JP2007246619A - Electric insulation composition and electric wire - Google Patents
Electric insulation composition and electric wire Download PDFInfo
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- JP2007246619A JP2007246619A JP2006069591A JP2006069591A JP2007246619A JP 2007246619 A JP2007246619 A JP 2007246619A JP 2006069591 A JP2006069591 A JP 2006069591A JP 2006069591 A JP2006069591 A JP 2006069591A JP 2007246619 A JP2007246619 A JP 2007246619A
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- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 238000009413 insulation Methods 0.000 title abstract 6
- 239000000843 powder Substances 0.000 claims abstract description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920001973 fluoroelastomer Polymers 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910052914 metal silicate Inorganic materials 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 6
- 229920001897 terpolymer Polymers 0.000 claims abstract description 6
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 9
- 238000010292 electrical insulation Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 239000012756 surface treatment agent Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- -1 cross-linking aids Substances 0.000 description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229910052916 barium silicate Inorganic materials 0.000 description 1
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005250 beta ray Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920005560 fluorosilicone rubber Polymers 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
Description
本発明は、機械的強度、耐熱性、耐油性及び耐寒性をバランス良く兼ね備えた、例えば、電気機器内配線や自動車用ハーネスの絶縁体として好適な電気絶縁組成物と、該電気絶縁組成物からなる被覆を備えた電線に関する。 The present invention has a good balance of mechanical strength, heat resistance, oil resistance and cold resistance, for example, an electrical insulation composition suitable as an insulator for wiring in electrical equipment and automotive harnesses, and the electrical insulation composition. It is related with the electric wire provided with the coating which becomes.
フッ素ゴムは、耐熱性、耐油性、耐薬品性、難燃性、可とう性に優れていることから、自動車、産業ロボット、電気機器、熱機器等の各種の用途で使用される電線・ケーブルの被覆材料として幅広く使用されている。 Fluoro rubber is excellent in heat resistance, oil resistance, chemical resistance, flame retardancy, and flexibility, so it can be used in various applications such as automobiles, industrial robots, electrical equipment, and thermal equipment. Widely used as a coating material.
近年においては、フッ素ゴムに種々の添加剤を配合し、用途に合致した要求に応じて、耐ガソリン性、耐変形性、耐磨耗性など各種特性を向上させた組成物が開発され、電線の被覆材料として使用されている。（例えば、特許文献１）。 In recent years, various additives such as gasoline resistance, deformation resistance, and wear resistance have been developed in accordance with the requirements that match the application by blending various additives with fluororubber. It is used as a coating material. (For example, patent document 1).
ここで、例えば、自動車のＡＴ装置内に配置されるような電線の被覆材料においては、高温やＡＴフルードに対する耐性に加え、優れた機械的強度と、低温下においても可とう性を損なわないような耐寒性が要求される。しかしながら、上記の特許文献１を含め、従来のフッ素ゴム電線では、耐寒性について考慮がされておらず、各種特性あるいは被覆をする際の成形性を向上させるがために耐寒性が犠牲となってしまい、低温下において小さい曲げ半径で屈曲させたときなどに、絶縁被覆にクラックが発生してしまうような問題が生じていた。 Here, for example, in a coating material for electric wires, which is arranged in an AT device of an automobile, in addition to resistance to high temperatures and AT fluid, excellent mechanical strength and flexibility are not impaired even at low temperatures. Cold resistance is required. However, in the conventional fluororubber electric wires including the above-mentioned Patent Document 1, no consideration is given to cold resistance, and the cold resistance is sacrificed in order to improve various properties or formability when coating. Thus, there has been a problem that cracks occur in the insulating coating when bent at a low bending radius at low temperatures.
本発明はこのような従来技術の問題点を解決するためになされたもので、その目的とするところは、機械的強度、耐熱性、耐油性及び耐寒性をバランス良く兼ね備えた電気絶縁組成物及び該電気絶縁組成物からなる被覆を備えた電線を提供することにある。 The present invention has been made to solve such problems of the prior art, and the object of the present invention is to provide an electrically insulating composition having a good balance of mechanical strength, heat resistance, oil resistance and cold resistance, and It is providing the electric wire provided with the coating | cover consisting of this electrical insulation composition.
