JP2006253076A - Electric wire for automobile - Google Patents

Electric wire for automobile Download PDF

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Publication number
JP2006253076A
JP2006253076A JP2005071270A JP2005071270A JP2006253076A JP 2006253076 A JP2006253076 A JP 2006253076A JP 2005071270 A JP2005071270 A JP 2005071270A JP 2005071270 A JP2005071270 A JP 2005071270A JP 2006253076 A JP2006253076 A JP 2006253076A
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mass
parts
wire
electric wire
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Tetsuya Ashida
哲哉 芦田
Yoshiji Miyashita
芳次 宮下
Teruichi Honda
照一 本田
Shigeki Isono
重樹 磯野
Takaaki Ozaki
高明 小崎
Yoshikazu Yotsui
良和 四ツ井
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Mitsubishi Cable Industries Ltd
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Mitsubishi Cable Industries Ltd
Ryosei Electro Circuit Systems Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an electric wire for an automobile with excellent flex resistance and shock resistance, sufficient abrasion resistance and good workability for forming a harness while attaining thin diameter of a conductor. <P>SOLUTION: In forming this electric wire for the automobile by covering an element-wire 1 comprising a plurality of stranded wires 2 with an insulating layer 3, the element wire 1 is made of a copper alloy containing tin of 0.05-0.7 mass% and has wire diameter of 0.05-0.12 mm, and it is made to have extension ratio of 15% or more and tensile strength of 250 MPa or more by annealing in a wire drawing step, and the stranded wire 2 is formed by twisting ten or more of the element wires 1 with a pitch which is 30 to 50 times of an outer diameter of the stranded wire. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、改善された導体構造を有する自動車用途の電線に関するものである。   The present invention relates to an electric wire for automobiles having an improved conductor structure.

排ガスの低減や燃費の向上を目的とした自動車の軽量化が活発となっている中、自動車に搭載される部品の軽量化が強く要求されている。その中で、ワイヤーハーネスも例外ではなく、軽量化を目的とした電線の細径化が進んで来ている。   While automobiles are becoming lighter for the purpose of reducing exhaust gas and improving fuel efficiency, there is a strong demand for reducing the weight of components mounted on automobiles. Among them, wire harnesses are no exception, and the diameter of electric wires for the purpose of weight reduction has been increasing.

図2は、従来の自動車用電線の構造の一例を示す断面図であり、同図の例では、7本の素線10が同心撚りされて撚り線20となっており、それが、絶縁層30によって被覆されている。
従来の自動車用電線の素線の材料には、主に軟銅が用いられているが(例えば、特許文献1参照)、細径化に伴って強度が低下し、例えば、耐屈曲性の低下(これによって、より少ない回数の曲げによって断線してしまう)や、配策時での断線のトラブルなどが発生することや、耐衝撃性が低下することも懸念される。
FIG. 2 is a cross-sectional view showing an example of the structure of a conventional automobile electric wire. In the example of FIG. 2, seven strands 10 are concentrically twisted to form a stranded wire 20, which is an insulating layer. 30.
As a material of the conventional wire of an automobile electric wire, soft copper is mainly used (see, for example, Patent Document 1). However, the strength is reduced as the diameter is reduced, for example, the bending resistance is reduced ( This may cause disconnection due to a smaller number of bends), occurrence of problems such as disconnection at the time of routing, and a decrease in impact resistance.

しかし、本発明者等の検討によれば、導体の強度向上のために銅合金を採用した態様(例えば、特許文献2)では、強度が高いが故に癖(捩れや湾曲した状態などの、線全体としてのもとの形態が弾性的に維持される性質)が残り、また、電線に「はじけ(可撓性が低下する現象)」が生じるため、ハーネス化における作業が困難となる。
また、細径化に伴って絶縁体層が薄くなり、電線全体の耐磨耗性が低下するという問題もある。
特開平06−275135号公報 特開平07−192535号公報
However, according to the study by the present inventors, in an embodiment in which a copper alloy is used to improve the strength of the conductor (for example, Patent Document 2), since the strength is high, wrinkles (twisted or curved state) The original shape as a whole is maintained elastically), and the electric wire is “bounced (a phenomenon in which flexibility is reduced)”, which makes it difficult to work on the harness.
In addition, as the diameter is reduced, the insulator layer becomes thinner, and there is a problem that the wear resistance of the entire electric wire is lowered.
Japanese Patent Laid-Open No. 06-275135 Japanese Patent Laid-Open No. 07-192535

本発明が解決しようとする課題は、上記問題を解決し、導体の細径化を達成しながらも、耐屈曲性および耐衝撃性に優れ、充分な耐磨耗性を有し、かつハーネス化のための作業性も良好な自動車用電線を提供することにある。   The problem to be solved by the present invention is to solve the above problems and achieve a reduction in the diameter of the conductor, while being excellent in bending resistance and impact resistance, having sufficient wear resistance, and being harnessed. It is to provide an electric wire for automobiles having good workability.

