JP2006348136A - Flame retardant resin composition and insulated wire and wire harness using the same - Google Patents
Flame retardant resin composition and insulated wire and wire harness using the same Download PDFInfo
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- JP2006348136A JP2006348136A JP2005174952A JP2005174952A JP2006348136A JP 2006348136 A JP2006348136 A JP 2006348136A JP 2005174952 A JP2005174952 A JP 2005174952A JP 2005174952 A JP2005174952 A JP 2005174952A JP 2006348136 A JP2006348136 A JP 2006348136A
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- parts
- wire
- halogen
- resin composition
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- 239000011342 resin composition Substances 0.000 title claims abstract description 45
- 239000003063 flame retardant Substances 0.000 title claims abstract description 44
- 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 title claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 75
- 229920005989 resin Polymers 0.000 claims abstract description 53
- 239000011347 resin Substances 0.000 claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 31
- 229920000573 polyethylene Polymers 0.000 claims abstract description 27
- 239000012968 metallocene catalyst Substances 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 33
- 230000003078 antioxidant effect Effects 0.000 claims description 31
- -1 imidazole compound Chemical class 0.000 claims description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims description 19
- 150000004706 metal oxides Chemical class 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- 239000011593 sulfur Substances 0.000 claims description 19
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 15
- 239000000347 magnesium hydroxide Substances 0.000 claims description 15
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 15
- 239000004711 α-olefin Substances 0.000 claims description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 55
- 239000011248 coating agent Substances 0.000 abstract description 21
- 238000000576 coating method Methods 0.000 abstract description 21
- 229910052736 halogen Inorganic materials 0.000 description 44
- 150000002367 halogens Chemical class 0.000 description 41
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 39
- 238000012360 testing method Methods 0.000 description 28
- 238000002156 mixing Methods 0.000 description 22
- 230000001681 protective effect Effects 0.000 description 21
- 235000001508 sulfur Nutrition 0.000 description 18
- 239000004020 conductor Substances 0.000 description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 239000000178 monomer Substances 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
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- 238000000034 method Methods 0.000 description 9
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- 239000002245 particle Substances 0.000 description 7
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- 239000011787 zinc oxide Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
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- 150000001875 compounds Chemical class 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 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 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
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- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 4
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
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- 229910052802 copper Inorganic materials 0.000 description 4
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- 238000002845 discoloration Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 4
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical class [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- XGIDEUICZZXBFQ-UHFFFAOYSA-N 1h-benzimidazol-2-ylmethanethiol Chemical compound C1=CC=C2NC(CS)=NC2=C1 XGIDEUICZZXBFQ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
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- 229920003355 Novatec® Polymers 0.000 description 3
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
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- 125000000524 functional group Chemical group 0.000 description 3
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- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 3
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- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 3
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- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
- OBMHSNXMHVKVSA-UHFFFAOYSA-L zinc;n-benzylcarbamodithioate Chemical compound [Zn+2].[S-]C(=S)NCC1=CC=CC=C1.[S-]C(=S)NCC1=CC=CC=C1 OBMHSNXMHVKVSA-UHFFFAOYSA-L 0.000 description 1
- KMNUDJAXRXUZQS-UHFFFAOYSA-L zinc;n-ethyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCN(C([S-])=S)C1=CC=CC=C1.CCN(C([S-])=S)C1=CC=CC=C1 KMNUDJAXRXUZQS-UHFFFAOYSA-L 0.000 description 1
- SZNCKQHFYDCMLZ-UHFFFAOYSA-L zinc;propan-2-yloxymethanedithioate Chemical compound [Zn+2].CC(C)OC([S-])=S.CC(C)OC([S-])=S SZNCKQHFYDCMLZ-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
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Abstract
【課題】難燃性、機械的特性、耐低温性に優れた難燃性樹脂組成物を提供すること。また、これを被覆材として用いたノンハロゲン系絶縁電線、このノンハロゲン系絶縁電線を含んだワイヤーハーネスを提供すること。
【解決手段】（Ａ）プロピレン系樹脂１００重量部に対し、（Ｂ）メタロセン系触媒の存在下で重合されたエチレン系重合体を１〜４０重量部、（Ｃ）金属水和物を３０〜２００重量部少なくとも含有させた組成物とする。また、当該組成物を被覆材に用いたノンハロゲン系絶縁電線とし、この電線をワイヤーハーネスの電線束中に使用する。
【選択図】 なしAn object of the present invention is to provide a flame retardant resin composition excellent in flame retardancy, mechanical properties and low temperature resistance. Also, provide a halogen-free insulated wire using this as a covering material, and a wire harness including the halogen-free insulated wire.
SOLUTION: (A) 1 to 40 parts by weight of an ethylene polymer polymerized in the presence of a metallocene catalyst and (C) 30 to 30 parts of a metal hydrate with respect to 100 parts by weight of a propylene resin. The composition contains at least 200 parts by weight. Moreover, it is set as the halogen-free insulated wire which used the said composition for the coating | covering material, and this wire is used in the wire bundle of a wire harness.
[Selection figure] None
Description
本発明は、難燃性樹脂組成物ならびにこれを用いた絶縁電線およびワイヤーハーネスに関し、さらに詳しくは、車両部品、電気・電子機器部品などに用いられる絶縁電線の被覆材として好適な難燃性樹脂組成物ならびにこれを用いた絶縁電線およびワイヤーハーネスに関するものである。 TECHNICAL FIELD The present invention relates to a flame retardant resin composition, an insulated wire and a wire harness using the same, and more particularly, a flame retardant resin suitable as a covering material for insulated wires used for vehicle parts, electrical / electronic device parts and the like. The present invention relates to a composition and an insulated wire and a wire harness using the composition.
従来、自動車部品などの車両部品、電気・電子機器部品などの配線に用いられる絶縁電線の被覆材としては、一般に、ハロゲン系難燃剤を添加した塩化ビニル樹脂組成物が広く用いられてきた。 Conventionally, a vinyl chloride resin composition to which a halogen-based flame retardant is added has been widely used as a covering material for insulated wires used for wiring of vehicle parts such as automobile parts and electrical / electronic equipment parts.
しかしながら、この種の塩化ビニル樹脂組成物は、ハロゲン元素を含有しているため、車両の火災時や電気・電子機器の焼却廃棄時などの燃焼時に有害なハロゲン系ガスを大気中に放出し、環境汚染の原因になるという問題があった。 However, since this type of vinyl chloride resin composition contains a halogen element, it releases harmful halogen-based gases to the atmosphere during combustion such as in the event of a vehicle fire or incineration and disposal of electrical and electronic equipment. There was a problem of causing environmental pollution.
そのため、地球環境への負荷を抑制するなどの観点から、近年では、ポリプロピレンなどのオレフィン系樹脂に、ノンハロゲン系難燃剤として水酸化マグネシウムなどの金属水和物を添加した、いわゆるノンハロゲン系難燃性樹脂組成物への代替が進められている。 Therefore, from the viewpoint of reducing the burden on the global environment, in recent years, so-called non-halogen flame retardant, in which a metal hydrate such as magnesium hydroxide is added as a non-halogen flame retardant to an olefin resin such as polypropylene. Alternatives to resin compositions are underway.
ところが、基本的にオレフィン系樹脂は燃えやすく、また、ノンハロゲン系難燃剤は、ハロゲン系難燃剤に比較して難燃化効果に劣る。したがって、ノンハロゲン系難燃性樹脂組成物では、十分な難燃性を確保するため、金属水和物を多量に添加する必要があり、これに起因して引張伸び、引張強度、耐摩耗性などの機械的特性が著しく低下するという問題があった。 However, olefinic resins are basically flammable, and non-halogen flame retardants are inferior in flame retardancy compared to halogen flame retardants. Therefore, in the halogen-free flame retardant resin composition, it is necessary to add a large amount of metal hydrate in order to ensure sufficient flame retardancy, resulting in tensile elongation, tensile strength, wear resistance, etc. There has been a problem that the mechanical properties of the material significantly deteriorated.
そこで、このような問題を改善するため、例えば、特許文献１には、複数のオレフィン系樹脂やゴムなどをベース樹脂として用い、さらに、このベース樹脂中に特定の官能基を特定量含有させることにより、ベース樹脂と金属水和物との親和性を高め、機械的特性を改善する技術が開示されている。 Therefore, in order to improve such a problem, for example, Patent Document 1 uses a plurality of olefin-based resins and rubber as a base resin, and further includes a specific functional group in the base resin. Discloses a technique for improving the mechanical properties by increasing the affinity between the base resin and the metal hydrate.
しかしながら、従来知られるノンハロゲン系難燃性樹脂組成物を、絶縁電線およびワイヤーハーネスに用いた場合、以下のような問題があった。 However, when the conventionally known non-halogen flame retardant resin composition is used for insulated wires and wire harnesses, there are the following problems.
すなわち、近年、ノンハロゲン系難燃性樹脂組成物は、組成物中の樹脂分を種々改良することにより、金属水和物などのノンハロゲン系難燃剤の添加量を抑制する試みがなされてはいるが、ハロゲン系難燃剤に比較すれば、その添加量が極めて多いことには変わりない。 That is, in recent years, attempts have been made to suppress the addition amount of non-halogen flame retardants such as metal hydrates by variously improving the resin content in the non-halogen flame retardant resin compositions. Compared with halogen-based flame retardants, the amount of addition remains the same.
そのため、従来のノンハロゲン系難燃性樹脂組成物は、高充填される金属水和物に起因して、難燃性や、引張伸び、引張強度、耐摩耗性などの機械的特性、耐低温性といった電線特性が未だ十分でないといった問題があった。 Therefore, the conventional non-halogen flame retardant resin composition has flame resistance, mechanical properties such as tensile elongation, tensile strength, and wear resistance, and low temperature resistance due to highly filled metal hydrate. There is a problem that the electric wire characteristics are still not sufficient.
そこで、本発明が解決しようとする課題は、難燃性、機械的特性、耐低温性に優れた難燃性樹脂組成物を提供することにある。 Therefore, the problem to be solved by the present invention is to provide a flame retardant resin composition excellent in flame retardancy, mechanical properties and low temperature resistance.
また、上記難燃性樹脂組成物を被覆材として用いたノンハロゲン系絶縁電線、このノンハロゲン系絶縁電線を含んだワイヤーハーネスを提供することにある。 Moreover, it is providing the halogen-free insulated wire which used the said flame-retardant resin composition as a coating | covering material, and the wire harness containing this halogen-free insulated wire.
これら課題を解決するため、本発明に係る難燃性樹脂組成物は、（Ａ）プロピレン系樹脂１００重量部に対し、（Ｂ）メタロセン系触媒の存在下で重合されたエチレン系重合体を１〜４０重量部、（Ｃ）金属水和物を３０〜２００重量部少なくとも含有してなることを要旨とする。 In order to solve these problems, the flame retardant resin composition according to the present invention includes 1 (B) ethylene polymer polymerized in the presence of a metallocene catalyst with respect to 100 parts by weight of (A) propylene resin. The gist is that it contains at least 30 to 200 parts by weight of (C) metal hydrate.
この場合、上記（Ｂ）エチレン系重合体は、エチレン−α−オレフィン共重合体であると良い。また、上記（Ｃ）金属水和物は、水酸化マグネシウムであると良い。 In this case, the (B) ethylene polymer is preferably an ethylene-α-olefin copolymer. The (C) metal hydrate is preferably magnesium hydroxide.
上記難燃性樹脂組成物は、上記成分以外にも、（Ａ）プロピレン系樹脂１００重量部に対し、さらに、（Ｄ）ヒンダードフェノール系酸化防止剤を０．３〜１５重量部、（Ｅ）イオウ系酸化防止剤を０．１〜２５重量部、（Ｆ）金属酸化物を０．１〜２５重量部含有していると良い。 In addition to the above components, the flame retardant resin composition may further include (D) a hindered phenolic antioxidant in an amount of 0.3 to 15 parts by weight with respect to 100 parts by weight of the propylene resin (E) It is preferable to contain 0.1 to 25 parts by weight of a sulfur-based antioxidant and 0.1 to 25 parts by weight of (F) a metal oxide.
この場合、上記（Ｅ）イオウ系酸化防止剤は、イミダゾール系化合物であると良い。また、上記（Ｆ）金属酸化物は、亜鉛（Ｚｎ）、アルミニウム（Ａｌ）、マグネシウム（Ｍｇ）、鉛（Ｐｂ）およびスズ（Ｓｎ）から選択される金属の酸化物１種または２種以上よりなると良い。 In this case, the (E) sulfur-based antioxidant is preferably an imidazole compound. The (F) metal oxide is one or more metal oxides selected from zinc (Zn), aluminum (Al), magnesium (Mg), lead (Pb) and tin (Sn). It would be nice.
一方、本発明に係るノンハロゲン系絶縁電線は、上記難燃性樹脂組成物を被覆材として用いたことを要旨とする。 On the other hand, the non-halogenous insulated wire according to the present invention uses the flame retardant resin composition as a covering material.
また、本発明に係るワイヤーハーネスは、上記ノンハロゲン系絶縁電線を含んでなることを要旨とする。 Moreover, the wire harness which concerns on this invention makes it a summary to comprise the said non-halogen-type insulated wire.
