JP6523602B2 - Polyvinyl chloride resin composition and insulation coated wire - Google Patents
Polyvinyl chloride resin composition and insulation coated wire Download PDFInfo
- Publication number
- JP6523602B2 JP6523602B2 JP2014016808A JP2014016808A JP6523602B2 JP 6523602 B2 JP6523602 B2 JP 6523602B2 JP 2014016808 A JP2014016808 A JP 2014016808A JP 2014016808 A JP2014016808 A JP 2014016808A JP 6523602 B2 JP6523602 B2 JP 6523602B2
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- JP
- Japan
- Prior art keywords
- wire
- acid
- polyvinyl chloride
- resin composition
- chloride resin
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims description 67
- 239000004800 polyvinyl chloride Substances 0.000 title claims description 63
- 229920000915 polyvinyl chloride Polymers 0.000 title claims description 63
- 238000009413 insulation Methods 0.000 title claims description 60
- -1 polyethylene Polymers 0.000 claims description 59
- 239000004014 plasticizer Substances 0.000 claims description 41
- 239000004698 Polyethylene Substances 0.000 claims description 30
- 229920000573 polyethylene Polymers 0.000 claims description 30
- 239000000314 lubricant Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 239000004020 conductor Substances 0.000 claims description 15
- 150000007524 organic acids Chemical class 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 9
- 239000012760 heat stabilizer Substances 0.000 claims description 9
- 229960001545 hydrotalcite Drugs 0.000 claims description 9
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 9
- 229920005989 resin Polymers 0.000 description 46
- 239000011347 resin Substances 0.000 description 46
- 239000012212 insulator Substances 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 238000005299 abrasion Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 11
- 239000000945 filler Substances 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000003607 modifier Substances 0.000 description 7
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000011810 insulating material Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 125000005591 trimellitate group Chemical group 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004064 recycling Methods 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
- 238000004804 winding Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- BDJRBEYXGGNYIS-UHFFFAOYSA-N Nonanedioid acid Natural products OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- 238000009863 impact test Methods 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 239000004135 Bone phosphate Substances 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 241000337007 Oceania Species 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-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
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- YCZJVRCZIPDYHH-UHFFFAOYSA-N ditridecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCCC YCZJVRCZIPDYHH-UHFFFAOYSA-N 0.000 description 2
- QQVHEQUEHCEAKS-UHFFFAOYSA-N diundecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCC QQVHEQUEHCEAKS-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 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
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- LKVQWLUFJXBHKH-UHFFFAOYSA-N 1-o-butyl 2-o-hexyl benzene-1,2-dicarboxylate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC LKVQWLUFJXBHKH-UHFFFAOYSA-N 0.000 description 1
- RIZUCYSQUWMQLX-UHFFFAOYSA-N 2,3-dimethylbenzoic acid Chemical compound CC1=CC=CC(C(O)=O)=C1C RIZUCYSQUWMQLX-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- DVVXXHVHGGWWPE-UHFFFAOYSA-N 2-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=CC=C1C(O)=O DVVXXHVHGGWWPE-UHFFFAOYSA-N 0.000 description 1
- CGMMPMYKMDITEA-UHFFFAOYSA-N 2-ethylbenzoic acid Chemical compound CCC1=CC=CC=C1C(O)=O CGMMPMYKMDITEA-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- YSJWNEDBIWZWOI-UHFFFAOYSA-N 2-hydroxy-3,4-dimethylbenzoic acid Chemical compound CC1=CC=C(C(O)=O)C(O)=C1C YSJWNEDBIWZWOI-UHFFFAOYSA-N 0.000 description 1
- BVIVNFSDRZMMQS-UHFFFAOYSA-N 2-hydroxy-4-(2,4,4-trimethylpentan-2-yl)benzoic acid Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(C(O)=O)C(O)=C1 BVIVNFSDRZMMQS-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- GADSJKKDLMALGL-UHFFFAOYSA-N 2-propylbenzoic acid Chemical compound CCCC1=CC=CC=C1C(O)=O GADSJKKDLMALGL-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- YEXOWHQZWLCHHD-UHFFFAOYSA-N 3,5-ditert-butyl-4-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=CC(C(C)(C)C)=C1O YEXOWHQZWLCHHD-UHFFFAOYSA-N 0.000 description 1
- WGLQHUKCXBXUDV-UHFFFAOYSA-N 3-aminophthalic acid Chemical compound NC1=CC=CC(C(O)=O)=C1C(O)=O WGLQHUKCXBXUDV-UHFFFAOYSA-N 0.000 description 1
- BKFXSOCDAQACQM-UHFFFAOYSA-N 3-chlorophthalic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1C(O)=O BKFXSOCDAQACQM-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 1
- 239000004605 External Lubricant Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 241001424392 Lucia limbaria Species 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000003490 Thiodipropionic acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
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Description
本発明は、電線を被覆する電気絶縁材料として有用なポリ塩化ビニル樹脂組成物、及び、それを利用して製造される絶縁被覆電線に関し、特に、非鉛系の成分によって構成され、耐寒性等の機械特性を保持しつつ薄肉に成形可能な加工性を有する電線被覆用のポリ塩化ビニル樹脂組成物、及び、自動車のワイヤーハーネス等への適用において電線の細径化による車両の軽量化に貢献可能であって、自動車の使用環境に適した絶縁被覆電線に関するものである。 TECHNICAL FIELD The present invention relates to a polyvinyl chloride resin composition useful as an electrical insulating material for coating a wire, and an insulation-coated wire manufactured using the same, and is particularly composed of a lead-free component, cold resistance, etc. Contributes to reducing the weight of vehicles by reducing the diameter of electric wires in applications to polyvinyl chloride resin compositions for electric wire coating that have processability that can be molded thinly while retaining the mechanical properties of the above, and wire harnesses for automobiles. The present invention relates to an insulation coated electric wire which is possible and suitable for a use environment of a car.
車載装置の電子化等に伴って、自動車内で使用される電気、電子配線回路の数が著しく増加して車内に占める空間が増大し、配線回路用電線による車両総重量の増加を招いている。このような電線の重量増加は、自動車の燃費の低下を生じるので、燃費向上の観点から、電線の軽量化は重要であるが、マイクロコンピュータを搭載して自動車を安全且つ快適に走行させるためには、電線の使用量の増加は避けられない。このため、近年、自動車用電線の軽量化が研究されている。又、電子機器の小型・精密化に伴って、ワイヤーハーネス及び絶縁被覆電線として使用する電線の細径化、及び、電線導体を被覆する絶縁体の肉厚を薄くする薄肉化が求められている。 With the digitization of in-vehicle devices, the number of electrical and electronic wiring circuits used in the vehicle has significantly increased, and the space occupied in the vehicle has increased, leading to an increase in the total weight of the vehicle due to the wiring circuit wires. . Since such an increase in the weight of the electric wire causes a decrease in the fuel consumption of the car, it is important to reduce the weight of the electric wire from the viewpoint of improving the fuel consumption, but in order to make the car run safely and comfortably by mounting a microcomputer. An increase in the amount of wire used is inevitable. Therefore, in recent years, weight reduction of electric wires for automobiles has been studied. In addition, along with the miniaturization and refinement of electronic devices, it is required to reduce the diameter of a wire used as a wire harness and an insulation coated wire, and to reduce the thickness of the insulator covering the wire conductor. .
一般に、自動車のワイヤーハーネスや電子機器等に使用される電線を被覆する絶縁体としては、ポリ塩化ビニルを主成分とする樹脂組成物が用いられている。このような被覆用のポリ塩化ビニル樹脂組成物には可塑剤が配合されており、その配合量の増加によって樹脂組成物の柔軟性が良くなり、耐寒性を高めることができるが、一方で、耐摩耗性等の機械特性が低下する。従って、電線の細径化及び薄肉化を進めると、更に耐摩耗性が低下し易くなる。これに対応するために、可塑剤の配合量を減らして樹脂組成物を硬くすることによって、耐摩耗性を向上させることは可能である。しかし、単に可塑剤の配合量を減らすだけでは、樹脂組成物の耐寒性が低下し、電線を低温で使用することが難しくなる。このようなことから、従来の塩化ビニル樹脂組成物では、絶縁被覆電線を肉薄にした時に機械的強度、特に耐摩耗性を維持可能な電線構造における電線サイズは公称導体断面積０．３５ｍｍ２程度で、肉厚は０．３５ｍｍ程度が限界となっている。 In general, a resin composition containing polyvinyl chloride as a main component is used as an insulator for covering a wire used in a wire harness of an automobile, an electronic device or the like. Such a polyvinyl chloride resin composition for coating contains a plasticizer, and by increasing the compounding amount, the flexibility of the resin composition is improved and the cold resistance can be enhanced, but on the other hand, Mechanical properties such as wear resistance deteriorate. Therefore, if the diameter and thickness of the wire are reduced, the wear resistance is further likely to be reduced. In order to cope with this, it is possible to improve the abrasion resistance by reducing the compounding amount of the plasticizer and hardening the resin composition. However, simply reducing the blending amount of the plasticizer reduces the cold resistance of the resin composition, making it difficult to use the electric wire at a low temperature. From these facts, in the conventional vinyl chloride resin composition, the wire size in the wire structure capable of maintaining the mechanical strength, particularly the wear resistance when making the insulation coated wire thin, is about a nominal conductor cross-sectional area of about 0.35 mm 2 The thickness is limited to about 0.35 mm.