本発明者等は、上記課題を解決すべく鋭意検討した結果、特定組成の銅合金を焼鈍することによって特定値以上の伸びと引張強さを付与し、この銅合金を用いて従来よりも細い素線とし、従来の7本よりも多い本数でかつ特定のピッチで撚り線にし、これを絶縁層で被覆した電線とすれば、耐屈曲性および耐衝撃性に優れ、充分な耐磨耗性を有し、かつハーネス化が可能であることを見出し、本発明完成に至った。   As a result of intensive studies to solve the above-mentioned problems, the present inventors imparted an elongation and a tensile strength exceeding a specific value by annealing a copper alloy having a specific composition, and this copper alloy is thinner than before. If the wire is twisted wire with a specific pitch and more than 7 wires, and this wire is covered with an insulating layer, it has excellent bending resistance and impact resistance, and sufficient wear resistance And the present invention has been completed.

即ち、本発明は、次の特徴を有するものである。
(1)複数本の素線からなる撚り線が、絶縁層によって被覆された構成を有し、
前記素線は、0.05〜0.7質量%のスズを含有する銅合金からなり、線径が0.05〜0.12mmとされ、伸線工程中に焼鈍されて伸びが15%以上かつ引張強さが250MPa以上とされたものであり、かつ、
前記撚り線は、前記素線を10本以上用いて撚られたものであり、その撚り線外径の30〜50倍のピッチを有するものとなっていることを特徴とする、自動車用電線。
(2)撚り線が、集合撚りにて撚り合わされたものである、上記(1)記載の自動車用電線。
(3)絶縁層の厚さが0.16〜0.25mmである、上記(1)または(2)記載の自動車用電線。
(4)熱可塑性樹脂成分(A)100質量部と、有機パーオキサイド(B)0.01〜0.6質量部と、(メタ)アクリレート系および/またはアリル系架橋助剤(C)0.03〜1.8質量部と、金属水和物50〜300質量部(D)とを含有し、かつ前記熱可塑性樹脂成分(A)の溶融温度以上で加熱および混練してなる難燃性樹脂組成物が、上記絶縁層の材料として用いられており、
前記熱可塑性樹脂成分(A)が、以下の(a)〜(d)成分:
(a)ビニル芳香族化合物をその構成成分の主体とした少なくとも2個の重合体ブロックAと、共役ジエン化合物をその構成成分の主体とした少なくとも1個の重合体ブロックBとからなるブロック共重合体、および/または、これを水素添加して得られる水添ブロック共重合体100質量部、
(b)非芳香族系ゴム用軟化剤0〜130質量部、
(c)エチレン・α−オレフィン共重合体400質量部を越え3800質量部以下、および
(d)示差走査熱量計により測定される融点(Tm)が163℃以下であり、かつ結晶融解熱量(△Hm)が55J/g以下であるアタクチックポリプロピレン重合体を主成分とするポリプロピレン樹脂200〜3800質量部
からなり、かつ
前記金属水和物(D)が、
(i)50質量部以上100質量部未満の場合は、その50質量部以上がシランカップリング剤で前処理されており、
(ii)100質量部以上300質量部以下の場合は、その少なくとも半量がシランカップリング剤で前処理されている、
上記(1)〜(3)のいずれかに記載の自動車用電線。
That is, the present invention has the following characteristics.
(1) A stranded wire composed of a plurality of strands has a configuration covered with an insulating layer,
The said strand consists of a copper alloy containing 0.05-0.7 mass% tin, a wire diameter shall be 0.05-0.12 mm, and it is annealed during a wire-drawing process and elongation is 15% or more. And the tensile strength is 250 MPa or more, and
The said strand wire is twisted using 10 or more of the said strand, It has a pitch 30 to 50 times the strand wire outer diameter, The electric wire for motor vehicles characterized by the above-mentioned.
(2) The automotive electric wire according to (1) above, wherein the stranded wire is twisted by collective twisting.
(3) The automotive electric wire according to (1) or (2), wherein the insulating layer has a thickness of 0.16 to 0.25 mm.
(4) 100 parts by mass of the thermoplastic resin component (A), 0.01 to 0.6 parts by mass of the organic peroxide (B), (meth) acrylate-based and / or allylic crosslinking aid (C) 0. Flame retardant resin containing 03 to 1.8 parts by mass and metal hydrate 50 to 300 parts by mass (D), and heated and kneaded at a temperature equal to or higher than the melting temperature of the thermoplastic resin component (A). A composition is used as a material for the insulating layer;
The thermoplastic resin component (A) includes the following components (a) to (d):
(A) a block copolymer comprising at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound 100 parts by mass of a combined block and / or a hydrogenated block copolymer obtained by hydrogenating this,
(B) 0 to 130 parts by mass of a non-aromatic rubber softener,
(C) The ethylene / α-olefin copolymer exceeds 400 parts by mass and is 3800 parts by mass or less, and (d) the melting point (Tm) measured by a differential scanning calorimeter is 163 ° C. or less and the heat of crystal fusion (Δ Hm) is composed of 200 to 3800 parts by mass of a polypropylene resin whose main component is an atactic polypropylene polymer having 55 J / g or less, and the metal hydrate (D)
(I) In the case of 50 parts by mass or more and less than 100 parts by mass, 50 parts by mass or more thereof are pretreated with a silane coupling agent,
(Ii) In the case of 100 parts by mass or more and 300 parts by mass or less, at least half of the quantity is pretreated with a silane coupling agent.
The automobile electric wire according to any one of the above (1) to (3).

