JPH04220458A - Resin composition for blow molding - Google Patents
Resin composition for blow moldingInfo
- Publication number
- JPH04220458A JPH04220458A JP40439090A JP40439090A JPH04220458A JP H04220458 A JPH04220458 A JP H04220458A JP 40439090 A JP40439090 A JP 40439090A JP 40439090 A JP40439090 A JP 40439090A JP H04220458 A JPH04220458 A JP H04220458A
- Authority
- JP
- Japan
- Prior art keywords
- blow molding
- weight
- nylon
- copper
- acid
- 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
- 238000000071 blow moulding Methods 0.000 title claims abstract description 10
- 239000011342 resin composition Substances 0.000 title claims abstract description 5
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 17
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 11
- 239000003365 glass fiber Substances 0.000 claims abstract description 8
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 8
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 150000004678 hydrides Chemical class 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 abstract description 11
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- 239000004677 Nylon Substances 0.000 description 10
- 229920001778 nylon Polymers 0.000 description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 239000005749 Copper compound Substances 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000001880 copper compounds Chemical class 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000004018 acid anhydride group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Chemical class COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 3
- 150000002497 iodine compounds Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002184 metal Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- ODLHGICHYURWBS-LKONHMLTSA-N trappsol cyclo Chemical compound CC(O)COC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)COCC(O)C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1COCC(C)O ODLHGICHYURWBS-LKONHMLTSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical class COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical class OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910003556 H2 SO4 Inorganic materials 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229910052742 iron 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
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical class COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- NISOCYUAQBTSBZ-UHFFFAOYSA-N n-methyl-n-(2-phenylethyl)prop-2-yn-1-amine Chemical compound C#CCN(C)CCC1=CC=CC=C1 NISOCYUAQBTSBZ-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- NIDNOXCRFUCAKQ-RNGGSSJXSA-N (1r,2r,3s,4s)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical class C1[C@@H]2C=C[C@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-RNGGSSJXSA-N 0.000 description 1
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N (2-methylphenyl)methanol Chemical compound CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical class O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical class CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical class FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical class ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical class C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- NMSZFQAFWHFSPE-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxycarbonyl)but-3-enoic acid Chemical class OC(=O)CC(=C)C(=O)OCC1CO1 NMSZFQAFWHFSPE-UHFFFAOYSA-N 0.000 description 1
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 241000156978 Erebia Species 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical class O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- 101100438229 Solanum tuberosum PCM4 gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-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
- NHQSYENHCTXNIG-UHFFFAOYSA-N [Cu+3].[O-]P([O-])[O-] Chemical compound [Cu+3].[O-]P([O-])[O-] NHQSYENHCTXNIG-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 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
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical class CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 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
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 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
- DYROSKSLMAPFBZ-UHFFFAOYSA-L copper;2-hydroxypropanoate Chemical compound [Cu+2].CC(O)C([O-])=O.CC(O)C([O-])=O DYROSKSLMAPFBZ-UHFFFAOYSA-L 0.000 description 1
- ZZBHLLYRFXFBLC-UHFFFAOYSA-N copper;decanedioic acid Chemical compound [Cu].OC(=O)CCCCCCCCC(O)=O ZZBHLLYRFXFBLC-UHFFFAOYSA-N 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- LZJJVTQGPPWQFS-UHFFFAOYSA-L copper;propanoate Chemical compound [Cu+2].CCC([O-])=O.CCC([O-])=O LZJJVTQGPPWQFS-UHFFFAOYSA-L 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical class C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001530 fumaric acid Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical class CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical class OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical class COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical class C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical class C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000001384 succinic acid Chemical class 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Chemical class CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical group OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明はポリアミド樹脂組成物に
関するものである。詳しくは、ブロー成形用のポリアミ
ド樹脂組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to polyamide resin compositions. Specifically, the present invention relates to a polyamide resin composition for blow molding.
【０００２】0002
【従来の技術】ポリアミド樹脂は、機械的特性，耐薬品
性，加工性等にすぐれた樹脂であり、幅広い用途に使用
されてはいるが、溶融粘度のせん断速度依存性が小さく
、滞留時の粘度低下が大きく、溶融張力が小さいなどと
いう、ブロー成形用材料として用いようとした場合に、
均一な肉厚をもった製品を、安定して生産することがで
きないという、きわめて重大な欠点を有している。[Prior Art] Polyamide resin is a resin with excellent mechanical properties, chemical resistance, processability, etc., and is used in a wide range of applications, but the dependence of melt viscosity on shear rate is small and When trying to use it as a material for blow molding, it has a large viscosity drop and low melt tension.
This method has a very serious drawback in that it is not possible to stably produce products with uniform wall thickness.
【０００３】すなわち、ブロー成形用材料として要求さ
れる性能しては、溶融粘度が高いことのみならず、生産
性という意味からは、成形機内では溶融粘度がなるべく
低く、パリソンを形成する時点では溶融粘度が高いこと
が必要であり、また、ドロータウンを防ぐという意味か
らは、滞留時の粘度低下が小さいことが必要であり、パ
リソンにガスを吹き込み、均一な肉厚をもった製品とす
るためには溶融張力が必要であるが、ポリアミド樹脂は
いずれの性能も不十分である。In other words, the performance required for a material for blow molding is not only high melt viscosity, but also from the perspective of productivity, the melt viscosity should be as low as possible in the molding machine, and the melt viscosity should be as low as possible at the time of forming the parison. It is necessary to have high viscosity, and in order to prevent draw town, it is necessary that the decrease in viscosity during retention is small. Melt tension is required for this purpose, but polyamide resins are insufficient in both properties.