本発明に係る難燃性樹脂組成物によれば、（Ａ）プロピレン系樹脂１００重量部に対し、（Ｂ）メタロセン系触媒の存在下で重合されたエチレン系重合体を１〜４０重量部、（Ｃ）金属水和物を３０〜２００重量部少なくとも含有しているので、燃焼時にハロゲン系ガスを発生することなく、難燃性、引張伸び、引張強度、耐摩耗性などの機械的特性、耐低温性に優れる。 According to the flame-retardant resin composition according to the present invention, 1 to 40 parts by weight of (B) an ethylene polymer polymerized in the presence of a metallocene catalyst with respect to 100 parts by weight of the propylene-based resin, (C) Since it contains at least 30 to 200 parts by weight of metal hydrate, mechanical properties such as flame retardancy, tensile elongation, tensile strength, and wear resistance are generated without generating a halogen-based gas during combustion. Excellent low temperature resistance.
この際、上記（Ｂ）エチレン系重合体が、エチレン−α−オレフィン共重合体であれば、上記作用効果に優れる。 Under the present circumstances, if the said (B) ethylene-type polymer is an ethylene-alpha-olefin copolymer, it will be excellent in the said effect.
また、上記（Ｃ）金属水和物が水酸化マグネシウムである場合には、難燃効果、耐熱効果に優れる点で有利である。 Moreover, when the said (C) metal hydrate is magnesium hydroxide, it is advantageous at the point which is excellent in a flame-retardant effect and a heat-resistant effect.
さらに、上記難燃性樹脂組成物が、上記（Ａ）〜（Ｃ）成分以外に、（Ａ）プロピレン系樹脂１００重量部に対し、（Ｄ）ヒンダードフェノール系酸化防止剤を０．３〜１５重量部、（Ｅ）イオウ系酸化防止剤を０．１〜２５重量部、（Ｆ）金属酸化物を０．１〜２５重量部含有している場合には、塩化ビニル樹脂などのハロゲンを含有する材料と接触する形態で使用された場合であっても、著しく材料劣化することがなく、長期にわたって耐熱性を有する。 Furthermore, in addition to the components (A) to (C), the flame retardant resin composition contains (D) a hindered phenol antioxidant in an amount of 0.3 to 100 parts by weight of the propylene resin. 15 parts by weight, (E) 0.1 to 25 parts by weight of a sulfur-based antioxidant, and (F) 0.1 to 25 parts by weight of a metal oxide, halogen such as vinyl chloride resin Even when used in contact with the contained material, the material does not significantly deteriorate and has heat resistance over a long period of time.
この際、上記（Ｅ）イオウ系酸化防止剤としてイミダゾール系化合物を用いた場合、上記（Ｆ）金属酸化物として、酸化亜鉛などの特定の金属の酸化物を用いた場合には、上記作用効果に優れる。 In this case, when an imidazole compound is used as the (E) sulfur-based antioxidant, and when an oxide of a specific metal such as zinc oxide is used as the (F) metal oxide, the above effects are obtained. Excellent.
一方、上記難燃性樹脂組成物を被覆材として用いた本発明に係るノンハロゲン系絶縁電線、このノンハロゲン系絶縁電線を電線束中に含んだ本発明に係るワイヤーハーネスによれば、難燃性、引張伸び、引張強度、耐摩耗性などの機械的特性、耐低温性に優れる。 On the other hand, according to the non-halogen-based insulated wire according to the present invention using the flame-retardant resin composition as a coating material, the wire harness according to the present invention including this non-halogen-based insulated wire in a wire bundle, flame retardancy, Excellent mechanical properties such as tensile elongation, tensile strength, wear resistance, and low temperature resistance.
さらに、上記難燃性樹脂組成物が上記（Ｄ）〜（Ｆ）成分を含有しておれば、ノンハロゲン系絶縁電線が、電線束中の塩化ビニル系絶縁電線、あるいは、電線束の外周を覆うハロゲン系ワイヤーハーネス保護材などと接触する形態で使用された場合であっても、その被覆材が著しく劣化することなく、長期にわたって耐熱性が発揮される。 Furthermore, if the said flame-retardant resin composition contains said (D)-(F) component, a non-halogen-type insulated wire will cover the outer periphery of the vinyl chloride-type insulated wire in a wire bundle, or a wire bundle. Even when used in contact with a halogen-based wire harness protective material or the like, the covering material does not deteriorate significantly, and heat resistance is exhibited over a long period of time.
したがって、このノンハロゲン系絶縁電線およびワイヤーハーネスを、例えば、自動車のエンジンルームなど、絶えず高温環境下に曝される部位などに使用した場合には、長期にわたって高い信頼性を確保することができる。 Therefore, when this non-halogen-based insulated electric wire and wire harness are used in a part that is constantly exposed to a high temperature environment such as an engine room of an automobile, for example, high reliability can be ensured over a long period of time.
以下、本発明の実施形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
＜本組成物の構成＞
本実施形態に係る難燃性樹脂組成物（以下、「本組成物」ということがある。）は、（Ａ）プロピレン系樹脂、（Ｂ）特定のエチレン系重合体、（Ｃ）金属水和物を少なくとも含有しており、各（Ａ）〜（Ｃ）成分は、それぞれ特定の配合割合とされている。
<Composition of this composition>
The flame-retardant resin composition according to the present embodiment (hereinafter sometimes referred to as “the present composition”) includes (A) a propylene resin, (B) a specific ethylene polymer, and (C) a metal hydration. The thing is contained at least and each (A)-(C) component is made into the specific mixture ratio, respectively.
本組成物において、（Ａ）プロピレン系樹脂は、機械的特性などに優れるなどの観点から、プロピレン単量体の含有率が５０重量％以上、好ましくは、７０重量％以上あるものを用いると良い。ここで、プロピレン系樹脂は、プロピレン単量体単独からなっていても良いし、必要に応じて、プロピレン単量体以外の他の単量体を１種または２種以上含んでいても良い。また、プロピレン系樹脂は、１種であっても良いし、２種以上の異なるプロピレン系樹脂の組み合わせであっても良い。 In the present composition, the propylene-based resin (A) having a propylene monomer content of 50% by weight or more, preferably 70% by weight or more is used from the viewpoint of excellent mechanical properties and the like. . Here, the propylene-based resin may consist of a propylene monomer alone, or may contain one or more monomers other than the propylene monomer as necessary. Further, the propylene resin may be one kind or a combination of two or more different propylene resins.
上記プロピレン単量体以外の他の単量体としては、例えば、エチレン、炭素数３〜２０のα−オレフィン、非共役ポリエンなどが挙げられる。 Examples of the monomer other than the propylene monomer include ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene.
炭素数３〜２０のα−オレフィンとしては、具体的には、例えば、プロピレン、１−ブテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン、１−トリデセン、１−テトラデセン、１−ペンタデセン、１−ヘキサデセン、１−ヘプタデセン、１−ノナデセン、１−エイコセン、９−メチル−１−デセン、１１−メチル−１−ドデセン、１２−エチル−１テトラデセンなどが挙げられる。 Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1 -Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicocene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl -1 tetradecene and the like.
非共役ポリエンとしては、具体的には、例えば、ジシクロペンタジエン、エチリデンノルボルネンなどが挙げられる。 Specific examples of the non-conjugated polyene include dicyclopentadiene and ethylidene norbornene.
また、上記プロピレン系樹脂は、ＪＩＳ Ｋ ６７５８に準拠して測定（温度２３０℃、加重２．１６ｋｇ下で測定）されるメルトフローレイト（ＭＦＲ）が０．１〜７ｇ／１０分、好ましくは、０．１〜５ｇ／１０分の範囲内にあると良い。ＭＦＲが０．１ｇ／１０分未満になると、組成物の流動性が悪くなる傾向が見られる。一方、ＭＦＲが７ｇ／１０分を越えると、機械的特性などが低下する傾向が見られる。したがって、ＭＦＲの選択には、これらに留意すると良い。 The propylene-based resin has a melt flow rate (MFR) measured in accordance with JIS K 6758 (measured at a temperature of 230 ° C. and a load of 2.16 kg) of 0.1 to 7 g / 10 minutes, preferably It is good to exist in the range of 0.1-5g / 10min. When MFR is less than 0.1 g / 10 min, the tendency of the fluidity of the composition to deteriorate is observed. On the other hand, when the MFR exceeds 7 g / 10 min, there is a tendency for the mechanical properties and the like to decrease. Therefore, these should be noted when selecting the MFR.
本組成物において、（Ｂ）特定のエチレン系重合体は、メタロセン系触媒の存在下で重合されたものである。上記エチレン系重合体は、メタロセン系触媒の存在下で重合されたものであれば、エチレンの単独重合体であっても良いし、エチレンとα−オレフィンとの共重合体であっても良い。また、上記エチレン系重合体は、１種であっても良いし、２種以上の異なるエチレン系重合体の組み合わせであっても良い。この際、エチレン−α−オレフィン共重合体を選択する場合には、直鎖状のものを選択すると良い。 In the present composition, (B) the specific ethylene polymer is polymerized in the presence of a metallocene catalyst. The ethylene polymer may be an ethylene homopolymer or a copolymer of ethylene and an α-olefin as long as it is polymerized in the presence of a metallocene catalyst. Moreover, the said ethylene polymer may be 1 type and the combination of 2 or more types of different ethylene polymers may be sufficient as it. At this time, when an ethylene-α-olefin copolymer is selected, a linear one may be selected.
上記α−オレフィンとしては、炭素数３〜２０のものが好ましく、具体的には、上述したものと同様のものが挙げられる。 As said alpha olefin, a C3-C20 thing is preferable and the thing similar to what was mentioned above specifically is mentioned.
ここで、上記メタロセン系触媒としては、具体的には、例えば、ビス（シクロペンタジエニル）ジルコニウムジクロライド、ビス（シクロペンタジエニル）ハフニウムジクロライド、エチレンビス（インデニル）ジルコニウムジクロライド、エチレンビス（インデニル）ハフニウムジクロライド、イソプロピリデン（シクロペンタジエニル−９−フルオレニル）ジルコニウムジクロライド、イソプロピリデン（シクロペンタジエニル−９−フルオレニル）ハフニウムジクロライド、イソプロピリデン（シクロペンタジエニル−２，７−ジメチル−９−フルオレニル）ジルコニウムジクロライド、イソプロピリデン（シクロペンタジエニル−２，７−ジメチル−９−フルオレニル）ハフニウムジクロライド、ジメチルシランジイルビス（２，４，５−トリメチルシクロペンタジエニル）ジルコニウムジクロライド、ジメチルシランジイルビス（２，４−ジメチルシクロペンタジエニル）ジルコニウムジクロライド、ジメチルシランジイルビス（２，４，５−トリメチルシクロペンタジエニル）ハフニウムジクロライド、ジメチルシランジイルビス（２，４−ジメチルシクロペンタジエニル）ハフニウムジクロライドなどを代表的なものとして例示することができ、特に限定されるものではない。また、これらは１種または２種以上併用しても良い。 Specific examples of the metallocene catalyst include bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, ethylene bis (indenyl) zirconium dichloride, and ethylene bis (indenyl). Hafnium dichloride, isopropylidene (cyclopentadienyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-9-fluorenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) ) Zirconium dichloride, isopropylidene (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, dimethylsilanediylbis (2,4 5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, dimethyl Silanediylbis (2,4-dimethylcyclopentadienyl) hafnium dichloride can be exemplified as a typical example, and is not particularly limited. These may be used alone or in combination of two or more.
この種のメタロセン系触媒は、一般に、重合活性点が単一であり、重合活性も高い。そのため、このようなメタロセン系触媒の存在下で重合されたエチレン系重合体は、他の触媒の存在下で重合されたエチレン系重合体に比較して、＜１＞結晶の大きさが均一であり、結晶を結ぶタイ分子も多く、均一なコモノマー組成を有している、＜２＞低密度・低分子量成分、高密度・高分子量成分が少なく、狭い分子量分布を有している、＜３＞密度も比較的低いなどといった特徴を有している。 In general, this type of metallocene catalyst has a single polymerization active site and high polymerization activity. Therefore, an ethylene polymer polymerized in the presence of such a metallocene catalyst has a <1> uniform crystal size compared to an ethylene polymer polymerized in the presence of another catalyst. There are many tie molecules that connect crystals, and have a uniform comonomer composition. <2> Low density / low molecular weight component, few high density / high molecular weight components, and narrow molecular weight distribution, <3 > It has characteristics such as relatively low density.
したがって、メタロセン系触媒の存在下で重合されたエチレン系重合体は、概ね、高強度を有し、低結晶性であることから、これを用いると、高充填される（Ｃ）金属水和物に起因する機械的特性の低下や、耐低温性の低下などを抑制することができる。 Accordingly, since the ethylene polymer polymerized in the presence of the metallocene catalyst generally has high strength and low crystallinity, when it is used, the (C) metal hydrate is highly filled. It is possible to suppress a decrease in mechanical properties due to the above, a decrease in low temperature resistance, and the like.
上記メタロセン系触媒の存在下で重合されたエチレン系重合体は、その相対密度が０．８６０〜０．９３０ｇ／ｃｍ３、好ましくは、０．８８０〜０．９２０ｇ／ｃｍ３の範囲内にあると良い。また、密度法により求めた結晶化度は、５５％以下、好ましくは、５０％以下であると良い。 The ethylene polymer polymerized in the presence of the metallocene catalyst has a relative density of 0.860 to 0.930 g / cm 3 , preferably 0.880 to 0.920 g / cm 3. And good. The crystallinity obtained by the density method is 55% or less, preferably 50% or less.
