JP6459552B2 - Insulated wire and cable using vinyl chloride resin composition - Google Patents
Insulated wire and cable using vinyl chloride resin composition Download PDFInfo
- Publication number
- JP6459552B2 JP6459552B2 JP2015011792A JP2015011792A JP6459552B2 JP 6459552 B2 JP6459552 B2 JP 6459552B2 JP 2015011792 A JP2015011792 A JP 2015011792A JP 2015011792 A JP2015011792 A JP 2015011792A JP 6459552 B2 JP6459552 B2 JP 6459552B2
- Authority
- JP
- Japan
- Prior art keywords
- fatty acid
- vinyl chloride
- chloride resin
- salt
- mass
- 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.)
- Active
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 84
- 239000011342 resin composition Substances 0.000 title claims description 39
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 94
- 239000000194 fatty acid Substances 0.000 claims description 94
- 229930195729 fatty acid Natural products 0.000 claims description 94
- 229910052751 metal Inorganic materials 0.000 claims description 51
- 239000002184 metal Substances 0.000 claims description 51
- -1 fatty acid zinc salt Chemical class 0.000 claims description 50
- 150000007973 cyanuric acids Chemical class 0.000 claims description 48
- 150000004665 fatty acids Chemical class 0.000 claims description 47
- 150000003839 salts Chemical class 0.000 claims description 47
- 239000011347 resin Substances 0.000 claims description 43
- 229920005989 resin Polymers 0.000 claims description 43
- LRQGFQDEQPZDQC-UHFFFAOYSA-N 1-Phenyl-1,3-eicosanedione Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 LRQGFQDEQPZDQC-UHFFFAOYSA-N 0.000 claims description 24
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 24
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 24
- 239000004020 conductor Substances 0.000 claims description 20
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 10
- 229920005601 base polymer Polymers 0.000 claims description 10
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 9
- 239000000347 magnesium hydroxide Substances 0.000 claims description 9
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 9
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 7
- 229960001545 hydrotalcite Drugs 0.000 claims description 7
- 239000004927 clay Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 125000005313 fatty acid group Chemical group 0.000 claims 2
- 230000008021 deposition Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 description 18
- 239000003381 stabilizer Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 10
- 238000002845 discoloration Methods 0.000 description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical class O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000004014 plasticizer Substances 0.000 description 7
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 238000007033 dehydrochlorination reaction Methods 0.000 description 4
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007765 extrusion coating Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000009954 braiding Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 150000002611 lead compounds Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000032683 aging Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000006084 composite stabilizer Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920005638 polyethylene monopolymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
Description
本発明は、塩化ビニル樹脂組成物を用いた絶縁電線及びケーブルに関し、特にＵＬ規格に従った電線（通称「ＵＬ電線」）に適用できる難燃性の塩化ビニル樹脂組成物を用いた絶縁電線及びケーブルに関する。 TECHNICAL FIELD The present invention relates to an insulated wire and cable using a vinyl chloride resin composition , and particularly to an insulated wire using a flame-retardant vinyl chloride resin composition applicable to an electric wire in accordance with UL standards (commonly referred to as “UL electric wire”), and Regarding cables.
電子機器類の内部配線に使用される絶縁電線は、機器の発火事故などに際して電線を伝って火が広がらぬように難燃性であることが求められている。 Insulated wires used for the internal wiring of electronic devices are required to be flame retardant so that the fire does not spread through the wires in the event of an ignition accident of the device.
内部配線材の難燃性の基準は、例えば米国のＵＬ７５８規格等で定められている。ＵＬ７５８が要求する項目には垂直燃焼試験（以下「ＶＷ−１試験」という。）がオプションとして設けられているが、ほとんどの絶縁電線がこの試験に合格してＵＬに認定されているため、オプションとはいえ、ＶＷ−１試験は、必須に近い項目である。 The flame retardance standard of the internal wiring material is determined by, for example, the UL758 standard in the United States. The vertical flammability test (hereinafter referred to as “VW-1 test”) is provided as an option for items required by UL758, but most insulated wires pass this test and are certified by UL. Nevertheless, the VW-1 test is an essential item.
従来から、このような絶縁電線の被覆材の主原料として塩化ビニル樹脂（ＰＶＣ）が用いられてきた。塩化ビニル樹脂は化学構造中にハロゲンである塩素を含んでおり、それ自体の難燃性は高い。しかし、塩化ビニル樹脂は硬質であるため、電線の絶縁材として使用する場合には軟化させるために可燃性の可塑剤を多量に添加して用いる。従って、難燃剤を添加しないと、上述した難燃性の基準を満たすことができない。 Conventionally, vinyl chloride resin (PVC) has been used as a main raw material for the covering material of such an insulated wire. Vinyl chloride resin contains chlorine, which is a halogen, in its chemical structure, and its flame retardancy is high. However, since vinyl chloride resin is hard, when used as an insulating material for electric wires, a large amount of a combustible plasticizer is added and used for softening. Therefore, unless the flame retardant is added, the above-described flame retardant standard cannot be satisfied.
この難燃剤としては、一般的に三酸化アンチモンが使用されてきた。しかし、三酸化アンチモンは劇薬であるため、製造に当たっては厳格な管理が必要となり、使用を避けたい材料である。更には、稀少な金属類でもあり、最近では価格も上昇傾向にある。 As this flame retardant, antimony trioxide has generally been used. However, since antimony trioxide is a powerful drug, strict management is required during production, and it is a material that should not be used. Furthermore, it is a rare metal and the price has been increasing recently.
そのため、三酸化アンチモンに代わる難燃剤として水酸化アルミニウムや水酸化マグネシウムなどの水酸化金属が用いられている(例えば、特許文献１参照)。 Therefore, metal hydroxides such as aluminum hydroxide and magnesium hydroxide are used as a flame retardant instead of antimony trioxide (see, for example, Patent Document 1).
特許文献１には、塩化ビニル樹脂と、水酸化アルミニウム及び／又は水酸化マグネシウムと、可塑剤と非鉛系安定剤とを含む塩化ビニル樹脂組成物であって、水酸化アルミニウム及び／又は水酸化マグネシウムの含有量が、前記塩化ビニル樹脂の含有量１００質量部に対し８〜２２質量部であり、アンチモンの含有量が１０００ｐｐｍ未満であり、成形後に架橋された塩化ビニル樹脂組成物が開示されている。 Patent Document 1 discloses a vinyl chloride resin composition containing a vinyl chloride resin, aluminum hydroxide and / or magnesium hydroxide, a plasticizer and a non-lead stabilizer, and the aluminum hydroxide and / or hydroxide. There is disclosed a vinyl chloride resin composition having a magnesium content of 8 to 22 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, an antimony content of less than 1000 ppm, and crosslinked after molding. Yes.
一方、塩化ビニル樹脂は成形加工時に１７０℃以上に加熱され、分子構造から塩素が離脱するので、引張伸びは低下し、高温環境下での耐電圧特性も著しく低下するという問題点も有する。これを防ぐために、従来は長期耐熱効果がある鉛及び鉛化合物系安定剤が使用されていたが、これらはＥＵのＲｏＨＳ指令で禁止物質に指定される環境負荷物質である。そのため、その代替として、現在は殆どの絶縁電線で非鉛系安定剤が使用されている。 On the other hand, the vinyl chloride resin is heated to 170 ° C. or higher during the molding process, and chlorine is released from the molecular structure. Therefore, the tensile elongation is lowered, and the withstand voltage characteristic under a high temperature environment is also significantly lowered. In order to prevent this, lead and lead compound-based stabilizers that have long-term heat resistance effects have been used in the past, but these are environmentally hazardous substances that are designated as prohibited substances by the EU RoHS directive. Therefore, as an alternative, lead-free stabilizers are currently used in most insulated wires.
非鉛系安定剤は、鉛及び鉛化合物系安定剤ほどの効果が得られないが、用途に合わせて、バリウム亜鉛系、水酸化カルシウム系、カルシウム亜鉛系、ハイドロタルサイト系、オクチル酸金属等の非鉛系安定剤が適宜使用されている(例えば、特許文献２及び３参照)。 Lead-free stabilizers are not as effective as lead and lead compound stabilizers, but barium zinc, calcium hydroxide, calcium zinc, hydrotalcite, metal octylate, etc. These lead-free stabilizers are used as appropriate (see, for example, Patent Documents 2 and 3).