ポリ塩化ビニルを主成分とする樹脂組成物で被覆した電線の薄肉化を進めるものとして、例えば、下記特許文献１がある。この文献では、ショアＤ硬度が７２以上のポリ塩化ビニルを主成分とする絶縁体の押出し成形によって絶縁被覆電線を形成して、肉厚が０．０８〜０．２ｍｍの薄肉電線を得ており、ｎ−トリメリット酸オクチルエステルの配合量を調整してショアＤ硬度が７２以上の絶縁体が調製される。 As a device for promoting thinning of a wire coated with a resin composition containing polyvinyl chloride as a main component, there is, for example, the following Patent Document 1. In this document, an insulation-coated wire is formed by extrusion of an insulator mainly composed of polyvinyl chloride having a Shore D hardness of 72 or more, and a thin-walled wire having a thickness of 0.08 to 0.2 mm is obtained. An insulator having a Shore D hardness of 72 or more is prepared by adjusting the blending amount of n-trimellitic acid octyl ester.
一方、環境問題や廃棄物処理及びリサイクル等の観点から、鉛系の添加剤の使用を回避することが求められつつあり、電線を被覆する絶縁材においても、このような要件に対応する技術の開発が進められている。下記特許文献２は、ポリ塩化ビニル樹脂に、可塑剤、非鉛系安定剤、非鉛系滑剤、及び、脂肪族アルコールの二塩基酸エステルを配合した電線被覆用塩化ビニル樹脂組成物の押出し成形によって形成される電線を開示し、可塑剤及び脂肪族アルコールの二塩基酸エステルについて、その配合量が所定条件を満たすように制限して樹脂組成物を調製することによって、電気絶縁性及び熱安定性に優れ、表面状態が良好な絶縁材で被覆された電線が得られることを記載する。 On the other hand, it is being sought to avoid the use of lead-based additives from the viewpoint of environmental problems and waste disposal and recycling, etc. In the insulating material for covering electric wires, too, Development is in progress. The following Patent Document 2 is an extrusion molding of a vinyl chloride resin composition for wire covering, in which a plasticizer, a lead-free stabilizer, a lead-free lubricant, and a dibasic acid ester of an aliphatic alcohol are mixed with a polyvinyl chloride resin. Disclosed a wire formed by the above method, and by preparing a resin composition by limiting the compounding amount of the plasticizer and the aliphatic alcohol dibasic acid ester to satisfy a predetermined condition, electrical insulation and thermal stability are disclosed. It is described that a wire coated with an insulating material having good properties and good surface condition is obtained.
上記特許文献１では、硬度が高い絶縁体によって薄肉電線を実現しているが、電線に必要とされる耐寒性は十分ではなく、現在のＩＳＯ６７２２に準拠する低温衝撃性を満足するものは得られないので、低温環境での使用に対応できない虞がある。又、特許文献１の絶縁体は、硬度が高くなった反面、成形性が低下するので、押出し成形における成形安定性が得られ難いという問題があり、生産コストの削減において不利となる。更に、鉛系添加剤の使用を回避するための改善も必要である。 Although the thin wire is realized by the insulator having high hardness in the above-mentioned Patent Document 1, the cold resistance required for the wire is not sufficient, and the one satisfying the low temperature impact according to the current ISO 6722 is obtained. Because it does not exist, there is a risk that it can not be used in low temperature environments. Further, the insulator of Patent Document 1 has a problem that the molding stability is difficult to be obtained in the extrusion molding because the moldability is lowered while the hardness is increased, and it is disadvantageous in the reduction of the production cost. In addition, improvements are also needed to avoid the use of lead-based additives.
又、上記特許文献２の樹脂組成物には、細径且つ薄肉電線としての押出し成形が行い難く、生産効率の点で問題があり、成形された絶縁被覆電線についても、樹脂表面に添加剤が経時的に凝集固化するブリードアウトが自動車の使用環境条件において生じるため、自動車のワイヤーハーネス等に適用する絶縁被覆電線としては十分ではない。 Further, in the resin composition of Patent Document 2 described above, extrusion molding as a thin and thin wire is difficult to carry out, and there is a problem in terms of production efficiency. Since a bleed out which coagulates and solidifies with time occurs in use environment conditions of a car, it is not enough as an insulation covering electric wire applied to a wire harness etc. of a car.
このように、絶縁材の特性に求められる要件は、年々厳しくなり、ワイヤーハーネスや耐熱・耐寒電線等の用途において、環境やリサイクルを配慮しつつ、より高い材料特性を備えるように改良が必要となっている。 As described above, the requirements for the characteristics of the insulating material become stricter year by year, and it is necessary to improve the material to have higher material characteristics while considering the environment and recycling in applications such as wire harnesses and heat resistant / cold resistant wires. It has become.
本発明は、環境及びリサイクルの観点から鉛系添加剤の使用を回避し、且つ、押出し成形が容易で成形安定性が良く、自動車の使用環境に適応可能な優れた耐摩耗性及び耐寒性を有するポリ塩化ビニル樹脂組成物を提供することを課題とする。
又、本発明は、好適な成形安定性で効率的に細径に製造可能な絶縁被覆電線であって、薄肉な絶縁部材の被覆であっても十分な耐摩耗性及び強度を発揮し、優れた耐寒性によって自動車のワイヤーハーネス等の使用環境に適応可能な絶縁被覆電線を提供することを課題とする。
The present invention avoids the use of lead-based additives from the viewpoint of environment and recycling, and has excellent wear resistance and cold resistance that is easy to extrude, has good molding stability, and can be adapted to the usage environment of automobiles. It is an object of the present invention to provide a polyvinyl chloride resin composition having the same.
Further, the present invention is an insulation-coated electric wire which can be efficiently manufactured to a small diameter with suitable forming stability, and even if it is a coating of a thin insulation member, it exhibits sufficient wear resistance and strength and is excellent It is an object of the present invention to provide an insulation coated wire which can be adapted to the usage environment of a wire harness of a car or the like due to cold resistance.
上記の課題を解決するために、絶縁部材を構成するポリ塩化ビニル樹脂組成物の配合について検討し、非鉛系の滑剤として特定のポリエチレンワックスを使用することによって、樹脂組成物で形成される絶縁部材の材料特性を改善すると共に、高い成形安定性で効率的に細径の絶縁被覆電線を形成することが可能となることを見出し、本発明を成すに至った。 In order to solve the above problems, the composition of the polyvinyl chloride resin composition constituting the insulating member is examined, and the insulation formed of the resin composition is achieved by using a specific polyethylene wax as a non-lead lubricant. The inventors have found that it is possible to improve the material properties of a member and efficiently form a thin-diameter insulation-coated wire with high forming stability and to achieve the present invention.
本発明の一態様によれば、ポリ塩化ビニル樹脂組成物は、ポリ塩化ビニル１００質量部に対して、可塑剤２４〜２８質量部、有機酸金属塩とハイドロタルサイトとの混合物からなる非鉛系熱安定剤４〜１０質量部、及び、極性基が導入された酸化型変性ポリエチレンワックスからなる非鉛系滑剤０．２〜０．４質量部を含有することを要旨とする。変性ポリエチレンワックスとして、平均分子量が２６００〜３２００のものを使用すると好ましい。 According to one aspect of the present invention, the polyvinyl chloride resin composition is a non-lead comprising a mixture of 24 to 28 parts by mass of a plasticizer, a metal salt of an organic acid and hydrotalcite per 100 parts by mass of polyvinyl chloride. The gist of the present invention is to contain 4 to 10 parts by mass of a thermal stabilizer and 0.2 to 0.4 parts by mass of a lead-free lubricant comprising an oxidized modified polyethylene wax having a polar group introduced therein . It is preferable to use a modified polyethylene wax having an average molecular weight of 2600 to 3200.
又、本発明の一態様によれば、絶縁被覆電線は、線状導体と、前記線状導体を被覆する絶縁部材とを有し、前記絶縁部材は上記ポリ塩化ビニル樹脂組成物を用いて形成されることを要旨とする。 Further, according to one aspect of the present invention, the insulation coated electric wire has a linear conductor and an insulating member for covering the linear conductor, and the insulating member is formed using the polyvinyl chloride resin composition. The point is to be
上記ポリ塩化ビニル樹脂組成物は、ワイヤーハーネス又は電線の絶縁部材に成形して電線の絶縁被覆に使用することができる。上記ポリ塩化ビニル樹脂組成物は、更に、充填材、改質剤などを含有してよい。充填材は、炭酸カルシウム、炭酸マグネシウム、クレー、焼成カオリン、タルク、シリカ、珪酸カルシウム、珪酸アルミニウム、珪酸マグネシウム、硫酸バリウムからなる群より選択される少なくとも１種であって良く、改質剤は、メチルメタクリレート、メチルメタクリレート−ブタジエン−スチレン共重合体、アクリロニトリル−ブタジエン−スチレン共重合体、（塩素化ポリエチレン及びエチレン−酢酸ビニル共重合体）からなる群より選択される少なくとも１種の樹脂であって良い。
上記絶縁被覆電線は、線状導体の断面積が０．０８〜１．２５ｍｍ２で、上記絶縁部材の肉厚が公称０．１６ｍｍ（最小０．１２ｍｍ）以上の管状であるような細径に形成することができ、自動車のワイヤーハーネスに使用することができる。
The said polyvinyl chloride resin composition can be shape | molded to the insulation member of a wire harness or an electric wire, and can be used for the insulation coating of an electric wire. The polyvinyl chloride resin composition may further contain a filler, a modifier and the like. The filler may be at least one selected from the group consisting of calcium carbonate, magnesium carbonate, clay, calcined kaolin, talc, silica, calcium silicate, aluminum silicate, magnesium silicate and barium sulfate, and the modifier is At least one resin selected from the group consisting of methyl methacrylate, methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, (chlorinated polyethylene and ethylene-vinyl acetate copolymer), good.