上記目的を達成するべく、本発明の請求項１による電気絶縁組成物は、フッ素ゴム１００重量部に対し、平均比表面積２００ｍ２／ｇ以上のシリカ粉末５〜２０重量部が配合されていることを特徴とするものである。
又、請求項２による電気絶縁組成物は、フッ素ゴム１００重量部に対し、平均比表面積２００ｍ２／ｇ以上のシリカ粉末５〜２０重量部と、平均粒径０．１〜２μｍの金属炭酸塩粉末及び／又は金属ケイ酸塩粉末を合計で１〜７０重量部と、酸化亜鉛粉末１〜１５重量部が配合されていることを特徴とするものである。
又、請求項３による電気絶縁組成物は、請求項１又は請求項２記載の電気絶縁組成物において、上記フッ素ゴムがフッ化ビニリデン系３元共重合体であることを特徴とするものである。
又、請求項４による電線は、請求項１乃至請求項３のいずれか１項記載の電気絶縁組成物からなる被覆を備えているものである。
In order to achieve the above object, the electrically insulating composition according to claim 1 of the present invention contains 5 to 20 parts by weight of silica powder having an average specific surface area of 200 m 2 / g or more per 100 parts by weight of fluororubber. It is characterized by.
The electrical insulating composition according to claim 2 is a metal carbonate having 5 to 20 parts by weight of silica powder having an average specific surface area of 200 m 2 / g or more and an average particle diameter of 0.1 to 2 μm with respect to 100 parts by weight of fluororubber. A total of 1 to 70 parts by weight of powder and / or metal silicate powder and 1 to 15 parts by weight of zinc oxide powder are blended.
An electrical insulating composition according to claim 3 is the electrical insulating composition according to claim 1 or 2, characterized in that the fluororubber is a vinylidene fluoride terpolymer. .
An electric wire according to a fourth aspect is provided with a coating made of the electrical insulating composition according to any one of the first to third aspects.
本発明による電気絶縁組成物は、フッ素ゴムに、平均比表面積が２００ｍ２／ｇ以上のシリカ粉末を配合することにより、耐寒性を低下させることなく優れた機械的強度を得ることができる。
又、粒径０．１〜２μｍの金属炭酸塩粉末及び／又は金属ケイ酸塩粉末を合計で１〜７０重量部更に配合することで、諸特性を低下させることなく押出成形性を向上させることができる。
又、酸化亜鉛粉末１〜１５重量部を更に配合することで、耐熱性を向上させることができる。
又、フッ素ゴムをフッ化ビニリデン系３元共重合体とすることで、耐熱性を更に向上させることができるともに、耐油性についても向上させることができる。
The electrical insulation composition according to the present invention can obtain excellent mechanical strength without deteriorating cold resistance by blending silica powder having an average specific surface area of 200 m 2 / g or more into fluororubber.
Also, by further blending 1 to 70 parts by weight of metal carbonate powder and / or metal silicate powder having a particle size of 0.1 to 2 μm, the extrusion moldability can be improved without reducing various properties. Can do.
Moreover, heat resistance can be improved by mix | blending 1-15 weight part of zinc oxide powder further.
Moreover, by using fluororubber as a vinylidene fluoride terpolymer, heat resistance can be further improved, and oil resistance can also be improved.
以下、本発明の電気絶縁組成物を構成する各成分について説明する。 Hereafter, each component which comprises the electrically insulating composition of this invention is demonstrated.