しかしながら、上述の従来技術では、水酸化アルミニウムや水酸化マグネシウム等の塩基性水和物を含んでいる場合に、例えば１００℃で２０日前後の促進試験を実施すると、塩基起因による変色が発生し、電線形状にした場合に、色相判別に苦慮する問題点があった。また、表面に肌荒れや凹凸が発生し、外観が悪くなるという問題点があった。 However, in the above-described prior art, when a basic hydrate such as aluminum hydroxide or magnesium hydroxide is contained, discoloration due to the base occurs when an accelerated test is performed at 100 ° C. for about 20 days. When the wire shape is used, there is a problem that it is difficult to distinguish the hue. In addition, there is a problem that the surface is rough and uneven, and the appearance is deteriorated.
そこで、本発明の目的は、絶縁層又はシースの塩基起因による変色を抑制でき、かつ絶縁層又はシース表面の肌荒れや凹凸の発生を抑制しうる塩化ビニル樹脂組成物を用いた絶縁電線及びケーブルを提供することにある。 An object of the present invention, the insulating layer or can suppress discoloration due sheath base caused, and an insulating layer or an insulating wire and cable using the vinyl chloride resin composition which can suppress the generation of surface roughening or irregularities in the sheath surface It is to provide.
本発明は、上記目的を達成するために、下記の塩化ビニル樹脂組成物を用いた絶縁電線及びケーブルを提供する。 The present invention, in order to achieve the above object, to provide an insulated wire and cable using the following vinyl chloride resin composition.
［１］導体と、前記導体の外周に被覆された、塩化ビニル樹脂組成物からなる絶縁層とを備えた絶縁電線において、前記塩化ビニル樹脂組成物は、水酸化アルミニウム又は水酸化マグネシウムからなる塩基性水和物を含み、更に塩化ビニル樹脂を含むベースポリマーに（Ａ）脂肪酸金属塩、（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体、（Ｃ）ステアロイルベンゾイルメタン、及び（Ｄ）高密度酸化ポリエチレンワックスが含有されており、前記塩化ビニル樹脂１００質量部に対する前記（Ａ）〜（Ｄ）の合計含量が１〜４．５質量部であって、前記（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体に対する前記（Ｃ）ステアロイルベンゾイルメタンの含有質量比（Ｃ／Ｂ）が０．２５〜６である絶縁電線。
［２］前記（Ａ）脂肪酸金属塩は、（Ａ１）脂肪酸亜鉛塩及び（Ａ２）脂肪酸亜鉛塩以外の脂肪酸金属塩であり、前記（Ａ２）脂肪酸亜鉛塩以外の脂肪酸金属塩に対する前記（Ａ１）脂肪酸亜鉛塩の含有質量比（Ａ１／Ａ２）が４〜９である前記［１］に記載の絶縁電線。
［３］前記（Ａ２）脂肪酸亜鉛塩以外の脂肪酸金属塩は、脂肪酸カルシウム塩、脂肪酸マグネシウム塩、及び脂肪酸アルミニウム塩から選ばれる１つ以上である前記［２］に記載の絶縁電線。
［４］前記（Ｄ）高密度酸化ポリエチレンワックスは、１５０℃における粘度が２５００〜８５０００ｃｐｓの範囲内のものであり、前記塩化ビニル樹脂１００質量部に対して０．０１〜２質量部含有される前記［１］〜［３］のいずれか１つに記載の絶縁電線。
［５］前記（Ａ）脂肪酸金属塩、前記（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体、前記（Ｃ）ステアロイルベンゾイルメタン、及び前記（Ｄ）高密度酸化ポリエチレンワックスの合計含量に対する前記（Ａ）脂肪酸金属塩の含有割合が３５質量％以上である前記［１］〜［４］のいずれか１つに記載の絶縁電線。
［６］ハイドロタルサイト、焼成クレー及び酸化チタンをさらに含有する前記［１］〜［５］のいずれか１つに記載の絶縁電線。
［７］絶縁電線の外周に塩化ビニル樹脂組成物からなるシースを備えたケーブルにおいて、前記塩化ビニル樹脂組成物は、水酸化アルミニウム又は水酸化マグネシウムからなる塩基性水和物を含み、更に塩化ビニル樹脂を含むベースポリマーに（Ａ）脂肪酸金属塩、（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体、（Ｃ）ステアロイルベンゾイルメタン、及び（Ｄ）高密度酸化ポリエチレンワックスが含有されており、前記塩化ビニル樹脂１００質量部に対する前記（Ａ）〜（Ｄ）の合計含量が１〜４．５質量部であって、前記（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体に対する前記（Ｃ）ステアロイルベンゾイルメタンの含有質量比（Ｃ／Ｂ）が０．２５〜６であるケーブル。
［８］前記（Ａ）脂肪酸金属塩は、（Ａ１）脂肪酸亜鉛塩及び（Ａ２）脂肪酸亜鉛塩以外の脂肪酸金属塩であり、前記（Ａ２）脂肪酸亜鉛塩以外の脂肪酸金属塩に対する前記（Ａ１）脂肪酸亜鉛塩の含有質量比（Ａ１／Ａ２）が４〜９である［７］に記載のケーブル。
［９］前記（Ａ２）脂肪酸亜鉛塩以外の脂肪酸金属塩は、脂肪酸カルシウム塩、脂肪酸マグネシウム塩、及び脂肪酸アルミニウム塩から選ばれる１つ以上である［８］に記載のケーブル。
［１０］前記（Ｄ）高密度酸化ポリエチレンワックスは、１５０℃における粘度が２５００〜８５０００ｃｐｓの範囲内のものであり、前記塩化ビニル樹脂１００質量部に対して０．０１〜２質量部含有される［７］〜［９］のいずれか１つに記載のケーブル。
［１１］前記（Ａ）脂肪酸金属塩、前記（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体、前記（Ｃ）ステアロイルベンゾイルメタン、及び前記（Ｄ）高密度酸化ポリエチレンワックスの合計含量に対する前記（Ａ）脂肪酸金属塩の含有割合が３５質量％以上である［７］〜［１０］のいずれか１つに記載のケーブル。
［１２］ハイドロタルサイト、焼成クレー及び酸化チタンをさらに含有する［７］〜［１１］のいずれか１つに記載のケーブル。
[1] In an insulated wire comprising a conductor and an insulating layer made of a vinyl chloride resin composition coated on the outer periphery of the conductor, the vinyl chloride resin composition is a base made of aluminum hydroxide or magnesium hydroxide. It includes sex hydrate, further (a) a fatty acid metal salt-based polymer containing a vinyl chloride resin, (B) a cyanuric acid derivative or isocyanuric acid derivative, (C) stearoylbenzoylmethane, and (D) a high density oxidized polyethylene wax The total content of (A) to (D) with respect to 100 parts by mass of the vinyl chloride resin is 1 to 4.5 parts by mass, and the (B) the cyanuric acid derivative or the isocyanuric acid derivative is (C) The insulated wire whose content mass ratio (C / B) of stearoyl benzoylmethane is 0.25-6.
[2] The (A) fatty acid metal salt is a fatty acid metal salt other than (A1) fatty acid zinc salt and (A2) fatty acid zinc salt, and (A1) the fatty acid metal salt other than (A2) fatty acid zinc salt. The insulated wire according to [1], wherein the fatty acid zinc salt content mass ratio (A1 / A2) is 4 to 9.
[3] The insulated wire according to [2], wherein the fatty acid metal salt other than the (A2) fatty acid zinc salt is one or more selected from a fatty acid calcium salt, a fatty acid magnesium salt, and a fatty acid aluminum salt.
[4] The (D) high-density oxidized polyethylene wax has a viscosity at 150 ° C. in the range of 2500 to 85000 cps, and is contained in an amount of 0.01 to 2 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. The insulated wire according to any one of [1] to [3].
[5] The (A) fatty acid relative to the total content of the (A) fatty acid metal salt, the (B) cyanuric acid derivative or isocyanuric acid derivative, the (C) stearoylbenzoylmethane, and the (D) high-density oxidized polyethylene wax. The insulated wire according to any one of [1] to [4], wherein the content of the metal salt is 35% by mass or more.
[6] hydrotalcite, insulated wire according to any one of [1] to [5] further comprises a baked formation clays and titanium oxide.
[7] In a cable having a sheath made of a vinyl chloride resin composition on the outer periphery of an insulated wire, the vinyl chloride resin composition contains a basic hydrate made of aluminum hydroxide or magnesium hydroxide, and further vinyl chloride The base polymer containing a resin contains (A) a fatty acid metal salt, (B) a cyanuric acid derivative or an isocyanuric acid derivative, (C) stearoylbenzoylmethane, and (D) a high-density oxidized polyethylene wax. The total content of (A) to (D) with respect to 100 parts by mass is 1 to 4.5 parts by mass, and the content mass ratio of (C) stearoylbenzoylmethane to (B) cyanuric acid derivative or isocyanuric acid derivative The cable whose (C / B) is 0.25-6.