The insulation coated wire has a cross-sectional area of 0.08 to 1.25 mm 2 for the linear conductor and a small diameter such that the thickness of the insulation member is nominally 0.16 mm (minimum 0.12 mm) or more It can be formed and used in wire harnesses for automobiles.
本発明によれば、鉛系添加剤を使用せずに非鉛系添加剤を利用して、押出し成形が容易で成形安定性が良く、耐摩耗性及び耐寒性に優れたポリ塩化ビニル樹脂組成物が提供され、これを利用して、薄肉な被覆絶縁部材で十分な耐摩耗性及び強度を発揮し、優れた耐寒性を有する細径の絶縁被覆電線を高い成形安定性で効率的に製造できるので、ワイヤーハーネス等に適用することによって自動車等の使用環境に十分に適応可能な細径の絶縁被覆電線が提供され、車両用電気・電子機器や車載装置の軽量化を可能にし、自動車の軽量化及び燃費向上に貢献することができる。 According to the present invention, a polyvinyl chloride resin composition which is easy to extrude, has excellent molding stability, and is excellent in wear resistance and cold resistance by using a lead-free additive without using a lead-based additive Article is provided, which is used to demonstrate sufficient wear resistance and strength with a thin coated insulation member and efficiently manufacture a thin insulated wire with excellent cold resistance with high forming stability As it can be used, by applying to wire harness etc., the small diameter insulation coated electric wire adaptable to use environment such as automobile etc. is provided, enables weight reduction of electric / electronic equipment for vehicles and in-vehicle device, It can contribute to weight reduction and fuel consumption improvement.
電線を被覆する絶縁体を構成する樹脂組成物には、必要とされる材料特性を付与するための添加剤が配合されている。添加剤の配合は、目的とする材料特性を向上させる一方で、他の材料特性を減退させる可能性が常にある。従って、添加剤の配合においては、通常、使用形態において求められる材料特性を全体的に考慮して、バランス良く材料特性が発揮されるように添加量を決定する。 In the resin composition that constitutes the insulator covering the electric wire, an additive for imparting the required material properties is blended. While the formulation of additives improves the intended material properties, there is always the possibility of diminishing other material properties. Therefore, in the formulation of the additive, the amount of addition is usually determined in such a manner that the material properties are exhibited in a well-balanced manner, in consideration of the entire material properties required in the use form.
本願発明者は、絶縁被覆電線の絶縁部材を構成するポリ塩化ビニル樹脂組成物に関して、細径電線の押出し成形が行い難くなる現象について調べたところ、電線サイズが細くなる或いは絶縁体厚が薄肉化されるにつれて、絶縁体材料としては可塑剤含有量が少なくなることが一因であるとの考えに至った。また、この問題を改善するために、単純に滑剤を増量して成形性を改善した場合は、電線表面に原料の一部がブリードアウトすることも確認した。成形性が良く、ブリードアウトも抑制される絶縁部材を構成可能な樹脂組成物を実現するために検討を重ねた結果、滑剤として、特定のポリエチレンワックスを使用することが有効であり、これを使用して効率的に摩擦を軽減して可塑剤と滑剤との配合バランスを好適に整えることで、成形性の改善及びブリードアウトの抑制が達成され、被覆する絶縁体が薄肉であっても好適な耐摩耗性を発揮し得る絶縁部材が得られることが判明した。 The inventor of the present application has investigated the phenomenon that extrusion molding of a fine diameter wire becomes difficult to carry out with regard to the polyvinyl chloride resin composition constituting the insulation member of the insulation coated wire, the wire size becomes thinner or the insulator thickness becomes thinner. It came to the thought that as an insulator material, a plasticizer content becomes low as one of the insulator materials. Moreover, in order to improve this problem, it was also confirmed that when the lubricant was simply increased to improve the formability, part of the raw material bled out on the wire surface. As a result of repeated studies to realize a resin composition capable of forming an insulating member having good moldability and suppression of bleed out, it is effective to use a specific polyethylene wax as a lubricant, which is used The moldability is improved and bleed-out is suppressed by efficiently reducing friction and appropriately adjusting the blending balance of the plasticizer and the lubricant, and it is preferable even if the insulator to be coated is thin. It turned out that the insulation member which can exhibit abrasion resistance is obtained.
本発明は、電線を被覆する絶縁体を構成するための、ポリ塩化ビニル樹脂を主成分とするポリ塩化ビニル樹脂組成物、及び、これを用いて成形される絶縁被覆電線に関し、ポリ塩化ビニル樹脂組成物は、（Ａ）ポリ塩化ビニル樹脂、（Ｂ）可塑剤、（Ｃ）有機酸金属塩とハイドロタルサイトとの混合物からなる非鉛系熱安定剤、及び、（Ｄ）非鉛系滑剤を含有し、（D）非鉛系滑剤として、変性ポリエチレンワックスが用いられる。以下に、本発明に係るポリ塩化ビニル樹脂組成物について詳細に説明する。 TECHNICAL FIELD The present invention relates to a polyvinyl chloride resin composition containing polyvinyl chloride resin as a main component, and an insulation coated wire molded using the same, for forming an insulator for covering a wire, and a polyvinyl chloride resin. The composition comprises (A) polyvinyl chloride resin, (B) plasticizer, (C) non-lead heat stabilizer comprising a mixture of metal salt of organic acid and hydrotalcite, and (D) non-lead lubricant And a modified polyethylene wax is used as the (D) non-lead lubricant. The polyvinyl chloride resin composition according to the present invention will be described in detail below.
本発明のポリ塩化ビニル樹脂組成物は、ポリ塩化ビニル樹脂１００質量部に対して、可塑剤２４〜２８質量部、非鉛系熱安定剤４〜１０質量部、及び、非鉛系滑剤として変性ポリエチレンワックス０．２〜０．４質量部を含有する。更に、必要に応じて、充填材、改質剤等をポリ塩化ビニル樹脂組成物に配合することができる。 The polyvinyl chloride resin composition of the present invention is modified as 24 to 28 parts by mass of a plasticizer, 4 to 10 parts by mass of a lead-free heat stabilizer, and 100 parts by mass of a polyvinyl chloride resin, and a lead-free lubricant It contains 0.2 to 0.4 parts by mass of polyethylene wax. Furthermore, if necessary, fillers, modifiers and the like can be blended into the polyvinyl chloride resin composition.
（Ａ）ポリ塩化ビニル樹脂として、平均重合度が１３００〜２０００程度のものを使用すると、耐寒性及び耐摩耗性に優れた樹脂組成物を得ることができる。平均重合度が１３００未満の樹脂を使用すると、電線特性の公的規格であるＩＳＯ６７２２に準拠した低温衝撃試験に適合する絶縁被覆電線を得ることが難しくなり、平均重合度が２０００を超えるものを使用すると、可塑剤の効力が効き難くなったり、不均一に作用して樹脂組成物の機械特性のバラツキが大きくなり、押出し成形時の成形安定性が低下して被覆樹脂と電線との同心性が損なわれ易くなる。市場で入手可能な平均重合度が１３００〜２０００の範囲のポリ塩化ビニル樹脂としては、例えば、信越化学工業製のＴＫ−１３００及び大洋塩ビ製のＴＨ−１３００（以上、平均重合度１３００）、信越化学工業製のＴＫ−１４００及び大洋塩ビ製のＴＨ−１４００（以上、平均重合度１４００）が挙げられる。 (A) When a polyvinyl chloride resin having an average degree of polymerization of about 1300 to 2000 is used, a resin composition excellent in cold resistance and abrasion resistance can be obtained. If a resin with an average degree of polymerization of less than 1300 is used, it becomes difficult to obtain an insulation coated wire conforming to a low temperature impact test according to ISO 6722 which is a public standard of the wire characteristics, and a resin with an average degree of polymerization of more than 2000 is used As a result, the effectiveness of the plasticizer becomes ineffective, or nonuniform action occurs, and the variation in mechanical properties of the resin composition becomes large, and the molding stability at the time of extrusion molding decreases, and the concentricity between the coating resin and the electric wire becomes It is easy to lose. Examples of polyvinyl chloride resins having an average degree of polymerization in the range of 1,300 to 2,000 available on the market include TK-1300 manufactured by Shin-Etsu Chemical Co., Ltd. and TH-1300 manufactured by Oceania PVC (average degree of polymerization 1300), Shin-Etsu Examples thereof include TK-1400 manufactured by Chemical Industry and TH-1400 manufactured by Oceania PVC (above, average polymerization degree 1400).