【０００４】この欠点を改良するために、従来より数多
くの検討がなされてきた（特開昭５３−１０１０４８号
公報、特開昭５５−１２０８２号公報、特開昭６０−１
７０６６４号公報、特開昭６０−１７１１３３号公報、
特開昭６２−２９０７２５号公報など）。しかしながら
、これらの組成物においても、いくらかの改良は見られ
るものの、いまだ溶融粘度のせん断速度依存性が小さく
、滞留時の分解ガス、ゲル化などの好ましからざる現象
が見られるなど、数多くの解決すべき問題点を有してい
る。[0004] In order to improve this drawback, many studies have been made in the past (Japanese Unexamined Patent Publications No. 101048/1982, No. 12082/1982, Japanese Unexamined Patent Publications No. 60/1982).
Publication No. 70664, Japanese Unexamined Patent Publication No. 171133/1983,
(Japanese Patent Application Laid-Open No. 62-290725, etc.). However, although some improvements have been made in these compositions, there are still many unresolved problems, such as the small dependence of melt viscosity on shear rate and unfavorable phenomena such as decomposition gas and gelation during retention. There are some issues that need to be addressed.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、ポリアミド
樹脂をブロー成形用材料として使用しようとする場合の
上記問題点のうち、溶融張力の高いすぐれたブロー成形
用材料を提供し、さらにこれらから製造された良好なブ
ロー中空成形品を提供するという課題を解決するもので
ある。SUMMARY OF THE INVENTION The present invention provides an excellent blow molding material with high melt tension, which solves the above-mentioned problems when polyamide resin is used as a blow molding material, and also solves the above problems. This solves the problem of providing a well-produced blow hollow molded product.
【０００６】[0006]
【課題を解決するための手段】本発明者は、上記課題を
解決するために研究を重ねた結果、ポリアミド樹脂に、
特定の熱可塑性樹脂を、特定の比率にて配合した場合に
のみ上記課題を解決できることを見い出し本発明を完成
した。すなわち本発明は、
（Ａ）ポリアミド樹脂
（Ｂ）芳香族ビニル化合物（Ｘ）と共役ジエン化合物の
水素化物（Ｙ）からなる共重合体のα，β−不飽和カル
ボン酸又はその誘導体の付加物
（Ｃ）他の熱可塑性樹脂
（Ｄ）ガラス繊維
（ただし、（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）各成分の配
合量をそれぞれ、Ａ、Ｂ、Ｃ、Ｄ重量％とするとき、６
０≦Ａ≦９７，３≦Ｂ＋Ｃ≦４０，０．０１≦Ｂ／Ｃ≦
９９，０．０５≦Ｄ／（Ａ＋Ｂ＋Ｃ）≦１，Ａ＋Ｂ＋Ｃ
＋Ｄ＝１００；（Ｘ），（Ｙ）各成分の共重合量をそれ
ぞれ、Ｘ，Ｙ重量％とするとき、３８＜Ｘ＜８０，２０
＜Ｙ＜６２，Ｘ＋Ｙ＝１００）であることを特徴とする
ブロー成形用樹脂組成物である。[Means for Solving the Problems] As a result of repeated research in order to solve the above problems, the present inventor has discovered that polyamide resin has the following properties:
The present invention has been completed by discovering that the above problem can be solved only when a specific thermoplastic resin is blended in a specific ratio. That is, the present invention provides an adduct of an α,β-unsaturated carboxylic acid or a derivative thereof of a copolymer consisting of (A) a polyamide resin (B) an aromatic vinyl compound (X) and a hydride of a conjugated diene compound (Y). (C) Other thermoplastic resin (D) Glass fiber (however, the blending amounts of each component (A), (B), (C), and (D) are A, B, C, and D weight percent, respectively) Time, 6
0≦A≦97, 3≦B+C≦40, 0.01≦B/C≦
99, 0.05≦D/(A+B+C)≦1, A+B+C
+D=100; When the copolymerization amounts of each component (X) and (Y) are X and Y weight%, respectively, 38<X<80, 20
<Y<62, X+Y=100).
【０００７】本発明において、成分（Ａ）であるポリア
ミド樹脂とは、ナイロン４，ナイロン６，ナイロン８，
ナイロン９，ナイロン１０，ナイロン１１，ナイロン１
２，ナイロン４６，ナイロン６６，ナイロン６１０，ナ
イロン６１２，ナイロン６３６，ナイロン１２１２など
の脂肪族ポリアミド樹脂や、ナイロン４Ｔ（Ｔ：テレフ
タル酸），ナイロン４Ｉ（Ｉ：イソフタル酸），ナイロ
ン６Ｔ，ナイロン６Ｉ，ナイロン１２Ｔ，ナイロン１２
Ｉなどの芳香族ポリアミド樹脂や、これらの共重合体、
ブレンドなどを例示することができる。In the present invention, the polyamide resin as component (A) includes nylon 4, nylon 6, nylon 8,
Nylon 9, Nylon 10, Nylon 11, Nylon 1
2. Aliphatic polyamide resins such as nylon 46, nylon 66, nylon 610, nylon 612, nylon 636, nylon 1212, nylon 4T (T: terephthalic acid), nylon 4I (I: isophthalic acid), nylon 6T, nylon 6I , nylon 12T, nylon 12
Aromatic polyamide resins such as I and copolymers thereof,
Examples include blends.