[8] The (A) fatty acid metal salt is a fatty acid metal salt other than (A1) fatty acid zinc salt and (A2) fatty acid zinc salt, and (A1) the fatty acid metal salt other than (A2) fatty acid zinc salt. The cable according to [7], wherein the fatty acid zinc salt content mass ratio (A1 / A2) is 4 to 9.
[9] The cable according to [8], wherein the fatty acid metal salt other than the (A2) fatty acid zinc salt is one or more selected from a fatty acid calcium salt, a fatty acid magnesium salt, and a fatty acid aluminum salt.
[10] The (D) high-density oxidized polyethylene wax has a viscosity at 150 ° C. in the range of 2500 to 85000 cps, and is contained in an amount of 0.01 to 2 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. The cable according to any one of [7] to [9].
[11] The (A) fatty acid relative to the total content of the (A) fatty acid metal salt, the (B) cyanuric acid derivative or isocyanuric acid derivative, the (C) stearoylbenzoylmethane, and the (D) high-density oxidized polyethylene wax. The cable according to any one of [7] to [10], wherein the metal salt content is 35% by mass or more.
[12] The cable according to any one of [7] to [11], further containing hydrotalcite, calcined clay, and titanium oxide.
本発明によれば、絶縁層又はシースの塩基起因による変色を抑制でき、かつ絶縁層又はシース表面の肌荒れや凹凸の発生を抑制しうる塩化ビニル樹脂組成物を用いた絶縁電線及びケーブルを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the insulated wire and cable using the vinyl chloride resin composition which can suppress discoloration by the base origin of an insulating layer or a sheath, and can suppress generation | occurrence | production of the rough skin and the unevenness | corrugation of an insulating layer or a sheath surface are provided. be able to.
〔塩化ビニル樹脂組成物〕
本発明の実施の形態に使用する塩化ビニル樹脂組成物は、塩化ビニル樹脂を含むベースポリマーに（Ａ）脂肪酸金属塩、（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体、（Ｃ）ステアロイルベンゾイルメタン、及び（Ｄ）高密度酸化ポリエチレンワックスが含有されており、前記塩化ビニル樹脂１００質量部に対する前記（Ａ）〜（Ｄ）の合計含量が１〜４．５質量部であって、前記（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体に対する前記（Ｃ）ステアロイルベンゾイルメタンの含有質量比（Ｃ／Ｂ）が０．２５〜６である。
[Vinyl chloride resin composition]
The vinyl chloride resin composition used in the embodiment of the present invention includes (A) a fatty acid metal salt, (B) a cyanuric acid derivative or an isocyanuric acid derivative, (C) stearoylbenzoylmethane, and a base polymer containing a vinyl chloride resin. (D) High-density oxidized polyethylene wax is contained, and the total content of (A) to (D) with respect to 100 parts by mass of the vinyl chloride resin is 1 to 4.5 parts by mass; The content ratio (C / B) of the (C) stearoylbenzoylmethane to the acid derivative or the isocyanuric acid derivative is 0.25 to 6.
（塩化ビニル樹脂を含むベースポリマー）
本発明の実施の形態に使用する塩化ビニル樹脂組成物は、ベースポリマーとして塩化ビニル樹脂を含有している。
(Base polymer including vinyl chloride resin)
The vinyl chloride resin composition used in the embodiment of the present invention contains a vinyl chloride resin as a base polymer.
塩化ビニル樹脂としては、塩化ビニルの単独重合体（すなわちポリ塩化ビニル）のほか、塩化ビニルと他の共重合可能なモノマーとの共重合体、及びこれらの混合物が挙げられる。塩化ビニルと共重合可能なモノマーとしては、酢酸ビニル、塩化ビニリデン、（メタ）アクリル酸、アクリロニトリル等が挙げられる。 Examples of the vinyl chloride resin include vinyl chloride homopolymers (that is, polyvinyl chloride), copolymers of vinyl chloride and other copolymerizable monomers, and mixtures thereof. Examples of the monomer copolymerizable with vinyl chloride include vinyl acetate, vinylidene chloride, (meth) acrylic acid, acrylonitrile and the like.
塩化ビニル樹脂は、平均重合度１０００〜２５００のものを用いることが好ましい。平均重合度１０００〜２０００のものが耐熱性、耐寒性、成形性の面からより好ましい。重合度が低くなると成形性は向上するが耐熱性、耐寒性が低下する。逆に重合度が高くなると耐熱性、耐寒性は向上するが、成形性が悪くなる。 It is preferable to use a vinyl chloride resin having an average degree of polymerization of 1000 to 2500. Those having an average degree of polymerization of 1000 to 2000 are more preferred in terms of heat resistance, cold resistance and moldability. When the degree of polymerization is lowered, moldability is improved, but heat resistance and cold resistance are lowered. Conversely, when the degree of polymerization is increased, heat resistance and cold resistance are improved, but moldability is deteriorated.
塩化ビニル樹脂は、必要に応じて、重合度の異なるものを２種以上ブレンドして用いても良い。また、本発明の効果を奏する限りにおいて、必要に応じて、ベースポリマーに、エチレン・酢酸ビニル共重合体、塩素化ポリエチレン等を添加しても良い。ベースポリマー中の塩化ビニル樹脂の含有割合は、８０質量％以上であることが好ましく、９０質量％以上であることがより好ましく、９５質量％以上であることがさらに好ましい。 If necessary, two or more types of vinyl chloride resins having different degrees of polymerization may be blended and used. In addition, as long as the effects of the present invention are exhibited, an ethylene / vinyl acetate copolymer, chlorinated polyethylene, or the like may be added to the base polymer as necessary. The content ratio of the vinyl chloride resin in the base polymer is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more.
（（Ａ）脂肪酸金属塩、（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体、（Ｃ）ステアロイルベンゾイルメタン、及び（Ｄ）高密度酸化ポリエチレンワックス）
本発明の実施の形態に使用する塩化ビニル樹脂組成物は、塩化ビニル樹脂を含むベースポリマーに（Ａ）脂肪酸金属塩、（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体、（Ｃ）ステアロイルベンゾイルメタン、及び（Ｄ）高密度酸化ポリエチレンワックスが含有されている。ベースポリマー中の塩化ビニル樹脂１００質量部に対する上記（Ａ）〜（Ｄ）の合計含量は、１〜４．５質量部である。これらの合計含量を上記範囲内とすることで本願発明の効果を奏する。（Ａ）〜（Ｄ）の合計含量は、塩化ビニル樹脂１００質量部に対して、１．１〜４．１質量部であることが好ましく、１．２〜３質量部であることがより好ましく、１．３〜２．５質量部であることがさらに好ましい。
((A) fatty acid metal salt, (B) cyanuric acid derivative or isocyanuric acid derivative, (C) stearoylbenzoylmethane, and (D) high density oxidized polyethylene wax)
The vinyl chloride resin composition used in the embodiment of the present invention includes (A) a fatty acid metal salt, (B) a cyanuric acid derivative or an isocyanuric acid derivative, (C) stearoylbenzoylmethane, and a base polymer containing a vinyl chloride resin. (D) High density oxidized polyethylene wax is contained. The total content of (A) to (D) with respect to 100 parts by mass of the vinyl chloride resin in the base polymer is 1 to 4.5 parts by mass. The effect of the present invention is achieved by setting the total content within the above range. The total content of (A) to (D) is preferably 1.1 to 4.1 parts by mass and more preferably 1.2 to 3 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. More preferably, the content is 1.3 to 2.5 parts by mass.
Ａ：脂肪酸金属塩
脂肪酸金属塩としては、例えば脂肪酸亜鉛塩を用いることが好ましく、脂肪酸亜鉛塩と脂肪酸カルシウム塩を併用することがより好ましい。また、必要に応じ、耐熱バランスを調整する上で脂肪酸マグネシウム塩や脂肪酸アルミニウム塩を併用しても良い。これらを用いる場合、（Ａ２）脂肪酸亜鉛塩以外の脂肪酸金属塩に対する（Ａ１）脂肪酸亜鉛塩の含有質量比（Ａ１／Ａ２）が４〜９であることが好ましい。
A: Fatty acid metal salt As the fatty acid metal salt, for example, a fatty acid zinc salt is preferably used, and a fatty acid zinc salt and a fatty acid calcium salt are more preferably used in combination. If necessary, a fatty acid magnesium salt or a fatty acid aluminum salt may be used in combination to adjust the heat-resistant balance. When using these, it is preferable that the content ratio (A1 / A2) of the (A1) fatty acid zinc salt to the fatty acid metal salt other than the (A2) fatty acid zinc salt is 4 to 9.