また、上記メタロセン系触媒の存在下で重合されたエチレン系重合体を得るために用いる重合方法としては、具体的には、例えば、高圧イオン重合法、溶液法、スラリー法、気相法などが挙げられる。 Specific examples of the polymerization method used for obtaining an ethylene polymer polymerized in the presence of the metallocene catalyst include, for example, a high-pressure ion polymerization method, a solution method, a slurry method, and a gas phase method. Can be mentioned.
なお、本組成物において適用される、メタロセン系触媒の存在下で重合されたエチレン系重合体は、市場で入手可能なものであり、例えば、日本ポリプロ（株）から「カーネル」（商品名）などが市販されている。 The ethylene polymer polymerized in the presence of the metallocene catalyst applied in the present composition is commercially available. For example, “Kernel” (trade name) from Nippon Polypro Co., Ltd. Are commercially available.
本組成物において、（Ｃ）金属水和物は、難燃剤としての機能を有している。 In the present composition, the (C) metal hydrate has a function as a flame retardant.
上記金属水和物としては、具体的には、例えば、水酸化マグネシウム、水酸化アルミニウム、水酸化ジルコニウム、水和珪酸マグネシウム、水和珪酸アルミニウム、塩基性炭酸マグネシウム、ハイドロタルサイトなど水酸基および／または結晶水を有する化合物などが挙げられる。これらは１種または２種以上含まれていても良い。これらのうち、好ましくは、水酸化マグネシウムを用いると良い。難燃効果、耐熱効果が高いからである。 Specific examples of the metal hydrate include, for example, magnesium hydroxide, aluminum hydroxide, zirconium hydroxide, hydrated magnesium silicate, hydrated aluminum silicate, basic magnesium carbonate, hydrotalcite and other hydroxyl groups and / or Examples thereof include compounds having crystal water. These may be contained alone or in combination of two or more. Of these, magnesium hydroxide is preferably used. This is because the flame retardancy and heat resistance are high.
ここで、水酸化マグネシウムは、一般に、合成品と天然品の２つに大別される。 Here, magnesium hydroxide is generally roughly divided into two types: synthetic products and natural products.
前者の合成品の水酸化マグネシウムは、例えば、海水または苦汁中に苛性アルカリまたは消石灰のスラリーを添加し、反応させて結晶成長させ、そしてこれを固液分離した後に、洗浄し、表面処理、乾燥などを経て製造されるものである。 The former synthetic magnesium hydroxide is prepared by adding a caustic or slaked lime slurry in seawater or bitter juice, reacting it, crystallizing it, separating it into solid and liquid, washing, surface treatment, drying, etc. It is manufactured through such as.
一方、後者の天然品の水酸化マグネシウムは、いわゆる、天然ブルーサイト鉱石由来のもので、水酸化マグネシウムを主成分とする天然ブルーサイト鉱石を湿式または乾式粉砕するなどして製造されるものである。 On the other hand, the latter natural product magnesium hydroxide is derived from so-called natural brucite ore, and is produced by wet or dry pulverization of natural brucite ore mainly composed of magnesium hydroxide. .
本組成物では、合成品、天然品の何れの水酸化マグネシウムであっても用いることができる。 In the present composition, any of a synthetic product and a natural product magnesium hydroxide can be used.
通常、水酸化マグネシウムなどの金属水和物を組成物中に単純に高充填しただけでは、組成物の機械的特性、耐低温性などを損ないやすい。 Usually, simply filling a composition with a metal hydrate such as magnesium hydroxide in a high amount tends to impair the mechanical properties, low-temperature resistance, etc. of the composition.
ところが、本組成物では、上記（Ｂ）特定のエチレン系重合体を含有しているので、水酸化マグネシウムなどの金属水和物を比較的多量に添加した場合であっても、機械的特性、耐低温性などを損ない難い。 However, since the present composition contains the specific ethylene polymer (B), even when a relatively large amount of a metal hydrate such as magnesium hydroxide is added, the mechanical properties, It is difficult to impair the low temperature resistance.
上記金属水和物は、その平均粒径（Ｄ５０）が０．５〜１０．０μｍ、好ましくは、０．６〜５．０μｍ、より好ましくは、０．７〜２．０μｍの範囲内にあると良い。 The metal hydrate has an average particle diameter (D50) in the range of 0.5 to 10.0 μm, preferably 0.6 to 5.0 μm, more preferably 0.7 to 2.0 μm. And good.
平均粒径（Ｄ５０）が０．５μｍ未満になると、粒子同士の二次凝集が起こりやすく、機械的特性も低下しやすくなる傾向が見られる。一方、平均粒径（Ｄ５０）が１０．０μｍを越えると、機械的特性が低下しやすくなり、また、被覆材として用いた場合に、外観荒れなどが生じる傾向が見られる。したがって、平均粒径（Ｄ５０）の選択には、これらに留意すると良い。 When the average particle diameter (D50) is less than 0.5 μm, secondary aggregation between particles tends to occur, and the mechanical properties tend to be deteriorated. On the other hand, when the average particle diameter (D50) exceeds 10.0 μm, the mechanical properties are liable to be deteriorated, and when used as a coating material, there is a tendency that the appearance becomes rough. Therefore, these should be noted in selecting the average particle diameter (D50).
また、上記金属水和物は、脂肪酸、脂肪酸金属塩、シランカップリング剤、チタネートカップリング剤などの表面処理剤により表面処理が施されていても良い。なお、表面処理された金属水和物を用いる場合、予め表面処理剤により表面処理された金属水和物を組成物中に配合しても良いし、未処理状態の金属水和物を表面処理剤とともに組成物中に配合して表面処理を行っても良く、特に限定されるものではない。 The metal hydrate may be subjected to a surface treatment with a surface treatment agent such as a fatty acid, a fatty acid metal salt, a silane coupling agent, or a titanate coupling agent. In addition, when using a surface-treated metal hydrate, a metal hydrate that has been surface-treated with a surface treatment agent in advance may be added to the composition, or an untreated metal hydrate may be surface-treated. The surface treatment may be carried out by blending in the composition together with the agent, and is not particularly limited.
本組成物において、上記（Ａ）〜（Ｃ）成分の配合割合は、（Ａ）プロピレン系樹脂１００重量部に対し、（Ｂ）特定のエチレン系重合体１〜４０重量部、（Ｃ）金属水和物３０〜２００重量部の範囲内にある。 In this composition, the blending ratio of the components (A) to (C) is (B) 1 to 40 parts by weight of a specific ethylene polymer and (C) a metal with respect to 100 parts by weight of the propylene resin (A). It exists in the range of 30-200 weight part of hydrates.
上記（Ｂ）特定のエチレン系重合体の配合割合が１重量部未満になると、引張伸びが低下する傾向が見られる。一方、４０重量部を越えると、引張強度、耐摩耗性が低下する傾向が見られる。したがって、配合割合の選択には、これらに留意すると良い。好ましくは、（Ａ）プロピレン系樹脂１００重量部に対して、（Ｂ）特定のエチレン系重合体は５〜３５重量部の範囲内にあると良い。 When the blending ratio of the specific ethylene polymer (B) is less than 1 part by weight, the tensile elongation tends to decrease. On the other hand, when it exceeds 40 parts by weight, there is a tendency that the tensile strength and the wear resistance are lowered. Therefore, these should be taken into consideration when selecting the blending ratio. Preferably, the specific ethylene polymer (B) is in the range of 5 to 35 parts by weight with respect to 100 parts by weight of the (A) propylene resin.
また、上記（Ｃ）金属水和物の配合割合が３０重量部未満になると、十分な難燃性が得られない傾向が見られる。一方、２００重量部を越えると、（Ｂ）特定のエチレン系重合体を配合しても機械的特性、耐低温性が低下する傾向が見られる。したがって、配合割合の選択には、これらに留意すると良い。好ましくは、（Ａ）プロピレン系樹脂１００重量部に対して、（Ｃ）金属水和物は５０〜１５０重量部の範囲内にあると良い。 Moreover, when the blending ratio of the (C) metal hydrate is less than 30 parts by weight, there is a tendency that sufficient flame retardancy cannot be obtained. On the other hand, when the amount exceeds 200 parts by weight, mechanical properties and low temperature resistance tend to be lowered even when a specific ethylene polymer (B) is blended. Therefore, these should be taken into consideration when selecting the blending ratio. Preferably, (A) metal hydrate is in the range of 50 to 150 parts by weight with respect to 100 parts by weight of (A) propylene-based resin.
本組成物中には、当該組成物の物性を損なわない範囲内で、（Ａ）プロピレン径樹脂、（Ｂ）特定のエチレン系重合体以外の他の樹脂成分が、必要に応じて含まれていても良い。他の樹脂成分としては、具体的には、例えば、ポリオレフィン、ゴムなどが挙げられる。これらは１種または２種以上含まれていても良い。 In the composition, other resin components other than (A) a propylene resin and (B) a specific ethylene-based polymer are included as necessary within the range not impairing the physical properties of the composition. May be. Specific examples of the other resin component include polyolefin and rubber. These may be contained alone or in combination of two or more.
上記ポリオレフィンとしては、高圧ラジカル重合法による低密度ポリエチレン、エチレン・α−オレフィン共重合体、エチレン−ビニルエステル共重合体、エチレン−α，β−不飽和カルボン酸アルキルエステル共重合体などが挙げられる。 Examples of the polyolefin include low-density polyethylene by high-pressure radical polymerization, ethylene / α-olefin copolymer, ethylene-vinyl ester copolymer, ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer, and the like. .
また、上記ゴムとしては、エチレンプロピレン系ゴム、ブタジエン系ゴム、イソプレン系ゴム、天然ゴム、ニトリルゴム、イソブチレンゴムなどが挙げられる。 Examples of the rubber include ethylene propylene rubber, butadiene rubber, isoprene rubber, natural rubber, nitrile rubber, and isobutylene rubber.
上記エチレン・α−オレフィン共重合体に用いられるα−オレフィン共重合体としては、チーグラー触媒などを用いる中低圧法およびその他の公知の方法によるものなどを用いることができる。α−オレフィンとしては、エチレンおよび炭素数３〜２０のα−オレフィン、具体的には、プロピレン、１−ブテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン、１−トリデセン、１−テトラデセン、１−ペンタデセン、１−ヘキサデセン、１−ヘプタデセン、１−ノナデセン、１−エイコセン、９−メチル−１−デセン、１１−メチル−１−ドデセン、１２−エチル−１テトラデセンなどが挙げられる。 As the α-olefin copolymer used for the ethylene / α-olefin copolymer, a medium-low pressure method using a Ziegler catalyst or the like and other known methods can be used. As the α-olefin, ethylene and an α-olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1 -Undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene , 12-ethyl-1 tetradecene, and the like.
上記エチレン−ビニルエステル共重合体に用いられるビニルエステル単量体としては、プロピオン酸ビニル、酢酸ビニル、カプロン酸ビニル、カプリル酸ビニル、ラウリル酸ビニル、ステアリン酸ビニル、トリフルオル酢酸ビニルなどが挙げられる。 Examples of the vinyl ester monomer used in the ethylene-vinyl ester copolymer include vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate.
上記エチレン−α，β−不飽和カルボン酸アルキルエステル共重合体に用いられる、α，β−不飽和カルボン酸アルキルエステル単量体としては、アクリル酸メチル、メタアクリル酸メチル、アクリル酸エチル、メタアクリル酸エチルなどが挙げられる。 Examples of the α, β-unsaturated carboxylic acid alkyl ester monomer used in the ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer include methyl acrylate, methyl methacrylate, ethyl acrylate, Examples include ethyl acrylate.
上記エチレンプロピレン系ゴムとしては、エチレンおよびプロピレンを主成分とするランダム共重合体および第３成分としてジシクロペンタジエン、エチリデンノルボルネンなどのジエンモノマーを加えたものを主成分とするランダム共重合体などが挙げられる。 Examples of the ethylene-propylene rubber include a random copolymer mainly composed of ethylene and propylene, and a random copolymer composed mainly of a diene monomer such as dicyclopentadiene or ethylidene norbornene as a third component. Can be mentioned.
上記ブタジエン系ゴムとは、ブタジエンを構成要素とする共重合体をいい、スチレン−ブタジエンブロック共重合体およびその水添または部分水添誘導体であるスチレン−エチレン−ブタジエン−スチレン共重合体、スチレン−エチレン／ブチレン−スチレンブロック共重合体、１，２−ポリブタジエン、無水マレイン酸変性のスチレン−エチレン−ブタジエン−スチレン共重合体、コアシェル構造を有する変性ブタジエンゴムなどが挙げられる。 The butadiene-based rubber refers to a copolymer having butadiene as a constituent element, and is a styrene-butadiene block copolymer and a hydrogenated or partially hydrogenated derivative thereof such as styrene-ethylene-butadiene-styrene copolymer, styrene- Examples thereof include ethylene / butylene-styrene block copolymers, 1,2-polybutadiene, maleic anhydride-modified styrene-ethylene-butadiene-styrene copolymers, and modified butadiene rubbers having a core-shell structure.