（Ｂ）可塑剤は、単体では加工性が低いポリ塩化ビニル樹脂に柔軟性を付与して熱加工し易くするために配合される。最終製品である自動車用電線に求められる諸特性（耐熱性、耐寒性、耐油性等）を勘案して、一般的にポリ塩化ビニル樹脂に対して使用される可塑剤から適宜選択して使用することとができる。具体的には、可塑剤として、フタル酸エステル系可塑剤、アジピン酸エステル系可塑剤、アゼライン酸エステル系可塑剤、セバシン酸エステル系可塑剤、マレイン酸エステル系可塑剤、フマル酸エステル系可塑剤、トリメリット酸エステル系可塑剤、ピロメリット酸エステル系可塑剤、イタコン酸エステル系可塑剤、クエン酸エステル系可塑剤、ポリエステル系可塑剤等のエステル化合物が挙げられる。その中でも、フタル酸エステル系可塑剤及びトリメリット酸エステル系可塑剤の中から１種又は２種以上を組みあわせて用いることが好ましい。フタル酸エステル系可塑剤としては、例えば、ジブチルフタレート、ブチルヘキシルフタレート、ジヘプチルフタレート、ジオクチルフタレート［又はビス（２−ヘチルヘキシル）フタレート］、ジイソノニルフタレート、ジイソデシルフタレート、ジウンデシルフタレート、ジトリデシルフタレート、ジラウリルフタレート、ジシクロヘキシルフタレート、ジオクチルテレフタレート等があり、トリメリット酸エステル系可塑剤としては、例えば、トリ（２−エチルヘキシル）トリメリテート、トリ（ｎ−オクチル）トリメリテート、トリ（イソノニル）トリメリテート等がある。中でも、ジウンデシルフタレート、ジトリデシルフタレート、ジイソノニルフタレート、ジイソデシルフタレート、トリ（２−エチルヘキシル）トリメリテート、トリ（ｎ−オクチル）トリメリテート、トリ（イソノニル）トリメリテート等が好ましく、特に、トリ（ｎ−オクチル）トリメリテート［ｎ−ＴＯＴＭ］が好適である。市場で入手可能なトリメリット酸エステル系可塑剤としては、例えば、ＡＤＥＫＡ製アデカサイザーＣ−８１０ＰＳ、Ｃ−８８０、Ｃ−８、Ｃ−８ＮＢ等がある。可塑剤は、ポリ塩化ビニル樹脂１００質量部に対して２４〜２８質量部となる割合で添加することが好ましく、添加割合が２４質量部より少ないと、樹脂組成物の加工性が低下して加工温度の上昇が必要となり、材料の熱劣化を招き易くなる。可塑剤の絶対量が少ないことから、耐低温性が悪化する。添加割合が２８質量部を超えると、樹脂組成物の耐摩耗性が低下する。 The plasticizer (B) is compounded in order to impart flexibility to a polyvinyl chloride resin having low processability by itself and to facilitate thermal processing. Considering various properties (heat resistance, cold resistance, oil resistance, etc.) required for the final product electric wire for electric wire, appropriately selected from plasticizers generally used for polyvinyl chloride resin Can do things. Specifically, as plasticizers, phthalic acid ester plasticizers, adipic acid ester plasticizers, azelaic acid ester plasticizers, sebacic acid ester plasticizers, maleic acid ester plasticizers, fumaric acid ester plasticizers And ester compounds such as trimellitic acid ester plasticizers, pyromellitic acid ester plasticizers, itaconic acid ester plasticizers, citric acid ester plasticizers, and polyester plasticizers. Among them, it is preferable to use one or a combination of two or more selected from phthalic acid ester plasticizers and trimellitic acid ester plasticizers. As a phthalate ester plasticizer, for example, dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate [or bis (2-hexylhexyl) phthalate], diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, There are dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate and the like, and examples of trimellitic acid ester plasticizers include tri (2-ethylhexyl) trimellitate, tri (n-octyl) trimellitate, tri (isononyl) trimellitate and the like. Among these, diundecyl phthalate, ditridecyl phthalate, diisononyl phthalate, diisodecyl phthalate, tri (2-ethylhexyl) trimellitate, tri (n-octyl) trimellitate, tri (isononyl) trimellitate etc. are preferable, and tri (n-octyl) trimellitate is particularly preferable. [N-TOTM] is preferred. Examples of commercially available trimellitic acid ester plasticizers include Adekasizer C-810PS, C-880, C-8, and C-8NB manufactured by Adeka. The plasticizer is preferably added in a proportion of 24 to 28 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin, and when the addition proportion is less than 24 parts by mass, the processability of the resin composition is reduced to process An increase in temperature is required, which tends to cause thermal degradation of the material. Because the absolute amount of the plasticizer is small, the low temperature resistance deteriorates. When the addition ratio exceeds 28 parts by mass, the abrasion resistance of the resin composition is reduced.
（Ｃ）熱安定剤は、ポリ塩化ビニル樹脂に特有の劣化機構の１つである脱塩化水素反応を抑制する目的で配合される。本発明では、電気絶縁性を考慮して、非鉛系の各種熱安定剤の中から、有機酸金属塩とハイドロタルサイトとの混合物が用いられる。
有機酸金属塩は、Ｃａ、Ｍｇ、Ｚｎ、Ｂａ及びＳｎからなる群より選択される金属原子と有機酸との塩である。塩を構成する有機酸について特に制限はなく、一塩基酸又は多塩基酸、脂肪族カルボン酸又は芳香族カルボン酸の何れであってもよい。有機酸として、例えば、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、ネオ酸、２−エチルヘキサン酸、ペラルゴン酸、カプリン酸、ウンデカン酸、ラウリン酸、トリデカン酸、ミリスチン酸、イソステアリン酸、ステアリン酸、１，２−ヒドロキシステアリン酸、ベヘン酸、モンダン酸、オレイン酸、エライジン酸、リノール酸、リノレン酸、チオグリコール酸、メルカプトプロピオン酸、オクチルメルカプトプロピオン酸などの一塩基脂肪族カルボン酸；安息香酸、モノクロロ安息香酸、ｐ−（ｔ−ブチル）安息香酸、ジメチルヒドロキシ安息香酸、３，５−ジ（ｔ−ブチル）−４−ヒドロキシ安息香酸、トルイル酸、ジメチル安息香酸、エチル安息香酸、クミン酸、ｎ−プロピル安息香酸、アミノ安息香酸、Ｎ，Ｎ−ジメチルアミノ安息香酸、アセトキシ安息香酸、サリチル酸、ｐ−（ｔ−オクチル）サリチル酸等の一塩基芳香族カルボン酸；シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、マレイン酸、フマル酸、シトラコン酸、メタコン酸、イタコン酸、チオジプロピオン酸等の二塩基脂肪族カルボン酸；フタル酸、イソフタル酸、テレフタル酸、オキシフタル酸、クロロフタル酸、アミノフタル酸等の二塩基芳香族カルボン酸；アニコット酸等の三塩基脂肪族カルボン酸；ヘミメリット酸、トリメリット酸等の三塩基芳香族カルボン酸；メロファン酸、ピロメリット酸等の四塩基芳香族カルボン酸；メリット酸等の六塩基芳香族カルボン酸などが挙げられる。
(C) The heat stabilizer is blended for the purpose of suppressing the dehydrochlorination reaction which is one of the degradation mechanisms peculiar to polyvinyl chloride resin. In the present invention, a mixture of an organic acid metal salt and hydrotalcite is used among various lead-free heat stabilizers in consideration of electrical insulation.
The organic acid metal salt is a salt of a metal atom selected from the group consisting of Ca, Mg, Zn, Ba and Sn and an organic acid. There is no restriction | limiting in particular about the organic acid which comprises a salt, Any of monobasic acid or polybasic acid, aliphatic carboxylic acid, or aromatic carboxylic acid may be sufficient. As an organic acid, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthate, caprylic acid, neoacid, 2-ethylhexanoic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristin Acids, isostearic acid, stearic acid, 1,2-hydroxystearic acid, behenic acid, mondanic acid, oleic acid, oleic acid, elidinic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopropionic acid and the like Aliphatic carboxylic acids; benzoic acid, monochlorobenzoic acid, p- (t-butyl) benzoic acid, dimethylhydroxybenzoic acid, 3,5-di (t-butyl) -4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid , Ethylbenzoic acid, Cuminic acid, n-Propylbenzoic acid, Aminobenzoic acid Monobasic aromatic carboxylic acids such as N, N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, p- (t-octyl) salicylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid , Dibasic aliphatic carboxylic acids such as suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, thiodipropionic acid; phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, Dibasic aromatic carboxylic acids such as chlorophthalic acid and aminophthalic acid; tribasic aliphatic carboxylic acids such as anicot acid; tribasic aromatic carboxylic acids such as hemimellitic acid and trimellitic acid; 4 such as merophonic acid and pyromellitic acid Base aromatic carboxylic acids; hexabasic aromatic carboxylic acids such as mellitic acid and the like can be mentioned.