（ａ）フッ素ゴム
本発明で使用されるフッ素ゴムとしては、例えば、テトラフルオロプロピレン−プロピレン共重合体、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体、フッ化ビニリデン−ヘキサフルオロプロピレン−テトラフルオロエチレン３元共重合体、フルオロシリコーン系ゴムなどが挙げられる。これらの中でも、フッ化ビニリデン−ヘキサフルオロプロピレン−テトラフルオロエチレン３元共重合体のようなフッ化ビニリデン系３元共重合体であれば、耐熱性を向上させることができるとともに、油に対して膨潤し難いため耐油性を向上させることができる。
(A) Fluoro rubber Examples of the fluoro rubber used in the present invention include tetrafluoropropylene-propylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene 3 Examples thereof include an original copolymer and a fluorosilicone rubber. Among these, a vinylidene fluoride terpolymer such as a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer can improve heat resistance and can be used against oil. Oil resistance can be improved because it does not swell easily.
（ｂ）シリカ粉末
本発明においては、耐寒性を低下させずに機械的強度を向上させるため平均比表面積が２００ｍ２／ｇ以上のシリカ粉末を配合する。シリカ粉末の比表面積が２００ｍ２／ｇ未満であると充分な耐寒性を得ることができない。
(B) Silica powder In the present invention, silica powder having an average specific surface area of 200 m 2 / g or more is blended in order to improve mechanical strength without reducing cold resistance. When the specific surface area of the silica powder is less than 200 m 2 / g, sufficient cold resistance cannot be obtained.
上記したシリカ粉末は、フッ素ゴム１００重量部に対し、５〜２０重量部配合する。シリカ粉末の配合量が５重量部未満では、機械的強度を向上させる効果が不十分であり、又、２０重量部を超えると、押出成形性が低下して成形が困難となってしまうとともに、耐寒性が低下してしまう。 The above silica powder is blended in an amount of 5 to 20 parts by weight with respect to 100 parts by weight of the fluororubber. When the blending amount of the silica powder is less than 5 parts by weight, the effect of improving the mechanical strength is insufficient, and when it exceeds 20 parts by weight, the extrusion moldability is deteriorated and molding becomes difficult. Cold resistance will decrease.
（ｃ）金属炭酸塩粉末、金属ケイ酸塩粉末
本発明においては、押出成形性を向上させることを目的として、金属炭酸塩粉末及び／又は金属ケイ酸塩粉末を配合することが好ましい。金属炭酸塩粉末としては、例えば、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム、などが挙げられ、これらの中でも炭酸カルシウムが好適に使用される。金属ケイ酸塩粉末としては、例えば、ケイ酸マグネシウム、ケイ酸カルシウム、ケイ酸バリウム、ケイ酸アルミニウムなどが上げられ、これらの中でもケイ酸アルミニウムが好適に使用される。これらは単独で用いても複数を混合して用いても構わない。金属炭酸塩粉末や金属ケイ酸塩粉末を配合する場合、これらの粒径は、０．１〜２μｍのものを使用する。０．１〜２μｍの範囲外であると機械的強度や耐熱性、耐寒性が低下する傾向にある。又、金属炭酸塩粉末や金属ケイ酸塩粉末の粒子形状は、扁平状でないものを使用した方が、耐寒性に優れた組成物を得ることができるため好ましい。
(C) Metal carbonate powder and metal silicate powder In the present invention, it is preferable to blend metal carbonate powder and / or metal silicate powder for the purpose of improving extrudability. Examples of the metal carbonate powder include magnesium carbonate, calcium carbonate, barium carbonate and the like. Among these, calcium carbonate is preferably used. Examples of the metal silicate powder include magnesium silicate, calcium silicate, barium silicate, and aluminum silicate. Among these, aluminum silicate is preferably used. These may be used alone or in combination. When a metal carbonate powder or a metal silicate powder is blended, those having a particle size of 0.1 to 2 μm are used. When it is out of the range of 0.1 to 2 μm, mechanical strength, heat resistance, and cold resistance tend to decrease. In addition, it is preferable to use a non-flat particle shape of the metal carbonate powder or metal silicate powder because a composition having excellent cold resistance can be obtained.
