JP5563771B2 - Fluorine-containing elastomer covered wire - Google Patents
Fluorine-containing elastomer covered wire Download PDFInfo
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- JP5563771B2 JP5563771B2 JP2009028630A JP2009028630A JP5563771B2 JP 5563771 B2 JP5563771 B2 JP 5563771B2 JP 2009028630 A JP2009028630 A JP 2009028630A JP 2009028630 A JP2009028630 A JP 2009028630A JP 5563771 B2 JP5563771 B2 JP 5563771B2
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- tetrafluoroethylene
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- 229920001971 elastomer Polymers 0.000 title claims description 17
- 229910052731 fluorine Inorganic materials 0.000 title claims description 17
- 239000011737 fluorine Substances 0.000 title claims description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 16
- 239000000806 elastomer Substances 0.000 title claims description 16
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 claims description 16
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 14
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 13
- 239000011247 coating layer Substances 0.000 claims description 12
- 239000004020 conductor Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 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 claims description 5
- 239000003063 flame retardant Substances 0.000 claims description 5
- 238000010894 electron beam technology Methods 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 230000003679 aging effect Effects 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 8
- 230000032683 aging Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- -1 perfluoroalkyl vinyl ether Chemical compound 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Description
本発明は、導体外周の被覆層として、テトラフルオロエチレン−プロピレン系共重合体とエチレン−テトラフルオロエチレン系共重合体からなるブレンドポリマを用いた含ふっ素エラストマ被覆電線に関するものである。 The present invention relates to a fluorine-containing elastomer-coated electric wire using a blend polymer comprising a tetrafluoroethylene-propylene copolymer and an ethylene-tetrafluoroethylene copolymer as a coating layer on the outer periphery of a conductor.
従来から、高耐熱性および可とう性が要求される電線の被覆材料として、テトラフルオロエチレン−プロピレン系共重合体が用いられている。テトラフルオロエチレン−プロピレン系共重合体は、可とう性、熱安定性、電気絶縁性、耐熱性、耐油性、耐薬品性、および難燃性に優れ、かつ、架橋可能な含ふっ素エラストマ共重合体である。 Conventionally, tetrafluoroethylene-propylene copolymers have been used as coating materials for electric wires that require high heat resistance and flexibility. Tetrafluoroethylene-propylene copolymer has excellent flexibility, thermal stability, electrical insulation, heat resistance, oil resistance, chemical resistance, and flame resistance, and is a crosslinkable fluorine-containing elastomer copolymer. It is a coalescence.
一方、エチレン−テトラフルオロエチレン系共重合体は、結晶性のふっ素樹脂であり、例えば熱器具用の配線に用いる場合には、テトラフルオロエチレン−プロピレン系共重合体に適宜ブレンドして耐カットスルー性を向上する手法が公知である。 On the other hand, the ethylene-tetrafluoroethylene copolymer is a crystalline fluororesin. For example, when used for a wiring for a heat appliance, the ethylene-tetrafluoroethylene copolymer is appropriately blended with the tetrafluoroethylene-propylene copolymer and cut-through resistant. Techniques for improving the properties are known.
このようなブレンドポリマーを導体上または電線外周に被覆し、電離性放射線等を照射して架橋することによって、含ふっ素エラストマ被覆電線を得ていた。 Such a blended polymer is coated on a conductor or the outer periphery of a wire, and irradiated with ionizing radiation or the like to crosslink to obtain a fluorine-containing elastomer-coated wire.
しかしながら、機器用電線のように小サイズの電線では、例えばＵＬ規格のＶＷ−１のような難燃性の厳しい試験において、芯線径と絶縁体厚さの組合せによっては合格しないケースがある。このような特殊サイズに対して、塩素系や臭素系の難燃剤を加えて高難燃化する手法があるが、最近の環境保護の趨勢から、これらの難燃剤を規制する傾向がある。 However, in the case of a small-sized electric wire such as a device electric wire, there is a case where it does not pass depending on the combination of the core wire diameter and the insulator thickness in a severe flame-retardant test such as UL standard VW-1. For such special sizes, there is a technique to increase the flame retardancy by adding a chlorinated or brominated flame retardant, but there is a tendency to regulate these flame retardants due to the recent trend of environmental protection.