上記イソプレンゴムとは、イソプレンを構成要素とする共重合体をいい、スチレン−イソプレンブロック共重合体およびその水添または部分水添誘導体であるスチレン−エチレン−イソプレン−スチレン共重合体、無水マレイン酸変性のスチレン−エチレン−イソプレン−スチレン共重合体、コアシェル構造を有する変性イソプレンゴムなどが挙げられる。 The isoprene rubber refers to a copolymer having isoprene as a constituent element, and is a styrene-isoprene block copolymer and a hydrogenated or partially hydrogenated derivative thereof such as a styrene-ethylene-isoprene-styrene copolymer, maleic anhydride. Examples thereof include a modified styrene-ethylene-isoprene-styrene copolymer and a modified isoprene rubber having a core-shell structure.
また、本組成物中には、当該組成物の物性を損なわない範囲内で、（Ｃ）金属水和物以外の他の添加剤が必要に応じて含まれていても良い。 Moreover, in this composition, the additive other than (C) metal hydrate may be contained as needed within the range which does not impair the physical property of the said composition.
他の添加剤としては、具体的には、例えば、酸化防止剤（ヒンダードフェノール系、イオウ系など）、金属酸化物（亜鉛、アルミニウム、マグネシウム、鉛、スズなどの金属の酸化物）、金属不活性化剤（銅害防止剤）、無機充填剤（硫酸カルシウム、珪酸カルシウム、クレー、珪藻土、タルク、アルミナ、珪砂、ガラス粉、酸化鉄、金属粉、グラファイト、炭化珪素、窒化珪素、シリカ、窒化ホウ素、窒化アルミニウム、カーボンブラック、雲母、ガラス板、セリサイト、パイロフィライト、アルミフレーク、黒鉛、シラスパルーン、金属パルーン、ガラスパルーン、軽石、ガラス繊維、炭素繊維、ウィスカー、金属繊維、グラファイト繊維、シリコンカーバイト繊維、アスベスト、ワラストナイトなど）、紫外線吸収剤、紫外線隠蔽剤、難燃助剤、架橋剤、架橋助剤、加工助剤（滑剤、ワックスなど）、着色用顔料などが挙げられる。これらは１種または２種以上含まれていても良い。 As other additives, specifically, for example, antioxidants (hindered phenols, sulfurs, etc.), metal oxides (oxides of metals such as zinc, aluminum, magnesium, lead, tin, etc.), metals Deactivator (copper damage inhibitor), inorganic filler (calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, Boron nitride, aluminum nitride, carbon black, mica, glass plate, sericite, pyrophyllite, aluminum flake, graphite, shirasu paroon, metal paroon, glass paroon, pumice, glass fiber, carbon fiber, whisker, metal fiber, graphite fiber , Silicon carbide fiber, asbestos, wollastonite, etc.), UV absorber, UV masking agent, Retardant agents, crosslinking agents, crosslinking aids, processing aids (lubricants, such as wax), and a coloring pigment. These may be contained alone or in combination of two or more.
なお、上記ポリオレフィン、ゴム、無機充填剤は、（Ａ）プロピレン系樹脂１００重量部に対して、それぞれ１００重量部程度まで含有させることが可能である。その配合割合が上限値を超えると、機械的特性などが低下する傾向が見られるので、この点留意すると良い。 In addition, the said polyolefin, rubber | gum, and an inorganic filler can be contained to about 100 weight part with respect to 100 weight part of (A) propylene-type resin, respectively. If the blending ratio exceeds the upper limit value, mechanical characteristics and the like tend to be reduced.
ここで、他の添加剤として、本組成物中に酸化防止剤を含有させる場合、用いる酸化防止剤は、１種であっても良いし、２種以上組み合わせて用いても良い。好ましくは、（Ｄ）ヒンダードフェノール系酸化防止剤と、（Ｅ）イオウ系酸化防止剤とを組み合わせて用い、さらに、（Ｆ）金属酸化物も同時に添加すると良い。本組成物中にこれら（Ｄ）〜（Ｆ）成分を組み合わせて含有させる意義は、次の通りである。 Here, as an additive, when an antioxidant is contained in the present composition, one kind of antioxidant may be used, or two or more kinds may be used in combination. Preferably, (D) a hindered phenol-based antioxidant and (E) a sulfur-based antioxidant are used in combination, and (F) a metal oxide is added at the same time. The significance of including these components (D) to (F) in combination in the present composition is as follows.
すなわち、例えば、自動車などの車両において絶縁電線を使用する場合、一般に、複数の絶縁電線をひとまとまりに束ねて電線束とし、この電線束の外周に、テープ状、チューブ状またはシート状などの種々の形状からなる保護材を巻回することによりワイヤーハーネスとして使用することが多い。 That is, for example, when using insulated wires in a vehicle such as an automobile, in general, a plurality of insulated wires are bundled together to form a bundle of wires, and a variety of tapes, tubes, sheets, and the like are provided on the outer periphery of the bundle of wires. It is often used as a wire harness by winding a protective material having the shape of
ワイヤーハーネスを構成する絶縁電線は、被覆材としてノンハロゲン系難燃性樹脂組成物を用いたノンハロゲン系絶縁電線に代替が進んできてはいるものの、これまでの実績などから、被覆材としてポリ塩化ビニルなどの塩化ビニル樹脂組成物を用いた塩化ビニル系絶縁電線も今だに使用されているのが実情である。 Insulated wires that make up wire harnesses are being replaced by non-halogen-based insulated wires that use non-halogen-based flame-retardant resin composition as a coating material. In fact, vinyl chloride insulated wires using a vinyl chloride resin composition such as these are still used.
そのため、ノンハロゲン系絶縁電線と塩化ビニル系絶縁電線との混在を完全に避けるのは困難な状況にある。このような状況の下、ノンハロゲン系絶縁電線が塩化ビニル系絶縁電線などと接触した状態で使用されると、電線束中のノンハロゲン系絶縁電線の被覆材が著しく劣化し、耐熱性が低下する。 For this reason, it is difficult to completely avoid the mixture of non-halogenous insulated wires and vinyl chloride-based insulated wires. Under such circumstances, when the non-halogenous insulated wire is used in contact with a vinyl chloride insulated wire or the like, the coating material of the non-halogenated insulated wire in the wire bundle is remarkably deteriorated and heat resistance is lowered.
さらに、将来的に、ワイヤーハーネスを構成する絶縁電線がノンハロゲン系絶縁電線に完全に切り替わったとしても、電線束に巻回されるワイヤーハーネス保護材の基材には、塩化ビニル樹脂組成物などのハロゲン系難燃性樹脂組成物が使用されていることが多い。そのため、ノンハロゲン系絶縁電線がハロゲンを含有する保護材と接触した状態で使用された場合にも、耐熱性が低下する。 Furthermore, even in the future, even if the insulated wire constituting the wire harness is completely switched to the non-halogenated insulated wire, the base material of the wire harness protective material wound around the wire bundle includes a vinyl chloride resin composition, etc. Halogen flame retardant resin compositions are often used. Therefore, even when the non-halogenous insulated wire is used in contact with a protective material containing halogen, the heat resistance is reduced.
この原因は、詳細なメカニズムまでは解明されていないが、ノンハロゲン系絶縁電線が、塩化ビニル系絶縁電線やハロゲンを含有する保護材と接触すると、ノンハロゲン系難燃性樹脂組成物からなる被覆材中の酸化防止剤が著しく消費されるか、あるいは、酸化防止剤そのものが塩化ビニル系絶縁電線や保護材中に移行するためではないかと推測される。 The cause of this is not clarified in detail, but when a non-halogenated insulated wire comes into contact with a vinyl chloride-based insulated wire or a protective material containing halogen, the coating material made of a non-halogenated flame-retardant resin composition is used. It is presumed that the antioxidant is significantly consumed, or that the antioxidant itself is transferred into the vinyl chloride insulated wire and the protective material.
ところが、上記（Ａ）〜（Ｃ）成分以外に、さらに、上記（Ｄ）〜（Ｆ）成分を含有させると、長期にわたって耐熱性を発現できるようになる。 However, when the components (D) to (F) are further contained in addition to the components (A) to (C), heat resistance can be expressed over a long period of time.
上記作用を効率良く得るため、これら（Ｄ）〜（Ｆ）成分の配合割合は、（Ａ）プロピレン系樹脂１００重量部に対し、（Ｄ）ヒンダードフェノール系酸化防止剤０．３〜１５重量部、（Ｅ）イオウ系酸化防止剤０．１〜２５重量部、（Ｆ）金属酸化物０．１〜２５重量部の範囲内にあると良い。 In order to obtain the above-mentioned action efficiently, the blending ratio of these components (D) to (F) is (D) hindered phenolic antioxidant 0.3 to 15 wt. Part (E) 0.1 to 25 parts by weight of a sulfur-based antioxidant and (F) 0.1 to 25 parts by weight of a metal oxide.
上記（Ｄ）ヒンダードフェノール系酸化防止剤の配合割合が０．３重量部未満になると、十分な耐熱性が得られない傾向が見られる。一方、１５重量部を越えると、その配合の効果も飽和し、さらに、当該組成物の使用中に添加剤が表面に滲み出してくる傾向が見られる。したがって、配合割合の選択には、これらに留意すると良い。好ましくは、（Ａ）プロピレン系樹脂１００重量部に対して、（Ｄ）ヒンダードフェノール系酸化防止剤は０．５〜１０重量部の範囲内、より好ましくは、０．７〜５重量部の範囲内にあると良い。 When the blending ratio of the (D) hindered phenol antioxidant is less than 0.3 parts by weight, there is a tendency that sufficient heat resistance cannot be obtained. On the other hand, when the amount exceeds 15 parts by weight, the effect of the blending is saturated, and the additive tends to ooze out to the surface during use of the composition. Therefore, these should be taken into consideration when selecting the blending ratio. Preferably, (A) the hindered phenolic antioxidant is in the range of 0.5 to 10 parts by weight, more preferably 0.7 to 5 parts by weight with respect to 100 parts by weight of the (A) propylene-based resin. It should be within the range.
また、上記（Ｅ）イオウ系酸化防止剤の配合量が０．１重量部未満になると、十分な耐熱性が得られない傾向が見られる。一方、２５重量部を越えると、その配合の効果も飽和し、さらに、当該組成物の使用中に添加剤が表面に滲み出してくる傾向が見られる。したがって、配合割合の選択には、これらに留意すると良い。好ましくは、（Ａ）プロピレン系樹脂１００重量部に対して、（Ｅ）イオウ系酸化防止剤は０．５〜２０重量部の範囲内、より好ましくは、０．７〜１０重量部の範囲内にあると良い。 Moreover, when the blending amount of the above (E) sulfur-based antioxidant is less than 0.1 parts by weight, there is a tendency that sufficient heat resistance cannot be obtained. On the other hand, when the amount exceeds 25 parts by weight, the effect of the blending is saturated, and the additive tends to ooze out to the surface during use of the composition. Therefore, these should be taken into consideration when selecting the blending ratio. Preferably, (A) the sulfur-based antioxidant is in the range of 0.5 to 20 parts by weight, more preferably in the range of 0.7 to 10 parts by weight with respect to (A) 100 parts by weight of the propylene-based resin. Good to be in.
また、上記（Ｆ）金属酸化物の配合量が０．１重量部未満になると、十分な耐熱性が得られない傾向が見られる。一方、２５重量部を越えると、その配合の効果も飽和し、機械的特性も低下する傾向が見られる。したがって、配合割合の選択には、これらに留意すると良い。好ましくは、（Ａ）プロピレン系樹脂１００重量部に対して、（Ｆ）金属酸化物は０．５〜２０重量部の範囲内、より好ましくは、０．７〜１０重量部の範囲内にあると良い。 Moreover, when the compounding amount of the (F) metal oxide is less than 0.1 parts by weight, there is a tendency that sufficient heat resistance cannot be obtained. On the other hand, when the amount exceeds 25 parts by weight, the blending effect is saturated and the mechanical properties tend to be lowered. Therefore, these should be taken into consideration when selecting the blending ratio. Preferably, (A) the metal oxide is in the range of 0.5 to 20 parts by weight, more preferably in the range of 0.7 to 10 parts by weight with respect to 100 parts by weight of the propylene-based resin (A). And good.
上記（Ｄ）ヒンダードフェノール系酸化防止剤としては、ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、チオジエチレンビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、Ｎ，Ｎ’−ヘキサン−１，６−ジイルビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニルプロピオンアミド）、ベンゼンプロパン酸，３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシ，Ｃ７−Ｃ９側鎖アルキルエステル、２，４−ジメチル−６−（１−メチルペンタデシル）フェノール、ジエチル［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ホスフォネート、３，３’，３”，３５，５’５”−ヘキサ−ｔｅｒｔ−ブチル−ａ，ａ’，ａ”−（メシチレン−２，４，６−トリイル）トリ−ｐ−クレゾール、カルシウムジエチルビス［［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ホスフォネート］、４，６−ビス（オクチルチオメチル）−ｏ−クレゾール、エチレンビス（オキシエチレン）ビス［３−（５−ｔｅｒｔ−ブチル−４−ヒドロキシ−ｍ−トリル）プロピオネート］、ヘキサメチレンビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、１，３，５−トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン、１，３，５−トリス［（４−ｔｅｒｔ−ブチル−３−ヒドロキシ−２，６−キシリル）メチル］−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン、２，６−ｔｅｒｔ−ブチル−４−（４，６−ビス（オクチルチオ）−１，３，５−トリアジン−２−イルアミノ）フェノール、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール、２，２’−メチレンビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−ブチリデンビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−チオビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、３，９−ビス［２−（３−（３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）−プロピオニルオキシ）−１，１−ジメチルエチル］−２，４，８，１０−テトラオキサスピロ（５，５）ウンデカンなどが挙げられる。これらは１種または２種以上含まれていても良い。 Examples of the (D) hindered phenol antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3 -(3,5-di-tert-butyl-4-hydroxyphenylpropionamide), benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1, -Dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ', 3 ", 35,5'5" -hexa-tert-butyl-a, a', a "-(mesitylene-2,4, 6-triyl) tri-p-cresol, calcium diethylbis [[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl) O-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5- Liazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5 -Triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) Phenol, 2,6-di-tert-butyl-4-methylphenol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert- Butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl)- And propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro (5,5) undecane. These may be contained alone or in combination of two or more.