導体抗張力を高めるために高強度の材料を用いた従来の同心撚り品(従来品)では、上記したとおり、癖が強いため、ハーネス化のための作業が困難であった。
これに対して、本発明では、極細線を多数本用いて撚っているので癖が著しく低減し、ハーネス化が容易である。
また、本発明では、焼鈍によって銅合金に特定値以上の伸びと引張強さを付与しているので、細径化に伴う耐屈曲性の低下が抑制されている。
さらには、素線を従来品よりも細径とし、これを従来品よりも多数本用いて撚っているので、撚り線の外周の凹凸が微細になり、絶縁層の肉厚が、従来品よりも均一化されたものとなっている。これによって、耐磨耗性の低下が改善されている。
さらには、本発明では、素線に対して伸線工程中に少なくとも1回の焼鈍を行なっているため、自動車電線に必要な特性である耐衝撃性に優れている。
従って、本発明によれば、自動車用電線の軽量化が可能である。
In the conventional concentric stranded product (conventional product) using a high-strength material in order to increase the conductor tensile strength, as described above, since the wrinkles are strong, the work for making a harness is difficult.
On the other hand, in this invention, since it twists using many extra fine wires, wrinkles reduce remarkably and it is easy to make a harness.
Moreover, in this invention, since the elongation and tensile strength more than a specific value are provided to the copper alloy by annealing, the fall of the bending resistance accompanying diameter reduction is suppressed.
Furthermore, since the strands are made thinner than the conventional product and are twisted using a larger number than the conventional product, the irregularities on the outer periphery of the stranded wire become finer, and the thickness of the insulating layer is smaller than the conventional product. It has become more uniform. This improves the reduction in wear resistance.
Furthermore, in the present invention, since the wire is annealed at least once during the wire drawing process, it is excellent in impact resistance, which is a characteristic required for automobile wires.
Therefore, according to this invention, the weight reduction of the electric wire for motor vehicles is possible.

本発明による自動車用電線は、図1に示すように、複数本の素線1からなる撚り線2が、絶縁層3によって被覆された構成を有する。素線1の材料は、銅合金であって、スズの含有率が0.05〜0.7質量%に特定されている。また、素線1の線径は、従来品の素線よりも細い0.05〜0.12mmが選択され、伸線工程中に焼鈍が施されて、伸びが15%以上、かつ引張強さが250MPa以上のものとなっている。また、撚り線2は、前記のとおり材料と強度と線径とを限定した素線1を10本以上用いて撚られたものであり、ピッチが、その撚り線外径の30〜50倍に限定されている。
このように各要素を限定した構成とすることによって、上記の作用効果が得られ、本発明の目的が達成される。
As shown in FIG. 1, the automotive electric wire according to the present invention has a configuration in which a stranded wire 2 composed of a plurality of strands 1 is covered with an insulating layer 3. The material of the strand 1 is a copper alloy, and the tin content is specified to be 0.05 to 0.7 mass%. Further, the wire diameter of the strand 1 is selected to be 0.05 to 0.12 mm, which is thinner than the conventional strand, and annealing is performed during the wire drawing process, the elongation is 15% or more, and the tensile strength. Is 250 MPa or more. Further, the stranded wire 2 is twisted using 10 or more strands 1 with limited material, strength and wire diameter as described above, and the pitch is 30 to 50 times the outer diameter of the stranded wire. Limited.
Thus, by setting each element as a limited structure, the above-described effects can be obtained, and the object of the present invention can be achieved.

素線の材料は、銅とスズとを含有する銅合金であって、スズの含有量は、0.05〜0.7質量%であり、好ましくは0.2〜0.5質量%である。スズの含有量を前記の範囲とすることにより、固溶硬化および伸線加工(冷間加工)による素線の強度を向上させることができる。
前記銅合金には、不可避的不純物が含まれていてもよい。
The material of the strand is a copper alloy containing copper and tin, and the tin content is 0.05 to 0.7% by mass, preferably 0.2 to 0.5% by mass. . By setting the content of tin in the above range, the strength of the wire by solid solution hardening and wire drawing (cold working) can be improved.
The copper alloy may contain inevitable impurities.