上記した金属炭酸塩粉末及び／又は金属ケイ酸塩粉末は、フッ素ゴム１００重量部に対し、１〜７０重量部配合することが好ましい。金属炭酸塩粉末及び／又は金属ケイ酸塩粉末の配合量が１重量部未満では、押出成形性を向上させる効果が不十分であり、又、７０重量部を超えると、機械的強度や耐熱性、耐寒性が低下してしまう。 The metal carbonate powder and / or metal silicate powder described above is preferably blended in an amount of 1 to 70 parts by weight with respect to 100 parts by weight of the fluororubber. If the blending amount of the metal carbonate powder and / or the metal silicate powder is less than 1 part by weight, the effect of improving the extrusion moldability is insufficient, and if it exceeds 70 parts by weight, the mechanical strength and heat resistance are increased. , Cold resistance will be reduced.
（ｄ）酸化亜鉛粉末
本発明においては、耐熱性を向上させることを目的として、酸化亜鉛粉末を配合することが好ましい。これにより、受酸剤としての作用により耐熱性を向上させることができる。
(D) Zinc oxide powder In this invention, it is preferable to mix | blend zinc oxide powder for the purpose of improving heat resistance. Thereby, heat resistance can be improved by the effect | action as an acid acceptor.
上記した酸化亜鉛粉末は、フッ素ゴム１００重量部に対し、１〜１５重量部配合する。酸化亜鉛粉末の配合量が１重量部未満では、耐熱性を向上させる効果が不十分であり、又、１５重量部を超えると、フッ素ゴムを架橋させる際に架橋阻害を起こし、耐熱性が低下してしまう。 The zinc oxide powder described above is blended in an amount of 1 to 15 parts by weight with respect to 100 parts by weight of the fluororubber. If the blending amount of zinc oxide powder is less than 1 part by weight, the effect of improving the heat resistance is insufficient, and if it exceeds 15 parts by weight, the crosslinking is inhibited when the fluororubber is crosslinked and the heat resistance is lowered. Resulting in.
これらのシリカ粉末、金属炭酸塩粉末、金属ケイ酸塩粉末は、例えば、ラウリン酸、ステアリン酸、オレイン酸などの高級脂肪酸、又はこれらのアルミニウム、マグネシウム、カルシウム塩などの高級脂肪酸金属塩、シランカップリング剤やチタネート系表面処理剤などの表面処理剤によって表面処理することができる。これら表面処理剤はフッ素ゴムとの親和性及び分散性を向上させ、機械的強度などを向上させるために好ましく使用される。これらの表面処理剤は、１種単独でも、２種以上を併用して使用しても良い。又、表面処理をする場合は、予め表面処理されたものを使用しても良いし、未処理若しくは表面処理済のものとともに表面処理剤を配合し、表面処理を行っても良い。 These silica powder, metal carbonate powder and metal silicate powder are, for example, higher fatty acid such as lauric acid, stearic acid and oleic acid, or higher fatty acid metal salts such as aluminum, magnesium and calcium salts, and silane cups. Surface treatment can be performed with a surface treatment agent such as a ring agent or a titanate surface treatment agent. These surface treatment agents are preferably used for improving the affinity and dispersibility with fluororubber and improving the mechanical strength and the like. These surface treatment agents may be used alone or in combination of two or more. Moreover, when surface-treating, what was surface-treated beforehand may be used, and a surface treatment agent may be mix | blended with an untreated or surface-treated thing, and surface treatment may be performed.
本発明においては、上記の成分以外にも、本発明の目的を阻害しない範囲内で、従来、電線、ケーブルにおいて一般的に使用されている各種の添加剤を配合しても良い。このような添加剤としては、例えば、難燃剤、老化防止剤、架橋剤、架橋助剤、滑剤、軟化剤、分散剤、着色剤などが挙げられる。 In the present invention, in addition to the above components, various additives that are conventionally used in electric wires and cables may be blended within a range that does not impair the object of the present invention. Examples of such additives include flame retardants, anti-aging agents, cross-linking agents, cross-linking aids, lubricants, softeners, dispersants, colorants, and the like.