【０００８】これらのポリアミド樹脂は、数平均分子量
５，０００〜１００，０００のものが好ましく、８，０
００〜５０，０００のものがより好ましく、１０，００
０〜３０，０００のものが最も好ましい。数平均分子量
が５，０００以下であると、組成物とした場合に十分な
溶融粘度が得られない。数平均分子量が１００，０００
以上であると、初期の溶融粘度は高いものの、滞留時の
粘度低下が大きく好ましくない。These polyamide resins preferably have a number average molecular weight of 5,000 to 100,000, with a number average molecular weight of 8.0 to 100,000.
00 to 50,000 is more preferable, and 10,00
0 to 30,000 is most preferred. When the number average molecular weight is 5,000 or less, sufficient melt viscosity cannot be obtained when used as a composition. Number average molecular weight is 100,000
If it is above, although the initial melt viscosity is high, the viscosity decreases greatly during residence, which is not preferable.
【０００９】本発明において、成分（Ｂ）である、芳香
族ビニル化合物（Ｘ）と共役ジエン化合物の水素化物（
Ｙ）からなる共重合体の、α，β−不飽和カルボン酸又
はその誘導体の付加物とは、芳香族ビニル化合物、例え
ばスチレン，α−メチルスチレン，ビニルトルエンなど
の化合物と、共役ジエン化合物、例えばブタジエン，イ
ソプレン，１，３−ペンタジエンなどの化合物の水素化
物からなる共重合体、好ましくはスチレンとブタジエン
の水素化物からなる共重合体に、α，β−不飽和カルボ
ン酸又はその誘導体が付加した共重合体を示す。In the present invention, component (B), a hydride of an aromatic vinyl compound (X) and a conjugated diene compound (
The adduct of α,β-unsaturated carboxylic acid or its derivative of the copolymer consisting of Y) is an aromatic vinyl compound, such as a compound such as styrene, α-methylstyrene, or vinyltoluene, and a conjugated diene compound, For example, an α,β-unsaturated carboxylic acid or a derivative thereof is added to a copolymer of a hydride of a compound such as butadiene, isoprene, or 1,3-pentadiene, preferably a copolymer of a hydride of styrene and butadiene. This shows the copolymer.
【００１０】ここで用いられるα，β−不飽和カルボン
酸又はその誘導体としては、マレイン酸，無水マレイン
酸，マレイン酸モノメチルエステル，マレイン酸モノメ
チルエステルの金属塩，フマル酸，フマル酸モノメチル
エステル，コハク酸，無水コハク酸，イタコン酸，アク
リル酸，メタクリル酸，ハイミック酸，無水ハイミック
酸，クロトン酸，フタル酸，無水フタル酸，メタクリル
酸の金属塩，アクリル酸の金属塩，マレイミド，フタル
イミド，グリシジルメタクリレート，グリシジルアクリ
レート，アリルグリシジルエーテル，ビニルグリシジル
エーテル，グリシジルイタコネートなどを例示すること
ができる。The α,β-unsaturated carboxylic acids or derivatives thereof used here include maleic acid, maleic anhydride, maleic acid monomethyl ester, metal salts of maleic acid monomethyl ester, fumaric acid, fumaric acid monomethyl ester, and succinic acid. Acid, succinic anhydride, itaconic acid, acrylic acid, methacrylic acid, himic acid, himic anhydride, crotonic acid, phthalic acid, phthalic anhydride, metal salts of methacrylic acid, metal salts of acrylic acid, maleimide, phthalimide, glycidyl methacrylate , glycidyl acrylate, allyl glycidyl ether, vinyl glycidyl ether, glycidyl itaconate, and the like.
【００１１】特に好ましいのは無水マレイン酸である。
α，β−不飽和カルボン酸又はその誘導体の上記共重合
体への付加量は、０．０１〜２０ｍｏｌ％の範囲が好ま
しく、特に０．０５〜１０ｍｏｌ％の範囲が好ましい。
付加量が０．０１ｍｏｌ％以下であると、ポリアミドに
対する混和性が見られず、成形品に相ハクリが見られる
などの好ましからざる結果を与える。Particularly preferred is maleic anhydride. The amount of α,β-unsaturated carboxylic acid or its derivative added to the copolymer is preferably in the range of 0.01 to 20 mol%, particularly preferably in the range of 0.05 to 10 mol%. If the amount added is less than 0.01 mol %, miscibility with polyamide is not observed and unfavorable results such as phase peeling are observed in the molded product are produced.
【００１２】付加量が２０ｍｏｌ％以上であると、ポリ
アミドの着色、ゲル化などが起こり好ましくない。本発
明において、成分（Ｂ）の、芳香族ビニル化合物（Ｘ）
と共役ジエンの水素化物（Ｙ）の共重合量をそれぞれＸ
，Ｙ重量％とするとき、３８＜Ｘ＜８０，２０＜Ｙ＜６
２（Ｘ＋Ｙ＝１００）の範囲が好ましく、３８＜Ｘ＜７
０，３０＜Ｙ＜６２（Ｘ＋Ｙ＝１００）の範囲が特に好
ましく、３８＜Ｘ＜６０，４０＜Ｙ＜６２（Ｘ＋Ｙ＝１
００）の範囲が最も好ましい。[0012] If the amount added is 20 mol % or more, coloring and gelation of the polyamide occur, which is undesirable. In the present invention, the aromatic vinyl compound (X) of component (B)
The amount of copolymerization of hydride (Y) of conjugated diene and
, Y weight%, 38<X<80, 20<Y<6
The range of 2(X+Y=100) is preferable, and 38<X<7
The range of 0,30<Y<62 (X+Y=100) is particularly preferable, and the range of 38<X<60,40<Y<62 (X+Y=1
00) is most preferred.