そこで、本発明の目的は、上記課題を解決し、難燃性をより向上し、かつ環境に配慮した含ふっ素エラストマ被覆電線を提供することにある。 Therefore, an object of the present invention is to provide a fluorine-containing elastomer-coated electric wire that solves the above-described problems, further improves flame retardancy, and is environmentally friendly.
上記目的を達成するために請求項１の発明は、テトラフルオロエチレン−プロピレン系共重合体６０〜８０質量％、エチレン−テトラフルオロエチレン系共重合体２０〜４０質量％からなるブレンドポリマ１００質量部に対して、三酸化アンチモンを０．５〜２０質量部添加し架橋してなる組成物を、導体の外周に被覆層として形成することにより、上記導体の芯線サイズが２２ＡＷＧ以下で、かつ上記被覆層の肉厚が０．４ｍｍ以上であり、耐熱老化性およびＵＬＶＷ−１の垂直難燃試験に合格する難燃性を有することを特徴とする含ふっ素エラストマ被覆電線である。 In order to achieve the above object, the invention of claim 1 is characterized in that 100 parts by mass of a blend polymer comprising 60 to 80% by mass of a tetrafluoroethylene-propylene copolymer and 20 to 40% by mass of an ethylene-tetrafluoroethylene copolymer. respect, antimony trioxide was added 0.5 to 20 parts by weight by crosslinking the composition, by forming a coating layer on the outer periphery of the conductor, the core size of the upper Symbol conductor below 22awg, and the It is a fluorine-containing elastomer-coated electric wire characterized by having a coating layer thickness of 0.4 mm or more, heat aging resistance, and flame retardancy that passes the vertical flame retardant test of ULVW-1.
請求項２の発明は、上記被覆層を架橋剤を用いて、または電子線や紫外線を照射して架橋処理してなる請求項１記載の含ふっ素エラストマ被覆電線である。 The invention of claim 2 is a fluorine-containing elastomer covered electric wire of the coating layer by using a crosslinking agent, or irradiation with electron beam or ultraviolet rays by crosslinking treatment according to claim 1.
本発明によれば、耐熱老化性及び難燃性に優れた含ふっ素エラストマ被覆電線を得ることができるという優れた効果を発揮するものである。 According to the present invention, an excellent effect is obtained that a fluorine-containing elastomer-coated electric wire excellent in heat aging resistance and flame retardancy can be obtained.
以下、本発明の好適な一実施の形態を詳述する。 Hereinafter, a preferred embodiment of the present invention will be described in detail.
本発明に用いるテトラフルオロエチレン−プロピレン系共重合体およびエチレン−テトラフルオロエチレン系共重合体は、それ自身高い難燃性を持っている。しかし、芯線サイズが２２ＡＷＧ以下で、かつ絶縁体としての被覆層の肉厚が０．４ｍｍ以上の電線構造（例えば、エアコンやレンジなどの熱機器用配線用途）においては、ＵＬ ＶＷ−１のような垂直難燃性を満足しない場合が生じる。 The tetrafluoroethylene-propylene copolymer and the ethylene-tetrafluoroethylene copolymer used in the present invention themselves have high flame retardancy. However, in an electric wire structure having a core wire size of 22 AWG or less and a coating layer thickness as an insulator of 0.4 mm or more (for example, wiring for a heat appliance such as an air conditioner or a range), as in UL VW-1 In some cases, the vertical flame retardancy is not satisfied.