上記の各構成材料を適宜に配合したものを、ロール、ニーダー、バンバリー、一軸混練機、二軸混練機などの公知の混練機を使用して充分に混練りすることによって本発明の電気絶縁組成物を得ることができる。 The electrical insulation composition of the present invention is obtained by kneading the above-described constituent materials appropriately using a known kneader such as a roll, kneader, banbury, uniaxial kneader, or biaxial kneader. You can get things.
上記の電気絶縁組成物を公知の方法によって導体周上に押出被覆し、その後、電気絶縁組成物の耐熱性を向上させるため適宜に架橋を施すことにより、本発明の他の態様による電線を得ることができる。 An electric wire according to another embodiment of the present invention is obtained by applying the above-mentioned electrical insulating composition onto a conductor circumference by a known method, and then appropriately crosslinking in order to improve the heat resistance of the electrical insulating composition. be able to.
架橋方法は特に限定されず、例えば、２，５−ジメチル−２，５−ジ（ｔ−ブチルペルオキシ）ヘキサン、１，３−ビス（ｔ−ブチルペルオキシイソプロピル）ベンゼン、１，１−ビス（ｔ−ブチルペルオキシ）−３，３，５−トリメチルシクロヘキサン、ジクミルパーオキサイドなどの有機過酸化物や、ポリオール、アミンなどを架橋剤として使用した化学架橋法、Ｘ線、γ線、電子線、陽子線、重陽子線、α線、β線などの電離性放射線を使用した照射架橋法などが挙げられる。 The crosslinking method is not particularly limited. For example, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t -Butylperoxy) -3,3,5-trimethylcyclohexane, organic peroxides such as dicumyl peroxide, chemical crosslinking method using polyol, amine, etc. as a crosslinking agent, X-ray, γ-ray, electron beam, proton An irradiation cross-linking method using ionizing radiation such as a ray, deuteron beam, α ray, β ray and the like.
以下に本発明の実施例を比較例と併せて説明する。この実施例で使用した各配合材料の詳細は表５に示す通りである。 Examples of the present invention will be described below together with comparative examples. Details of each compounding material used in this example are as shown in Table 5.
表３に示した配合材料を表１，２に示した配合部数により２軸混練機で十分に混練し、得られた電気絶縁組成物を１８０℃×１０分、６０ｋｇｆ／ｃｍ２の条件にてプレス加硫し、厚さ約１ｍｍのシート状サンプルを作製した。 The compounding materials shown in Table 3 were sufficiently kneaded with a biaxial kneader according to the number of blending parts shown in Tables 1 and 2, and the resulting electrical insulating composition was subjected to conditions of 180 ° C. × 10 minutes and 60 kgf / cm 2 . Press vulcanized to prepare a sheet-like sample having a thickness of about 1 mm.
ここで、この様にして得られた合計１２種類のシート状サンプルについて、機械的強度（引張破断強度、引張破断伸び）、耐熱性、耐油性、耐寒性、押出成形性について、それぞれ評価を行った。結果は各配合材料の配合部数と共に表１，２に併せて示した。 Here, the total 12 types of sheet-like samples thus obtained were evaluated for mechanical strength (tensile breaking strength, tensile breaking elongation), heat resistance, oil resistance, cold resistance, and extrusion moldability, respectively. It was. The results are shown in Tables 1 and 2 together with the number of blended parts of each blended material.