（Ａ）脂肪酸金属塩の含有割合は、（Ａ）〜（Ｄ）の合計含量に対して３５質量％以上であることが好ましい。 (A) It is preferable that the content rate of a fatty-acid metal salt is 35 mass% or more with respect to the total content of (A)-(D).
脂肪酸金属塩の役割をカルシウム塩及び亜鉛塩を例に以下に説明する。
(C17H35COO)2Zn + 2HCL → ZnCL2 ＋ C17H35COOH
(C17H35COO)2Ca + ZnCL2 → (C17H35COO)2Zn +CaCL2
The role of the fatty acid metal salt will be described below using calcium salt and zinc salt as examples.
(C 17 H 35 COO) 2 Zn + 2HCL → ZnCL 2 + C 17 H 35 COOH
(C 17 H 35 COO) 2 Ca + ZnCL 2 → (C 17 H 35 COO) 2 Zn + CaCL 2
熱や光により、塩化ビニル樹脂から発生する塩化水素を金属石鹸が捕捉し、金属塩が生成する。脂肪酸亜鉛と脂肪酸カルシウムを比較すると、脂肪酸亜鉛の方がその捕捉力が高いため、塩化亜鉛がまず生成する。塩化亜鉛が塩化ビニル樹脂混和物中に存在すると、短波長の色調となり、着色は改善される。しかし、塩化亜鉛は、塩化ビニル樹脂の脱塩化水素を促進することや脂肪酸亜鉛の大量添加は混和物の系が外部滑性過多となるため適量添加が必要となる。一方、脂肪酸カルシウムは、塩化水素を捕捉する以外に、上式の通り、塩化亜鉛との交換反応も進むので脱塩化水素抑制にも働く。 The metal soap captures hydrogen chloride generated from the vinyl chloride resin by heat and light, and a metal salt is generated. When fatty acid zinc and fatty acid calcium are compared, zinc chloride is first produced because fatty acid zinc has higher scavenging power. If zinc chloride is present in the vinyl chloride resin blend, it will have a short wavelength tone and coloration will be improved. However, zinc chloride promotes the dehydrochlorination of the vinyl chloride resin and the addition of a large amount of fatty acid zinc requires the addition of an appropriate amount because the system of the admixture becomes excessive in external lubricity. On the other hand, in addition to capturing hydrogen chloride, fatty acid calcium also acts to suppress dehydrochlorination because an exchange reaction with zinc chloride proceeds as shown in the above formula.
脂肪酸マグネシウム塩は、塩化水素捕捉能がカルシウム塩より優れ、上述の亜鉛塩で示した例で生成する塩化物が更に塩化ビニル樹脂からの脱塩化水素反応を促進させないため、脂肪酸亜鉛塩や脂肪酸カルシウム塩と併用されることが好ましい。 Fatty acid magnesium salt has better hydrogen chloride scavenging ability than calcium salt, and the chloride produced in the example shown in the above zinc salt does not further promote the dehydrochlorination reaction from the vinyl chloride resin. It is preferably used in combination with a salt.
脂肪酸金属塩を構成する脂肪酸としては、例えば、Ｃ８〜Ｃ２２の飽和脂肪酸やＣ８〜Ｃ２２の不飽和脂肪酸を用いることができる。特にステアリン酸金属塩であることが好ましいが、金属当量を合わせた添加量とすればどの脂肪酸種を用いても良い。脂肪酸種は、単独で用いる場合のみならず、２種以上を併用してもよい。 As a fatty acid which comprises a fatty acid metal salt, a C8-C22 saturated fatty acid and a C8-C22 unsaturated fatty acid can be used, for example. In particular, a stearic acid metal salt is preferable, but any fatty acid species may be used as long as the added amount is a combination of metal equivalents. The fatty acid species may be used not only alone but also in combination of two or more.
Ｂ：シアヌル酸誘導体又はイソシアヌル酸誘導体
シアヌル酸誘導体又はイソシアヌル酸誘導体としては、イソシアヌル酸誘導体を用いることが好ましく、例えば、イソシアヌル酸トリス（２−ヒドロキシエチル）を用いることが特に好ましい。なお、ここでいう「又は」には、シアヌル酸誘導体、イソシアヌル酸誘導体をそれぞれ単独で使用する場合のほか、シアヌル酸誘導体とイソシアヌル酸誘導体とを併用する場合も含まれる。
B: Cyanuric acid derivative or isocyanuric acid derivative As the cyanuric acid derivative or isocyanuric acid derivative, it is preferable to use an isocyanuric acid derivative, for example, it is particularly preferable to use isocyanuric acid tris (2-hydroxyethyl). Here, “or” includes not only the case where the cyanuric acid derivative and the isocyanuric acid derivative are used alone, but also the case where the cyanuric acid derivative and the isocyanuric acid derivative are used in combination.
上記シアヌル酸誘導体又はイソシアヌル酸誘導体（例えばイソシアヌル酸トリス（２−ヒドロキシエチル））の役割は、金属塩のキレート化による塩化ビニル樹脂からの脱塩化水素を抑制するためのものである。 The role of the cyanuric acid derivative or isocyanuric acid derivative (for example, isocyanuric acid tris (2-hydroxyethyl)) is to suppress dehydrochlorination from the vinyl chloride resin due to chelation of the metal salt.
金属塩化物は、ポリエンとπ錯体を生成し、着色することが知られているが、本系材料が無色のキレート化合物を作るため、着色低減にも効果が発現する。但し、本系材料は、塩化ビニル樹脂との相溶性に劣るため、適量化が必要となる。 Metal chlorides are known to form π complexes with polyenes and become colored. However, since this material forms a colorless chelate compound, the effect is also exhibited in reducing coloring. However, since this system material is inferior in compatibility with a vinyl chloride resin, an appropriate amount is required.
Ｃ：ステアロイルベンゾイルメタン
ステアロイルベンゾイルメタンの役割を以下に説明する。
一般に塩化ビニル樹脂のアリル塩安定化剤としては、ジベンゾイルメタン（ＤＢＭ）が用いられてきた。脂肪酸塩や金属化合物下で、次式（I）、（II）の通り働く。すなわち、アリル塩を安定化することで、結果として着色抑制剤として働く。
In general, dibenzoylmethane (DBM) has been used as an allyl salt stabilizer for vinyl chloride resins. Works under the following formulas (I) and (II) under fatty acid salts and metal compounds. That is, by stabilizing the allyl salt, it acts as a color inhibitor as a result.
ＤＢＭの欠点としては、光増感性があることは知られているが、他にアリル塩を安定化するために１／２モルの金属塩を必要とすることと、反応が２段階であることである。１段階でより早期にアリル塩を安定化させる材料として、本発明においてはステアロイルベンゾイルメタンを用いた。下記に反応式（III）を示す。金属塩存在下で、アリル塩を１段階で安定化させる。
上記（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体に対する上記（Ｃ）ステアロイルベンゾイルメタンの含有質量比（Ｃ／Ｂ）は、０．２５〜６である。当該含有質量比を上記範囲内とすることで本発明の効果を奏する。好ましい含有質量比（Ｃ／Ｂ）は０．２５〜５であり、より好ましくは０．２５〜４であり、さらに好ましくは０．２５〜３である。 The content ratio (C / B) of the (C) stearoylbenzoylmethane to the (B) cyanuric acid derivative or isocyanuric acid derivative is 0.25 to 6. The effect of this invention is show | played by making the said content mass ratio into the said range. A preferable content ratio (C / B) is 0.25 to 5, more preferably 0.25 to 4, and still more preferably 0.25 to 3.