本発明において、テトラフルオロエチレン−プロピレン系共重合体とエチレン−テトラフルオロエチレン系共重合体からなるブレンドポリマ１００質量部に対して、三酸化アンチモンを０．５〜２０質量部、好ましくは５〜１５質量部添加することにより、機械的な特性や、耐熱性を損なうことなく難燃性を向上することを見出した。 In the present invention, 0.5 to 20 parts by mass of antimony trioxide, preferably 5 to 5 parts by mass with respect to 100 parts by mass of a blend polymer composed of a tetrafluoroethylene-propylene copolymer and an ethylene-tetrafluoroethylene copolymer. It has been found that by adding 15 parts by mass, flame retardancy is improved without impairing mechanical properties and heat resistance.
三酸化アンチモンの添加量を０．５〜２０質量部に制限したのは、０．５質量部未満では、難燃性に対する効果がなく、また、２０質量部を越えてもそれ以上の難燃効果はなく、むしろ耐熱性を低下させるからである。酸化アンチモンの平均粒径は、難燃性の観点から１〜２μｍのものを用いるとよい。 The amount of addition of antimony trioxide is limited to 0.5 to 20 parts by mass. If the amount is less than 0.5 parts by mass, there is no effect on the flame retardancy. This is because there is no effect and rather the heat resistance is lowered. The average particle diameter of antimony oxide is preferably 1 to 2 μm from the viewpoint of flame retardancy.
テトラフルオロエチレン−プロピレン系共重合体は、主成分であるテトラフルオロエチレンおよびプロピレンと、これらと共重合可能な成分とで構成される。 The tetrafluoroethylene-propylene copolymer is composed of tetrafluoroethylene and propylene, which are main components, and components copolymerizable therewith.
テトラフルオロエチレンおよびプロピレンと共重合可能な成分として、例えば、エチレン、ブテン−１、イソブテン、アクリル酸およびそのアルキルエステル、メタクリル酸およびそのアルキルエステル、ふっ化ビニル、ふっ化ビニリデン、ヘキサフルオロプロペン、クロロエチルビニルエーテル、グリシジルビニルエーテル、クロロトリフルオロエチレン、パーフルオロアルキルビニルエーテルなどが挙げられる。 Components copolymerizable with tetrafluoroethylene and propylene include, for example, ethylene, butene-1, isobutene, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, vinyl fluoride, vinylidene fluoride, hexafluoropropene, chloro Examples include ethyl vinyl ether, glycidyl vinyl ether, chlorotrifluoroethylene, and perfluoroalkyl vinyl ether.
テトラフルオロエチレン−プロピレン系共重合体は、耐熱性、成形性などの面から、テトラフルオロエチレンとプロピレンとのモル比が９０／１０〜４５／５５の範囲であることが好ましい。主成分以外の成分の含有量は、主成分に対して３０モル％以下の範囲であることが望ましい。 The tetrafluoroethylene-propylene copolymer preferably has a molar ratio of tetrafluoroethylene to propylene in the range of 90/10 to 45/55 from the viewpoints of heat resistance and moldability. The content of components other than the main component is preferably in the range of 30 mol% or less with respect to the main component.
また、エチレン−テトラフルオロエチレン系共重合体としては、エチレン−テトラフルオロエチレン−フルオロオレフィン共重合体を用いることが好ましい。フルオロオレフィンとしては、例えばクロロトリフルオロエチレン、ふっ化ビニリデン、トリフルオロエチレン、１，１−ジヒドロパーフルオロプロペン−１、１，１−ジヒドロパーフルオロブテン、１，１，５−トリヒドロパーフルオロペンテン−１、１，１，７−トリヒドロパーフルオロペンテン−１、１，１，２−トリヒドロパーフルオロヘキセン−１、１，１，２−トリヒドロパーフルオロオクテン−１、パーフルオロ（メチルビニルエーテル）、パーフルオロ（エチルビニルエーテル）、ヘキサフルオロプロペン、パーフルオロブテン−１などが挙げられる。 Moreover, it is preferable to use an ethylene-tetrafluoroethylene-fluoroolefin copolymer as the ethylene-tetrafluoroethylene-based copolymer. Examples of the fluoroolefin include chlorotrifluoroethylene, vinylidene fluoride, trifluoroethylene, 1,1-dihydroperfluoropropene-1,1,1-dihydroperfluorobutene, 1,1,5-trihydroperfluoropentene. -1,1,1,7-trihydroperfluoropentene-1,1,1,2-trihydroperfluorohexene-1,1,1,2-trihydroperfluorooctene-1, perfluoro (methyl vinyl ether) ), Perfluoro (ethyl vinyl ether), hexafluoropropene, perfluorobutene-1, and the like.