素線の線径は、0.05〜0.12mmであり、好ましくは0.08〜0.10mmである。素線の線径を前記の範囲とすることにより、個々の素線の癖が低減し、これによって電線全体としての癖も低減する。また、素線の線径が0.05mmより小さいと生産性が低下し、0.12mmより大きいと、集合撚りして得られる集合撚り線の断面形状が円形から外れ、絶縁層の厚さを薄くできなくなり、細径というメリットがなくなる。   The wire diameter of the strand is 0.05 to 0.12 mm, preferably 0.08 to 0.10 mm. By setting the wire diameter of the wire within the above range, wrinkles of individual wires are reduced, thereby reducing wrinkles of the entire electric wire. Also, if the wire diameter is smaller than 0.05 mm, the productivity is reduced, and if it is larger than 0.12 mm, the cross-sectional shape of the collective stranded wire obtained by collective twisting is out of a circle, and the thickness of the insulating layer is reduced. It cannot be made thin, and the merit of small diameter is lost.

素線の機械的性質のうち、伸びは15%以上であり、好ましくは20〜25%である。また、引張強さは250MPa以上であり、好ましくは300〜350MPaである。
伸び、引張強さは、JIS C 3002に準拠して求められる。
これらの特性を得るために、素線の伸線工程中に焼鈍を少なくとも1回行う。焼鈍を施すための方法は、公知の方法を用いてよく、通電焼鈍が生産性の点で好ましいが、管状炉内を通過させる焼鈍、バッチ式の焼鈍等であってもよい。
Of the mechanical properties of the strands, the elongation is 15% or more, preferably 20 to 25%. Moreover, tensile strength is 250 Mpa or more, Preferably it is 300-350 Mpa.
The elongation and tensile strength are determined according to JIS C 3002.
In order to obtain these characteristics, annealing is performed at least once during the wire drawing step. As a method for performing the annealing, a known method may be used, and electric annealing is preferable from the viewpoint of productivity, but may be annealing through a tubular furnace, batch annealing, or the like.

撚り線は、上記素線を10本以上、好ましくは15〜50本を用いる。本発明では、従来には無い極細線の素線を、多数本用いて撚ったものであるため、電線の耐屈曲性が向上する。また、10本以上の極細の素線の撚り線とすることにより、撚り線の外周表面の凸凹が小さくなり、導体全体の断面形状が円形に近くなり、絶縁厚さを薄くすることができ、さらに、全周にわたり絶縁層の厚さのばらつきも小さくなる。
その結果、絶縁層全体で耐磨耗性が向上すると同時に、部位毎の耐磨耗性のばらつきも小さくなる。
As the stranded wire, 10 or more, preferably 15 to 50 strands are used. In the present invention, since a number of strands of extra fine wires that have not been conventionally used are twisted, the bending resistance of the electric wire is improved. In addition, by making the strands of 10 or more ultrafine strands, the irregularities on the outer peripheral surface of the strands are reduced, the cross-sectional shape of the entire conductor is close to a circle, and the insulation thickness can be reduced, Furthermore, the variation in the thickness of the insulating layer is reduced over the entire circumference.
As a result, the wear resistance of the entire insulating layer is improved and, at the same time, the variation in wear resistance for each part is reduced.

撚り線の撚り方は、通常、集合撚りでよいが、素線の本数によって可能であれば同心撚りであってもよい。集合撚りは、素線を集めて撚り合わせただけのものであり、製造コストが安いというメリットがある。同心撚りは、図1、2の例のように、素線を同心円状に並べて、断面が多角形状、円形状になるように撚り合わせたものである。これらの撚りは、用途に応じて適宜選択すればよい。   The twisting method of the twisted wire may be generally collective twisting, but may be concentric twisting if possible depending on the number of strands. Collective twisting is simply a matter of collecting and twisting strands, and has the advantage of low manufacturing costs. Concentric twisting is a method in which strands are arranged concentrically and twisted so that the cross section becomes a polygonal shape or a circular shape, as in the examples of FIGS. What is necessary is just to select these twists suitably according to a use.

撚り線の撚りピッチは、撚り線外径の30〜50倍、好ましくは40〜50倍である。「撚りピッチ」とは、素線を、撚り合わせに沿ってたどったときに、撚りが一回転する間に進む距離である。
撚り線外径は、撚り線の一断面に関しては、例えば、図1に符号Dで示すように、差し渡しが最大となる部分の径寸法である。撚り線全体に関しては、その全長のうちの任意の断面において測定した各撚り線外径を平均して、その撚り線の撚り線外径としてよい。
The twist pitch of the stranded wire is 30 to 50 times, preferably 40 to 50 times the stranded wire outer diameter. The “twist pitch” is the distance traveled during one turn of the twist when the strands are traced along the twist.
The outer diameter of the stranded wire is, for example, the diameter dimension of the portion where the passing is maximized, as indicated by a symbol D in FIG. Regarding the entire stranded wire, the stranded wire outer diameter of the stranded wire may be averaged by averaging the stranded wire outer diameters measured in an arbitrary cross section of the entire length.