【００１３】芳香族ビニル化合物（Ｘ）の共重合量がＸ
≦３８もしくはＸ≧８０（Ｙ≦２０もしくはＹ≧６２）
となると、組成物とした場合に十分な溶融粘度が得られ
ず好ましくない。本発明において、成分（Ｃ）である他
の熱可塑性樹脂とは、成分（Ｂ）以外のオレフィン系ポ
リマー、ポリフェニレンエーテルから選択される少くな
とも１種の熱可塑性樹脂である。[0013] The amount of copolymerization of the aromatic vinyl compound (X) is
≦38 or X≧80 (Y≦20 or Y≧62)
In this case, a sufficient melt viscosity cannot be obtained when the composition is prepared, which is not preferable. In the present invention, the other thermoplastic resin as component (C) is at least one thermoplastic resin selected from olefin polymers and polyphenylene ether other than component (B).
【００１４】上記成分（Ｂ）以外のオレフィン系ポリマ
ーとしては、結晶性ポリオレフィン（例えば、ポリエチ
レン、ポリプロピレンなど）、熱可塑性エラストマー（
例えば、スチレン−ブタジエン共重合体、スチレン−イ
ソプレン共重合体あるいはこれらの水素化物、１，２−
ポリブタジエンなど）、末端にのみ酸無水基を有するオ
レフィン系ポリマー（例えば本発明者が、ＷＯ８９−０
８１２０にて提案した重合体）などが挙げられる。Olefinic polymers other than the above component (B) include crystalline polyolefins (eg, polyethylene, polypropylene, etc.), thermoplastic elastomers (
For example, styrene-butadiene copolymer, styrene-isoprene copolymer or their hydrides, 1,2-
polybutadiene, etc.), olefinic polymers having acid anhydride groups only at the terminals (for example, the present inventor has
8120) and the like.
【００１５】本発明に用いられる結晶性ポリオレフィン
，熱可塑性エラストマー，ポリフェニレンエーテルには
、前記のα，β−不飽和カルボン酸又はその誘導体が付
加していてもよい。ここで、成分（Ａ），（Ｂ），（Ｃ
）の配合量をそれぞれＡ，Ｂ，Ｃ重量％とすると、６０
≦Ａ≦９７，３≦Ｂ＋Ｃ≦４０，０．０１≦Ｂ／Ｃ≦９
９である。The above-mentioned α,β-unsaturated carboxylic acid or derivative thereof may be added to the crystalline polyolefin, thermoplastic elastomer, and polyphenylene ether used in the present invention. Here, components (A), (B), (C
) is 60% by weight of A, B, and C, respectively.
≦A≦97, 3≦B+C≦40, 0.01≦B/C≦9
It is 9.
【００１６】Ａ＜６０（Ｂ＋Ｃ＞４０）であると、溶融
粘度は高くなるものの、溶融張力が低くなり良好な製品
を得ることができない。また耐熱性、剛性も著しく低下
してしまう。Ａ＞９７（Ｂ＋Ｃ＜３）であると、十分な
溶融粘度が得られず、また、滞留時の粘度低下も大きい
。Ｂ／Ｃ＜０．０１であると、十分な溶融粘度が得られ
ない。Ｂ／Ｃ＞９９であると、溶融粘度は高いものの、
溶融張力が低く、良好な製品を得ることができない。If A<60 (B+C>40), although the melt viscosity will be high, the melt tension will be low, making it impossible to obtain a good product. Moreover, heat resistance and rigidity are also significantly reduced. When A>97 (B+C<3), sufficient melt viscosity cannot be obtained and the viscosity decreases greatly during retention. When B/C<0.01, sufficient melt viscosity cannot be obtained. When B/C>99, although the melt viscosity is high,
The melt tension is low and it is not possible to obtain a good product.
【００１７】本発明において、成分（Ｄ）であるガラス
繊維とは、通常の熱可塑性樹脂に配合されるものであれ
ば特にその種類は限定されないが、シラン系，チタン系
，アルミニウム系などのカップリング剤で処理されてい
るものが特に好ましい。ガラス繊維（Ｄ）の配合量をＤ
重量％とすると、０．０５≦Ｄ／（Ａ＋Ｂ＋Ｃ）≦１（
Ａ＋Ｂ＋Ｃ＋Ｄ＝１００）の範囲が好ましい。Ｄ／（Ａ
＋Ｂ＋Ｃ）＜０．０５であると、ガラス繊維による補強
効果が見られない。Ｄ／（Ａ＋Ｂ＋Ｃ）＞１であると、
溶融張力が低くなり、良好な製品を得ることができない
。[0017] In the present invention, the glass fiber as component (D) is not particularly limited in type as long as it can be blended with ordinary thermoplastic resins, but glass fibers such as silane-based, titanium-based, aluminum-based, etc. Particularly preferred are those treated with a ring agent. The blending amount of glass fiber (D) is D
In weight%, 0.05≦D/(A+B+C)≦1(
A+B+C+D=100) is preferred. D/(A
+B+C)<0.05, no reinforcing effect by glass fibers is observed. If D/(A+B+C)>1,
Melt tension becomes low, making it impossible to obtain a good product.