エチレン−テトラフルオロエチレン系共重合体は、エチレン単位とテトラフルオロエチレン単位とフルオロオレフィン単位とで構成されており、それぞれの含有モル比は１０〜４０／９０〜６０／０．１〜２０であることが好ましい。 The ethylene-tetrafluoroethylene copolymer is composed of an ethylene unit, a tetrafluoroethylene unit, and a fluoroolefin unit, and the content molar ratio thereof is 10-40 / 90-60 / 0.1-20. It is preferable.
テトラフルオロエチレン−プロピレン系共重合体６０〜８０ｍａｓｓ％、エチレン−テトラフルオロエチレン系共重合体２０〜４０ｍａｓｓ％の範囲に限定したのは、テトラフルオロエチレン−プロピレン系共重合体が６０ｍａｓｓ％未満（エチレン−テトラフルオロエチレン系共重合体が４０ｍａｓｓ％より多い）では可とう性と伸びが低下するからである。また、テトラフルオロエチレン−プロピレン系共重合体が８０ｍａｓｓ％を超える（エチレン−テトラフルオロエチレン系共重合体が２０ｍａｓｓ％より少ない）と、引張強さが低下するからである。 Tetrafluoroethylene-propylene copolymer is limited to the range of 60 to 80 mass% and ethylene-tetrafluoroethylene copolymer is limited to 20 to 40 mass% because the tetrafluoroethylene-propylene copolymer is less than 60 mass% (ethylene This is because the flexibility and elongation decrease when the tetrafluoroethylene copolymer is more than 40 mass%. Moreover, if the tetrafluoroethylene-propylene copolymer exceeds 80 mass% (the ethylene-tetrafluoroethylene copolymer is less than 20 mass%), the tensile strength decreases.
上記で得られた被覆電線を、電子線や紫外線等を照射したり、有機過酸化物を用いて周知の方法で架橋処理して用いることが望ましい。 It is desirable to use the coated electric wire obtained above by irradiating an electron beam, ultraviolet rays, or the like, or by performing a crosslinking treatment by a known method using an organic peroxide.
なお、本発明においては、前記した成分に加えて架橋助剤、上記以外の難燃助剤、酸化防止剤、滑剤、安定剤、充填剤、着色剤、シリコーン等を添加してもよい。 In the present invention, in addition to the above-described components, a crosslinking aid, a flame retardant aid other than the above, an antioxidant, a lubricant, a stabilizer, a filler, a colorant, silicone, and the like may be added.
以上の構成によれば、小サイズ厚肉電線に対しても優れた難燃性を有する含ふっ素エラストマ被覆電線を得ることができる。 According to the above configuration, it is possible to obtain a fluorine-containing elastomer-coated electric wire having excellent flame retardancy even for a small-sized thick electric wire.
（実施例１〜５）
表１に示す配合剤を２５０℃に加熱したニーダーにより１５分間均一に混練してコンパウンドを形成する。これを１２０℃に保持した６インチオープンロールで約２ｍｍの厚さにシート成形した後、シートペレタイザーによって５ｍｍ角のペレットに加工した。
(Examples 1-5)
The compounding agents shown in Table 1 are uniformly kneaded with a kneader heated to 250 ° C. for 15 minutes to form a compound. This was formed into a sheet having a thickness of about 2 mm with a 6-inch open roll maintained at 120 ° C., and then processed into a 5 mm square pellet by a sheet pelletizer.