ハイドロタルサイトは、一般式：［Ｍｇ1-xＡｌx（ＯＨ）2］x+ ［（ＣＯ3）x/2・ｍＨ2Ｏ］x- で表される不定比化合物であり（式中、ｘは０より大きく０．３３以下の数である）、正に荷電した基本層：［Ｍｇ1-xＡｌx（ＯＨ）2］x+ と、負に荷電した中間層：［（ＣＯ3）x/2・ｍＨ2Ｏ］x- とからなる層状の結晶構造を有する。天然には、Ｍｇ6Ａｌ2（ＯＨ）16ＣＯ3・４Ｈ2Ｏとして得られ、人工的には、主としてＭｇ4.5Ａｌ2（ＯＨ）13ＣＯ3・３．５Ｈ2Ｏの合成品が調製及び市販されている。 Hydrotalcite is a non - stoichiometric compound represented by the general formula: [Mg 1-x Al x (OH) 2 ] x + [(CO 3 ) x / 2 · m H 2 O] x- (wherein x is Is a number greater than 0 and less than or equal to 0.33), the positively charged base layer: [Mg 1 -x Al x (OH) 2 ] x + and the negatively charged intermediate layer: [(CO 3 ) x / It has a layered crystal structure of 2 · mH 2 O] x- . Naturally, it is obtained as Mg 6 Al 2 (OH) 16 CO 3. 4 H 2 O, and artificially prepared mainly as a synthetic product of Mg 4.5 Al 2 (OH) 13 CO 3. 3.5 H 2 O It is marketed.
市場で入手可能な有機酸金属塩とハイドロタルサイトとの混合物としては、例えば、（株）ＡＤＥＫＡ社製アデカスタブＲＵＰ１０３、（株）ＡＤＥＫＡ社製アデカスタブＲＵＰ１４が挙げられる。熱安定剤として配合される、有機酸金属塩とハイドロタルサイトとの混合物の添加量は、ポリ塩化ビニル樹脂１００質量部に対して４〜１０質量部の割合となる様に調整するとよい。４質量未満であると樹脂組成物の熱安定性が満足に得られず、自動車用電線としての使用環境において耐摩耗性が低下する虞があり、１０質量部を超えると、混練あるいは押出加工時に十分な剪断力が得られず、電線絶縁体として十分な品質が得られ難く、製造コストの観点においても不利となる。 As a mixture of the organic acid metal salt and hydrotalcite which are commercially available, for example, Adekastab RUP 103 manufactured by ADEKA Co., Ltd. and Adekastab RUP 14 manufactured by ADEKA Co., Ltd. can be mentioned. The addition amount of the mixture of an organic acid metal salt and hydrotalcite mixed as a heat stabilizer may be adjusted so as to be 4 to 10 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. If the amount is less than 4 parts by mass, the thermal stability of the resin composition can not be satisfactorily obtained, and there is a possibility that the abrasion resistance may be reduced in the use environment as an automotive wire. Sufficient shear force can not be obtained, and sufficient quality as a wire insulator can not be obtained easily, which is disadvantageous in terms of manufacturing cost.
（Ｄ）非鉛系滑剤として使用する変性ポリエチレンワックスは、酸化型が好ましく、分子量（粘度法に従った測定による平均分子量）が２６００〜３２００のものが好ましい。酸化型変性ポリエチレンは、既知の方法によるポリエチレンの酸化によって極性基（水酸化、カルボキシル基）をポリエチレンに導入したものであり、ポリ塩化ビニル樹脂組成物に対してブリードアウトを生じ難い。従って、上記変性ポリエチレンワックスの添加によって、樹脂組成物の成形加工が容易且つ円滑になって、細径の電線と共に押し出し成形して高弾性の樹脂組成物で構成される薄肉の絶縁部材を形成することが可能になる。又、成形安定性が向上するので、外観の良い細径の絶縁被覆電線を高速で効率良く製造することが可能になる。変性ポリエチレンワックスの分子量が２６００未満であると、絶縁被覆電線の成形加工時や自動車用電線としての使用環境下において液状物のブリードアウトを生じ易くなる。分子量が３２００を超えるものを用いると、樹脂間での滑性を十分に付与することが難しくなり、成形した絶縁被覆電線の外観不良や寸法不良を生じ易くなる。非変性のポリエチレンワックスを用いると、樹脂組成物と押出機内の滑性が過剰になって外部滑剤としての作用が強くなり、押出し成形時にシリンダ内やヘッド部でスリップを起こし易くなるため、成形安定性が却って低下し、絶縁被覆電線の寸法不良が増加し易くなる。変性ポリエチレンワックスは、塩化ビニル樹脂１００質量部に対して０．２〜０．４質量部程度となる割合で添加することが好ましい。配合割合が０．２質量未満であると、効果が十分に得られず、成形した絶縁被覆電線の外観不良や寸法不良を生じ易くなり、０．４質量部を超えると、成形加工時や自動車用電線としての使用環境下においてブリードアウトを生じ易くなる。使用可能な市販の変性ポリエチレンワックスとしては、例えば、三井化学社製のハイワックス３１０ＭＰ、ハイワックス２２０３Ａ等を挙げることができる。 The modified polyethylene wax used as the lead-free lubricant (D) is preferably an oxidized type, and preferably has a molecular weight (average molecular weight measured by a viscosity method) of 2600 to 3200. The oxidized modified polyethylene is obtained by introducing a polar group (hydroxyl group, carboxyl group) into polyethylene by oxidation of polyethylene according to a known method, and hardly bleeds out to a polyvinyl chloride resin composition. Therefore, the addition of the modified polyethylene wax facilitates and facilitates the molding process of the resin composition, and forms a thin-walled insulating member composed of a highly elastic resin composition by extrusion molding with a small diameter wire. It becomes possible. In addition, since the molding stability is improved, it is possible to efficiently manufacture an insulation-coated wire with a fine diameter and a good appearance at a high speed. When the molecular weight of the modified polyethylene wax is less than 2600, bleeding of the liquid is likely to occur in the forming process of the insulation coated wire or in the use environment as a wire for automobile. When the molecular weight exceeds 3200, it becomes difficult to sufficiently impart lubricity between the resins, and it becomes easy to cause appearance defects and dimensional defects of the molded insulation coated wire. When non-modified polyethylene wax is used, the resin composition and the inside of the extruder become excessively slippery and the function as an external lubricant becomes strong, and it becomes easy to cause slippage in the cylinder and the head during extrusion, so that molding stability is achieved. On the contrary, the property is lowered and dimensional defects of the insulation coated wire tend to increase. The modified polyethylene wax is preferably added in a proportion of about 0.2 to 0.4 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. If the blending ratio is less than 0.2 mass, the effect can not be sufficiently obtained, and appearance defects and dimensional defects of the molded insulation coated wire tend to occur, and if it exceeds 0.4 parts by mass, molding processing and automobiles Bleed-out is likely to occur in the use environment as an electric wire. As a commercially available modified polyethylene wax which can be used, high wax 310MP, high wax 2203A etc. made by Mitsui Chemicals, Inc. can be mentioned, for example.
本発明のポリ塩化ビニル樹脂組成物は、上述の（Ａ）ポリ塩化ビニル樹脂、（Ｂ）可塑剤、（Ｃ）有機酸金属塩とハイドロタルサイトとの混合物からなる非鉛系熱安定剤、及び、（Ｄ）非鉛系滑剤として用いる変性ポリエチレンワックスに加えて、必要に応じて、充填材、改質剤等を配合することができる。 The polyvinyl chloride resin composition of the present invention comprises the above-mentioned polyvinyl chloride resin (A), a plasticizer (B), a lead-free heat stabilizer comprising a mixture of a metal salt of an organic acid and hydrotalcite, And, in addition to the modified polyethylene wax used as the (D) lead-free lubricant, fillers, modifiers and the like can be blended, if necessary.
充填材は、一般的に、樹脂組成物の物性を低下させずに増量や補強等を行うことを目的として配合され、本発明では、充填材の配合によって樹脂組成物の摩耗性や低温衝撃性を改善することが可能である。本発明の充填材には、ポリ塩化ビニル樹脂の充填材として通常用いられるものから適宜選択して使用することができ、例えば、炭酸カルシウム、炭酸マグネシウム、クレー、焼成カオリン、タルク、シリカ、珪酸カルシウム、珪酸アルミニウム、珪酸マグネシウム、硫酸バリウム等の無機材料を挙げることができ、複数種の充填材を組みあわせた混合物として用いても良い。細径電線に薄肉の絶縁部材を形成する点や樹脂組成物の均質性等の観点から、ＢＥＴ比表面積が９．０〜１５．０ｍ２／ｇ程度の炭酸カルシウムを用いることが好ましく、ポリ塩化ビニル樹脂１００質量部に対して、好ましくは２〜１０質量部程度の割合で配合するとよい。 The filler is generally blended for the purpose of increasing or reinforcing the resin composition without reducing the physical properties of the resin composition, and in the present invention, the abradability and low-temperature impact resistance of the resin composition are achieved by blending the filler. It is possible to improve. The filler of the present invention can be appropriately selected from those commonly used as a filler of polyvinyl chloride resin and used, for example, calcium carbonate, magnesium carbonate, clay, calcined kaolin, talc, silica, calcium silicate Inorganic materials such as aluminum silicate, magnesium silicate and barium sulfate may be mentioned, and they may be used as a mixture in which a plurality of fillers are combined. It is preferable to use calcium carbonate having a BET specific surface area of about 9.0 to 15.0 m 2 / g from the viewpoint of forming a thin insulating member on a fine electric wire, the homogeneity of the resin composition, etc. It is good to mix | blend in the ratio of about 2-10 mass parts preferably with respect to 100 mass parts of vinyl resins.