Ｄ：高密度酸化ポリエチレンワックス
ポリオレフィンワックスには、ポリエチレンホモポリマータイプ、酸化ポリエチレンタイプ、高密度酸化ポリエチレンタイプ、ポリプロピレンタイプ、エチレン・アクリル酸共重合タイプ、エチレン・酢酸ビニル共重合タイプ、酸化エチレン・酢酸ビニル共重合タイプ、低分子量アイオノマータイプ、エチレン−無水マレイン酸共重合タイプ、プロピレン−無水マレイン酸共重合タイプなど、さまざまなワックスが存在する。これらの中でも、以下の点に着眼し、高密度酸化ポリエチレンワックスを選定した。
（１）塩化ビニル樹脂、及び（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体や（Ｃ）ステアロイルベンゾイルメタンとの相溶性を考慮し、極性基を保有するワックスであること。
（２）国際規格ＡＳＴＭ−Ｄ３９５４ベースの滴点が本発明の塩化ビニル樹脂組成物の混練温度（１３０〜１５０℃）付近にあるワックスであること。
（３）本発明の塩化ビニル樹脂組成物の混練温度付近での粘度が高く、内部滑剤として働くワックスであること。
D: High density oxidized polyethylene wax For polyolefin wax, polyethylene homopolymer type, oxidized polyethylene type, high density oxidized polyethylene type, polypropylene type, ethylene / acrylic acid copolymer type, ethylene / vinyl acetate copolymer type, ethylene oxide / acetic acid Various waxes exist such as vinyl copolymer type, low molecular weight ionomer type, ethylene-maleic anhydride copolymer type, propylene-maleic anhydride copolymer type. Among these, high-density oxidized polyethylene wax was selected by focusing on the following points.
(1) It is a wax having a polar group in consideration of compatibility with vinyl chloride resin and (B) cyanuric acid derivative or isocyanuric acid derivative or (C) stearoylbenzoylmethane.
(2) The wax has a dropping point based on the international standard ASTM-D3954 near the kneading temperature (130 to 150 ° C.) of the vinyl chloride resin composition of the present invention.
(3) A wax having a high viscosity around the kneading temperature of the vinyl chloride resin composition of the present invention and acting as an internal lubricant.
本発明の実施形態における高密度酸化ポリエチレンワックスは、密度が０．９５〜１．１ｇ／ｃｍ３、酸価が１〜４５ＫＯＨｍｇ／ｇ、軟化点が１００〜１５０℃であることが好ましい。密度は０．９６〜１．０ｇ／ｃｍ３であることがより好ましく、酸価は７〜４１ＫＯＨｍｇ／ｇであることがより好ましい。 The high density oxidized polyethylene wax in the embodiment of the present invention preferably has a density of 0.95 to 1.1 g / cm 3 , an acid value of 1 to 45 KOHmg / g, and a softening point of 100 to 150 ° C. The density is more preferably 0.96 to 1.0 g / cm 3 , and the acid value is more preferably 7 to 41 KOH mg / g.
また、本発明の実施形態における高密度酸化ポリエチレンワックスは、１５０℃における粘度が２５００〜８５０００ｃｐｓの範囲内のものであり、前述の塩化ビニル樹脂１００質量部に対して０．０１〜２質量部含有されることが好ましい。１５０℃における粘度が８５００〜８５０００ｃｐｓの範囲内のものであり、前述の塩化ビニル樹脂１００質量部に対して０．０４〜０．１質量部含有されることが混練効率向上の観点からより好ましい。 Moreover, the high density oxidized polyethylene wax in the embodiment of the present invention has a viscosity at 150 ° C. in the range of 2500 to 85000 cps, and is contained in an amount of 0.01 to 2 parts by mass with respect to 100 parts by mass of the aforementioned vinyl chloride resin. It is preferred that The viscosity at 150 ° C. is in the range of 8500 to 85000 cps, and 0.04 to 0.1 parts by mass with respect to 100 parts by mass of the aforementioned vinyl chloride resin is more preferable from the viewpoint of improving the kneading efficiency.
また、本発明の効果を奏する限りにおいて、必要に応じて、高密度酸化ポリエチレンワックス以外のポリオレフィンワックスをさらに添加しても良い。 Moreover, as long as the effect of the present invention is exhibited, a polyolefin wax other than the high density oxidized polyethylene wax may be further added as necessary.
（可塑剤）
本発明の実施の形態に使用する塩化ビニル樹脂組成物には、可塑剤として、従来公知の可塑剤を添加することができる。特に限定はされないが、トリメリテート系可塑剤を使用することが好ましく、例えばトリメリット酸トリ２−エチルヘキシル、トリメリット酸トリノルマルアルキル、トリメリット酸トリイソデシル等を挙げることができる。耐熱性、コストの観点からトリメリット酸トリ２−エチルヘキシルを用いることがより好ましい。可塑剤の含有量は、塩化ビニル樹脂１００質量部に対して、３０〜８０質量部であることが好ましく、３５〜５５質量部であることがより好ましい。
(Plasticizer)
A conventionally known plasticizer can be added as a plasticizer to the vinyl chloride resin composition used in the embodiment of the present invention. Although there is no particular limitation, it is preferable to use a trimellitate plasticizer, and examples thereof include tri-2-ethylhexyl trimellitic acid, tri-normal alkyl trimellitic acid, triisodecyl trimellitic acid, and the like. From the viewpoint of heat resistance and cost, it is more preferable to use tri-2-ethylhexyl trimellitic acid. The plasticizer content is preferably 30 to 80 parts by mass and more preferably 35 to 55 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
（安定剤）
本発明の実施の形態に使用する塩化ビニル樹脂組成物には、安定剤として、従来公知の安定剤を添加することができる。特に限定はされないが、安定剤は、鉛を含有しない非鉛系安定剤を用いることが、法規制上好ましい。非鉛系安定剤としては、ハイドロタルサイト系安定剤や、カルシウム−亜鉛系の複合安定剤を挙げることができる。前述の脂肪酸金属塩としてステアリン酸カルシウムやステアリン酸亜鉛等を添加した場合、これらを安定剤として機能させることもできる。
(Stabilizer)
A conventionally known stabilizer can be added as a stabilizer to the vinyl chloride resin composition used in the embodiment of the present invention. Although not particularly limited, it is preferable in terms of laws and regulations to use a lead-free stabilizer that does not contain lead. Examples of non-lead stabilizers include hydrotalcite stabilizers and calcium-zinc composite stabilizers. When calcium stearate, zinc stearate, or the like is added as the aforementioned fatty acid metal salt, these can also function as a stabilizer.
（その他の添加剤）
本発明の実施の形態に使用する塩化ビニル樹脂組成物には、上記添加剤に加え、必要に応じて、難燃剤、充填剤、架橋剤、架橋助剤、紫外線吸収剤、光安定剤、滑剤、酸化防止剤、着色剤、加工性改良剤、その他の改質剤などを単独で又は２種以上を組み合わせて用いることもできる。
(Other additives)
In addition to the above additives, the vinyl chloride resin composition used in the embodiment of the present invention includes a flame retardant, a filler, a cross-linking agent, a cross-linking aid, an ultraviolet absorber, a light stabilizer, and a lubricant as necessary. , Antioxidants, colorants, processability improvers, other modifiers and the like can be used alone or in combination of two or more.
難燃剤として、例えば、三酸化アンチモン、金属水和物が挙げられる。金属水酸化物としては、水酸化マグネシウム、水酸化アルミニウム、ハイドロタルサイト、カルシウムアルミネート水和物、水酸化カルシウム、水酸化バリウム、ハードクレー等が使用される。 Examples of the flame retardant include antimony trioxide and metal hydrate. As the metal hydroxide, magnesium hydroxide, aluminum hydroxide, hydrotalcite, calcium aluminate hydrate, calcium hydroxide, barium hydroxide, hard clay and the like are used.
充填剤として、焼成クレー、水和クレー、カーボンブラック、シリカ、炭酸カルシウム、珪酸アルミニウム、酸化チタン、フェライト系磁性粉、タルク等が挙げられる。 Examples of the filler include calcined clay, hydrated clay, carbon black, silica, calcium carbonate, aluminum silicate, titanium oxide, ferrite magnetic powder, and talc.
本発明の実施の形態に使用する塩化ビニル樹脂組成物は、成形後に架橋を施しても良い。架橋の方法は、従来公知の方法を使用でき、特に限定はされないが、化学架橋、シラン架橋、放射線架橋等の方法を用いることができる。架橋度は、ゲル分率で４０〜６５％であることが好ましく、４９〜６０％であることがより好ましい。 The vinyl chloride resin composition used in the embodiment of the present invention may be crosslinked after molding. A conventionally known method can be used as the crosslinking method, and there is no particular limitation, but methods such as chemical crosslinking, silane crosslinking, and radiation crosslinking can be used. The degree of crosslinking is preferably 40 to 65%, more preferably 49 to 60% in terms of gel fraction.