このうち、特に好ましいのは、ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、３，３’，３”，３５，５’５”−ヘキサ−ｔｅｒｔ−ブチル−ａ，ａ’，ａ”−（メシチレン−２，４，６−トリイル）トリ−ｐ−クレゾールなどである。 Of these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,3 ′, 3 ″, 35,5′5 ″ -hexa- is particularly preferable. tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol.
また、上記（Ｅ）イオウ系酸化防止剤としては、イミダゾール系化合物、チアゾール系化合物、スルフェンアミド系化合物、チウラム系化合物、ジチオカルバミン酸塩系化合物、キサントゲン酸塩系化合物などが挙げられる。これらは１種または２種以上含まれていても良い。なお、上記イミダゾール系化合物はイオウ（Ｓ）原子を含んでいる。 Examples of the (E) sulfur antioxidant include imidazole compounds, thiazole compounds, sulfenamide compounds, thiuram compounds, dithiocarbamate compounds, xanthate compounds, and the like. These may be contained alone or in combination of two or more. The imidazole compound contains a sulfur (S) atom.
上記イミダゾール系化合物としては、２−メルカプトベンズイミダゾール、２−メルカプトメチルベンズイミダゾール、４−メルカプトメチルベンズイミダゾール、５−メルカプトメチルベンズイミダゾールなどやこれらの亜鉛塩などが挙げられる。 Examples of the imidazole compound include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, 4-mercaptomethylbenzimidazole, 5-mercaptomethylbenzimidazole, and zinc salts thereof.
また、上記チアゾール系化合物としては、２−メルカプトベンズチアゾール、ジ−２−ベンズチアゾ−ルジスルフィド、２−メルカプトベンズチアゾールの亜鉛塩、２−メルカプトベンズチアゾールのシクロヘキシルアミン塩、２−（Ｎ，Ｎ−ジエチルチオカルバモイルチオ）ベンズチアゾール、２−（４’−モルホリノジチオ）ベンズチアゾールなどが挙げられる。 Examples of the thiazole compound include 2-mercaptobenzthiazole, di-2-benzthiazol disulfide, 2-mercaptobenzthiazole zinc salt, 2-mercaptobenzthiazole cyclohexylamine salt, 2- (N, N- And diethylthiocarbamoylthio) benzthiazole and 2- (4′-morpholinodithio) benzthiazole.
また、上記スルフェンアミド系化合物としては、Ｎ−シクロヘキシル−２−ベンズチアゾールスルフェンアミド、Ｎ−ｔｅｒｔ−ブチル−２−ベンズチアゾールスルフェンアミド、Ｎ−オキシジエチレン−２−ベンズチアゾールスルフェンアミド、Ｎ，Ｎ−ジイソプロピル−２−ベンズチアゾールスルフェンアミド、Ｎ，Ｎ’−ジシクロヘキシル−２−ベンズチアゾールスルフェンアミドなどが挙げられる。 Examples of the sulfenamide-based compound include N-cyclohexyl-2-benzthiazole sulfenamide, N-tert-butyl-2-benzthiazole sulfenamide, N-oxydiethylene-2-benzthiazole sulfenamide, N, N-diisopropyl-2-benzthiazole sulfenamide, N, N′-dicyclohexyl-2-benzthiazole sulfenamide and the like can be mentioned.
また、上記チウラム系化合物としては、テトラメチルチウラムモノスルファイド、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、ジペンタメチレンチウラムテトラスルフィド、テトラキス（２−エチルヘキシル）チウラムジスルフィドなどが挙げられる。 Examples of the thiuram compounds include tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide, tetrakis (2-ethylhexyl) thiuram disulfide and the like.
また、上記ジチオカルバミン酸塩系化合物としては、ジメチルジチオカルバミン酸亜鉛、ジエチルジチオカルバミン酸亜鉛、ジ−ｎ−ブチルジチオカルバミン酸亜鉛、Ｎ−エチル−Ｎ−フェニルジチオカルバミン酸亜鉛、Ｎ−ペンタメチレンジチオカルバミン酸亜鉛、ジベンジルジチオカルバミン酸亜鉛などが挙げられる。 Examples of the dithiocarbamate compound include zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, Examples thereof include zinc benzyldithiocarbamate.
また、上記キサントゲン酸塩系化合物としては、イソプロピルキサントゲン酸ナトリウム、イソプロピルキサントゲン酸亜鉛、ブチルキサントゲン酸亜鉛などが挙げられる。 Examples of the xanthate-based compound include sodium isopropyl xanthate, zinc isopropyl xanthate, and zinc butyl xanthate.
上記イオウ系酸化防止剤のうち、特に好ましいのは、イミダゾール系化合物であり、より具体的には、２−メルカプトベンズイミダゾール、２−メルカプトメチルベンズイミダゾール、２−メルカプトベンズイミダゾールの亜鉛塩などである。 Of the above sulfur antioxidants, imidazole compounds are particularly preferable, and more specifically, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptobenzimidazole, and the like. .
また、上記（Ｆ）金属酸化物としては、亜鉛（Ｚｎ）、アルミニウム（Ａｌ）、マグネシウム（Ｍｇ）、鉛（Ｐｂ）、スズ（Ｓｎ）などの金属の酸化物、前記金属の合金の酸化物などが挙げられる。これらは１種または２種以上含まれていても良い。これらのうち、特に好ましいのは、酸化亜鉛など、亜鉛（Ｚｎ）の酸化物である。 The (F) metal oxide includes zinc (Zn), aluminum (Al), magnesium (Mg), lead (Pb), tin (Sn) and other metal oxides, and metal alloy oxides. Etc. These may be contained alone or in combination of two or more. Among these, an oxide of zinc (Zn) such as zinc oxide is particularly preferable.
また、本組成物では、各種物性を高めるために一般的に用いられる官能基が樹脂成分に対して導入されていても良い。本組成物の基本的特性である難燃性、機械的特性、耐低温性などを妨げるものではないからである。 Moreover, in this composition, the functional group generally used in order to improve various physical properties may be introduce | transduced with respect to the resin component. This is because it does not hinder the basic properties of the composition, such as flame retardancy, mechanical properties, and low temperature resistance.
具体的な官能基としては、カルボン酸基または酸無水基、エポキシ基、ヒドロキシル基、アミノ基、アルケニル環状イミノエーテル基、シラン基などが挙げられる。これらは１種または２種以上導入されていても良い。 Specific examples of the functional group include a carboxylic acid group or an acid anhydride group, an epoxy group, a hydroxyl group, an amino group, an alkenyl cyclic imino ether group, and a silane group. One or more of these may be introduced.
また、本組成物は、必要に応じて、架橋されていても良い。架橋手段としては、過酸化物架橋、シラン架橋、電子線架橋などが挙げられ、特に限定されるものではない。 Moreover, this composition may be bridge | crosslinked as needed. Examples of the crosslinking means include peroxide crosslinking, silane crosslinking, electron beam crosslinking, and the like, and are not particularly limited.
＜本組成物の製造方法＞
上述した本組成物の製造方法は、特に限定されるものではなく、公知の製造方法を用いることができる。例えば、（Ａ）〜（Ｃ）成分と、必要に応じて、他の樹脂成分、他の添加剤などとを任意に配合し、これらを通常のタンブラーなどでドライブレンドしたり、あるいは、バンバリミキサー、加圧ニーダー、混練押出機、二軸押出機、ロールなどの通常の混練機で溶融混練して均一に分散したりすることにより当該組成物を得ることができる。
<Method for producing the present composition>
The manufacturing method of this composition mentioned above is not specifically limited, A well-known manufacturing method can be used. For example, components (A) to (C) and, if necessary, other resin components, other additives and the like are arbitrarily blended, and these are dry blended with a normal tumbler or the like, or a Banbury mixer The composition can be obtained by melt-kneading with a normal kneader such as a pressure kneader, a kneading extruder, a twin-screw extruder, or a roll and uniformly dispersing.
＜本組成物の作用＞
本組成物によれば、上記（Ａ）〜（Ｃ）成分を少なくとも含有しているので、燃焼時にハロゲン系ガスを発生することなく、難燃性、引張伸び、引張強度、耐摩耗性などの機械的特性、耐低温性に優れる。機械的特性、耐低温性に優れるのは、主に、（Ｂ）特定のエチレン系共重合体の特徴により、高充填される（Ｃ）金属水和物による機械的特性などの低下を抑制することができるためである。
<Operation of the composition>
According to the present composition, since it contains at least the above components (A) to (C), such as flame retardancy, tensile elongation, tensile strength, wear resistance, etc. without generating a halogen-based gas during combustion. Excellent mechanical properties and low temperature resistance. The excellent mechanical properties and low temperature resistance are mainly due to (B) the characteristics of the specific ethylene copolymer, and suppress the deterioration of the mechanical properties due to the highly filled (C) metal hydrate. Because it can.
また、上記（Ａ）〜（Ｃ）成分以外に、上記（Ｄ）〜（Ｆ）成分がセットで含有されている場合には、塩化ビニル樹脂などのハロゲンを含有する材料と接触する形態で使用された場合であっても、著しく材料劣化することがなく、長期にわたって十分な耐熱性を有する。 In addition to the components (A) to (C), when the components (D) to (F) are contained as a set, they are used in contact with a halogen-containing material such as a vinyl chloride resin. Even if it is done, it does not deteriorate material remarkably and has sufficient heat resistance for a long time.
この理由は、次のように推測される。すなわち、従来、ゴム系材料では、フェノール系酸化防止剤とイオウ系酸化防止剤を併用することにより、高温使用時の性能において相乗効果が得られることは知られている。しかしながら、本組成物のような、分子構造の全く異なるプロピレン系樹脂をベース樹脂として用いる場合、（Ｄ）ヒンダードフェノール系酸化防止剤と（Ｅ）イオウ系酸化防止剤とを併用しただけでは、ゴム系材料に見られるような相乗効果は全く期待できない。 The reason is estimated as follows. That is, it has been conventionally known that a rubber-based material can provide a synergistic effect in performance when used at a high temperature by using a phenol-based antioxidant and a sulfur-based antioxidant in combination. However, when a propylene resin having a completely different molecular structure, such as the present composition, is used as the base resin, only (D) a hindered phenol antioxidant and (E) a sulfur antioxidant are used in combination. A synergistic effect as seen in rubber materials cannot be expected at all.
ところが、プロピレン系樹脂をベース樹脂として用いた場合であっても、（Ｄ）ヒンダードフェノール系酸化防止剤、（Ｅ）イオウ系酸化防止剤の存在下の下、さらに、（Ｆ）金属酸化物が存在している場合には、明らかに長期にわたって材料が劣化することなく、耐熱性が改善される。 However, even when propylene resin is used as the base resin, (D) in the presence of a hindered phenol antioxidant, (E) sulfur antioxidant, and (F) metal oxide. In the case where is present, the heat resistance is clearly improved without deterioration of the material over a long period of time.
よって詳細なメカニズムまでは不明であるが、本組成物中に（Ｄ）〜（Ｆ）成分をさらに含有させた場合には、（Ｆ）金属酸化物が、（Ｅ）イオウ系酸化防止剤の触媒的な役割を果たすことにより、プロピレン系樹脂中においても、（Ｄ）ヒンダードフェノール系酸化防止剤と（Ｅ）イオウ系酸化防止剤による相乗効果などが生じ、長期耐熱性を改善する効果が発現されるものと推測される。 Therefore, although the detailed mechanism is unknown, when (D)-(F) component is further contained in this composition, (F) metal oxide is (E) sulfur type antioxidant. By playing a catalytic role, there is a synergistic effect of (D) hindered phenolic antioxidant and (E) sulfurous antioxidant in propylene-based resin, which has the effect of improving long-term heat resistance. Presumed to be expressed.
次に、本実施形態に係るノンハロゲン系絶縁電線およびワイヤーハーネスについて説明する。 Next, the non-halogenous insulated wire and wire harness according to this embodiment will be described.
＜ノンハロゲン系絶縁電線＞
本実施形態に係るノンハロゲン系絶縁電線は、上述した本組成物を被覆材の材料として用いたものである。このノンハロゲン系絶縁電線の構成としては、導体の外周に直接、被覆材が被覆されていても良いし、導体とこの被覆材との間に、他の中間部材、例えば、シールド導体や他の絶縁体などが介在されていても良い。
<Non-halogen insulated wires>
The non-halogenous insulated wire according to the present embodiment uses the above-described composition as a covering material. As the configuration of this non-halogen insulated wire, the outer periphery of the conductor may be coated directly with a coating material, or another intermediate member such as a shield conductor or other insulation is provided between the conductor and this coating material. A body or the like may be interposed.