改質剤は、樹脂組成物に他の機能性を付与することを目的として配合され、本発明では、樹脂組成物の耐衝撃性を向上させる衝撃吸収剤を添加することができる。本発明の衝撃吸収剤には、ポリ塩化ビニルの衝撃吸収剤として通常用いられるものから適宜選択して使用することができ、例えば、メチルメタクリレート（ＭＭＡ）、メチルメタクリレート−ブタジエン−スチレン共重合体（ＭＢＳ）、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ）、（塩素化ポリエチレン、エチレン−酢酸ビニル共重合体（ＥＶＡ）等）のエラストマー性を有する樹脂が挙げられる。衝撃吸収剤は、ポリ塩化ビニル樹脂１００質量部に対して、好ましくは２〜８質量部程度の割合で使用するとよい。 The modifier is blended for the purpose of imparting other functionality to the resin composition, and in the present invention, an impact absorber which improves the impact resistance of the resin composition can be added. The shock absorber of the present invention may be appropriately selected from those commonly used as polyvinyl chloride shock absorbers, and examples thereof include methyl methacrylate (MMA), methyl methacrylate-butadiene-styrene copolymer ( Examples of the resin include elastomers such as MBS), acrylonitrile-butadiene-styrene copolymer (ABS), and (chlorinated polyethylene, ethylene-vinyl acetate copolymer (EVA), etc.). The impact absorbing agent is preferably used in a proportion of about 2 to 8 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin.
上述の（Ａ）〜（Ｄ）の成分、及び、必要に応じて利用する上述の添加剤を用いて、常法に従って均一な溶融混合物を調製することによって、本発明のポリ塩化ビニル樹脂組成物が得られる。この樹脂組成物を電線の絶縁被覆用の樹脂として用いて、電線（銅線等の導電性金属で形成される線状導体）と共に押出し成形することによって、管状に固化した樹脂組成物が絶縁体となって電線を被覆する絶縁部材が形成され、絶縁部材で電線が被覆された絶縁被覆電線が得られる。本発明のポリ塩化ビニル樹脂組成物は、細径薄肉の押出し成形における成形安定性に優れており、公称導体断面積が０．０８〜１．２５ｍｍ２程度の電線を用いて、絶縁部材の肉厚が公称０．１６ｍｍ（最小０．１２ｍｍ）以上の薄肉の絶縁被覆電線を、効率良く製造することができる。従って、０．３５ｍｍ２以下の細径の絶縁被覆電線を製造する上で非常に有利である。得られる絶縁被覆電線は、樹脂表面の外観が良く、自動車のワイヤーハーネス等としての使用環境に十分耐えられる耐熱性、耐寒性、硬度及び耐摩耗性を有し、添加成分のブリードアウトも抑制されるので、長期間の使用に十分耐えることができる。又、鉛を使用しないので、廃棄物処理やリサイクルにおいても安心して取り扱うことができる。 Polyvinyl chloride resin composition of the present invention by preparing a homogeneous molten mixture according to a conventional method using the above-mentioned components (A) to (D) and, if necessary, the above-mentioned additives Is obtained. This resin composition is used as a resin for insulation coating of a wire, and the resin composition solidified in a tubular shape is extruded by extrusion molding with a wire (a linear conductor formed of a conductive metal such as a copper wire). As a result, an insulation member covering the electric wire is formed, and an insulation coated electric wire in which the electric wire is covered with the insulation member is obtained. The polyvinyl chloride resin composition of the present invention is excellent in molding stability in thin-diameter thin-walled extrusion molding, and using a wire having a nominal conductor cross-sectional area of about 0.08 to 1.25 mm 2 , it is possible to use the meat of the insulating member A thin-walled insulation coated wire having a thickness of nominally 0.16 mm or more (minimum 0.12 mm) can be efficiently produced. Therefore, it is very advantageous in producing a small diameter insulation coated wire of 0.35 mm 2 or less. The resulting coated insulation wire has a good appearance on the resin surface, has heat resistance, cold resistance, hardness and wear resistance enough to withstand the use environment as a wire harness for automobiles, etc., and bleed out of added components is also suppressed Can withstand long-term use. In addition, since lead is not used, it can be handled safely in waste disposal and recycling.
＜試料の調製原料＞
ポリ塩化ビニル樹脂組成物を調製するための原料、及び、絶縁被覆電線用の線状導体として、以下のものを用意した。
（Ａ）ポリ塩化ビニル樹脂（ＰＶＣ、重合度：１３００、１７００及び２０００の３種）
（Ｂ）可塑剤：ｎ−トリオクチルトリメリテート（ｎ−ＴＯＴＭ）
（Ｃ）熱安定剤：ステアリン酸Ｚｎとハイドロタルサイトとの混合物
（Ｄ）滑剤：酸化型変性ポリエチレンワックス（平均分子量：１５００、２０００、２６００、３２００及び４０００の６種）及び非変性のポリエチレンワックス（平均分子量：２０００、３０００及び４０００の３種）
充填材：炭酸カルシウム（ＢＥＴ比表面積：１２．２ｍ２／ｇ）
改質剤：ＭＢＳ
絶縁被覆電線用線状導体：銅線（サイズ：０．１３sq及び０．３５sq）
<Preparation raw material of sample>
The following were prepared as a raw material for preparing a polyvinyl chloride resin composition, and a linear conductor for an insulation coated wire.
(A) Polyvinyl chloride resin (PVC, degree of polymerization: 1300, 1700 and 2000 three types)
(B) Plasticizer: n-trioctyl trimellitate (n-TOTM)
(C) Heat stabilizer: Mixture of Zn stearate and hydrotalcite (D) Lubricant: oxidized modified polyethylene wax (average molecular weight: 6 types of 1500, 2000, 2600, 3200 and 4000) and non-modified polyethylene wax (Average molecular weight: 3 types of 2000, 3000 and 4000)
Filler: calcium carbonate (BET specific surface area: 12.2 m 2 / g)
Modifier: MBS
Wire conductor for insulation coated wire: Copper wire (size: 0.13sq and 0.35sq)
＜試料の調製及び評価＞
表１〜表２に示す樹脂組成の配合割合（表中、質量部で数値を示す）に従って上述の調製用原料を配合し、１８０℃のオープンロールを用いて均一に混練して、試料Ａ１〜Ａ１５，Ｂ１〜Ｂ１０のポリ塩化ビニル樹脂組成物を調製した。
得られた試料Ａ１〜Ａ１５，Ｂ１〜Ｂ１０のポリ塩化ビニル樹脂組成物の各々について、表中に記載するサイズの銅線をセットした押出機（φ４０ｍｍ、材料押出し温度：１８５℃、大宮精機製）に投入して、樹脂の肉厚が０．２ｍｍとなる設定でポリ塩化ビニル樹脂組成物を銅線と共に同心状に押し出し成形を行って、銅線を被覆する絶縁部材を樹脂組成物によって形成し、試料Ａ１〜Ａ１５，Ｂ１〜Ｂ１０の絶縁被覆電線を得た。
得られた絶縁被覆電線の各試料について、以下のように、絶縁被覆電線の外観評価を行い、電線構造の評価として、同心率及び外径安定性を求めた。更に、硬度、耐寒性、耐摩耗性、耐低温性、耐低温衝撃性、及び、ブリードアウトの有無について以下のように評価した。評価の結果を表１及び２に示す。尚、電線構造の評価において評価基準に満たなかった試料については、耐摩耗性、耐低温性及び耐低温衝撃性の評価は省略した。
<Preparation of samples and evaluation>
According to the compounding ratio of the resin composition shown in Tables 1 and 2 (in the table, the numerical values are indicated in parts by mass), the above-mentioned raw materials for preparation are blended, and uniformly kneaded using an open roll at 180 ° C. Polyvinyl chloride resin compositions of A15 and B1 to B10 were prepared.
An extruder (φ 40 mm, material extrusion temperature: 185 ° C., manufactured by Omiya Seiki) in which copper wires of the size described in the table were set for each of the obtained polyvinyl chloride resin compositions of samples A1 to A15 and B1 to B10. Into the resin, and extruding the polyvinyl chloride resin composition concentrically with the copper wire in a setting where the thickness of the resin is 0.2 mm, and forming the insulating member for covering the copper wire with the resin composition Insulating coated wires of samples A1 to A15 and B1 to B10 were obtained.
About each sample of the obtained insulation coating electric wire, the appearance evaluation of the insulation coating electric wire was performed as follows, and concentricity and outer diameter stability were calculated | required as evaluation of a wire structure. Furthermore, hardness, cold resistance, abrasion resistance, low temperature resistance, low temperature impact resistance, and the presence or absence of bleed out were evaluated as follows. The results of the evaluation are shown in Tables 1 and 2. In addition, evaluation of abrasion resistance, low temperature resistance, and low temperature impact resistance was abbreviate | omitted about the sample which did not satisfy the evaluation standard in evaluation of a wire structure.