絶縁層の厚さは、好ましくは0.16〜0.2mmである。
絶縁層の材料は、絶縁電線としても細径であるよう、薄くても絶縁機能を十分に有しているものが好ましく、なかでも、撚り癖を矯正できる程度の硬さを有する材料がより好ましい。
このような材料の例としては、特開2002−105255号公報に記載の難燃性樹脂組成物などが挙げられる。この公報に記載の難燃性樹脂組成物は、概括的には、熱可塑性樹脂成分(A)100質量部と、有機パーオキサイド(B)0.01〜0.6質量部と、(メタ)アクリレート系および/またはアリル系架橋助剤(C)0.03〜1.8質量部と、金属水和物50〜300質量部(D)とを含有し、熱可塑性樹脂成分(A)の溶融温度以上で加熱されかつ混練されてなる難燃性樹脂組成物である。
ここで、熱可塑性樹脂成分(A)は、以下の(a)〜(d)成分からなる。
(a)ビニル芳香族化合物をその構成成分の主体とした少なくとも2個の重合体ブロックAと、共役ジエン化合物をその構成成分の主体とした少なくとも1個の重合体ブロックBとからなるブロック共重合体、および/またはこれを水素添加して得られる水添ブロック共重合体100質量部。
(b)非芳香族系ゴム用軟化剤0〜130質量部。
(c)エチレン・α−オレフィン共重合体400質量部を越え3800質量部以下。
(d)示差走査熱量計により測定される融点(Tm)が163℃以下であり、かつ結晶融解熱量(△Hm)が55J/g以下であるアタクチックポリプロピレン重合体を主成分とするポリプロピレン樹脂200〜3800質量部。
また、金属水和物(D)は、(i)50質量部以上100質量部未満の場合には、その50質量部以上がシランカップリング剤で前処理されたものであり、(ii)100質量部以上300質量部以下の場合には、その少なくとも半量がシランカップリング剤で前処理されたものである。
前記の難燃性樹脂組成物において、(d)は、示差走査熱量計により測定(昇温速度10℃/分・窒素雰囲気下)される融点(Tm)が163℃以下であり、かつ結晶融解熱量(△Hm)が55J/g以下であるアタクチックポリプロピレン重合体を主成分とするポリプロピレン樹脂200〜3800質量部であるが、代わりに、ポリプロピレン樹脂200質量部を越え2500質量部以下としてもよい。
前記の難燃性樹脂組成物を用いて得られる絶縁層は、機械特性、難燃性および耐熱性に優れるとともに、耐油性、耐磨耗性に優れ、圧接加工性にも優れている。さらに再溶融可能な材料を用いて形成されるため、リサイクル性にも富む。
The thickness of the insulating layer is preferably 0.16 to 0.2 mm.
The material of the insulating layer is preferably a material having a sufficient insulation function even if it is thin, such as a thin diameter as an insulated wire, and more preferably a material having a hardness that can correct twisted wrinkles. .
Examples of such materials include flame retardant resin compositions described in JP-A No. 2002-105255. The flame-retardant resin composition described in this publication generally includes 100 parts by mass of the thermoplastic resin component (A), 0.01 to 0.6 parts by mass of the organic peroxide (B), and (meta). Melting thermoplastic resin component (A) containing 0.03-1.8 parts by mass of acrylate-based and / or allyl-based crosslinking aid (C) and 50-300 parts by mass (D) of metal hydrate It is a flame retardant resin composition that is heated at a temperature or higher and kneaded.
Here, the thermoplastic resin component (A) is composed of the following components (a) to (d).
(A) a block copolymer comprising at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound 100 parts by mass of a hydrogenated block copolymer obtained by combining and / or hydrogenating this.
(B) 0 to 130 parts by mass of a non-aromatic rubber softener.
(C) More than 400 parts by mass of ethylene / α-olefin copolymer and 3800 parts by mass or less.
(D) A polypropylene resin 200 mainly composed of an atactic polypropylene polymer having a melting point (Tm) measured by a differential scanning calorimeter of 163 ° C. or lower and a crystal melting heat (ΔHm) of 55 J / g or lower. -3800 mass parts.
Further, when the metal hydrate (D) is (i) 50 parts by mass or more and less than 100 parts by mass, 50 parts by mass or more thereof are pretreated with a silane coupling agent, and (ii) 100 In the case of not less than 300 parts by mass and not more than 300 parts by mass, at least half of it is pretreated with a silane coupling agent.
In the flame retardant resin composition, (d) has a melting point (Tm) measured by a differential scanning calorimeter (temperature increase rate: 10 ° C./min. Under nitrogen atmosphere) of 163 ° C. or lower and crystal melting. The amount of heat (ΔHm) is 200 to 3800 parts by mass of a polypropylene resin whose main component is an atactic polypropylene polymer having 55 J / g or less, but instead, it may be more than 200 parts by mass of polypropylene resin and 2500 parts by mass or less. .
The insulating layer obtained using the flame retardant resin composition is excellent in mechanical properties, flame retardancy and heat resistance, oil resistance and wear resistance, and is excellent in pressure contact processability. Furthermore, since it is formed using a remeltable material, it is rich in recyclability.