評価方法は以下の通りである。
（機械的強度）
ＪＩＳ３００５に準拠して、引張破断強度と引張破断伸びを測定した。合否の基準としては、引張破断強度が１０ＭＰａ以上、引張破断伸びが１５０％以上のものを合格と判定した。
（耐熱性）
ＪＩＳ３００５に準拠して、２５０℃×４日加熱後の強度残率と伸び残率を測定した。合否の基準としては、強度及び伸びの残率が５０％以上を合格と判定した。
（耐油性）
市販されているＡＴフルードに１６５℃×５日浸漬後、強度残率、伸び残率を測定した。合否の基準としては、強度及び伸びの残率が５０％以上を合格とした。
（耐寒性）
シート状サンプルを１．５ｍｍ幅の短冊状に切り取り、−４５℃×３時間冷却後、−４５℃雰囲気中で１２．５Φの金属マンドレルに巻付け、クラックの有無を目視にて確認し評価した。合否の基準としては、巻付け時にクラックが発生していないものを合格とした。
（押出成形性）
架橋前の配合物について、スイングダイレオメーターにて６０℃、３．５ｋｇｆ／ｃｍ２、１．６６Ｈzにおけるトルクを測定した。この状態でのトルクが大きくなると押出成型が困難となるため、合否の基準としては、２Ｎ・ｍ以上を不合格とした。
The evaluation method is as follows.
(Mechanical strength)
Based on JIS3005, the tensile breaking strength and the tensile breaking elongation were measured. As a pass / fail criterion, a sample having a tensile strength at break of 10 MPa or more and a tensile elongation at break of 150% or more was determined to be acceptable.
(Heat-resistant)
Based on JIS3005, the residual strength rate and the residual elongation rate after heating at 250 ° C. for 4 days were measured. As a pass / fail criterion, it was determined that the remaining ratio of strength and elongation was 50% or more as acceptable.
(Oil resistance)
After immersing in a commercially available AT fluid at 165 ° C. for 5 days, the residual strength rate and the residual elongation rate were measured. As a pass / fail standard, the remaining ratio of strength and elongation was 50% or more.
(Cold resistance)
A sheet sample was cut into a 1.5 mm width strip, cooled to -45 ° C x 3 hours, wound around a 12.5Φ metal mandrel in a -45 ° C atmosphere, and visually checked for the presence or absence of cracks. . As a pass / fail criterion, a product that did not crack during winding was regarded as acceptable.
(Extrudability)
About the compound before bridge | crosslinking, the torque in 60 degreeC, 3.5 kgf / cm < 2 >, 1.66Hz was measured with the swing direometer. When the torque in this state increases, extrusion molding becomes difficult, and therefore, 2 N · m or more is rejected as a criterion for pass / fail.
本実施例による電線は、何れも機械的強度（引張破断強度、引張破断伸び）、耐熱性、耐寒性、耐油性及びについて合格する値を示しており、機械的強度、耐熱性、耐油性及び耐寒性に優れたものであることが確認された。 The electric wires according to the present examples all have acceptable values for mechanical strength (tensile rupture strength, tensile rupture elongation), heat resistance, cold resistance, oil resistance, and mechanical strength, heat resistance, oil resistance, and It was confirmed that it was excellent in cold resistance.
実施例１と比較例１を比較すると、シリカ粉末の平均比表面積が２００ｍ２／ｇ未満の比較例１は、実施例１と比べて耐寒性に劣り、クラックが生じていることが確認された。 When Example 1 and Comparative Example 1 were compared, it was confirmed that Comparative Example 1 in which the average specific surface area of the silica powder was less than 200 m 2 / g was inferior in cold resistance compared to Example 1 and cracks were generated. .
実施例１〜３と比較例２を比較すると、シリカ粉末が本発明の範囲（５〜１５重量部）に満たない量で配合されている比較例２は、実施例１〜３と比べて機械的強度が劣ることが確認された。又、実施例１〜３と比較例３を比較すると、シリカ粉末が本発明の範囲（５〜１５重量部）を超えた量で配合されている比較例３は、実施例１〜３と比べて押出成形性に劣ることが確認された。 When Examples 1 to 3 are compared with Comparative Example 2, Comparative Example 2 in which the silica powder is blended in an amount less than the range of the present invention (5 to 15 parts by weight) is more mechanical than Examples 1 to 3. It was confirmed that the mechanical strength was inferior. Further, when Examples 1 to 3 are compared with Comparative Example 3, Comparative Example 3 in which the silica powder is blended in an amount exceeding the range of the present invention (5 to 15 parts by weight) is compared with Examples 1 to 3. Thus, it was confirmed that the extrusion formability was poor.