また、導体は、その導体径や導体の材質など、特に限定されるものではなく、用途に応じて適宜定めることができる。また、被覆材の厚さについても、特に制限はなく、導体径などを考慮して適宜定めることができる。 In addition, the conductor is not particularly limited, such as its conductor diameter or conductor material, and can be appropriately determined according to the application. Further, the thickness of the covering material is not particularly limited, and can be appropriately determined in consideration of the conductor diameter and the like.
上記ノンハロゲン系絶縁電線の製造方法としては、バンバリミキサー、加圧ニーダー、ロールなどの通常用いられる混練機を用いて溶融混練した本組成物を、通常の押出成形機などを用いて導体の外周に押出被覆するなどして製造することができ、特に限定されるものではない。 As a method for producing the above halogen-free insulated wire, the present composition melt-kneaded using a commonly used kneader such as a Banbury mixer, a pressure kneader, or a roll is applied to the outer periphery of the conductor using a normal extruder or the like. It can be manufactured by extrusion coating, and is not particularly limited.
＜ワイヤーハーネス＞
本実施形態に係るワイヤーハーネスは、上記ノンハロゲン系絶縁電線単独からなる単独電線束が、ワイヤーハーネス保護材により被覆されて形成されていても良いし、上記ノンハロゲン系絶縁電線と塩化ビニル系絶縁電線とを少なくとも含んでなる混在電線束が、ワイヤーハーネス保護材により被覆されて形成されていても良い。
<Wire harness>
The wire harness according to the present embodiment may be formed by coating a single wire bundle composed of the above non-halogen-based insulated wires alone with a wire harness protection material, and the non-halogen-based insulated wires and the vinyl chloride-based insulated wires. The mixed electric wire bundle which contains at least may be formed by being covered with a wire harness protective material.
ここで、塩化ビニル系絶縁電線とは、塩化ビニル樹脂組成物を被覆材の材料として用いたものである。塩化ビニル樹脂とは、塩化ビニル単量体を主成分とする樹脂をいい、この樹脂は、塩化ビニルの単独重合体であっても良いし、他の単量体との共重合体であっても良い。具体的な塩化ビニル樹脂としては、ポリ塩化ビニル、エチレン塩化ビニル共重合体、プロピレン塩化ビニル共重合体などが挙げられる。 Here, the vinyl chloride-based insulated wire is one using a vinyl chloride resin composition as a covering material. Vinyl chloride resin refers to a resin mainly composed of a vinyl chloride monomer. This resin may be a homopolymer of vinyl chloride or a copolymer with other monomers. Also good. Specific examples of the vinyl chloride resin include polyvinyl chloride, ethylene vinyl chloride copolymer, propylene vinyl chloride copolymer, and the like.
なお、塩化ビニル系絶縁電線の被覆材以外の構成や電線の製造方法については、上述したノンハロゲン系絶縁電線とほぼ同様であるので説明は省略する。 In addition, about the structure other than the covering material of a vinyl chloride type insulated wire, and the manufacturing method of an electric wire, since it is substantially the same as the non-halogen-type insulated wire mentioned above, description is abbreviate | omitted.
また、上記単独電線束とは、上記ノンハロゲン系絶縁電線のみがひとまとまりに束ねられた電線束をいう。一方、混在電線束とは、上記ノンハロゲン系絶縁電線と塩化ビニル系絶縁電線とを少なくとも含み、これら絶縁電線が混在状態でひとまとまりに束ねられた電線束をいう。この際、単独電線束および混在電線束に含まれる各電線の本数は、任意に定めることができ、特に限定されるものではない。 The single electric wire bundle refers to an electric wire bundle in which only the non-halogenous insulated electric wires are bundled together. On the other hand, the mixed electric wire bundle means an electric wire bundle that includes at least the non-halogen-based insulated wires and the vinyl chloride-based insulated wires, and these insulated wires are bundled together in a mixed state. At this time, the number of each electric wire included in the single electric wire bundle and the mixed electric wire bundle can be arbitrarily determined and is not particularly limited.
また、上記ワイヤーハーネス保護材は、複数本の絶縁電線が束ねられた電線束の外周を覆い、内部の電線束を外部環境などから保護する役割を主に有するものである。 Moreover, the said wire harness protective material mainly has a role which covers the outer periphery of the electric wire bundle in which the several insulated electric wire was bundled, and protects an internal electric wire bundle from external environments.
このワイヤーハーネス保護材を構成する基材としては、ノンハロゲン系樹脂組成物、塩化ビニル樹脂組成物または当該塩化ビニル樹脂組成物以外のハロゲン系樹脂組成物などが挙げられる。 As a base material which comprises this wire harness protective material, halogen-type resin compositions other than a halogen-free resin composition, a vinyl chloride resin composition, or the said vinyl chloride resin composition, etc. are mentioned.
ノンハロゲン系樹脂組成物としては、ポリエチレン、ポリプロピレン、プロピレン−エチレン共重合体などのポリオレフィンに、ノンハロゲン系難燃剤などの各種添加剤を添加してなるポリオレフィン系難燃性樹脂組成物や、上述した本組成物などを用いることができる。 Non-halogen-based resin compositions include polyolefin-based flame-retardant resin compositions obtained by adding various additives such as non-halogen-based flame retardants to polyolefins such as polyethylene, polypropylene, and propylene-ethylene copolymers, and the above-described books. A composition or the like can be used.
また、塩化ビニル樹脂組成物としては、上述した塩化ビニル系絶縁電線材料として説明したものを用いることができる。 Moreover, as a vinyl chloride resin composition, what was demonstrated as a vinyl chloride type insulated wire material mentioned above can be used.
また、塩化ビニル樹脂組成物以外のハロゲン系樹脂組成物としては、上記ポリオレフィンにハロゲン系難燃剤などの各種添加剤を添加したものなどが挙げられる。 Moreover, as halogen-type resin compositions other than a vinyl chloride resin composition, what added various additives, such as a halogen-type flame retardant, to the said polyolefin, etc. are mentioned.
また、このワイヤーハーネス保護材としては、テープ状に形成された基材の少なくとも一方の面に粘着剤が塗布されたものや、チューブ状、シート状などに形成された基材を有するものなどを、用途に応じて適宜選択して用いることができる。 Moreover, as this wire harness protective material, the thing with which the adhesive was apply | coated to the at least one surface of the base material formed in tape shape, the thing which has the base material formed in tube shape, sheet shape, etc. , And can be appropriately selected and used depending on the application.
ここで、本実施形態に係るワイヤーハーネスとしては、上述した電線束の種類とワイヤーハーネス保護材の種類により、次のような組み合わせのワイヤーハーネスを例示することができる。 Here, as a wire harness which concerns on this embodiment, the wire harness of the following combinations can be illustrated with the kind of electric wire bundle mentioned above and the kind of wire harness protective material.
すなわち、本実施形態に係るワイヤーハーネスは、ノンハロゲン系絶縁電線単独からなる単独電線束を塩化ビニル系ワイヤーハーネス保護材により被覆したワイヤーハーネス、ノンハロゲン系絶縁電線単独からなる単独電線束をノンハロゲン系ワイヤーハーネス保護材により被覆したワイヤーハーネス、ノンハロゲン系絶縁電線単独からなる単独電線束をハロゲン系ワイヤーハーネス保護材により被覆したワイヤーハーネス、ノンハロゲン系絶縁電線と塩化ビニル系絶縁電線とを少なくとも含んでなる混在電線束を塩化ビニル系ワイヤーハーネス保護材により被覆したワイヤーハーネス、ノンハロゲン系絶縁電線と塩化ビニル系絶縁電線とを少なくとも含んでなる混在電線束をノンハロゲン系ワイヤーハーネス保護材により被覆したワイヤーハーネス、ノンハロゲン系絶縁電線と塩化ビニル系絶縁電線とを少なくとも含んでなる混在電線束をハロゲン系ワイヤーハーネス保護材により被覆したワイヤーハーネスなどを例示することができる。 That is, the wire harness according to the present embodiment is a wire harness in which a single wire bundle made of a single halogen-free insulated wire is covered with a vinyl chloride wire harness protective material, and a single wire bundle made up of a single halogen-free insulated wire is a non-halogen wire harness. Wire harness covered with a protective material, single wire bundle consisting of a single halogen-free insulated wire alone, coated with a halogen-based wire harness protective material, a mixed wire bundle comprising at least a non-halogen-based insulated wire and a vinyl chloride-based insulated wire A wire harness coated with a vinyl chloride wire harness protective material, and a mixed wire bundle comprising at least a non-halogen insulated wire and a vinyl chloride insulated wire covered with a non-halogen wire harness protective material Harness, and the like can be exemplified non-halogenous insulated wire and the wiring harness a mixed wire bundle comprising at least a vinyl chloride insulated wires were coated with halogen-wiring-harness protective material.
＜ノンハロゲン系絶縁電線およびワイヤーハーネスの作用＞
上記ノンハロゲン系絶縁電線、このノンハロゲン系絶縁電線を電線束中に含んだワイヤーハーネスによれば、上記本組成物を絶縁電線の被覆材としているので、難燃性、引張伸び、引張強度、耐摩耗性などの機械的特性、耐低温性に優れる。
<Operation of non-halogen insulated wires and wire harness>
According to the non-halogenous insulated wire and the wire harness including the non-halogenated insulated wire in the wire bundle, since the composition is used as a covering material for the insulated wire, flame retardancy, tensile elongation, tensile strength, abrasion resistance Excellent mechanical properties such as heat resistance and low temperature resistance.
特に、上記本組成物が上記（Ｄ）〜（Ｆ）成分を含有している場合には、ノンハロゲン系絶縁電線が、電線束中の塩化ビニル系絶縁電線、あるいは、電線束の外周を覆う塩化ビニル系ワイヤーハーネス保護材や当該塩化ビニル系ワイヤーハーネス保護材以外のハロゲン系ワイヤーハーネス保護材などと接触する形態で使用された場合でも、被覆材が著しく劣化することなく、長期にわたって十分な耐熱性が発揮される。 In particular, when the composition contains the components (D) to (F), the halogen-free insulated wire is a chloride chloride covering the outer periphery of the vinyl chloride insulated wire in the wire bundle or the wire bundle. Even when used in contact with vinyl-based wire harness protective materials or halogen-based wire harness protective materials other than the vinyl chloride-based wire harness protective materials, the coating material does not deteriorate significantly, and it has sufficient heat resistance over a long period of time. Is demonstrated.
そのため、上記ノンハロゲン系絶縁電線およびワイヤーハーネスを、自動車のエンジンルームなど、絶えず高温環境下に曝される部位などに使用すれば、安価なコストで、長期にわたり高い信頼性を確保することができる。 Therefore, if the non-halogenous insulated wire and the wire harness are used in a part that is constantly exposed to a high temperature environment such as an engine room of an automobile, high reliability can be secured for a long time at a low cost.
以上、本実施形態に係る難燃性樹脂組成物ならびにこれを用いた絶縁電線およびワイヤーハーネスについて説明したが、上記実施形態は本発明を何ら限定するものではなく、その趣旨を逸脱しない範囲内で種々の変形・改良が可能なものである。 As described above, the flame-retardant resin composition according to the present embodiment and the insulated wire and the wire harness using the same have been described. However, the embodiment does not limit the present invention at all, and the scope of the invention is not deviated. Various modifications and improvements are possible.
以下に本発明を実施例により具体的に説明するが、本発明はこれらによって限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
（供試材料および製造元など）
本実施例において使用した供試材料を製造元、商品名、物性値などとともに示す。
(Test material and manufacturer)
The test materials used in this example are shown together with the manufacturer, product name, physical property values, and the like.
（Ａ）プロピレン系樹脂：
（ａ１）ポリプロピレン［日本ポリプロ（株）製、商品名「ノバテックＰＰ ＥＣ−７」、ＭＦＲ＝１．５ｇ／１０分］
（ａ２）ポリプロピレン［日本ポリプロ（株）製、商品名「ノバテックＰＰ ＢＣ６ＤＲ」、ＭＦＲ＝２．５ｇ／１０分］
（ａ３）ポリプロピレン［日本ポリプロ（株）製、商品名「ノバテックＰＰ ＥＣ−９」、ＭＦＲ＝０．５ｇ／１０分］
(A) Propylene resin:
(A1) Polypropylene [made by Nippon Polypro Co., Ltd., trade name “NOVATEC PP EC-7”, MFR = 1.5 g / 10 min]
(A2) Polypropylene [made by Nippon Polypro Co., Ltd., trade name “Novatech PP BC6DR”, MFR = 2.5 g / 10 min]
(A3) Polypropylene [manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC PP EC-9”, MFR = 0.5 g / 10 min]
（Ｂ）メタロセン系触媒の存在下で重合されたエチレン系重合体
（ｂ１）メタロセンポリエチレン［日本ポリプロ（株）製、商品名「カーネル ＫＦ２８３」、密度０．９２１ｇ／ｃｍ３］
（ｂ２）メタロセンポリエチレン［日本ポリプロ（株）製、商品名「カーネル ＫＳ２４０Ｔ」、密度０．８８０ｇ／ｃｍ３］
（ｂ３）メタロセンポリエチレン［三井化学（株）製、商品名「エボリュー ＳＰ１５２０」、密度０．９１３ｇ／ｃｍ３］
（ｂ＊１）直鎖状低密度ポリエチレン［日本ポリエチレン（株）製、商品名「ノバテック ＵＥ３２０」、密度０．９２２ｇ／ｃｍ３］
なお、（ｂ＊１）は、メタロセン系触媒の存在下で重合されたものでないため、本組成物における（Ｂ）成分ではないが、比較するうえでの便宜上、（Ｂ）成分の欄に記載している。
(B) Ethylene polymer polymerized in the presence of a metallocene catalyst (b1) Metallocene polyethylene [manufactured by Nippon Polypro Co., Ltd., trade name “Kernel KF283”, density 0.921 g / cm 3 ]
(B2) Metallocene polyethylene [manufactured by Nippon Polypro Co., Ltd., trade name “Kernel KS240T”, density 0.880 g / cm 3 ]
(B3) Metallocene polyethylene [manufactured by Mitsui Chemicals, trade name “Evolue SP1520”, density 0.913 g / cm 3 ]
(B * 1) Linear low-density polyethylene [manufactured by Nippon Polyethylene Co., Ltd., trade name “NOVATEC UE320”, density 0.922 g / cm 3 ]
Note that (b * 1) is not polymerized in the presence of a metallocene-based catalyst, and thus is not the component (B) in the present composition, but is described in the column of the component (B) for convenience in comparison. is doing.