【００１８】本発明に用いることのできる銅化合物また
は銅化合物とヨウ素化合物の混合物としては、ヨウ化第
一銅，塩化第一銅，塩化第二銅，臭化第一銅，臭化第二
銅，ギ酸銅，酢酸銅，プロピオン酸銅，ステアリン酸銅
，シュウ酸銅，セバシン酸銅，乳酸銅，安息香酸銅，サ
リチル酸銅，硫酸銅，硝酸銅，リン酸銅，亜リン酸銅，
あるいは銅キレート化合物などのような銅化合物または
、これらの銅化合物とヨウ化リチウム，ヨウ化カリウム
，ヨウ化ナトリウム，ヨウ化カルシウム，ヨウ化亜鉛，
ヨウ化銀などのようなヨウ素化合物の混合物を例示する
ことができる。特に好ましいのは、酢酸銅とヨウ化カリ
ウムの混合物，ヨウ化銅とヨウ化カリウムの混合物であ
る。Examples of the copper compound or the mixture of a copper compound and an iodine compound that can be used in the present invention include cuprous iodide, cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide. , copper formate, copper acetate, copper propionate, copper stearate, copper oxalate, copper sebacate, copper lactate, copper benzoate, copper salicylate, copper sulfate, copper nitrate, copper phosphate, copper phosphite,
Or copper compounds such as copper chelate compounds, or combinations of these copper compounds with lithium iodide, potassium iodide, sodium iodide, calcium iodide, zinc iodide,
Mixtures of iodine compounds such as silver iodide can be exemplified. Particularly preferred are mixtures of copper acetate and potassium iodide, and mixtures of copper iodide and potassium iodide.
【００１９】銅化合物または銅化合物とヨウ素化合物の
混合物の、本発明の組成物１００重量部への配合量は、
０．００１〜５重量部の範囲が好ましく、０．００５〜
４重量部の範囲が特に好ましい。配合量が０．００１重
量部以下であると、配合する目的である耐熱性の向上が
見られない。５重量部以上であると組成物の機械的強度
に好ましからざる影響を与える。The amount of the copper compound or the mixture of the copper compound and the iodine compound added to 100 parts by weight of the composition of the present invention is as follows:
The range is preferably from 0.001 to 5 parts by weight, and from 0.005 to 5 parts by weight.
A range of 4 parts by weight is particularly preferred. If the blending amount is 0.001 part by weight or less, the improvement in heat resistance, which is the purpose of blending, will not be observed. If the amount is 5 parts by weight or more, the mechanical strength of the composition will be adversely affected.
【００２０】本発明の組成物に必要に応じて、通常の熱
可塑性樹脂に添加される添加剤、例えば安定剤，紫外線
吸収剤，滑剤，核剤，染料，顔料，離型剤，可塑剤，難
燃剤，無機充填剤などを配合することも特に制限される
ものではない。本発明の組成物の調整は、ブラベンダー
，ニーダー，バンバリーミキサー，押出機等の従来公知
の技術によって達成される。If necessary, the composition of the present invention may contain additives that are added to ordinary thermoplastic resins, such as stabilizers, ultraviolet absorbers, lubricants, nucleating agents, dyes, pigments, mold release agents, plasticizers, There are no particular restrictions on the addition of flame retardants, inorganic fillers, etc. Preparation of the compositions of the present invention is accomplished by conventionally known techniques such as Brabenders, kneaders, Banbury mixers, extruders, and the like.
【００２１】[0021]
【実施例】以下に本発明の実施例を示すが、本発明はそ
の要旨を超えない限り以下の実施例に限定されるもので
はない。本発明に用いた原料及び試験方法を以下に示す
。
〔１〕 原 料
（１） Ｎｙ６６（Ａ）ナイロン６６；硫酸相対粘
度（ＪＩＳ Ｋ６８１０，９８％ Ｈ２ ＳＯ４
）２．６３（アミノ末端基濃度４６ｍｇｅｑ／Ｋｇ）
（２） Ｎｙ６６（Ｂ）ナイロン６６；硫酸相対粘
度（ＪＩＳ Ｋ６８１０，９８％ Ｈ２ ＳＯ４
）２．６０（アミノ末端基濃度８０ｍｇｅｑ／Ｋｇ）
（３） Ｎｙ６ナイロン６；硫酸相対粘度（ＪＩＳ
Ｋ６８１０，９８％Ｈ２ ＳＯ４ ）２．９０（４
） ＭＨＴＲ（Ａ）水素添加した変性スチレン−ブ
タジエン共重合体；旭化成工業（株）製 タフテック
Ｍ１９５３（登録商標），酸価１０（ｍｇＣＨ３
ＯＮａ／ｇ，滴定法）、スチレン成分約４０重量％、引
張モジュラス２，３００Ｋｇ／ｃｍ２
（５） ＭＨＴＲ（Ｂ）水素添加した変性スチレン
−ブタジエン共重合体；旭化成工業（株）製 タフテ
ック Ｍ１９４３（登録商標），酸価１０（ｍｇＣＨ
３ ＯＮａ／ｇ，滴定法）、スチレン成分約２０重量％
（６） ＨＴＲ（Ａ）水素添加したスチレン−ブタ
ジエン共重合体；旭化成工業（株）製 タフテック
Ｈ１０５１（登録商標），スチレン成分約４０重量％
（７） ＨＴＲ（Ｂ）水素添加したスチレン−ブタ
ジエン共重合体；旭化成工業（株）製 タフテック
Ｈ１０５２（登録商標），スチレン成分約２０重量％
（８） ＭＥＰエチレン−プロピレン共重合体の無
水マレイン酸付加物；エクソン化学（株）製 ＥＸＸ
ＥＬＯＲ ＶＡ１８０３（登録商標），無水マレイン
酸付加量０．７重量％
（９） ＥＰ
エチレン−プロピレン共重合体；三井石油化学工業（株
）製，タフマー Ｐ０１８０（登録商標）（１０）
ＨＤ−ＰＥ高密度ポリエチレン；旭化成工業（株）製
サンテック Ｊ３２０（登録商標）（１１）
ＴＨＰＢ製造例１に示した、両末端に酸無水基を有する
水素化ポリブタジエン
（１２） ＭＰＰＥ製造例２に示した、数平均分子量
約２０，０００のポリ（２，６−ジメチル−１，４−フ
ェニレンエーテル）に無水マレイン酸を０．７ｍｏｌ％
付加したもの
