depending on the purpose, and various fillers may be used alone or two or more fillers may be used in combination. The blending amount is generally the same as that of the resin component, i.e. (
A) + (C) + (F) - 5 to 100 parts by weight
The amount is 200 parts by weight, preferably 10 to 150 parts by weight.
この配合割合が少ないと補強効果が充分に得られず、ま
た多過ぎると成形性が低下することがある。If the blending ratio is too low, a sufficient reinforcing effect cannot be obtained, and if it is too high, moldability may deteriorate.
さらに目的に応じて染料、顔料、可塑剤、滑剤。Furthermore, dyes, pigments, plasticizers, and lubricants depending on the purpose.
離型剤、カップリング剤１発泡剤、耐熱剤、耐候剤ある
いは難燃剤等を適量添加することもできる。Appropriate amounts of a mold release agent, a coupling agent, a blowing agent, a heat resistant agent, a weather resistant agent, a flame retardant, etc. can also be added.
また、本発明により得られる組成物は、パイプ。The composition obtained by the present invention can also be used for pipes.
チューブ、棒、射出成形品等に加工することが可能であ
り、さらに後加工としてメツキ塗装などを施すこともで
きる。It can be processed into tubes, rods, injection molded products, etc., and can also be coated with plating as post-processing.
次に、本発明を実施例および比較例に基いて、さらに詳
しく説明する。Next, the present invention will be explained in more detail based on Examples and Comparative Examples.
なお、以下の各側において得られたポリアミド樹脂組成
物の各種物性は、次の如き試験方法に基いて測定したも
のである。The various physical properties of the polyamide resin compositions obtained on each side below were measured based on the following test methods.
跋腋片■作戊汰
試験片は、組成物をスクリューインライン式射出成形機
で成形して作成した。このときのシリンダー温度は、（
Ａ）ポリアミド樹脂としてナイロン６６を用いた場合は
２８０’Ｃ，ナイロン６／６６を用いた場合は２６５°
Ｃ、ナイロン６を用いた場合は２５０°Ｃとした。また
、金型温度は６０°Ｃとした。The axillary piece ■The Bota test piece was prepared by molding the composition using a screw in-line injection molding machine. The cylinder temperature at this time is (
A) 280'C when using nylon 66 as the polyamide resin, 265° when using nylon 6/66
When C and nylon 6 were used, the temperature was 250°C. Moreover, the mold temperature was 60°C.
μｍ口に件評ＪＬ析汰
ＡＳＴＭ−Ｄ−６３８に準拠し、１号試験片を１５０°
Ｃのオーブン中に６００時間入れ、引張強度の低下を観
察した。In accordance with JL analysis ASTM-D-638, the No. 1 test piece was 150°
The sample was placed in a C oven for 600 hours, and a decrease in tensile strength was observed.
実施例１〜６及び比較例１〜８
第１表に示す配合のポリアミド組成物（ＰＡ）、プロピ
レン樹脂組成物（ＰＰ）、及び変性ポリオレフィン（Ｆ
）を用意した。なお、第１表中、各樹脂成分（Ａ）、（
Ｃ）、 （Ｆ）の配合割合は、これらの樹脂成分の合計
に対する割合であり、各添加物（ＢＬ（Ｄ）、（Ｅ）の
配合割合は、樹脂成分（Ａ）＋（Ｃ）＋ （Ｆ） −１
００重量部に対する割合である。またポリアミド組成物
（ＰＡ）及びプロピレン樹脂組成物（ＰＰ）は、ヘンシ
ェルミキサーを用いてあらかじめ各樹脂に添加剤を添加
した状態でそれぞれ５分間乾式混合を行い、得られた各
混合物をベント付同方向二軸押出機（内径３００ｍｍ）
を用いて溶融混練し、それぞれの組成物のペレットを作
成した。なお、ベレット作成時の加熱温度は、ポリアミ
ド組成物（ＰＡ）においてナイロン６６を用いた場合は
２８０°Ｃ５ナイロン６／６６を用いた場合は２６５°
Ｃ，ナイロン６を用いた場合は２５０°Ｃとし、またプ
ロピレン樹脂組成物（ＰＰ）は２２０°Ｃとした。Examples 1 to 6 and Comparative Examples 1 to 8 Polyamide compositions (PA), propylene resin compositions (PP), and modified polyolefins (F
) was prepared. In addition, in Table 1, each resin component (A), (
The blending ratio of C) and (F) is the ratio to the total of these resin components, and the blending ratio of each additive (BL(D), (E) is the resin component (A) + (C) + ( F) -1
00 parts by weight. In addition, the polyamide composition (PA) and propylene resin composition (PP) were dry mixed for 5 minutes using a Henschel mixer with additives added to each resin in advance, and the resulting mixtures were mixed in a vented container. Directional twin screw extruder (inner diameter 300mm)
Pellets of each composition were prepared by melt-kneading the compositions. The heating temperature when making the pellet is 280°C when nylon 66 is used in the polyamide composition (PA) and 265°C when nylon 6/66 is used.
The temperature was set at 250°C when C. and nylon 6 was used, and the temperature was set at 220°C when the propylene resin composition (PP) was used.