（Ｃ）金属水和物：
（ｃ１）水酸化マグネシウム［神島化学工業（株）製、商品名「マグシーズＷ−Ｘ３」、平均粒径Ｄ５０＝２．５μｍ］
（ｃ２）水酸化マグネシウム［神島化学工業（株）製、商品名「マグシーズＷ−Ｈ４」、平均粒径Ｄ５０＝３．５μｍ］
(C) Metal hydrate:
(C1) Magnesium hydroxide [manufactured by Kamishima Chemical Co., Ltd., trade name “Magsees W-X3”, average particle size D50 = 2.5 μm]
(C2) Magnesium hydroxide [manufactured by Kamishima Chemical Co., Ltd., trade name “Magsees W-H4”, average particle size D50 = 3.5 μm]
（Ｄ）ヒンダードフェノール系酸化防止剤：
（ｄ１）ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］［チバスペシャルティケミカルズ（株）製、商品名「イルガノックス１０１０」］
（ｄ２）１，３，５−トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン［チバスペシャルティケミカルズ（株）製、商品名「イルガノックス３１１４」］
（ｄ３）オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート［チバスペシャルティケミカルズ（株）製、商品名「イルガノックス１０７６」］
（ｄ４）３，９−ビス［２−（３−（３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）−プロピオニルオキシ）−１，１−ジメチルエチル］−２，４，８，１０−テトラオキサスピロ（５，５）ウンデカン［旭電化工業（株）製、商品名「アデカＡＯ−８０」］
(D) Hindered phenolic antioxidant:
(D1) Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] [trade name “Irganox 1010” manufactured by Ciba Specialty Chemicals Co., Ltd.]
(D2) 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione [ Product name “Irganox 3114” manufactured by Ciba Specialty Chemicals Co., Ltd.]
(D3) Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate [manufactured by Ciba Specialty Chemicals Co., Ltd., trade name “Irganox 1076”]
(D4) 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro (5,5) undecane [Asahi Denka Kogyo Co., Ltd., trade name "ADEKA AO-80"]
（Ｅ）イオウ系酸化防止剤：
（ｅ１）２−メルカプトベンズイミダゾール［大内新興化学工業（株）製、商品名「ノクラックＭＢ」］
（ｅ２）２−メルカプトメチルベンズイミダゾール［大内新興化学工業（株）製、商品名「ノクラックＭＭＢ」］
（ｅ３）２−メルカプトベンズイミダゾールの亜鉛塩［大内新興化学工業（株）製、商品名「ノクラックＭＢＺ」］
(E) Sulfur-based antioxidant:
(E1) 2-mercaptobenzimidazole [Ouchi Shinsei Chemical Co., Ltd., trade name “NOCRACK MB”]
(E2) 2-Mercaptomethylbenzimidazole [Ouchi Shinsei Chemical Co., Ltd., trade name “NOCRACK MMB”]
(E3) Zinc salt of 2-mercaptobenzimidazole [Ouchi Shinsei Chemical Co., Ltd., trade name “NOCRACK MBZ”]
（Ｆ）金属酸化物：
（ｆ１）酸化亜鉛（亜鉛華）［ハクスイテック（株）製、商品名「酸化亜鉛２種」］
(F) Metal oxide:
(F1) Zinc oxide (zinc flower) [manufactured by Hakusui Tech Co., Ltd., trade name “Zinc oxide 2 types”]
（ｘ１）スチレン−エチレン／ブチレン−スチレンブロック共重合体（ＳＥＢＳ）［クレイトンポリマージャパン（株）製、商品名「ＦＧ１９０１Ｘ」］
（ｘ２）エチレン−酢酸ビニル共重合体（ＥＶＡ）［三井・デュポンポリケミカル（株）製、商品名「ＨＰＲ ＶＲ１０３」］
（ｘ３）スチレン−エチレン／ブチレン−スチレンブロック共重合体（ＳＥＢＳ）［旭化成ケミカルズ（株）製、商品名「タフテックＨ１０５３」］
（ｘ４）スチレン−エチレン／ブチレン−スチレンブロック共重合体（ＳＥＢＳ）［旭化成ケミカルズ（株）製、商品名「タフテックＭ１９１３」］
（ｘ５）スチレン−エチレン／ブチレン−スチレンブロック共重合体（ＳＥＢＳ）［旭化成ケミカルズ（株）製、商品名「タフテックＨ１０４１」］
（ｙ１）２’，３−ビス［［３−［３、５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル］プロピオニル］］プロピオノヒドラジド［チバスペシャルティケミカルズ（株）製、商品名「イルガノックスＭＤ１０２４」］
なお、（ｘ１）〜（ｘ５）は、ポリオレフィンまたはゴムであり、（ｙ１）は、金属不活性化剤である。
(X1) Styrene-ethylene / butylene-styrene block copolymer (SEBS) [manufactured by Kraton Polymer Japan Co., Ltd., trade name “FG1901X”]
(X2) Ethylene-vinyl acetate copolymer (EVA) [Mitsui / DuPont Polychemical Co., Ltd., trade name “HPR VR103”]
(X3) Styrene-ethylene / butylene-styrene block copolymer (SEBS) [Asahi Kasei Chemicals Co., Ltd., trade name "Tuftec H1053"]
(X4) Styrene-ethylene / butylene-styrene block copolymer (SEBS) [trade name “Tuftec M1913” manufactured by Asahi Kasei Chemicals Corporation]
(X5) Styrene-ethylene / butylene-styrene block copolymer (SEBS) [manufactured by Asahi Kasei Chemicals Corporation, trade name “Tuftec H1041”]
(Y1) 2 ′, 3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide [Ciba Specialty Chemicals Co., Ltd., trade name “Irganox MD1024” ]]
(X1) to (x5) are polyolefin or rubber, and (y1) is a metal deactivator.
塩化ビニル系絶縁電線およびワイヤーハーネス保護材の材料：
ポリ塩化ビニル樹脂［東ソー（株）製、商品名「４０００Ｍ３」、重合度１３００］
ジイソノニルフタレート（ＤＩＮＰ）［大日本インキ化学（株）製、商品名「モノサイザーＤＩＮＰ」］
ジオクチルフタレート（ＤＯＰ）［大日本インキ化学（株）製、商品名「モノサイザーＤＯＰ」］
重質炭酸カルシウム［丸尾カルシウム（株）製、商品名「スーパー＃１７００」］
カルシウム亜鉛系安定剤［堺化学（株）製、商品名「ＯＷ−８００」］
スチレンブタジエンゴム［ＪＳＲ（株）製、商品名「１０１３Ｎ」］
天然ゴム［ＲＳＳ２号］
酸化亜鉛［ハクスイテック（株）製、商品名「酸化亜鉛２種」］
ロジン系樹脂［荒川化学工業（株）製、商品名「エステルガムＨ」］
Materials for protecting vinyl chloride insulated wires and wire harness:
Polyvinyl chloride resin [manufactured by Tosoh Corporation, trade name “4000M3”, polymerization degree 1300]
Diisononyl phthalate (DINP) [Dainippon Ink Chemical Co., Ltd., trade name "Monocizer DINP"]
Dioctyl phthalate (DOP) [Dainippon Ink Chemical Co., Ltd., trade name "Monocizer DOP"]
Heavy calcium carbonate [Maruo Calcium Co., Ltd., trade name "Super # 1700"]
Calcium zinc stabilizer [made by Sakai Chemical Industry Co., Ltd., trade name “OW-800”]
Styrene butadiene rubber [trade name “1013N” manufactured by JSR Corporation]
Natural rubber [RSS2]
Zinc oxide [made by Hakusuitec Co., Ltd., trade name "Zinc oxide 2 types"]
Rosin resin [Arakawa Chemical Industry Co., Ltd., trade name "Ester Gum H"]
（組成物および絶縁電線の作製）
初めに、二軸混練機を用いて、後述の表に示す各成分を混合温度２３０℃にて混合した後、ペレタイザーにてペレット状に成形して本実施例に係る組成物と比較例に係る組成物を得た。次いで、得られた各組成物を、５０ｍｍ押出機により、軟銅線を７本撚り合わせた軟銅撚線の導体（断面積０．５ｍｍ２）の外周に０．２０ｍｍ厚で押出被覆し、本実施例に係るノンハロゲン系絶縁電線および比較例に係るノンハロゲン系絶縁電線を作製した。
(Production of composition and insulated wire)
First, using a twin-screw kneader, the components shown in the table below are mixed at a mixing temperature of 230 ° C., then formed into pellets with a pelletizer, and the composition according to this example and the comparative example A composition was obtained. Next, each of the obtained compositions was extrusion-coated at a thickness of 0.20 mm on the outer periphery of an annealed copper stranded wire conductor (cross-sectional area 0.5 mm 2 ) obtained by twisting 7 anodized copper wires with a 50 mm extruder. Non-halogen-based insulated wires according to examples and non-halogen-based insulated wires according to comparative examples were produced.
次いで、ポリ塩化ビニル樹脂（重合度１３００）１００重量部に対して、可塑剤としてＤＩＮＰ（ジイソノニルフタレート）４０重量部、充填剤として重質炭酸カルシウム２０重量部、安定剤としてカルシウム亜鉛系安定剤５重量部をオープンロールを用いて１８０℃で混合し、ペレタイザーにてペレット状に成形したポリ塩化ビニル樹脂コンパウンドを、５０ｍｍ押出機により、軟銅線を７本撚り合わせた軟銅撚線の導体（断面積０．５ｍｍ２）の外周に０．３０ｍｍ厚で押出被覆し、塩化ビニル系絶縁電線を作製した。 Subsequently, for 100 parts by weight of the polyvinyl chloride resin (degree of polymerization 1300), 40 parts by weight of DINP (diisononyl phthalate) as a plasticizer, 20 parts by weight of heavy calcium carbonate as a filler, and calcium zinc-based stabilizer 5 as a stabilizer Conductor (cross-sectional area) of an annealed copper strand in which 7 parts of an annealed copper wire are twisted by a 50 mm extruder using a polyvinyl chloride resin compound that is mixed at 180 ° C by weight using an open roll and formed into a pellet by a pelletizer. The outer periphery of 0.5 mm 2 ) was extrusion coated with a thickness of 0.30 mm to produce a vinyl chloride-based insulated wire.
（ワイヤーハーネスの作製）
次に、得られた本実施例に係るノンハロゲン系絶縁電線、比較例に係るノンハロゲン系絶縁電線および塩化ビニル系絶縁電線を用いて、ワイヤーハーネスを作製した。すなわち、任意の数のノンハロゲン系絶縁電線と、任意の数の塩化ビニル系絶縁電線を混在させた混在電線束を作製し、その外周に、ワイヤーハーネス保護材として、粘着剤付テープを巻き付けることによりワイヤーハーネスを作製した。
(Production of wire harness)
Next, a wire harness was produced using the obtained non-halogenous insulated wire according to this example, the non-halogenated insulated wire according to the comparative example, and the vinyl chloride-based insulated wire. That is, by creating a mixed wire bundle in which an arbitrary number of non-halogenous insulated wires and an arbitrary number of vinyl chloride insulated wires are mixed, and by wrapping adhesive tape as a wire harness protective material around the outer periphery A wire harness was produced.
この際、粘着剤付テープは、ポリ塩化ビニル樹脂コンパウンドからなる基材の片側表面全体に、粘着剤として０．０２ｍｍ厚の粘着層を設けたものであり、当該テープの全体厚さは０．１３ｍｍとした。ここで、粘着剤付テープ材料として使用したポリ塩化ビニル樹脂コンパウンドは、ポリ塩化ビニル樹脂（重合度１３００）１００重量部に対して、可塑剤としてＤＯＰ（ジオクチルフタレート）６０重量部、充填剤として重質炭酸カルシウム２０重量部、安定剤としてカルシウム亜鉛系安定剤５重量部を配合したものを用いた。また、粘着剤には、スチレンブタジエンゴム７０重量部に対して、天然ゴム３０重量部と、酸化亜鉛２０重量部、ロジン系樹脂８０重量部を配合したものを用いた。 In this case, the pressure-sensitive adhesive tape is obtained by providing a 0.02 mm thick pressure-sensitive adhesive layer as a pressure-sensitive adhesive on the entire surface of one side of a base material made of a polyvinyl chloride resin compound. It was set to 13 mm. Here, the polyvinyl chloride resin compound used as a tape material with an adhesive is 60 parts by weight of DOP (dioctyl phthalate) as a plasticizer and heavy as a filler with respect to 100 parts by weight of the polyvinyl chloride resin (degree of polymerization 1300). 20 parts by weight of calcium carbonate and 5 parts by weight of calcium zinc stabilizer as a stabilizer were used. The pressure-sensitive adhesive used was a blend of 30 parts by weight of natural rubber, 20 parts by weight of zinc oxide, and 80 parts by weight of rosin resin with respect to 70 parts by weight of styrene butadiene rubber.