その後、このペレットを、ヘッドが１８０℃、第１シリンダーが２２０℃、第２シリンダーおよびダイスが２５０℃に設定された４０ｍｍ押出機（Ｌ／Ｄ＝２４）内にそれぞれ圧入する。その後、２６ＡＷＧ（導体径０．４０５ｍｍ）の銅撚線の外周に厚さ０．５５ｍｍに押出して被覆層を形成すると共に、この被覆層に１４Ｍｒａｄの電子線を照射することによって架橋を行い、含ふっ素エラストマ被覆電線を作製する。 Thereafter, the pellets are press-fitted into a 40 mm extruder (L / D = 24) in which the head is set to 180 ° C., the first cylinder is set to 220 ° C., and the second cylinder and the die are set to 250 ° C. Thereafter, cross-linking by 26AWG to form a coating layer extruded to a thickness of 0.55mm on the outer circumference of a copper twisted wire (conductor diameter 0. 405 mm), it is irradiated with an electron beam of 14Mrad in the coating layer, Prepare a fluorine-containing elastomer-coated wire.
（比較例１〜４）
比較例１〜４も実施例と同様の方法にて作製する。
(Comparative Examples 1-4)
Comparative examples 1 to 4 are also produced by the same method as in the examples.
次に、実施例１〜５および比較例１〜４で作製したそれぞれの含ふっ素エラストマ被覆電線における機械特性、難燃性、耐熱老化性について評価した。 Next, mechanical properties, flame retardancy, and heat aging resistance in each of the fluorine-containing elastomer-coated wires prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were evaluated.
それぞれの特性の評価は、以下に示す方法で行った。 Evaluation of each characteristic was performed by the method shown below.
引張特性：
それぞれの含ふっ素エラストマ被覆電線から導体を抜脱した被覆層について、ＪＩＳ−Ｋ−６３０１に準じた引張試験を行い、引張強さ（ＭＰａ）、伸び（％）を測定した。この引張試験におけるそれぞれの引張強さ、伸びの値を初期値とする。
Tensile properties:
A tensile test according to JIS-K-6301 was performed on the coating layer in which the conductor was removed from each fluorine-containing elastomer-coated electric wire, and tensile strength (MPa) and elongation (%) were measured. The values of tensile strength and elongation in this tensile test are taken as initial values.
難燃性：
ＵＬ ｓｕｂｊｅｃｔ７５８に準拠した垂直燃焼試験（ＶＷ−１）を行い、１分以内に自己消火したものを合格、１分を越えるものを不合格とした。
Flame retardance:
A vertical combustion test (VW-1) based on UL subject 758 was conducted, and self-extinguishing within 1 minute was accepted, and over 1 minute was rejected.
耐熱老化性（耐熱性）：
それぞれの含ふっ素エラストマ被覆電線から導体を抜脱した被覆層について、空気置換量２００回／ｈｒのギヤーオープン（２３２℃）中で７日間保持した後、ＪＩＳ−Ｋ−６３０１に準じた引張試験を行い、引張特性での引張試験における初期値に対する引張強さ残率（％）、伸び残率（％）を測定した。
Heat aging resistance (heat resistance):
The coating layer obtained by removing the conductor from each fluorine-containing elastomer-coated electric wire was held in a gear open (232 ° C.) with an air displacement of 200 times / hr for 7 days, and then subjected to a tensile test according to JIS-K-6301. The tensile strength residual rate (%) and the residual elongation rate (%) with respect to the initial values in the tensile test with tensile properties were measured.
実施例１〜５および比較例１〜４で作製したそれぞれの含ふっ素被覆電線における各試験結果を表１に示す。 Table 1 shows the test results of the respective fluorine-containing coated wires produced in Examples 1 to 5 and Comparative Examples 1 to 4.