（外観評価）
絶縁被覆電線試料の樹脂表面を目視によって観察し、ざらつきや導体の拠り目、凹凸がないものを○印（中でも表面状態が特に良好なものは◎印）で、これらの何れかが見られるものを×印で記載する。
(Appearance evaluation)
The resin surface of the insulation-coated wire sample is visually observed, and those with no roughness, roughness of the conductor, no unevenness are marked with ○ (especially those with particularly good surface condition are ◎), and any of these can be seen Indicated by ×.
（電線の同心率）
絶縁被覆電線試料の径方向断面において、絶縁部材の肉厚（銅線を被覆する樹脂層の径方向の厚さ）を１サンプルにつき４箇所で１０サンプル測定して、肉厚の最小値ａと最大値ｂとを求め、下記式に従って同心率αを計算し、１０サンプル中細小の同心率αが８０％以上のものを○印で、これを下回るものを×印で記載する。
同心率： α＝（ｂ／ａ）×１００
(Concentricity of wire)
In the radial cross section of the insulation coated wire sample, measure the thickness of the insulation member (the thickness in the radial direction of the resin layer covering the copper wire) at 10 points per sample, and measure the minimum thickness a The maximum value b is determined, the concentricity ratio α is calculated according to the following formula, and in 10 samples, those with a concentricity ratio α of 80% or more are indicated by ○ and those below are indicated by ×.
Concentricity ratio: α = (b / a) × 100
（外径安定性）
レーザー外測計を用いて、絶縁被覆電線試料の電線径を測定し、この際に、電線を回転させることによって相対的にレーザーを電線の周囲を１周回させて、最大径ｘ及び最小径ｙを求め、変形率ｚ［％］を下記式に従って算出した。
変形率： ｚ＝（ｘ／ｙ）×１００
更に、電線を軸方向に１０ｃｍずらして上記の外径測定及び変形率の算出を行い、この作業を３０回繰り返して、ｎ＝３０の変形率データを収集した。このデータから、規格値を９０％以上として工程能力指数Ｃｐｋを算出した。Ｃｐｋが１．６７以上のものを○印で、これを下回るものを×印で記載する。
(Outside stability)
The wire diameter of the insulation coated wire sample is measured using a laser external measurement meter, and at this time, the laser is made to go around the wire relatively by rotating the wire, and the maximum diameter x and the minimum diameter y The deformation ratio z [%] was calculated according to the following equation.
Deformation rate: z = (x / y) × 100
Further, the wire was shifted by 10 cm in the axial direction to measure the outer diameter and calculate the deformation rate, and this operation was repeated 30 times to collect n = 30 deformation rate data. From this data, the process capability index Cpk was calculated with a standard value of 90% or more. Those with Cpk of 1.67 or more are indicated by 印, and those with less than Cpk are indicated by ×.
（硬度）
日本工業規格ＪＩＳ Ｋ７２１５の規定に基づいて、タイプＤのデュロメーターを用いて絶縁被覆電線試料の硬度の測定を行った。針を試料に落としてから１０秒後のデュロメーターの値を読み取り、この値を硬度の測定値とした。測定値が大きいほど試料が硬いことを示す。
(hardness)
The hardness of the insulation coated wire sample was measured using a type D durometer based on the Japanese Industrial Standard JIS K7215. Ten seconds after dropping the needle onto the sample, the value of the durometer was read, and this value was taken as the measurement value of hardness. The larger the measurement value, the harder the sample.
（耐寒性）
日本工業規格ＪＩＳ Ｋ６７２３の規定に従って、絶縁被覆電線試料の耐寒性試験を行った。この試験において測定される脆化温度に基づいて耐寒温度を決定した。
(Cold resistance)
The cold resistance test of the insulation coated wire sample was conducted in accordance with the Japanese Industrial Standard JIS K 6723. The cold resistant temperature was determined based on the embrittlement temperature measured in this test.
（耐摩耗性）
国際規格ＩＳＯ６７２２ ９・３項に準拠して、絶縁被覆電線試料の耐摩耗試験（スクレープ試験）を行った。スクレープ試験では、２３℃において、ブレードにかかる荷重を７Ｎに設定して電線試料に沿って往復させ、内部の銅線に導通するまでの往復回数を測定した。電線試料を軸中心に９０度回転させて同じ測定を繰り返し、１本の電線について計４回の測定を行った。４回の測定における最小値が２５０回以上のものを○印で、１００回以上で２５０回未満のものを△印で、１００回に満たないものを×印で記載する。
(Abrasion resistance)
The abrasion resistance test (screpe test) of the insulation coated wire sample was performed in accordance with the international standard ISO 6722 9/3. In the scrape test, at 23 ° C., the load applied to the blade was set to 7 N and reciprocated along the wire sample to measure the number of reciprocations until the internal copper wire was conducted. The wire sample was rotated 90 degrees around the axis, the same measurement was repeated, and a total of four measurements were performed for one wire. The minimum value in four measurements is described as ○ for those with a minimum value of 250 or more, with Δ for 100 or more and less than 250, and with x for less than 100.
（耐低温性：巻付試験）
低温特性を評価する国際規格ＩＳＯ６７２２ ８・１項に準拠して、絶縁被覆電線試料の低温巻付試験を行った。低温巻付試験では、電線試料の外径の５倍の外径を有するマンドレル及び電線試料を−４０℃に４時間以上冷却した後、マンドレルに電線試料を巻き付け、巻き付け後に導体部分の露出がないことを確認して、電線試料の導体と被覆する樹脂の外周面との間に１０００Ｖの電圧を１分間印加し、樹脂における絶縁破壊の有無を調べた。絶縁破壊を生じないものを○印で、生じたものを×印で記載する。
(Low temperature resistance: winding test)
The low temperature winding test of the insulation coated wire sample was conducted in accordance with the international standard ISO 6722 8.1.1 which is to evaluate the low temperature characteristics. In the low temperature winding test, after cooling the mandrel and the wire sample having an outer diameter five times the outer diameter of the wire sample to -40 ° C for 4 hours or more, the wire sample is wound around the mandrel and the conductor portion is not exposed after winding. After confirming that, a voltage of 1000 V was applied for 1 minute between the conductor of the wire sample and the outer peripheral surface of the resin to be coated, and the presence or absence of dielectric breakdown in the resin was examined. Those that do not cause dielectric breakdown are indicated by 印, and those that are generated are indicated by ×.
（耐低温衝撃性）
低温特性を評価する国際規格ＩＳＯ６７２２ ８・２項に準拠して、絶縁被覆電線試料の低温衝撃試験を行った。低温衝撃試験では、１００ｇのハンマー（重り）を含む試験治具を−１５℃に１６時間以上冷却した。電線試料を−１５℃に４時間以上冷却して静置し、冷却したハンマーを１００ｍｍの高さから電線試料上に自由落下させ、落下の衝撃による樹脂の割れの有無を目視によって調べた。目視によって割れが見られない場合には、更に、電線試料の導体と被覆する樹脂の外周面との間に１０００Ｖの電圧を１分間印加し、樹脂における絶縁破壊の有無を調べた。絶縁破壊を生じないものを○印で記載し、絶縁破壊を生じたもの、及び、割れが見られたものを×印で記載する。
(Low temperature impact resistance)
The low temperature impact test of the insulation coated wire sample was carried out in accordance with the international standard ISO 6722 8-2 clause for evaluating the low temperature characteristics. In the low temperature impact test, a test jig containing 100 g of a hammer (weight) was cooled to -15 ° C for 16 hours or more. The wire sample was cooled to −15 ° C. for 4 hours or more and allowed to stand, and the cooled hammer was allowed to freely fall onto the wire sample from a height of 100 mm, and the presence or absence of resin cracking due to impact of drop was visually inspected. When no cracks were visually observed, a voltage of 1000 V was applied for 1 minute between the conductor of the wire sample and the outer peripheral surface of the resin to be coated, and the presence or absence of dielectric breakdown in the resin was examined. Those with no dielectric breakdown are described by ○, and those with dielectric breakdown and those with cracks are indicated by x.
（ブリードアウトの有無）
電線を被覆する樹脂を、幅２０ｍｍ×厚さ１ｍｍ×長さ１５０ｍｍに成形した試料を半分の長さに折り曲げて、１８０℃折り曲げの状態で、４０℃の雰囲気中に２４時間放置した後に試料を開いて、内側における液状物のブリードアウトの有無を目視により調べた。ブリードアウトが見られないものを○印で、ブリードアウトが生じたものを×印で記載する。
(Without bleed-out)
A sample obtained by molding a resin for coating an electric wire into a width of 20 mm × thickness 1 mm × length 150 mm is bent to a half length and left in an atmosphere of 40 ° C. for 24 hours in a 180 ° C. bending state. It was opened, and the presence or absence of the bleed-out of the liquid inside was visually checked. Those with no bleed-out are indicated by ○, and those with bleed-out are indicated by ×.