（試験方法）
以上のように作製した各絶縁電線について、難燃性試験、引張伸び試験、引張強度試験、耐摩耗性試験、耐低温性試験を行った。また、各絶縁電線の耐熱性を調べるため、耐熱性Ａ試験、耐熱性Ｂ試験を行った。以下に各試験方法および評価方法について説明する。
(Test method)
Each insulated wire produced as described above was subjected to a flame retardancy test, a tensile elongation test, a tensile strength test, an abrasion resistance test, and a low temperature resistance test. Moreover, in order to investigate the heat resistance of each insulated wire, the heat resistance A test and the heat resistance B test were done. Each test method and evaluation method will be described below.
（難燃性試験）
ＪＡＳＯ Ｄ６１１−９４に準拠して行った。すなわち、絶縁電線を３００ｍｍの長さに切り出して試験片とした。次いで、各試験片を鉄製試験箱に入れて水平に支持し、口径１０ｍｍのブンゼンバーナーを用いて還元炎の先端を試験片中央部の下側から３０秒以内で燃焼するまで当て、炎を静かに取り去った後の残炎時間を測定した。この残炎時間が１５秒以内のものを合格とし、１５秒を超えるものを不合格とした。
(Flame retardancy test)
This was performed in accordance with JASO D611-94. That is, the insulated wire was cut into a length of 300 mm to obtain a test piece. Next, each test piece is put in an iron test box and supported horizontally, and the tip of the reducing flame is applied using a Bunsen burner having a diameter of 10 mm until it burns within 30 seconds from the lower side of the center of the test piece. The afterflame time after removal was measured. Those having a residual flame time of 15 seconds or less were accepted and those exceeding 15 seconds were rejected.
（引張伸び試験、引張強度試験）
ＪＡＳＯ Ｄ６１１−９４に準拠して行った。すなわち、絶縁電線を１５０ｍｍの長さに切り出し、導体を取り除いて被覆材のみの管状試験片とした後、その中央部に５０ｍｍの間隔で標線を記した。次いで、２３±５℃の室温下にて試験片の両端を引張試験機のチャックに取り付けた後、引っ張り速度２００ｍｍ／分で引っ張り、試験片の破断時の荷重および標線間の距離を測定した。引張伸びについては１２５％以上のものを合格とし、１２５％未満のものを不合格とした。一方、引張強度については１５．７ＭＰａ以上のものを合格とし、１５．７ＭＰａ未満のものを不合格とした。
(Tensile elongation test, tensile strength test)
This was performed in accordance with JASO D611-94. That is, the insulated wire was cut out to a length of 150 mm, the conductor was removed to form a tubular test piece made of only a covering material, and then marked lines were drawn at intervals of 50 mm in the center. Next, after both ends of the test piece were attached to the chuck of a tensile tester at room temperature of 23 ± 5 ° C., the test piece was pulled at a pulling speed of 200 mm / min, and the load at the time of breaking the test piece and the distance between the marked lines were measured. . About tensile elongation, the thing of 125% or more was set as the pass, and the thing less than 125% was made unsuccessful. On the other hand, the tensile strength of 15.7 MPa or more was accepted, and the tensile strength of less than 15.7 MPa was rejected.
（耐摩耗性試験）
ＪＡＳＯ Ｄ６１１−９４に準拠し、ブレード往復法により行った。すなわち、絶縁電線を７５０ｍｍの長さに切り出して試験片とした。次いで、２５℃の室温下にて、台上に固定した試験片の被覆材の表面を軸方向に１０ｍｍの長さにわたってブレードを往復させ、被覆材の摩耗によってブレードが導体に接触するまでの往復回数を測定した。この際、ブレードにかける荷重は７Ｎとし、ブレードは毎分５０回の速度で往復させた。次いで、試験片を１００ｍｍ移動させて、時計方向に９０℃回転させ、上記の測定を繰り返した。この測定を同一試験片について合計３回行い、最低値が１５０回以上のものを合格とし、１５０回未満のものを不合格とした。
(Abrasion resistance test)
In accordance with JASO D611-94, the blade reciprocation method was used. That is, the insulated wire was cut into a length of 750 mm to obtain a test piece. Next, at room temperature of 25 ° C., the blade is reciprocated over a length of 10 mm in the axial direction on the surface of the coating material of the test piece fixed on the table, and the reciprocation until the blade contacts the conductor due to wear of the coating material. The number of times was measured. At this time, the load applied to the blade was 7 N, and the blade was reciprocated at a speed of 50 times per minute. Next, the test piece was moved 100 mm, rotated 90 ° clockwise, and the above measurement was repeated. This measurement was performed a total of 3 times for the same test piece, and those having a minimum value of 150 times or more were accepted and those less than 150 were rejected.
（耐低温性試験）
各絶縁電線１本を−４０℃±２℃で４時間冷却した後、自己径巻き付けにより被覆材に亀裂が生じないものを合格とし、亀裂が生じたものを不合格とした。
(Low temperature resistance test)
After each insulated wire was cooled at −40 ° C. ± 2 ° C. for 4 hours, a coating material that did not crack due to self-diameter winding was accepted, and a cracked material was rejected.
（耐熱性Ａ試験）
各絶縁電線１本を１５０℃で７２時間熱老化させた後、自己径巻き付けにより被覆材に亀裂が生じず、導体が露出しないものを合格とし、導体が露出したものを不合格とした。なお、後述する表では、合格したもののうち、被覆材の変色が比較的小さかったものを◎、変色が比較的大きかったものを○で表示している。
(Heat resistance A test)
After heat aging each insulated wire at 150 ° C. for 72 hours, the coating material was not cracked due to self-diameter winding and the conductor was not exposed. In the table which will be described later, among those that have passed, those whose discoloration of the coating material was relatively small are indicated by ◎, and those whose discoloration was relatively large are indicated by ◯.
（耐熱性Ｂ試験）
ワイヤーハーネス、すなわち、ノンハロゲン系絶縁電線と塩化ビニル系絶縁電線をそれぞれ任意の数にて混在させた混在電線束の外周に、塩化ビニル系粘着剤付テープを巻き付けたものを１５０℃で７２時間熱老化させた後、混在電線束中より任意のノンハロゲン系絶縁電線を１本取り出し、自己径巻き付けにより被覆材から導体が露出しないものを合格とし、導体が露出したものを不合格とした。なお、後述する表では、合格したもののうち、被覆材の変色が比較的小さかったものを◎、変色が比較的大きかったものを○で表示するとともに、被覆材の表面にひび割れ（導体は露出していない）が生じたものを△で表示している。
(Heat resistance B test)
Heat a wire harness, that is, a vinyl chloride adhesive tape wrapped around the outer circumference of a mixed wire bundle in which an arbitrary number of non-halogen insulated wires and vinyl chloride insulated wires are mixed together at 150 ° C for 72 hours. After aging, one arbitrary non-halogen-based insulated wire was taken out from the mixed wire bundle, and the case where the conductor was not exposed from the coating material by self-diameter winding was regarded as acceptable, and the case where the conductor was exposed was regarded as unacceptable. In addition, in the table to be described later, among those that passed, ◎ indicates that the discoloration of the coating material was relatively small, and ○ indicates that the discoloration was relatively large, and cracked on the surface of the coating material (the conductor is exposed). ) Is indicated by Δ.
以下の表１〜５に組成物の成分配合および評価結果を示す。 Tables 1 to 5 below show the composition of the composition and the evaluation results.
表１によれば、（Ｂ）特定のエチレン系重合体の配合割合が、本発明に規定される配合割合にない比較例１１および比較例１２に係る絶縁電線は、引張伸びまたは引張強度もしくは耐摩耗性に劣ることが分かる。また、（Ｂ）成分として、同じエチレン系重合体であっても、メタロセン系触媒の存在下で重合されていない直鎖状低密度ポリエチレンを用いた比較例１３に係る絶縁電線は、引張伸び、耐低温性に劣ることが分かる。 According to Table 1, the insulated wire according to Comparative Example 11 and Comparative Example 12 in which the blending ratio of the specific ethylene polymer (B) is not in the blending ratio defined in the present invention is the tensile elongation or tensile strength or resistance. It turns out that it is inferior to abrasion. Further, as the component (B), the insulated wire according to Comparative Example 13 using the linear low density polyethylene that is not polymerized in the presence of the metallocene catalyst, even in the same ethylene polymer, has a tensile elongation, It turns out that it is inferior to low temperature resistance.
また、表２によれば、（Ｃ）金属水和物が、本発明に規定される配合割合にない比較例２１および比較例２２に係る絶縁電線は、難燃性や、引張伸び、引張強度、耐摩耗性、耐低温性に劣ることが分かる。 Further, according to Table 2, the insulated wires according to Comparative Example 21 and Comparative Example 22 in which (C) the metal hydrate is not in the blending ratio defined in the present invention are flame retardant, tensile elongation, and tensile strength. It can be seen that the wear resistance and the low temperature resistance are inferior.
これらに対し、表１〜５によれば、本発明の一実施例に係る難燃性樹脂組成物を用いた各絶縁電線は、いずれも、難燃性や、引張伸び、引張強度、耐摩耗性などの機械的特性、耐低温性に優れていることが分かる。 On the other hand, according to Tables 1 to 5, each insulated wire using the flame retardant resin composition according to one embodiment of the present invention is flame retardant, tensile elongation, tensile strength, wear resistance. It can be seen that it has excellent mechanical properties such as heat resistance and low temperature resistance.
加えて、表１〜５によれば、（Ｄ）ヒンダードフェノール系酸化防止剤、（Ｅ）イオウ系酸化防止剤、（Ｆ）金属酸化物を上述した配合割合の範囲内で組み合わせて用いた場合、（Ｄ）〜（Ｆ）成分の配合割合が、上述した上限値または下限値に近くなると、耐熱性が低下する傾向が見られるものの、上述した好ましい範囲内であれば、耐熱性に優れていることが分かる。 In addition, according to Tables 1 to 5, (D) a hindered phenol-based antioxidant, (E) a sulfur-based antioxidant, and (F) a metal oxide were used in combination within the above-described blending ratio. In this case, when the blending ratio of the components (D) to (F) is close to the above-described upper limit value or lower limit value, although the heat resistance tends to decrease, the heat resistance is excellent as long as it is within the above-described preferable range. I understand that
したがって、被覆材を形成する組成物中に、さらに（Ｄ）〜（Ｆ）成分をセットで配合した場合には、塩化ビニル樹脂などのハロゲンを含有する材料と接触する形態で使用された場合であっても被覆材が劣化することがなく、長期にわたって優れた耐熱性を有することが確認できた。 Therefore, when the components (D) to (F) are further blended as a set in the composition for forming the coating material, the composition is used in contact with a halogen-containing material such as a vinyl chloride resin. Even if it exists, it has confirmed that it had the heat resistance excellent over the long term, without a coating material deteriorating.
Claims (8)
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|---|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09204818A (en) * | 1996-01-26 | 1997-08-05 | Mitsubishi Cable Ind Ltd | Electrical insulation members, power cables and connection members for power cables |
| JPH1143610A (en) * | 1997-07-28 | 1999-02-16 | Fujikura Ltd | High thermal conductive insulating material for super low temperature and superconducting cable |
| JP2003192846A (en) * | 2001-12-26 | 2003-07-09 | Furukawa Electric Co Ltd:The | Insulated resin composition having excellent heat resistance and weather resistance and insulated electric wire |
| JP2005015760A (en) * | 2003-06-03 | 2005-01-20 | Auto Network Gijutsu Kenkyusho:Kk | Non-crosslinked flame retardant resin composition and insulated wire and wire harness using the same |
-
2005
- 2005-06-15 JP JP2005174952A patent/JP2006348136A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09204818A (en) * | 1996-01-26 | 1997-08-05 | Mitsubishi Cable Ind Ltd | Electrical insulation members, power cables and connection members for power cables |
| JPH1143610A (en) * | 1997-07-28 | 1999-02-16 | Fujikura Ltd | High thermal conductive insulating material for super low temperature and superconducting cable |
| JP2003192846A (en) * | 2001-12-26 | 2003-07-09 | Furukawa Electric Co Ltd:The | Insulated resin composition having excellent heat resistance and weather resistance and insulated electric wire |
| JP2005015760A (en) * | 2003-06-03 | 2005-01-20 | Auto Network Gijutsu Kenkyusho:Kk | Non-crosslinked flame retardant resin composition and insulated wire and wire harness using the same |
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| US20110067921A1 (en) * | 2008-06-27 | 2011-03-24 | Autonetworks Technologies, Ltd. | Flame-retardant composition, covered electric wire, and wiring harness |
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