表１に示すように、本発明である実施例１〜５の含ふっ素エラストマ被覆電線は、いずれも引張強さが１２ＭＰａ以上、伸びが１５０％（好ましくは２００％）以上、難燃性が合格、熱老化後の引張強さ残率および伸び残率が８０％以上であり、機械特性、難燃性、耐熱性の全てにおいて優れている。 As shown in Table 1, each of the fluorine-containing elastomer-coated wires of Examples 1 to 5 according to the present invention has a tensile strength of 12 MPa or more, an elongation of 150% (preferably 200%) or more, and a flame retardance pass. Moreover, the tensile strength residual ratio and elongation residual ratio after heat aging are 80% or more, and they are excellent in all of mechanical properties, flame retardancy, and heat resistance.
これに対して、比較例１は三酸化アンチモンが規定量未満であり、難燃性が不合格となった。比較例２は、三酸化アンチモンが規定量を越えた（２１質量部）ものであり、難燃性は合格するが、耐熱老化性が著しく低下し目標を下回った。 On the other hand, in Comparative Example 1, antimony trioxide was less than the prescribed amount, and the flame retardancy was rejected. In Comparative Example 2, antimony trioxide exceeded the specified amount (21 parts by mass), and the flame retardancy passed, but the heat aging resistance was significantly lowered and was below the target.
よって、三酸化アンチモンの添加量は、テトラフルオロエチレン−プロピレン系共重合体とエチレン−テトラフルオロエチレン系共重合体からなるブレンドポリマ１００質量部に対して、０．５〜２０質量部がよい。 Therefore, the addition amount of antimony trioxide is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the blend polymer composed of a tetrafluoroethylene-propylene copolymer and an ethylene-tetrafluoroethylene copolymer.
また、テトラフルオロエチレン−プロピレン系共重合体が規定より多い比較例３は引張強さが低く、規定より少ない比較例４は伸びと耐熱性が大幅に低下している。 Further, Comparative Example 3 having more tetrafluoroethylene-propylene copolymer than specified has low tensile strength, and Comparative Example 4 having less than specified has significantly reduced elongation and heat resistance.
従って、テトラフルオロエチレン−プロピレン系共重合体６０〜８０ｍａｓｓ％、エチレン−テトラフルオロエチレン系共重合体２０〜４０ｍａｓｓ％の範囲がよい。 Therefore, the range of tetrafluoroethylene-propylene copolymer 60 to 80 mass% and ethylene-tetrafluoroethylene copolymer 20 to 40 mass% is preferable.
以上本発明の実施例を説明したが、本発明は、電線被覆材の他に、耐熱性が要求されるゴムパッキンやシール材として応用することも可能である。 Although the embodiments of the present invention have been described above, the present invention can also be applied as a rubber packing or a seal material that requires heat resistance in addition to the wire coating material.
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| WO2020180148A3 (en) * | 2019-03-06 | 2020-10-29 | 주식회사 삼일씨엔에프 | Flame-retardant paint and method for producing same |
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| JP2016017123A (en) * | 2014-07-07 | 2016-02-01 | 日立金属株式会社 | Fluorine-containing elastomer composition, and insulated wire and cable using the same |
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| TW201803930A (en) * | 2016-03-11 | 2018-02-01 | 旭硝子股份有限公司 | Fluororesin composition, molding material, and molded object |
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| JP7544306B1 (en) | 2023-12-14 | 2024-09-03 | 住友電気工業株式会社 | Insulated wire and heat shrink tubing |
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| EP0332932A3 (en) * | 1988-03-07 | 1990-09-26 | AUSIMONT U.S.A. Inc. | Modified fluoropolymers for low flame/low smoke plenum cables |
| JPH02103805A (en) * | 1988-10-08 | 1990-04-16 | Hitachi Cable Ltd | Cable coated with fluorine-containing elastomer |
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| JP5388158B2 (en) * | 2007-01-26 | 2014-01-15 | 日立金属株式会社 | Fluorine-containing elastomer covered wire |
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| WO2020180148A3 (en) * | 2019-03-06 | 2020-10-29 | 주식회사 삼일씨엔에프 | Flame-retardant paint and method for producing same |
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