（１３） ＧＦガラス繊維；旭ファイバーグラス（株
）製 ０３ＪＡ ＦＴ−２Ａ（１０μｍφ，３ｍｍ
チョップドストランド）
（１４） ＨＳ−１酢酸銅；和光純薬工業（株）製（
１５） ＨＳ−２ヨウ化カリウム；和光純薬工業（株
）製（１６） ＨＳ−３ビス（２，６−ジ−ｔ−ブチ
ル−４−メチルフェニル）ペンタエリトール−ジ−ホス
ファイト：アデカアーガス化学（株）製 ＭＡＲＫＰ
ＥＰ−３６（１７） ＨＳ−４テトラキス（２，２，
６，６−テトラメチル−４−ピペリジル）−１，２，３
，４−ブタンテトラカルボキシレート；アデカアーガス
（株）製 ＭＡＲＫ ＬＡ−５７
（１８） ＨＳ−５４，４′−ブチリデン−ビス−（
３−メチル−６−ｔ−ブチルフェノール）；吉富製薬（
株） ヨシノックスＢＢ
〔２〕 試験方法
（１） 溶融張力
図１に示す（株）東洋精機製作所製 メルトテンショ
ンテスターにて、押出速度２０ｍｍ／ｍｉｎにて測定を
行なった。なお、図中１は圧力ゲージ、２は押出棒、３
は加熱炉、４は測定ゲージ、５は引取ロール、６は樹脂
を示す。[Examples] Examples of the present invention are shown below, but the present invention is not limited to the following examples unless it exceeds the gist thereof. The raw materials and test methods used in the present invention are shown below. [1] Raw material (1) Ny66 (A) Nylon 66; Sulfuric acid relative viscosity (JIS K6810, 98% H2 SO4
) 2.63 (amino end group concentration 46 mgeq/Kg) (2) Ny66 (B) Nylon 66; Sulfuric acid relative viscosity (JIS K6810, 98% H2 SO4
) 2.60 (amino end group concentration 80 mgeq/Kg) (3) Ny6 nylon 6; sulfuric acid relative viscosity (JIS
K6810, 98%H2SO4)2.90(4
) MHTR (A) Hydrogenated modified styrene-butadiene copolymer; Tuftec M1953 (registered trademark) manufactured by Asahi Kasei Industries, Ltd., acid value 10 (mg CH3
ONa/g, titration method), styrene component approximately 40% by weight, tensile modulus 2,300 Kg/cm2 (5) MHTR (B) Hydrogenated modified styrene-butadiene copolymer; Tuftec M1943 (registered) manufactured by Asahi Kasei Industries, Ltd. Trademark), acid value 10 (mgCH
3 ONa/g, titration method), styrene component approximately 20% by weight
(6) HTR (A) Hydrogenated styrene-butadiene copolymer; Tuftec manufactured by Asahi Kasei Industries, Ltd.
H1051 (registered trademark), styrene component approximately 40% by weight
(7) HTR (B) Hydrogenated styrene-butadiene copolymer; Tuftec manufactured by Asahi Kasei Industries, Ltd.
H1052 (registered trademark), styrene component approximately 20% by weight
(8) Maleic anhydride adduct of MEP ethylene-propylene copolymer; EXX manufactured by Exxon Chemical Co., Ltd.
ELOR VA1803 (registered trademark), maleic anhydride addition amount 0.7% by weight (9) EP ethylene-propylene copolymer; manufactured by Mitsui Petrochemical Industries, Ltd., Tafmer P0180 (registered trademark) (10)
HD-PE high-density polyethylene; Suntec J320 (registered trademark) (11) manufactured by Asahi Kasei Industries, Ltd.
Hydrogenated polybutadiene (12) having acid anhydride groups at both ends, shown in THPB Production Example 1. Poly(2,6-dimethyl-1,4- 0.7 mol% maleic anhydride in (phenylene ether)
Added item (13) GF glass fiber; manufactured by Asahi Fiberglass Co., Ltd. 03JA FT-2A (10μmφ, 3mm
(chopped strand) (14) HS-1 copper acetate; manufactured by Wako Pure Chemical Industries, Ltd. (
15) HS-2 potassium iodide; manufactured by Wako Pure Chemical Industries, Ltd. (16) HS-3 bis(2,6-di-t-butyl-4-methylphenyl)pentaerytol-di-phosphite: ADEKA MARKP manufactured by Argus Chemical Co., Ltd.
EP-36 (17) HS-4 Tetrakis (2,2,
6,6-tetramethyl-4-piperidyl)-1,2,3
,4-butanetetracarboxylate; manufactured by Adeka Argus Co., Ltd. MARK LA-57 (18) HS-54,4'-butylidene-bis-(
3-methyl-6-t-butylphenol); Yoshitomi Pharmaceutical (
Yoshinox BB Co., Ltd. [2] Test method (1) Melt tension Measurement was performed at an extrusion speed of 20 mm/min using a melt tension tester manufactured by Toyo Seiki Seisakusho Co., Ltd. shown in Figure 1. In the figure, 1 is a pressure gauge, 2 is an extrusion rod, and 3 is a pressure gauge.
4 is a heating furnace, 4 is a measuring gauge, 5 is a take-up roll, and 6 is a resin.