架橋助剤として、トリメチロールプロパントリメタクリレート、ジペンタエリスリトールヘキサアクリレート等を使用することができ、塩化ビニル樹脂１００質量部に対して、例えば２〜２０質量部添加することができる。２質量部未満では、架橋が不十分になる場合があり、２０質量部を超えると成形時に架橋してしまう場合がある。 As a crosslinking aid, trimethylolpropane trimethacrylate, dipentaerythritol hexaacrylate, or the like can be used. For example, 2 to 20 parts by mass can be added to 100 parts by mass of the vinyl chloride resin. If it is less than 2 parts by mass, crosslinking may be insufficient, and if it exceeds 20 parts by mass, it may be crosslinked during molding.
〔絶縁電線〕
本発明の実施形態に係る絶縁電線は、導体と、導体の外周に被覆された、本発明の実施形態に使用する上記塩化ビニル樹脂組成物からなる絶縁層とを備えたことを特徴とする。
[Insulated wire]
An insulated wire according to an embodiment of the present invention includes a conductor and an insulating layer made of the vinyl chloride resin composition used in the embodiment of the present invention, which is coated on the outer periphery of the conductor.
図１は、本発明の実施の形態に係る絶縁電線の一例を示す横断面図である。
図１に示すように、本実施の形態に係る絶縁電線１０は、導体１と、導体１の外周に被覆された絶縁層２とを備える。被覆される導体１としては、例えば外径０．１５〜７ｍｍφ程度の導体を使用することができる。錫メッキ軟銅線を撚り合わせた導体などを好適に使用することができるが、これに限定されるものではない。導体１は、図１のように１本である場合に限られず、複数本であってもよい。
FIG. 1 is a cross-sectional view showing an example of an insulated wire according to an embodiment of the present invention.
As shown in FIG. 1, the
絶縁層２は、本発明の実施の形態に使用する上記の塩化ビニル樹脂組成物から構成されている。押出被覆等の成形手段により絶縁層として被覆した後、電子線照射等の方法により塩化ビニル樹脂を架橋することにより絶縁電線を得ることができる。なお、押出被覆は、架橋前の塩化ビニル系樹脂組成物をロール、バンバリー、押出機などで混練し、得られたペレットコンパウンドと導体とをクロスヘッドダイを付設した従来公知の電線用押出機で電線被覆押出成形することなどにより行うことができる。 The insulating layer 2 is comprised from said vinyl chloride resin composition used for embodiment of this invention. After being coated as an insulating layer by molding means such as extrusion coating, an insulated wire can be obtained by crosslinking the vinyl chloride resin by a method such as electron beam irradiation. The extrusion coating is a conventionally known electric wire extruder in which the vinyl chloride resin composition before crosslinking is kneaded with a roll, a banbury, an extruder, etc., and the resulting pellet compound and conductor are attached with a crosshead die. It can be carried out by, for example, wire-coating extrusion molding.
本実施の形態においては、絶縁体を、単層で構成してもよく、また、多層構造とすることもできる。さらに、必要に応じて、セパレータ、編組等を施してもよい。 In this embodiment mode, the insulator may be a single layer or a multilayer structure. Furthermore, you may give a separator, a braiding, etc. as needed.
〔ケーブル〕
本発明の実施形態に係るケーブルは、本発明の実施形態に使用する上記塩化ビニル樹脂組成物を被覆材料（シースないし絶縁層及びシース）として使用したことを特徴とする。
〔cable〕
The cable according to the embodiment of the present invention is characterized in that the above-described vinyl chloride resin composition used in the embodiment of the present invention is used as a coating material (sheath or insulating layer and sheath).
図２は、本発明の実施の形態に係るケーブルの一例を示す横断面図である。
図２に示すように、本実施の形態に係るケーブル２０は、導体１に絶縁層２を被覆した絶縁電線３本を紙等の介在４と共に撚り合わせた三芯撚り線と、三芯撚り線の外周に施された押え巻きテープ５と、その外周に押出被覆されたシース３とを備える。絶縁電線は単芯でもよく、三芯以外の多芯撚り線であってもよい。
FIG. 2 is a cross-sectional view showing an example of a cable according to the embodiment of the present invention.
As shown in FIG. 2, the cable 20 according to the present embodiment includes a three-core stranded wire obtained by twisting together three insulated wires in which a conductor 1 is coated with an insulating layer 2 together with an interposition 4 such as paper. The presser wound tape 5 is provided on the outer periphery, and the sheath 3 is extrusion-coated on the outer periphery. The insulated wire may be a single core or a multi-core stranded wire other than a three-core wire.
シース３は、本発明の実施の形態に使用する上記の塩化ビニル樹脂組成物から構成されている。絶縁体２も上記の塩化ビニル樹脂組成物から構成されていてもよい。押出被覆等の成形手段により絶縁層やシース層として被覆した後、電子線照射等の方法により塩化ビニル樹脂を架橋することによりケーブルを得ることができる。 The sheath 3 is comprised from said vinyl chloride resin composition used for embodiment of this invention. The insulator 2 may also be composed of the above vinyl chloride resin composition. After being coated as an insulating layer or a sheath layer by molding means such as extrusion coating, a cable can be obtained by crosslinking the vinyl chloride resin by a method such as electron beam irradiation.
本実施の形態においては、シースを、単層で構成してもよく、また、多層構造とすることもできる。さらに、必要に応じて、セパレータ、編組等を施してもよい。 In the present embodiment, the sheath may be composed of a single layer or a multilayer structure. Furthermore, you may give a separator, a braiding, etc. as needed.
本発明の実施形態に係る絶縁電線ないしケーブルの外径は、例えば０．４〜１１ｍｍφである。その用途としては、ドライヤー、炊飯器、トランス口出部、照明器具、エアコンなどの機器内の高温部での配線等を挙げることができる。 The outer diameter of the insulated wire or cable according to the embodiment of the present invention is, for example, 0.4 to 11 mmφ. Examples of the use include wiring in a high-temperature part in equipment such as a dryer, a rice cooker, a transformer outlet, a lighting fixture, and an air conditioner.
〔本発明の実施形態の効果〕
（１）本発明の実施形態によれば、水酸化アルミニウムや水酸化マグネシウム等の塩基性水和物を含んでいても、絶縁層又はシースの塩基起因による変色を抑制でき、かつ絶縁層又はシース表面の肌荒れや凹凸の発生を抑制しうる（良好な外観を可能とする）塩化ビニル樹脂組成物を用いた絶縁電線及びケーブルを提供することができる。
[Effect of the embodiment of the present invention]
(1) According to the embodiment of the present invention, even if a basic hydrate such as aluminum hydroxide or magnesium hydroxide is contained, discoloration due to the base of the insulating layer or sheath can be suppressed, and the insulating layer or sheath can suppress the occurrence of skin roughness and unevenness of the surface (to allow good appearance) can provide insulated wire and cable using the vinyl chloride resin composition.
（２）本発明の実施形態によれば、（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体に対する（Ｃ）ステアロイルベンゾイルメタンの含有質量比（Ｃ／Ｂ）が低い値（例えば１以下、さらには０．５以下、さらには０．４未満）であっても、絶縁層又はシースの塩基起因による変色を抑制しうる塩化ビニル樹脂組成物を用いた絶縁電線及びケーブルを提供することができるため、材料コスト（製造コスト）を下げることができる。 (2) According to the embodiment of the present invention, the content ratio (C / B) of (C) stearoylbenzoylmethane to the (B) cyanuric acid derivative or isocyanuric acid derivative is low (for example, 1 or less, and further 0.1. 5 or less, more capable of providing insulated wire and cable with even less than 0.4), the insulating layer or the vinyl chloride resin composition which can suppress the discoloration due to the sheath of the base due, material costs (Manufacturing cost) can be reduced.
（３）（Ａ２）脂肪酸亜鉛塩以外の脂肪酸金属塩に対する（Ａ１）脂肪酸亜鉛塩の含有質量比（Ａ１／Ａ２）が４以上となると外滑性過多により混練時間が長くかかってしまう傾向にあるが、本発明の実施形態によれば、（Ａ２）脂肪酸亜鉛塩以外の脂肪酸金属塩に対する（Ａ１）脂肪酸亜鉛塩の含有質量比（Ａ１／Ａ２）が４以上であっても、混練時間を短縮でき、混練成形性が改善された電線被覆材料、並びにこれを用いた絶縁電線及びケーブルを提供することができる。 (3) If the mass ratio (A1 / A2) of (A1) fatty acid zinc salt to fatty acid metal salt other than (A2) fatty acid zinc salt is 4 or more, kneading time tends to take longer due to excessive slipperiness. However, according to the embodiment of the present invention, the kneading time is shortened even if the mass ratio (A1 / A2) of (A1) fatty acid zinc salt to fatty acid metal salt other than (A2) fatty acid zinc salt is 4 or more. It is possible to provide an electric wire coating material with improved kneadability and an insulated electric wire and a cable using the same.