上記難燃性樹脂組成物の好ましい組成の例としては次のものが挙げられる。
熱可塑性樹脂成分(A)100質量部、
有機パーオキサイド(B)として、2,5−ジメチル−2,5−ビス(tert−ブチルパーオキシ)ヘキサンまたは2,5−ジメチル−2,5−ビス(tert−ブチルパーオキシ)−3−ヘキシン0.1〜0.6質量部、
(メタ)アクリレート系および/またはアリル系架橋助剤(C)として、トリエチレングリコールジメタクリレート0.03〜1.2質量部、および
金属水和物(D)として、シランカップリング剤で表面処理された水酸化マグネシウム100〜280質量部
の組成の混合物を、熱可塑性樹脂成分(A)の溶融温度以上で加熱および混練して、前記難燃性樹脂組成物を得る。
ここで、熱可塑性樹脂成分(A)は、以下の(a)〜(d)成分からなる。
(a)スチレンをその構成成分の主体とする少なくとも2個の重合体ブロックAと、イソプレンをその構成成分の主体としかつイソプレンの90〜100質量%が1,4−ミクロ構造を有し、かつ該イソプレンに基づく脂肪族二重結合の少なくとも90%が水素添加されたところの重合体ブロックBとからなる重量平均分子量が50,000〜550,000の水添ブロック共重合体100質量部、
(b)芳香族環成分の少ないパラフィン系軟化剤30〜100質量部、
(c)密度0.890g/cm以上のシングルサイト触媒を用いて合成されたエチレン・α−オレフィン共重合体700〜2500質量部、
(d)示差走査熱量計により測定される融点(Tm)が160℃以下であり、かつ結晶融解熱量(△Hm)が40J/g以下である、プロピレンと1−ブテンが共重合したアタクチックポリプロピレン重合体を主成分とするポリプロピレン樹脂200〜3800質量部。
Examples of the preferred composition of the flame retardant resin composition include the following.
100 parts by mass of the thermoplastic resin component (A),
2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane or 2,5-dimethyl-2,5-bis (tert-butylperoxy) -3-hexyne as the organic peroxide (B) 0.1 to 0.6 parts by mass,
(Meth) acrylate-based and / or allyl-based crosslinking aid (C), 0.03-1.2 parts by mass of triethylene glycol dimethacrylate, and metal hydrate (D), surface treatment with silane coupling agent The flame retardant resin composition is obtained by heating and kneading the mixture having a composition of 100 to 280 parts by weight of magnesium hydroxide at a temperature equal to or higher than the melting temperature of the thermoplastic resin component (A).
Here, the thermoplastic resin component (A) is composed of the following components (a) to (d).
(A) at least two polymer blocks A having styrene as a main component, isoprene as a main component, and 90 to 100% by mass of isoprene has a 1,4-microstructure, and 100 parts by weight of a hydrogenated block copolymer having a weight average molecular weight of 50,000 to 550,000 consisting of polymer block B in which at least 90% of the aliphatic double bonds based on the isoprene are hydrogenated,
(B) 30 to 100 parts by mass of a paraffin softener having a small aromatic ring component;
(C) 700-2500 parts by mass of an ethylene / α-olefin copolymer synthesized using a single-site catalyst having a density of 0.890 g / cm 3 or more,
(D) An atactic polypropylene copolymerized with propylene and 1-butene having a melting point (Tm) measured by a differential scanning calorimeter of 160 ° C. or lower and a crystal melting heat (ΔHm) of 40 J / g or lower. 200-3800 parts by mass of a polypropylene resin mainly composed of a polymer.

また、不飽和カルボン酸(例、マレイン酸等)またはその誘導体で変性したポリオレフィン樹脂を、当該熱可塑性樹脂成分(A)に対し、0〜20質量%添加しても良い。当該変性したポリオレフィン樹脂を添加する場合には、当該変性したポリオレフィン樹脂も熱可塑性樹脂成分(A)に含めて考える。
さらに、当該熱可塑性樹脂成分(A)に、熱可塑性樹脂成分(A)100重量部に対して、0.5〜12重量部のシリコーン化合物を添加してもよい。
Moreover, you may add 0-20 mass% of polyolefin resin modified with unsaturated carboxylic acid (for example, maleic acid etc.) or its derivative with respect to the said thermoplastic resin component (A). When the modified polyolefin resin is added, the modified polyolefin resin is also included in the thermoplastic resin component (A).
Furthermore, you may add a 0.5-12 weight part silicone compound to the said thermoplastic resin component (A) with respect to 100 weight part of thermoplastic resin components (A).

以下、本発明を実施例および比較例を挙げて詳細に説明するが、本発明は、これら実施例に限られるものではない。
本実施例では、半硬質Cu−0.3Sn(スズ含有量0.3質量%)製の素線を用いて、表1に示す電線(サイズ0.22SQ)を製造した。
また、比較例1として軟銅製の素線を用い、比較例2として硬質Cu−0.3Sn製の素線を用いて、表1に示す電線(サイズ0.22SQ)を製造した。実施例1、比較例1および2で用いられた絶縁層の材料は、いずれも薄肉用PVC絶縁材である。
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples.
In the present Example, the electric wire (size 0.22SQ) shown in Table 1 was manufactured using the strand made from semi-hard Cu-0.3Sn (tin content 0.3 mass%).
Moreover, the wire (size 0.22SQ) shown in Table 1 was manufactured using the strand made from an annealed copper as the comparative example 1, and using the strand made from hard Cu-0.3Sn as the comparative example 2. The materials of the insulating layers used in Example 1 and Comparative Examples 1 and 2 are all thin-walled PVC insulating materials.

Figure 2006253076
Figure 2006253076

表1において、素線の伸びおよび引張強さはJIS C 3002に準拠して測定した。測定は焼鈍後の素線について行った。   In Table 1, the elongation and tensile strength of the strands were measured according to JIS C 3002. The measurement was performed on the wire after annealing.

また、実施例1、比較例1および2で得られた電線について特性評価を行った。結果を表2に示す。なお、各特性の評価方法は以下の通りである。
導体抗張力:撚り線の状態で引張り試験を行い、破断荷重を求める。サンプル形状などについては、JIS C 3002に準じる。単位はNである。
耐衝撃性:長さ1mのサンプルの一端を外部支持体に固定し、他端におもりを付けて吊り下げる。この状態で、おもりを1mの高さから落下させ、電線(導体)が破断する荷重を求める。単位はkgである。比較例1の結果の値を1とし、それに対する実施例、比較例2の、それぞれの結果の比の値を表2に示す。
耐磨耗性:JASO D 611 ブレード往復法により、絶縁体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する。比較例1の結果の値を1とし、それに対する実施例、比較例2の、それぞれの結果の比の値を表2に示す。
耐屈曲性:サンプルの一端を外部支持体に固定し、他端に引張り荷重をかける。電線の中間部を曲率半径4mmとなるように屈曲させて(マンドレル使用)、電線(導体)が破断する屈曲の回数を求める。比較例2の結果の値を1とし、それに対する実施例の結果の比の値を表2に示す。
ハーネス化評価:ハーネスレイアウトに組み、作業性を確認する。
Further, the electric wires obtained in Example 1 and Comparative Examples 1 and 2 were evaluated for characteristics. The results are shown in Table 2. In addition, the evaluation method of each characteristic is as follows.
Conductor tensile strength: A tensile test is performed in the state of a stranded wire to determine a breaking load. The sample shape and the like conform to JIS C 3002. The unit is N.
Impact resistance: One end of a sample having a length of 1 m is fixed to an external support, and a weight is attached to the other end and suspended. In this state, the weight is dropped from a height of 1 m, and the load at which the electric wire (conductor) breaks is obtained. The unit is kg. The value of the result of the comparative example 1 is set to 1, and the ratio value of each result of the Example and the comparative example 2 is shown in Table 2.
Abrasion resistance: JASO D 611 The number of reciprocations until the blade contacts the conductor due to abrasion of the insulator is measured by a blade reciprocation method. The value of the result of the comparative example 1 is set to 1, and the ratio value of each result of the Example and the comparative example 2 is shown in Table 2.
Bending resistance: One end of the sample is fixed to an external support, and a tensile load is applied to the other end. The middle part of the electric wire is bent so as to have a curvature radius of 4 mm (using a mandrel), and the number of times of bending at which the electric wire (conductor) breaks is obtained. The value of the result of the comparative example 2 is 1, and the value of the ratio of the result of the example to that is shown in Table 2.
Harnessing evaluation: Assembled in the harness layout and confirmed workability.

Figure 2006253076
Figure 2006253076

上記表1、2の通り、本発明の電線は、自動車用電線として充分な導体抗張力を有し、また従来品に比べ耐衝撃性、耐磨耗性、耐屈曲性に優れ、かつハーネス化も可能であることが確認できた。   As shown in Tables 1 and 2 above, the electric wires of the present invention have sufficient conductor tensile strength as electric wires for automobiles, and are superior in impact resistance, wear resistance, and bending resistance compared to conventional products, and are also harnessed. It was confirmed that it was possible.

上記の通り、本発明による自動車用電線は、従来品に比べて導体の細径化が達成されながらも、耐屈曲性および耐衝撃性については優れており、また、充分な耐磨耗性を有し、ハーネス化の作業性も良好である。   As described above, the electric wire for automobiles according to the present invention is superior in bending resistance and impact resistance while achieving a smaller conductor diameter than conventional products, and has sufficient wear resistance. And has good workability for harnessing.

本発明による自動車用電線の構成を模式的に示した断面図(電線の長手方向に垂直な断面で切断した場合の図)である。It is sectional drawing (figure at the time of cut | disconnecting in a cross section perpendicular | vertical to the longitudinal direction of an electric wire) which showed typically the structure of the electric wire for motor vehicles by this invention. 従来の自動車用電線の構成を模式的に示した断面図である。It is sectional drawing which showed the structure of the conventional automotive electric wire typically.

符号の説明Explanation of symbols

1 素線
2 撚り線
3 絶縁層
1 Wire 2 Stranded wire 3 Insulating layer

Claims (4)

複数本の素線からなる撚り線が、絶縁層によって被覆された構成を有し、
前記素線は、0.05〜0.7質量%のスズを含有する銅合金からなり、線径が0.05〜0.12mmとされ、伸線工程中に焼鈍されて伸びが15%以上かつ引張強さが250MPa以上とされたものであり、かつ、
前記撚り線は、前記素線を10本以上用いて撚られたものであり、その撚り線外径の30〜50倍のピッチを有するものとなっていることを特徴とする、
自動車用電線。
A stranded wire composed of a plurality of strands has a configuration covered with an insulating layer,
The said strand consists of a copper alloy containing 0.05-0.7 mass% tin, a wire diameter shall be 0.05-0.12 mm, and it is annealed during a wire-drawing process and elongation is 15% or more. And the tensile strength is 250 MPa or more, and
The stranded wire is twisted using 10 or more strands, and has a pitch of 30 to 50 times the stranded wire outer diameter,
Electric wire for automobiles.
撚り線が、集合撚りにて撚り合わされたものである、請求項1記載の自動車用電線。   The automobile electric wire according to claim 1, wherein the stranded wire is twisted by collective twisting. 絶縁層の厚さが0.16〜0.25mmである、請求項1または2記載の自動車用電線。   The electric wire for motor vehicles of Claim 1 or 2 whose thickness of an insulating layer is 0.16-0.25 mm. 熱可塑性樹脂成分(A)100質量部と、有機パーオキサイド(B)0.01〜0.6質量部と、(メタ)アクリレート系および/またはアリル系架橋助剤(C)0.03〜1.8質量部と、金属水和物50〜300質量部(D)とを含有し、かつ前記熱可塑性樹脂成分(A)の溶融温度以上で加熱および混練してなる難燃性樹脂組成物が、上記絶縁層の材料として用いられており、
前記熱可塑性樹脂成分(A)が、以下の(a)〜(d)成分:
(a)ビニル芳香族化合物をその構成成分の主体とした少なくとも2個の重合体ブロックAと、共役ジエン化合物をその構成成分の主体とした少なくとも1個の重合体ブロックBとからなるブロック共重合体、および/または、これを水素添加して得られる水添ブロック共重合体100質量部、
(b)非芳香族系ゴム用軟化剤0〜130質量部、
(c)エチレン・α−オレフィン共重合体400質量部を越え3800質量部以下、および
(d)示差走査熱量計により測定される融点(Tm)が163℃以下であり、かつ結晶融解熱量(△Hm)が55J/g以下であるアタクチックポリプロピレン重合体を主成分とするポリプロピレン樹脂200〜3800質量部
からなり、かつ
前記金属水和物(D)が、
(i)50質量部以上100質量部未満の場合は、その50質量部以上がシランカップリング剤で前処理されており、
(ii)100質量部以上300質量部以下の場合は、その少なくとも半量がシランカップリング剤で前処理されている、
請求項1〜3のいずれかに記載の自動車用電線。
100 parts by mass of thermoplastic resin component (A), 0.01 to 0.6 parts by mass of organic peroxide (B), (meth) acrylate-based and / or allylic crosslinking aid (C) 0.03-1 A flame retardant resin composition comprising .8 parts by mass and 50 to 300 parts by mass of metal hydrate (D) and heated and kneaded at a temperature equal to or higher than the melting temperature of the thermoplastic resin component (A). , Used as a material for the insulating layer,
The thermoplastic resin component (A) includes the following components (a) to (d):
(A) a block copolymer comprising at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound 100 parts by mass of a combined block and / or a hydrogenated block copolymer obtained by hydrogenating this,
(B) 0 to 130 parts by mass of a non-aromatic rubber softener,
(C) The ethylene / α-olefin copolymer exceeds 400 parts by mass and is 3800 parts by mass or less, and (d) the melting point (Tm) measured by a differential scanning calorimeter is 163 ° C. or less and the heat of crystal fusion (Δ Hm) is composed of 200 to 3800 parts by mass of a polypropylene resin whose main component is an atactic polypropylene polymer having 55 J / g or less, and the metal hydrate (D)
(I) In the case of 50 parts by mass or more and less than 100 parts by mass, 50 parts by mass or more thereof are pretreated with a silane coupling agent,
(Ii) In the case of 100 parts by mass or more and 300 parts by mass or less, at least half of the quantity is pretreated with a silane coupling agent.
The electric wire for motor vehicles in any one of Claims 1-3.
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CN102254596A (en) * 2011-04-25 2011-11-23 江苏天地龙电缆有限公司 Anti-termite shockproof low-temperature resistant breakthrough grounding wire cable
CN102254597A (en) * 2011-04-25 2011-11-23 江苏天地龙电缆有限公司 Photovoltaic cable and manufacture method thereof

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