【００２２】[0022]
【製造例１】（ＴＨＰＢの合成）両末端に酸無水基を有
する水素添加ポリブタジエン（ＮＩＳＳＯ−ＰＢ，ＧＩ
−３０００ 日本曹達（株）製）３００ｇ、ピリジン
１５．８ｇを酢酸エチルエステルに溶解する。この混合
液を氷冷した後、乾燥窒素雰囲気下、無水トリメリット
酸クロライド４２．１ｇを酢酸エチルエステル２００ｍ
ｌに溶解した溶液を１時間かけて滴下した。滴下終了後
室温まで昇温し、さらに８時間攪拌した。沈澱してくる
不溶物を濾別し、濾液をロータリーエバポレーターにて
濃縮した。残渣をクロロホルム５００ｍｌに溶解し、不
溶物を濾別後、濾液をシリカゲルカラムに通し、精製を
行なった。溶媒をロータリーエバポレーターにて留去す
ると２９５ｇの微黄色粘調な液状ポリマーが得られた。[Production Example 1] (Synthesis of THPB) Hydrogenated polybutadiene having acid anhydride groups at both ends (NISSO-PB, GI
-3000 (manufactured by Nippon Soda Co., Ltd.) and 15.8 g of pyridine were dissolved in ethyl acetate. After cooling this mixture on ice, 42.1 g of trimellitic anhydride chloride was added to 200 m of ethyl acetate under a dry nitrogen atmosphere.
A solution dissolved in 1 ml was added dropwise over 1 hour. After the dropwise addition was completed, the temperature was raised to room temperature, and the mixture was further stirred for 8 hours. The precipitated insoluble matter was filtered off, and the filtrate was concentrated using a rotary evaporator. The residue was dissolved in 500 ml of chloroform, and after filtering off insoluble matter, the filtrate was passed through a silica gel column for purification. When the solvent was distilled off using a rotary evaporator, 295 g of a slightly yellow viscous liquid polymer was obtained.
【００２３】赤外吸収スペクトル、 １Ｈ−ＮＭＲによ
り、末端に無水トリメリット酸基が結合していることを
確認した。末端基定量から求めた数平均分子量は４，８
６０であった。It was confirmed by infrared absorption spectrum and 1H-NMR that a trimellitic anhydride group was bonded to the terminal. The number average molecular weight determined from the terminal group amount is 4.8
It was 60.
【００２４】[0024]
【製造例２】（ＭＰＰＥの合成）数平均分子量約２０，
０００のポリ（２，６−ジメチル−１，４−フェニレン
エーテル）１００重量部、無水マレイン酸３重量部、２
，５−ジメチル−ジ（ｔ−ブチルパーオキシ）ヘキサン
（日本油脂（株）製 パーヘキサ２５Ｂ）１重量部を
、３０ｍｍφ２軸押出機（ＰＣＭ３０ 池貝鉄工（株
）製 Ｌ／Ｄ＝１７）中で、３００〜３２０℃の温度
で混合し、更にペレット化し目的物を得た。得られたポ
リマーをトルエン−メタノールにて再沈澱をくり返し、
真空乾燥を行った後、ナトリウムメチラートにて無水マ
レイン酸の付加量を滴定により求めた所、０．７ｍｏｌ
％の無水マレイン酸が付加していた。[Production Example 2] (Synthesis of MPPE) Number average molecular weight approximately 20,
000 poly(2,6-dimethyl-1,4-phenylene ether) 100 parts by weight, maleic anhydride 3 parts by weight, 2
, 1 part by weight of 5-dimethyl-di(t-butylperoxy)hexane (Perhexa 25B manufactured by Nippon Oil & Fats Co., Ltd.) in a 30 mmφ twin screw extruder (PCM30 manufactured by Ikegai Iron Works Co., Ltd. L/D = 17). The mixture was mixed at a temperature of 300 to 320°C and further pelletized to obtain the desired product. The obtained polymer was repeatedly reprecipitated with toluene-methanol,
After vacuum drying, the amount of maleic anhydride added was determined by titration with sodium methylate, and it was found to be 0.7 mol.
% maleic anhydride was added.
【００２５】[0025]
【実施例１〜１３，比較例１〜１０】Ｎｙ６６（Ａ），
Ｎｙ６６（Ｂ），Ｎｙ６，ＭＨＴＲ（Ａ），ＭＨＴＲ（
Ｂ），ＨＴＲ（Ａ），ＨＴＲ（Ｂ），ＭＥＰ，ＥＰ，Ｈ
Ｄ−ＰＥ，ＴＨＰＢ，ＭＰＰＥ，ＧＦ，ＨＳ−１〜５を
表１〜４に示す組成で、池貝鉄工（株）製 ＰＣＭ４
５（Ｌ／Ｄ＝３３．５）２軸押出機中で、２７５〜２９
５℃のシリンダー設定温度で溶融混合し、更にペレット
化して組成物を得た。この組成物の評価結果を表５，表
６に示す。[Examples 1 to 13, Comparative Examples 1 to 10] Ny66(A),
Ny66 (B), Ny6, MHTR (A), MHTR (
B), HTR (A), HTR (B), MEP, EP, H
D-PE, THPB, MPPE, GF, HS-1 to 5 with the composition shown in Tables 1 to 4, PCM4 manufactured by Ikegai Iron Works Co., Ltd.
5 (L/D=33.5) in a twin-screw extruder, 275-29
The mixture was melt-mixed at a cylinder temperature of 5° C. and further pelletized to obtain a composition. The evaluation results of this composition are shown in Tables 5 and 6.