＜試料の評価結果＞
試料Ａ１〜Ａ１５は、（Ａ）ポリ塩化ビニル樹脂に配合する添加剤として、（Ｂ）可塑剤、（Ｃ）熱安定剤及び（Ｄ）滑剤に加えて、充填材及び改質剤を用いて調製したポリ塩化ビニル樹脂組成物で銅線を被覆した絶縁被覆電線であり、（Ｄ）滑剤として変性ポリエチレンワックスを使用し、何れも良好な特性を有している。試料Ｂ１〜Ｂ１０は、ポリ塩化ビニル樹脂組成物における配合割合等を変化させた場合や使用する滑剤を変更した場合の影響を調べるためのものであり、絶縁被覆電線の特性の何れかにおいて減退が見られる。
<Evaluation result of sample>
Samples A1 to A15 contain, as additives added to (A) polyvinyl chloride resin, in addition to (B) plasticizer, (C) heat stabilizer and (D) lubricant, a filler and a modifier. It is the insulation coated electric wire which coat | covered the copper wire with the prepared polyvinyl chloride resin composition, modified polyethylene wax is used as a (D) lubricant, and all have a favorable characteristic. Samples B1 to B10 are for examining the effects of changing the blending ratio or the like in the polyvinyl chloride resin composition or changing the lubricant used, and there is a decline in any of the properties of the insulation coated wire Seen.
表１によれば、試料Ａ１〜Ａ３及び試料Ａ５〜７において使用されるポリ塩化ビニル樹脂は、重合度が異なるが、何れの樹脂組成物も良好な評価結果を示しており、重合度が１３００〜２０００の範囲のポリ塩化ビニル樹脂を好適に使用できることが判る。これらの比較において、ポリ塩化ビニル樹脂の重合度の増加によって樹脂組成物の耐寒性及び耐摩耗性が向上する傾向が見られ、この傾向は、銅線のサイズが０．１３sq及び０．３５sqの何れにおいても同様である。又、試料Ａ２と試料Ａ８の比較、試料Ａ４と試料Ａ６との比較において、可塑剤の配合量が増加すると樹脂組成物の耐寒性が向上するが、硬度及び耐摩耗性が低下することが判る。この点は、表２の試料Ｂ１〜Ｂ６との比較によって明白である。更に、可塑剤の不足によって樹脂組成物の外観不良を生じ、耐低温衝撃性が低下することが試料Ｂ１〜Ｂ３から明らかであり、特に、重合度が高いポリ塩化ビニル樹脂を用いた場合には樹脂組成物の耐低温性が低下して絶縁部材にクラックやピンホール等が生じ易くなる。従って、可塑剤の配合量は、これらの特性のバランスを考慮して決定する必要があり、試料Ａ１〜８及びＢ１〜Ｂ６から、ポリ塩化ビニル樹脂１００質量部に対して可塑剤の割合が２４〜２８質量部の場合に好適な絶縁被覆電線が得られることが判る。 According to Table 1, the polyvinyl chloride resins used in Samples A1 to A3 and Samples A5 to 7 have different degrees of polymerization, but all resin compositions show good evaluation results, and the degree of polymerization is 1300. It can be seen that polyvinyl chloride resin in the range of ̃2000 can be suitably used. In these comparisons, it can be seen that the increase in the degree of polymerization of polyvinyl chloride resin tends to improve the cold resistance and the abrasion resistance of the resin composition, and this tendency indicates that the copper wire size is 0.13sq and 0.35sq. The same is true in any case. In addition, in comparison of sample A2 with sample A8 and sample A4 with sample A6, it can be understood that when the blending amount of the plasticizer is increased, the cold resistance of the resin composition is improved, but the hardness and the wear resistance are reduced. . This point is clear by comparison with the samples B1 to B6 in Table 2. Furthermore, it is clear from the samples B1 to B3 that the poor appearance of the resin composition occurs due to the lack of the plasticizer and the low temperature impact resistance decreases, and particularly when polyvinyl chloride resin having a high degree of polymerization is used. The low temperature resistance of the resin composition is reduced, and cracks, pinholes and the like are easily generated in the insulating member. Therefore, the blending amount of the plasticizer needs to be determined in consideration of the balance of these characteristics, and the ratio of the plasticizer to 100 parts by mass of the polyvinyl chloride resin is 24 from the samples A1 to 8 and B1 to B6. It turns out that a suitable insulation coated electric wire is obtained in the case of -28 mass parts.
試料Ａ９〜Ａ１２及びＡ１４、及び、試料Ｂ８〜Ｂ１０においては、（Ｄ）滑剤として使用する変性ポリエチレンワックスの分子量が異なるが、何れも良好な特性を有している。中でも、分子量２６００（試料Ａ１４）〜３２００（試料Ａ１１）においては非常に良好な外観が得られることが判る。
尚、（Ｄ）滑剤として非変性のポリエチレンワックスを使用すると、試料Ｂ８〜Ｂ１０の結果から判るように、ポリエチレンワックスの分子量に関係なく、樹脂表面の外観不良を生じ、成形安定性も減退して同心率及び外径安定性の評価が低下する。従って、滑剤としての有効性は、変性ポリエチレンワックスと非変性のポリエチレンワックスとでは大きく異なる。
Samples A9 to A12 and A14 and samples B8 to B10 differ in molecular weight of the modified polyethylene wax used as the lubricant (D), but all have good properties. Above all, it can be seen that in the molecular weights 2600 (sample A14) to 3200 (sample A11), a very good appearance can be obtained.
In addition, when a non-modified polyethylene wax is used as the lubricant (D), as seen from the results of samples B8 to B10, the appearance of the resin surface becomes poor regardless of the molecular weight of the polyethylene wax, and the molding stability decreases. Assessment of concentricity and outer diameter stability is reduced. Therefore, the effectiveness as a lubricant is largely different between the modified polyethylene wax and the non-modified polyethylene wax.
試料Ａ１３〜Ａ１５及び試料Ｂ７においては、（Ｄ）滑剤として使用する変性ポリエチレンワックスの添加量が異なり、変性ポリエチレンワックスの添加によって樹脂組成物に耐低温衝撃性が付与され（試料Ｂ７）、添加量の増加によって樹脂組成物の外観が良好になる（試料Ａ１３〜１５）。これらの結果から、ポリ塩化ビニル樹脂１００質量部に対して０．２〜０．４質量が、変性ポリエチレンワックスの適正量であると言える。 In samples A13 to A15 and sample B7, the addition amount of the modified polyethylene wax used as the lubricant (D) is different, and the addition of the modified polyethylene wax imparts low temperature impact resistance to the resin composition (sample B7), the addition amount Increases the appearance of the resin composition (Samples A13-15). From these results, it can be said that 0.2 to 0.4 mass is an appropriate amount of the modified polyethylene wax with respect to 100 parts by mass of the polyvinyl chloride resin.
表１において、銅線のサイズが小さい試料Ａ１〜Ａ３，Ａ８と銅線のサイズが大きい試料Ａ４〜Ａ７との比較から、銅線のサイズが小さい方が絶縁被覆電線の耐摩耗性が低いことが理解される。つまり、細径の絶縁被覆電線の作成においては、耐摩耗性の付与が基本的な要件である。従って、電線を被覆する樹脂が耐摩耗性を保持するように可塑剤の配合を抑制し、耐寒性等の他の特性を良好に発揮し得るようにバランスを考慮して変性ポリエチレンワックスを添加することは、細径・薄肉の絶縁被覆電線を形成する上で非常に重要である。 In Table 1, from the comparison of samples A1 to A3 and A8 with small copper wire size and samples A4 to A7 with large copper wire size, the smaller the copper wire size, the lower the abrasion resistance of the insulation coated wire. Is understood. That is, in the production of a small diameter insulation coated wire, provision of wear resistance is a basic requirement. Therefore, the composition of the plasticizer is suppressed so that the resin covering the electric wire maintains the abrasion resistance, and the modified polyethylene wax is added in consideration of balance so that other characteristics such as cold resistance can be exhibited well. Is very important in forming thin-diameter, thin-walled insulation coated wires.
本発明は、電気絶縁材料として優れた特性を発揮するポリ塩化ビニル樹脂及び非鉛系の成分を用いて、加工性が良い電線被覆用のポリ塩化ビニル樹脂組成物、及び、機械特性に優れた絶縁被覆電線を提供する。特に、効率的に製造でき、耐寒性、耐摩耗等に優れた細径の絶縁被覆電線が提供され、ワイヤーハーネス等への適用による自動車の軽量化に有用であり、自動車産業への貢献が大である。 The present invention uses a polyvinyl chloride resin and a lead-free component that exhibit excellent properties as an electrical insulating material, a polyvinyl chloride resin composition for wire coating having good processability, and excellent mechanical properties. Provide an insulation coated wire. In particular, a thin-diameter insulation coated wire which can be efficiently manufactured, excellent in cold resistance, wear resistance, etc. is provided, which is useful for reducing the weight of automobiles by application to wire harnesses, etc., contributing greatly to the automobile industry. It is.
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| JP2017155093A (en) * | 2016-02-29 | 2017-09-07 | 矢崎エナジーシステム株式会社 | Polyvinyl chloride resin composition, and wire and cable prepared therewith |
| JP2017199457A (en) | 2016-04-25 | 2017-11-02 | 矢崎総業株式会社 | High flex insulation wire and wire harness |
| WO2018180690A1 (en) * | 2017-03-27 | 2018-10-04 | 古河電気工業株式会社 | Molded body of chlorine-containing heat-resistant crosslinked resin, method for producing said body, silane masterbatch, masterbatch mixture, and heat-resistant product |
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