実施例１，４と実施例５を比較すると、金属炭酸塩粉末が本発明の好ましい範囲（１〜７０重量部）を超えて配合されている実施例５は、実用上問題ない範囲だが、実施例１，４と比べて耐熱性と機械的強度が劣ることが確認された。又、実施例５は、耐寒性の試験においてクラックは発生していなかったものの、金属マンドレルに巻付ける際に、実施例１，４と比べて可撓性に劣り、巻付けにやや力が必要であったことが確認された。又、実施例１，４と実施例６を比較すると、金属炭酸塩粉末を配合していない実施例６は、実使用上問題ない程度だが実施例１，４と比べて押出成形性に劣ることが確認された。 When Examples 1 and 4 are compared with Example 5, Example 5 in which the metal carbonate powder is blended in excess of the preferred range (1 to 70 parts by weight) of the present invention is a practically problematic range. It was confirmed that heat resistance and mechanical strength were inferior to those of Examples 1 and 4. In Example 5, no crack was generated in the cold resistance test, but when wound around a metal mandrel, it was inferior in flexibility compared to Examples 1 and 4 and required a little force for winding. It was confirmed that Further, when Examples 1 and 4 are compared with Example 6, Example 6 in which the metal carbonate powder is not blended is not problematic in practical use but is inferior in extrusion moldability as compared with Examples 1 and 4. Was confirmed.
又、実施例１，７と実施例８を比較すると、酸化亜鉛粉末が本発明の好ましい範囲（１〜１５重量部）を超えて配合されている実施例８は、架橋阻害を起こし耐熱性に劣ることが確認された。尚、酸化亜鉛粉末を配合していない実施例９について、本試験においては実施例１，７と同等の耐熱性を有していることが確認されたが、加熱時間を延長した追試験を行ったところ、長期の加熱においては、実施例１，７と比べて加熱後の強度及び伸びの低下が大きいことが確認された。 Further, when Examples 1 and 7 are compared with Example 8, Example 8 in which the zinc oxide powder is blended exceeding the preferable range (1 to 15 parts by weight) of the present invention causes crosslinking inhibition and is heat resistant. Inferiority was confirmed. In addition, about Example 9 which does not mix | blend zinc oxide powder, although it was confirmed in this test that it has heat resistance equivalent to Example 1, 7, the follow-up test which extended heating time was done. As a result, it was confirmed that the strength and elongation after heating were greatly reduced in the long-term heating as compared with Examples 1 and 7.
以上詳述したように本発明によれば、機械的強度、耐熱性、耐油性及び耐寒性をバランス良く兼ね備えた電気絶縁組成物を得ることができる。その為、この電気絶縁組成物は、例えば、電気機器内配線や自動車用ハーネスの絶縁体などとして好適である。特に、自動車のＡＴ装置内に配置されるような電線の被覆材料として最適なものである。又、使用用途としてはこれらに限定されることはなく、例えば、コード状ヒータの絶縁被覆材料、チューブの構成材料などとしても使用可能である。 As described above in detail, according to the present invention, it is possible to obtain an electrical insulating composition having a good balance of mechanical strength, heat resistance, oil resistance and cold resistance. Therefore, this electrical insulating composition is suitable as, for example, an electrical device wiring or an insulator for an automobile harness. In particular, it is optimal as a coating material for electric wires that are arranged in an AT device of an automobile. Further, the usage is not limited to these, and for example, it can be used as an insulating coating material for a cord-shaped heater, a constituent material for a tube, and the like.
Claims (4)
The electric wire provided with the coating | cover consisting of the electrical-insulation composition of any one of Claims 1 thru | or 3.
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