以下に、本発明を実施例及び比較例に基づいて更に詳しく説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited thereto.
図１の構造の絶縁電線１０を下記の通りの方法で製造し、評価を行なった。
The
（１）塩化ビニル樹脂組成物の作製
表１に示す各材料を記載された割合で配合し、１４０℃に加熱したオープンロールミキサーで混練混合してペレット化し、各実施例及び比較例の塩化ビニル樹脂組成物を得た。用いた材料は、表２に示す通りである。
(1) Preparation of vinyl chloride resin composition The materials shown in Table 1 were blended in the proportions described, kneaded and mixed with an open roll mixer heated to 140 ° C, and pelletized. A resin composition was obtained. The materials used are as shown in Table 2.
参考として混練性の評価を以下の方法で行なった結果、実施例１〜６及び比較例１では〇であり、比較例２〜３では×であった。
１４０℃に加熱したオープンロールミキサーで混練する際、５分以内で、フロントロールに巻き付いた混和物シートの外観が滑らかで、シートにたるみが生じないものを〇、外観荒れやシートにたるみが生じたものを×とした。×のものは、外部滑性が過多であることから生じる現象であり、連続混練機やバッチ式ミキサーで量産化した場合、均一に分散した混練物が得られない。
As a result of the evaluation of kneadability by the following method as a reference, the results were ○ in Examples 1 to 6 and Comparative Example 1, and × in Comparative Examples 2 to 3.
When kneading with an open roll mixer heated to 140 ° C, within 5 minutes, the admixture sheet wound around the front roll has a smooth appearance that does not cause sagging, and rough appearance and sagging occur in the sheet. Was marked with x. The case of x is a phenomenon caused by excessive external lubricity, and when mass-produced with a continuous kneader or batch mixer, a uniformly dispersed kneaded material cannot be obtained.
（２）絶縁電線の作製
導体として、外径０．１６ｍｍφ錫メッキ軟銅線の２６本撚り導体（外径０．９４ｍｍφ）を使用した。該導体上に上記の塩化ビニル樹脂組成物を溶融押出法により押出成形し、各塩化ビニル樹脂組成物で導体を被覆した試料（絶縁電線）を得た。塩化ビニル樹脂組成物から成る絶縁層の厚さは、０．５ｍｍとなった。電線製造条件は、シリンダー温度１７０℃、ヘッド温度１８０℃にて、線速４００ｍ／分にて作業を実施した。
(2) Production of insulated wire As a conductor, a 26-stranded conductor (outer diameter 0.94 mmφ) of an outer diameter 0.16 mmφ tin-plated annealed copper wire was used. The vinyl chloride resin composition described above was extruded on the conductor by a melt extrusion method to obtain a sample (insulated wire) in which the conductor was coated with each vinyl chloride resin composition. The thickness of the insulating layer made of the vinyl chloride resin composition was 0.5 mm. The electric wire was manufactured under the conditions of a cylinder temperature of 170 ° C., a head temperature of 180 ° C., and a wire speed of 400 m / min.
（３）絶縁電線の評価１（色相変化）
上記各例の絶縁電線について、３００ｍｍの長さに切断した電線を１００℃で５００時間、ギヤーオーブン（強制循環式空気加熱老化試験機）に曝露し、曝露前後の色相変化を確認した。色相変化は５人による目視比較試験を行い、曝露前後で５人とも変色無と判断したものを◎、４人が変色無と判断したものを○、０〜３人が変色無と判断したものを×とした。表１に評価結果を示す。
(3) Evaluation 1 of insulated wires (change in hue)
About the insulated wire of each said example, the electric wire cut | disconnected to the length of 300 mm was exposed to gear oven (forced circulation type air heating aging test machine) at 100 degreeC for 500 hours, and the hue change before and behind exposure was confirmed. Hue change was evaluated by visual comparison test by 5 people, before and after exposure all 5 people judged no discoloration ◎ 4 people judged no discoloration ○, 0-3 people judged no discoloration Was marked with x. Table 1 shows the evaluation results.
（４）絶縁電線の評価２（外観）
上記各例の絶縁電線について、外観を目視で評価した。表面に艶があり、表面がスムーズだったものを◎、表面がスムーズだが艶消し状態となったものを○、表面に肌荒れ又は凹凸を生じたものを×とした。表１に評価結果を示す。
(4) Evaluation 2 of insulated wires (appearance)
About the insulated wire of each said example, the external appearance was evaluated visually. The case where the surface was glossy and the surface was smooth was marked with ◎, the surface where the surface was smooth but in a matte state was marked with ○, and the surface with rough or uneven surface was marked with ×. Table 1 shows the evaluation results.
（５）総合判定
総合判定は、色相変化及び外観のいずれかの評価が×であったものを不合格とした。結果を表１に示す。
(5) Comprehensive judgment Comprehensive judgment rejected the thing in which either evaluation of the hue change and the external appearance was x. The results are shown in Table 1.
本発明の規定する範囲内である実施例１〜６においては、色相変化及び外観ともに良好であり、総合判定は合格であった。 In Examples 1 to 6 within the range defined by the present invention, both the hue change and the appearance were good, and the comprehensive judgment was acceptable.
比較例１においては、（Ｄ）高密度酸化ポリエチレンワックスを含有しておらず、Ａ＋Ｂ＋Ｃ＋Ｄの合計含量も少なく、また、Ｃ／Ｂの質量比及びＡ１／（Ａ２＋Ａ３）の質量比が小さいため、色相変化の結果が悪く、総合判定は不合格であった。 In Comparative Example 1, since (D) high-density oxidized polyethylene wax was not contained, the total content of A + B + C + D was small, and the mass ratio of C / B and A1 / (A2 + A3) were small. The result of the change was bad and the overall judgment was unacceptable.
比較例２においては、ポリエチレンワックスを含有するが、（Ｄ）高密度酸化ポリエチレンワックスを含有しておらず、Ｃ／Ｂの質量比及びＡ１／（Ａ２＋Ａ３）の質量比が大きいため、色相変化及び外観ともに結果が悪く、総合判定は不合格であった。 In Comparative Example 2, it contains polyethylene wax, but does not contain (D) high-density oxidized polyethylene wax, and because the mass ratio of C / B and the mass ratio of A1 / (A2 + A3) are large, the hue change and Both the appearance and the result were bad, and the comprehensive judgment was unacceptable.
比較例３においては、（Ｃ）ステアロイルベンゾイルメタン及び（Ｄ）高密度酸化ポリエチレンワックスを含有しておらず、Ｃ／Ｂの質量比及びＡ１／（Ａ２＋Ａ３）の質量比が小さいため、色相変化の結果が悪く、総合判定は不合格であった。 In Comparative Example 3, (C) stearoyl benzoylmethane and (D) high-density oxidized polyethylene wax were not contained, and the mass ratio of C / B and A1 / (A2 + A3) were small. The result was bad and the overall judgment was unacceptable.
以上の通り、（Ａ）脂肪酸金属塩、（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体、（Ｃ）ステアロイルベンゾイルメタン、及び（Ｄ）高密度酸化ポリエチレンワックスの４種を前述した適量域で用いることにより、塩化ビニル樹脂の塩基性化合物存在下での低温長期の変色抑制ができることを見出した。さらには、上記変色抑制と良好な押出成形（良好な外観）とを両立できることを見出した。 As described above, by using four types of (A) fatty acid metal salt, (B) cyanuric acid derivative or isocyanuric acid derivative, (C) stearoyl benzoylmethane, and (D) high-density oxidized polyethylene wax in the above-described appropriate amount range. The present inventors have found that low-temperature and long-term discoloration can be suppressed in the presence of a basic compound of a vinyl chloride resin. Furthermore, it discovered that the said discoloration suppression and favorable extrusion molding (good appearance) can be made compatible.
なお、本発明は、上記実施の形態及び実施例に限定されず種々に変形実施が可能である。 In addition, this invention is not limited to the said embodiment and Example, A various deformation | transformation implementation is possible.