上記（ＰＡ）組成物ベレット、（ＰＰ）組成物ペレット
及び（Ｆ）変性ポリオレフィンのペレットをヘンシェル
ミキサーにより５分間乾式混合を行い、得られたベレッ
トの混合物をベント付同方向二軸押出機（内径３００ａ
ｎ）により溶融混練し、ペレットを作成した。なお、こ
のベレット作成時の加熱温度も、ポリアミド組成物（Ｐ
Ａ）にナイロン６６を用いた場合は２８０°Ｃ，ナイロ
ン６／６６を用いた場合は２６５°Ｃ，ナイロン６を用
いた場合は２５０°Ｃとした。The above (PA) composition pellets, (PP) composition pellets, and (F) modified polyolefin pellets were dry mixed for 5 minutes using a Henschel mixer, and the resulting pellet mixture was transferred to a codirectional twin-screw extruder with a vent (inner diameter 300a
n) to prepare pellets. In addition, the heating temperature at the time of making this pellet also depends on the polyamide composition (P
In A), the temperature was 280°C when nylon 66 was used, 265°C when nylon 6/66 was used, and 250°C when nylon 6 was used.
得られたそれぞれのベレットを、射出成形機を使用して
試験片とし、熱劣化性を評価した。Each of the obtained pellets was made into a test piece using an injection molding machine, and thermal deterioration properties were evaluated.
それぞれの試験結果を第２表に示す。The results of each test are shown in Table 2.
比較例９
全成分をそれぞれ単独で用意し、それらを−括して乾式
混合し、この混合物を溶融混練に供した以外は上記実施
例と同様の操作を行い、熱劣化性を評価した。この試験
結果も第２表に示す。Comparative Example 9 The same operations as in the above Example were performed, except that all the components were individually prepared, dry-mixed together, and this mixture was melt-kneaded, and the thermal deterioration properties were evaluated. The results of this test are also shown in Table 2.
（以下余白）
＊１：ナイロン６６．相対粘度 ２．８５．アミノ末端
基濃度 ５．２Ｘ１０−’当量７ｇ本２：ナイロン６／
６６、共重合比（ナイロン６／ナイロン６６）＝１５／
８５．相対粘度２．９０．アミノ末端基濃度 ４．７Ｘ
１０−’当量／ｇ
＊３：ナイロン６．相対粘度 ３．１０．アミノ末端基
濃度 ４．９Ｘ１０−５当量／ｇ
＊４：酢酸第２銅
＊５：プロピレン単独重合体、ＪＩＳ Ｋ ６７５
８でのＭＦＲが１８ｇ／１０分のプロピレン単独重合体
（昭和電工■製、ショウアロマ−ＭＡ６１０Ｈ）
＊６：プロピレンブロツク共重合体、 ＪＩＳ Ｋ
６７５８でのＭＦＲが１６ ｇ／ｌ ０分のプロビレ−
エチレンブロック共重合体（昭和電工■製、ショウアロ
マ−ＭＫ５１１）＊７：商品名ＭＡＲＫ ＣＤＡ−１
，）リアゾール系、アデカ・アーガス社製
＊８：ラジカル連鎖禁止剤、商品名イルガノックス−１
０１０，日本チバ・ガイキー製＊９：過酸化物分解剤、
商品名ＭＡＲＫ ＡＯ５０３、アデカ・アーガス社製
＊１０ニゲラフト変性ポリプロピレン、２３０’ＣのＭ
ＦＲが１．０ｇ／１０分を有するアイツククチイックポ
リプロピレンに、無水マレイン酸を０．３５重量％付加
したグラフト変性ポリプロピレン
＊１１： グリシジルメタクリレートグラフト化エチ
レン−酢酸ビニル共重合体、特公昭５５−１２４４９号
公報記載の方法を参考にして製造した。即ち、エチレン
−酢酸ビニル共重合体ペレットに、予めジクミルパーオ
キサイドを溶解したグリシジルメタクリレートを混合し
、室温で浸透させた。次いで、このグリシジルメタクリ
レート含浸ペレットを、内径３０ＩＩＩＩ１１のベント
付同方向二軸押出機を用いて、先端温度１７０°Ｃで押
出し、グラフト重合したエポキシ基含有共重合体ペレッ
トを得た（グリシジルメタクリレート含量２賀ｔ％）。(Left below) *1: Nylon 66. Relative viscosity 2.85. Amino end group concentration 5.2X10-' equivalent weight 7g Book 2: Nylon 6/
66, copolymerization ratio (nylon 6/nylon 66) = 15/
85. Relative viscosity 2.90. Amino end group concentration 4.7X
10-' equivalent/g *3: Nylon 6. Relative viscosity 3.10. Amino terminal group concentration 4.9X10-5 equivalent/g *4: Cupric acetate *5: Propylene homopolymer, JIS K 675
Propylene homopolymer with MFR at 8 of 18 g/10 min (manufactured by Showa Denko ■, Showaromer-MA610H) *6: Propylene block copolymer, JIS K
MFR at 6758 is 16 g/l.
Ethylene block copolymer (manufactured by Showa Denko ■, Showaromer-MK511) *7: Product name MARK CDA-1
,) Riazole type, manufactured by Adeka Argus *8: Radical chain inhibitor, trade name Irganox-1
010, manufactured by Nippon Ciba Geikie *9: peroxide decomposer,
Product name MARK AO503, manufactured by Adeka Argus *10 Niger raft modified polypropylene, 230'C M
Graft-modified polypropylene obtained by adding 0.35% by weight of maleic anhydride to organic polypropylene having an FR of 1.0 g/10 min. *11: Glycidyl methacrylate grafted ethylene-vinyl acetate copolymer, Japanese Patent Publication No. 1987- It was produced with reference to the method described in Japanese Patent No. 12449. That is, glycidyl methacrylate in which dicumyl peroxide had been dissolved in advance was mixed with ethylene-vinyl acetate copolymer pellets, and the mixture was allowed to penetrate at room temperature. Next, the glycidyl methacrylate-impregnated pellets were extruded using a vented co-directional twin-screw extruder with an inner diameter of 30III11 at a tip temperature of 170°C to obtain graft-polymerized epoxy group-containing copolymer pellets (glycidyl methacrylate content: 2 gat%).
第
表
〔発明の効果〕
以上説明したように、本発明によれば、ポリアミドとプ
ロピレン重合体のそれぞれの優れた特性を併せ有し、さ
らに耐熱劣化性に優れたポリアミド樹脂組成物を製造す
ることができ、耐熱性を要求される使用環境に適した樹
脂組成物を容易に得ることができる。また各種充填剤な
どを加えることにより強度なども向上させることができ
、自動車部品、電機器具５機械部品、工業部品などの強
度や耐熱変形性の要求される用途に好適なポリアミド樹
脂組成物を提供することができる。Table 1 [Effects of the Invention] As explained above, according to the present invention, it is possible to produce a polyamide resin composition that has both the excellent properties of polyamide and propylene polymer and also has excellent heat deterioration resistance. This makes it possible to easily obtain a resin composition suitable for use environments that require heat resistance. Strength can also be improved by adding various fillers, etc., providing polyamide resin compositions suitable for applications that require strength and heat deformation resistance, such as automobile parts, electrical appliances, mechanical parts, and industrial parts. can do.
Claims (1)
たポリアミド組成物と、 プロピレン重合体（Ｃ）に耐熱安定剤（Ｄ）と銅害防止
剤（Ｅ）とを添加したプロピレン樹脂組成物と、 変性ポリオレフィン（Ｆ） の三者を溶融混合することを特徴とするポリアミド樹脂
組成物。(1) A polyamide composition in which a copper compound (B) is added to a polyamide resin (A), and a propylene resin composition in which a heat stabilizer (D) and a copper damage inhibitor (E) are added to a propylene polymer (C). A polyamide resin composition characterized by melt-mixing three components: a polyolefin (F) and a modified polyolefin (F).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2865189A JPH02208359A (en) | 1989-02-09 | 1989-02-09 | Polyamide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2865189A JPH02208359A (en) | 1989-02-09 | 1989-02-09 | Polyamide resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02208359A true JPH02208359A (en) | 1990-08-17 |
Family
ID=12254415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2865189A Pending JPH02208359A (en) | 1989-02-09 | 1989-02-09 | Polyamide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02208359A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02212533A (en) * | 1989-02-10 | 1990-08-23 | Tonen Sekiyukagaku Kk | Polymer composition |
| JPH04122771A (en) * | 1990-09-14 | 1992-04-23 | Ube Ind Ltd | Polyamide composition |
| WO2018009684A1 (en) * | 2016-07-07 | 2018-01-11 | Medtronic Vascular Inc. | Medical device and plasticized nylon material |
| WO2019035484A1 (en) * | 2017-08-18 | 2019-02-21 | 三井化学株式会社 | Semi-aromatic polyamide resin composition and molded body thereof |
-
1989
- 1989-02-09 JP JP2865189A patent/JPH02208359A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02212533A (en) * | 1989-02-10 | 1990-08-23 | Tonen Sekiyukagaku Kk | Polymer composition |
| JPH04122771A (en) * | 1990-09-14 | 1992-04-23 | Ube Ind Ltd | Polyamide composition |
| WO2018009684A1 (en) * | 2016-07-07 | 2018-01-11 | Medtronic Vascular Inc. | Medical device and plasticized nylon material |
| CN109475667A (en) * | 2016-07-07 | 2019-03-15 | 美敦力瓦斯科尔勒公司 | Medical device and plasticized nylons material |
| JP2019528094A (en) * | 2016-07-07 | 2019-10-10 | メドトロニック ヴァスキュラー インコーポレイテッド | Medical devices and plasticized nylon materials |
| US10513597B2 (en) | 2016-07-07 | 2019-12-24 | Medtronic Vascular, Inc. | Medical device and plasticized nylon material |
| WO2019035484A1 (en) * | 2017-08-18 | 2019-02-21 | 三井化学株式会社 | Semi-aromatic polyamide resin composition and molded body thereof |
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