【００２６】[0026]
【実施例１４〜２６，比較例１１〜２０】実施例１〜１
３の組成物を（株）日本製鋼所製ブロー成形機（ＪＳＷ
−ＪＢ１０５ＣＰ，ダイス外／内＝９０ｍｍφ／７０ｍ
ｍφ）により２３０〜２５０℃で約９０ｍｍφの直径を
有し、肉厚２〜３ｍｍのパリソンを作成し、さらに縦１
５０ｍｍ、横８５ｍｍ、高さ２２０ｍｍの容器を成形し
た。[Examples 14-26, Comparative Examples 11-20] Examples 1-1
The composition of No. 3 was molded using a blow molding machine manufactured by Japan Steel Works, Ltd. (JSW).
-JB105CP, die outside/inside = 90mmφ/70m
A parison with a diameter of about 90 mmφ and a wall thickness of 2 to 3 mm was prepared at 230 to 250°C using
A container measuring 50 mm, width 85 mm, and height 220 mm was molded.
【００２７】実施例１〜１３の組成物より得られた成形
品（実施例１４〜２６）はピンホールもなく、良好な成
形品であった。一方、比較例１〜１０の組成物を同一の
成形条件により成形した成形品（比較例１１〜２０）は
、いずれも破れが見られ、全く商品価値のないものであ
った。The molded articles obtained from the compositions of Examples 1 to 13 (Examples 14 to 26) had no pinholes and were good molded articles. On the other hand, the molded products (Comparative Examples 11 to 20) obtained by molding the compositions of Comparative Examples 1 to 10 under the same molding conditions were all found to be torn and had no commercial value.
【００２８】[0028]
【表１】[Table 1]
【００２９】[0029]
【表２】[Table 2]
【００３０】[0030]
【表３】[Table 3]
【００３１】[0031]
【表４】[Table 4]
【００３２】[0032]
【表５】[Table 5]
【００３３】[0033]
【表６】[Table 6]
【図１】本発明の実施例に供するメルトテンションテス
ターの略図である。FIG. 1 is a schematic diagram of a melt tension tester used in an embodiment of the present invention.
Claims (1)
ニル化合物（Ｘ）と共役ジエン化合物の水素化物（Ｙ）
からなる共重合体のα，β−不飽和カルボン酸又はその
誘導体の付加物 （Ｃ）他の熱可塑性樹脂 （Ｄ）ガラス繊維 （ただし、（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）各成分の配
合量をそれぞれ、Ａ、Ｂ、Ｃ、Ｄ重量％とするとき、６
０≦Ａ≦９７，３≦Ｂ＋Ｃ≦４０，０．０１≦Ｂ／Ｃ≦
９９，０．０５≦Ｄ／（Ａ＋Ｂ＋Ｃ）≦１，Ａ＋Ｂ＋Ｃ
＋Ｄ＝１００；（Ｘ），（Ｙ）各成分の共重合量をそれ
ぞれ、Ｘ，Ｙ重量％とするとき、３８＜Ｘ＜８０，２０
＜Ｙ＜６２，Ｘ＋Ｙ＝１００）であることを特徴とする
ブロー成形用樹脂組成物。Claim 1: (A) polyamide resin (B) hydride of aromatic vinyl compound (X) and conjugated diene compound (Y)
(C) Other thermoplastic resins (D) Glass fibers (provided that (A), (B), (C), (D ) When the amount of each component is A, B, C, D weight%, 6
0≦A≦97, 3≦B+C≦40, 0.01≦B/C≦
99, 0.05≦D/(A+B+C)≦1, A+B+C
+D=100; When the copolymerization amounts of each component (X) and (Y) are X and Y weight%, respectively, 38<X<80, 20
<Y<62, X+Y=100) A resin composition for blow molding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02404390A JP3140471B2 (en) | 1990-12-20 | 1990-12-20 | Resin composition for blow molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02404390A JP3140471B2 (en) | 1990-12-20 | 1990-12-20 | Resin composition for blow molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04220458A true JPH04220458A (en) | 1992-08-11 |
| JP3140471B2 JP3140471B2 (en) | 2001-03-05 |
Family
ID=18514068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02404390A Expired - Fee Related JP3140471B2 (en) | 1990-12-20 | 1990-12-20 | Resin composition for blow molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3140471B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101464782B1 (en) * | 2006-08-23 | 2014-11-26 | 바스프 에스이 | Polyamide molding materials with improved thermal aging and hydrolysis stability |
| JP2019172759A (en) * | 2018-03-27 | 2019-10-10 | テクノＵｍｇ株式会社 | Thermoplastic resin composition and molded article |
| CN112424288A (en) * | 2018-07-31 | 2021-02-26 | 东丽株式会社 | Polyamide resin composition for blow-molded article in contact with high-pressure hydrogen, and blow-molded article using same |
-
1990
- 1990-12-20 JP JP02404390A patent/JP3140471B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101464782B1 (en) * | 2006-08-23 | 2014-11-26 | 바스프 에스이 | Polyamide molding materials with improved thermal aging and hydrolysis stability |
| US9505912B2 (en) | 2006-08-23 | 2016-11-29 | Basf Se | Polyamide molding materials with improved thermal aging and hydrolysis stability |
| JP2019172759A (en) * | 2018-03-27 | 2019-10-10 | テクノＵｍｇ株式会社 | Thermoplastic resin composition and molded article |
| CN112424288A (en) * | 2018-07-31 | 2021-02-26 | 东丽株式会社 | Polyamide resin composition for blow-molded article in contact with high-pressure hydrogen, and blow-molded article using same |
| CN112424288B (en) * | 2018-07-31 | 2023-06-02 | 东丽株式会社 | Polyamide resin composition for blow-molded article in contact with high-pressure hydrogen and blow-molded article thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3140471B2 (en) | 2001-03-05 |
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