１０：絶縁電線、２０：ケーブル
１：導体、２：絶縁層
３：シース、４：介在、５：押さえ巻きテープ
10: Insulated wire, 20: Cable 1: Conductor, 2: Insulating layer 3: Sheath, 4: Intervening, 5: Pressing tape
Claims (12)
前記塩化ビニル樹脂組成物は、水酸化アルミニウム又は水酸化マグネシウムからなる塩基性水和物を含み、更に塩化ビニル樹脂を含むベースポリマーに（Ａ）脂肪酸金属塩、（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体、（Ｃ）ステアロイルベンゾイルメタン、及び（Ｄ）高密度酸化ポリエチレンワックスが含有されており、
前記塩化ビニル樹脂１００質量部に対する前記（Ａ）〜（Ｄ）の合計含量が１〜４．５質量部であって、前記（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体に対する前記（Ｃ）ステアロイルベンゾイルメタンの含有質量比（Ｃ／Ｂ）が０．２５〜６である絶縁電線。 In an insulated wire comprising a conductor and an insulating layer made of a vinyl chloride resin composition, coated on the outer periphery of the conductor,
The vinyl chloride resin composition includes a basic hydrate composed of aluminum hydroxide or magnesium hydroxide, and further includes (A) a fatty acid metal salt, (B) a cyanuric acid derivative or isocyanuric acid in a base polymer including a vinyl chloride resin. A derivative, (C) stearoylbenzoylmethane, and (D) a high density oxidized polyethylene wax,
The total content of (A) to (D) with respect to 100 parts by mass of the vinyl chloride resin is 1 to 4.5 parts by mass, and the (C) stearoylbenzoylmethane with respect to the (B) cyanuric acid derivative or isocyanuric acid derivative. Insulated electric wire whose contained mass ratio (C / B) is 0.25-6.
前記塩化ビニル樹脂組成物は、水酸化アルミニウム又は水酸化マグネシウムからなる塩基性水和物を含み、更に塩化ビニル樹脂を含むベースポリマーに（Ａ）脂肪酸金属塩、（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体、（Ｃ）ステアロイルベンゾイルメタン、及び（Ｄ）高密度酸化ポリエチレンワックスが含有されており、The vinyl chloride resin composition includes a basic hydrate composed of aluminum hydroxide or magnesium hydroxide, and further includes (A) a fatty acid metal salt, (B) a cyanuric acid derivative or isocyanuric acid in a base polymer including a vinyl chloride resin. A derivative, (C) stearoylbenzoylmethane, and (D) a high density oxidized polyethylene wax,
前記塩化ビニル樹脂１００質量部に対する前記（Ａ）〜（Ｄ）の合計含量が１〜４．５質量部であって、前記（Ｂ）シアヌル酸誘導体又はイソシアヌル酸誘導体に対する前記（Ｃ）ステアロイルベンゾイルメタンの含有質量比（Ｃ／Ｂ）が０．２５〜６であるケーブル。 The total content of (A) to (D) with respect to 100 parts by mass of the vinyl chloride resin is 1 to 4.5 parts by mass, and the (C) stearoylbenzoylmethane with respect to the (B) cyanuric acid derivative or isocyanuric acid derivative. The cable whose containing mass ratio (C / B) is 0.25-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015011792A JP6459552B2 (en) | 2015-01-23 | 2015-01-23 | Insulated wire and cable using vinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015011792A JP6459552B2 (en) | 2015-01-23 | 2015-01-23 | Insulated wire and cable using vinyl chloride resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016135836A JP2016135836A (en) | 2016-07-28 |
| JP6459552B2 true JP6459552B2 (en) | 2019-01-30 |
Family
ID=56512061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015011792A Active JP6459552B2 (en) | 2015-01-23 | 2015-01-23 | Insulated wire and cable using vinyl chloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6459552B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112382436B (en) * | 2020-09-10 | 2022-04-08 | 杭州富通电线电缆有限公司 | Cable capable of repelling rats and ants and processing method thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5790033A (en) * | 1980-11-26 | 1982-06-04 | Shin Etsu Polymer Co Ltd | Vinyl chloride resin composition |
| JP2000302913A (en) * | 1999-04-21 | 2000-10-31 | Kyodo Chem Co Ltd | Stabilizer for chlorine-containing resin and chlorine- containing resin composition |
| JP4342212B2 (en) * | 2003-05-23 | 2009-10-14 | 株式会社Ａｄｅｋａ | Vinyl chloride resin composition for transparent wires |
| JP2005220223A (en) * | 2004-02-05 | 2005-08-18 | Asahi Denka Kogyo Kk | Vinyl chloride resin composition |
| JP2008001840A (en) * | 2006-06-23 | 2008-01-10 | Mitsubishi Plastics Ind Ltd | Transparent vinyl chloride resin composition and molded article |
| JP4942513B2 (en) * | 2007-03-02 | 2012-05-30 | 株式会社Ａｄｅｋａ | Vinyl chloride resin composition |
| JP2012021122A (en) * | 2010-07-16 | 2012-02-02 | Adeka Corp | Vinyl chloride-based resin composition |
| JP5716653B2 (en) * | 2011-12-21 | 2015-05-13 | 日立金属株式会社 | Polyvinyl chloride resin composition, electric wire and cable using the same |
| JP2013231134A (en) * | 2012-04-27 | 2013-11-14 | Furukawa Electric Co Ltd:The | Vinyl chloride resin composition, and wire and cable using the same |
| JP6148535B2 (en) * | 2013-05-23 | 2017-06-14 | 矢崎総業株式会社 | Wire covering material and covered wire |
| JP6206229B2 (en) * | 2014-02-05 | 2017-10-04 | 日立金属株式会社 | Vinyl chloride resin composition, insulated wire using the same, and method for producing insulated wire |
| JP6229591B2 (en) * | 2014-05-07 | 2017-11-15 | 日立金属株式会社 | Vinyl chloride resin composition, and insulated wire and cable using the same |
-
2015
- 2015-01-23 JP JP2015011792A patent/JP6459552B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016135836A (en) | 2016-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5323332B2 (en) | Flame retardant insulated wire | |
| JP2011026427A (en) | Vinyl chloride resin composition and insulated wire using the same | |
| JP6684053B2 (en) | Vinyl chloride resin composition, and insulated wire and cable using the same | |
| JP6850420B2 (en) | Insulated electric wires and cables using non-halogen flame-retardant resin composition | |
| CN107610821B (en) | Vinyl chloride resin composition, and insulated wire and cable | |
| CN111909468B (en) | Vinyl chloride resin composition, insulated wire, cable, method for producing insulated wire, and method for producing cable | |
| JP2015074709A (en) | Vinyl chloride resin composition, electric wire, and cable | |
| WO2005056667A1 (en) | Crosslinkable flame-retardant resin composition, and insulated electrical wire and wire harness each obtained with the same | |
| JP2025071344A (en) | Resin composition, insulated wire, and method for producing resin composition | |
| JP6229591B2 (en) | Vinyl chloride resin composition, and insulated wire and cable using the same | |
| JP5641497B2 (en) | Heat-resistant and flame-retardant resin composition, insulated wire, and tube | |
| JP6859377B2 (en) | Vinyl chloride resin composition, and insulated wires and cables using it | |
| JP6459552B2 (en) | Insulated wire and cable using vinyl chloride resin composition | |
| JP2018002781A (en) | Vinyl chloride resin composition, and insulated wire and cable using the same | |
| JP2000195336A (en) | Resin composition for wire coating and insulated wire | |
| JP7363557B2 (en) | Flame-retardant resin compositions, flame-retardant insulated wires and flame-retardant cables | |
| JP6402675B2 (en) | Vinyl chloride resin composition, and insulated wire and cable using the same | |
| JP2016095992A (en) | Electric wires and cables | |
| JP6206229B2 (en) | Vinyl chloride resin composition, insulated wire using the same, and method for producing insulated wire | |
| JP5813424B2 (en) | Flame retardant resin composition | |
| JP2023015841A (en) | Resin composition, and insulated cable | |
| CN106280056A (en) | Vinyl chloride resin composition, insulated wire using same, and method for producing insulated wire | |
| JP2017019943A (en) | Polyvinyl chloride resin composition, and wire and cable prepared therewith | |
| CN106280057B (en) | Vinyl chloride resin composition, insulated wire using same, and method for producing insulated wire | |
| JP2022153974A (en) | Vinyl chloride resin composition and insulated wire using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20171020 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20180327 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180622 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180703 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180720 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20181204 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20181217 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6459552 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |