JP2000219814A - Flame-retardant resin composition and insulated electric wire, tube, heat-shrinkable tube, flat cable and high- voltage wire for dc - Google Patents

Flame-retardant resin composition and insulated electric wire, tube, heat-shrinkable tube, flat cable and high- voltage wire for dc

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Publication number
JP2000219814A
JP2000219814A JP11117559A JP11755999A JP2000219814A JP 2000219814 A JP2000219814 A JP 2000219814A JP 11117559 A JP11117559 A JP 11117559A JP 11755999 A JP11755999 A JP 11755999A JP 2000219814 A JP2000219814 A JP 2000219814A
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JP
Japan
Prior art keywords
acetate
flame
resin composition
retardant resin
ethylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP11117559A
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Japanese (ja)
Other versions
JP4379947B2 (en
Inventor
Kiyoaki Moriuchi
清晃 森内
Hiroshi Hayami
宏 早味
Satoshi Yadoshima
悟志 宿島
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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Priority to JP11755999A priority Critical patent/JP4379947B2/en
Publication of JP2000219814A publication Critical patent/JP2000219814A/en
Application granted granted Critical
Publication of JP4379947B2 publication Critical patent/JP4379947B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Compositions Of Macromolecular Compounds (AREA)
  • Inorganic Insulating Materials (AREA)
  • Organic Insulating Materials (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition exhibiting excellent flame-retardancy and mechanical strength and free from the generation of harmful gas by compounding a thermoplastic resin with specific amount of a metal hydroxide, an acetate or calcium carbonate. SOLUTION: The objective resin composition is produced by compounding (A) 100 pts.wt. of a thermoplastic resin (preferably an ethylene-α-olefin copolymer such as ethylene-vinyl acetate copolymer) with (B) 100-250 pts.wt. of a metal hydroxide (e.g. magnesium hydroxide or calcium hydroxide), (C) 5-50 pts.wt. of an acetate (preferably magnesium acetate, sodium acetate, etc., having a particle diameter of 0.5-5 μm) or (D) 5-80 pts.wt. of calcium carbonate (preferably having a primary particle diameter of <=4 μm and treated with a surface- treating agent such as fatty acid-based agent or oil and fat-based agent). The composition can be applied to a conductor by extrusion coating with a melt extruder, etc., to obtain a flame-retardant insulated wire or flat cable.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、燃焼時にハロゲン
化水素等の有害ガスの発生がなく、機械的強度に優れる
難燃性樹脂組成物と該組成物を用いた絶縁電線、チュー
ブ、熱収縮チューブ、フラットケーブル及び直流用高圧
電線に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition which does not generate harmful gases such as hydrogen halide during combustion and has excellent mechanical strength, and an insulated wire, tube, and heat shrink using the composition. The present invention relates to a tube, a flat cable, and a high-voltage electric wire for direct current.

【０００２】[0002]

【従来の技術及び課題】電子機器や自動車の分野に使用
される絶縁電線の絶縁体やチューブ、熱収縮チューブ、
フラットケーブルの絶縁体及びテレビジョン、電磁調理
器、複写機等に使用される直流用高圧電線の絶縁体やシ
ースの機械的強度は、抗張力（破断伸び時の引張強さ）
が１．０ｋｇ／ｍｍ2 以上あることが一般に要求されて
おり、例えば、電子機器分野で幅広く認められているＵ
Ｌ規格を参考にすると、ポリエチレン等のプラスチック
を絶縁体とする絶縁電線やチューブ、熱収縮チューブ、
フラットケーブルでは、初期抗張力１．０６ｋｇ／ｍｍ
2 以上あることが要求されている。また、上記の分野で
使用される絶縁電線及びチューブ、熱収縮チューブ、フ
ラットケーブル及び直流用高圧電線には難燃性も要求さ
れ、一般に自動車分野では水平難燃性、電子機器分野で
は垂直難燃性が要求されている。2. Description of the Related Art Insulators and tubes of insulated wires used in the field of electronic devices and automobiles, heat-shrinkable tubes,
The mechanical strength of insulators and sheaths of flat cable insulators and DC high-voltage electric wires used in televisions, electromagnetic cookers, copiers, etc. is tensile strength (tensile strength at break elongation).
Is generally required to be at least 1.0 kg / mm 2 , for example, U which is widely recognized in the field of electronic devices.
In reference to the L standard, insulated wires and tubes, heat-shrinkable tubes,
For a flat cable, the initial tensile strength is 1.06 kg / mm
Two or more are required. Insulated wires and tubes, heat-shrinkable tubes, flat cables and DC high-voltage wires used in the above fields are also required to be flame-retardant. Is required.

【０００３】垂直難燃性の試験方法としては、例えば図
１に示したSubject ７５８に記載されるＵＬ規格の垂直
試験（ＶＷ−１試験）が著名であり、この試験は絶縁電
線及びチューブ、熱収縮チューブ、フラットケーブル、
直流用高圧電線の試料５を止め具３により垂直に設置
し、その下部よりバーナー２の炎を１５秒間着火を５回
繰り返した時に、それぞれ６０秒以内に消火し、下部に
敷いた脱脂綿４が燃焼落下物によって類焼したり、試料
の上部に取り付けたクラフト紙１が燃えたり、焦げたり
してはならないという燃焼試験であり、このバーナーに
よる着火を同一試料について５回繰り返すものである。
チューブの場合は、ＶＷ−１試験の他に、チューブの内
径に等しい金属棒を挿入してＶＷ−１試験と同様の試験
を行うオールチュービングフレームテストによって難燃
性を評価する場合もある。また、熱収縮チューブの場合
も、熱収縮後の内径に等しい金属棒に熱収縮チューブを
被覆してＶＷ−１試験と同様の試験を行うオールチュー
ビングフレームテストで難燃性を評価する場合がある。As a vertical flame retardancy test method, for example, a UL standard vertical test (VW-1 test) described in Subject 758 shown in FIG. Shrink tubing, flat cable,
A DC high-voltage electric wire sample 5 was placed vertically by the stopper 3, and when the flame of the burner 2 was ignited 5 times from the lower portion for 15 seconds, the fire was extinguished within 60 seconds, and the cotton wool 4 laid at the lower portion was removed. This is a combustion test in which the burning of the kraft paper 1 attached to the upper part of the sample must not be burned or burned by a burning falling object, and the ignition by the burner is repeated five times for the same sample.
In the case of a tube, in addition to the VW-1 test, the flame retardancy may be evaluated by an all-tubing frame test in which a metal rod equal to the inner diameter of the tube is inserted and a test similar to the VW-1 test is performed. Also, in the case of a heat-shrinkable tube, flame retardancy may be evaluated by an all-tubing frame test in which a metal rod having an inner diameter equal to the inner diameter after heat-shrinkage is coated with the heat-shrinkable tube and a test similar to the VW-1 test is performed. .

【０００４】上述のような絶縁電線の絶縁体やチュー
ブ、熱収縮チューブ、フラットケーブルの絶縁体の機械
的強度と難燃性を満足させる材料としては、古くから軟
質ポリ塩化ビニル組成物のようなポリ塩化ビニルを主体
とする樹脂組成物が知られており、機械的強度と難燃性
の両面に優れ、しかも安価であることから電子機器や自
動車の分野で使用される絶縁電線やフラットケーブルの
構成材料として幅広く利用されている。ところが、ポリ
塩化ビニルを用いた樹脂組成物は一旦着火すると、塩化
水素ガス等の人体に有害な燃焼ガスを発生するだけでな
く、樹脂組成物中に加工安定性の点から鉛系化合物等の
重金属物質を配合したものが多く、環境にとって必ずし
も好ましくない側面を有している。As materials for satisfying the mechanical strength and flame retardancy of the insulators and tubes of the above-mentioned insulated wires, the heat-shrinkable tubes, and the insulators of the flat cables, there have long been used materials such as soft polyvinyl chloride compositions. A resin composition mainly composed of polyvinyl chloride is known, and is excellent in both mechanical strength and flame retardancy, and is inexpensive, so that it is used for insulated wires and flat cables used in the field of electronic devices and automobiles. It is widely used as a constituent material. However, once ignited, a resin composition using polyvinyl chloride not only generates a combustion gas harmful to the human body such as hydrogen chloride gas, but also contains a lead compound or the like in the resin composition from the viewpoint of processing stability. Many contain heavy metal substances, and have aspects that are not necessarily favorable to the environment.

【０００５】このような問題の配慮から、ポリエチレン
等のエチレン重合体に含リン系の難燃剤を配合した難燃
性樹脂組成物や水酸化アルミニウム、水酸化マグネシウ
ム等の難燃剤を配合したいわゆるノンハロゲン難燃性樹
脂組成物が知られており、実用化されているものであ
る。ところが、含リン系難燃剤は急性の経口毒性を示す
ものや、絶縁電線やフラットケーブルの樹脂組成物中に
配合すると、導体を腐食させてしまう等の問題がある。
一方、金属水酸化物の難燃剤はエチレン系重合体等のプ
ラスチックに対する難燃効果は小さく、ポリ塩化ビニル
樹脂組成物と同等の難燃性を発現させるには、製品の形
態やサイズによって一概に言えないが、例えばポリエチ
レン等のエチレン系重合体１００重量部に対して、金属
水酸化物を１００重量部以上配合する必要があり、この
ようにベース樹脂中に金属水酸化物を大量に配合する
と、樹脂組成物の機械的強度が著しく低下するという問
題があった。In consideration of such problems, a flame-retardant resin composition comprising a phosphorus-containing flame retardant blended with an ethylene polymer such as polyethylene or a so-called non-halogen blend comprising a flame retardant such as aluminum hydroxide or magnesium hydroxide is blended. Flame-retardant resin compositions are known and have been put to practical use. However, phosphorus-containing flame retardants exhibit problems such as acute oral toxicity and corrosion of conductors when incorporated into resin compositions of insulated wires and flat cables.
On the other hand, the flame retardant of metal hydroxide has a small flame-retardant effect on plastics such as ethylene-based polymers. Although it cannot be said, for example, it is necessary to mix 100 parts by weight or more of a metal hydroxide with respect to 100 parts by weight of an ethylene-based polymer such as polyethylene. In addition, there is a problem that the mechanical strength of the resin composition is significantly reduced.

【０００６】ＵＬ規格に準拠する機器内配線用の絶縁電
線は、通常、３０Ｖ定格で０．１５ｍｍ以上、３００Ｖ
で０．４ｍｍ以上、６００Ｖ定格で０．８ｍｍ以上と最
小厚みが定められており、また、機器内配線用の絶縁電
線は、配線の引き回しを容易にするため、絶縁電線の外
径は出来るだけ細いことが好ましく、導体も特殊な場合
を除いて、おおよそ１．０ｍｍφ以下のものが使用され
る（住友電工（株）発行「電子ワイヤー製品要覧」１３
頁参照）。ところが導体外径が１．０ｍｍ以下で、しか
も絶縁被覆の厚みが０．１ｍｍ以上１．０ｍｍ以下でＶ
Ｗ−１試験に合格し、しかも初期破断抗張力等の機械的
強度を満足するハロゲンを含まないポリオレフィン絶縁
電線は、これまで知られていなかったが、最近、ＵＬ規
格を満たした薄肉高強度ノンハロゲン絶縁電線が開発さ
れている（特許第２５２５９８２号、第２５２５９６８
号）。この絶縁電線はＶＷ−１試験の規格である６０秒
以内の消火は満たすが、２０秒以上燃え続ける場合があ
り、更に難燃性の高いノンハロゲン難燃電線の開発が望
まれていた。[0006] Insulated wires for wiring in equipment conforming to the UL standard are generally rated at 30 V, at least 0.15 mm, and 300 V.
The minimum thickness is specified as 0.4 mm or more at 600 V and 0.8 mm or more at 600 V rating. Also, the outer diameter of the insulated wire for equipment wiring should be as small as possible to facilitate wiring routing. It is preferable that the conductor is thin, and a conductor having a diameter of about 1.0 mmφ or less is used except for a special case (refer to “Summary of Electronic Wire Products” published by Sumitomo Electric Industries, Ltd.
Page). However, if the conductor outer diameter is 1.0 mm or less and the thickness of the insulating coating is 0.1 mm or more and 1.0 mm or less, V
Polyolefin insulated wires that pass the W-1 test and do not contain halogen that satisfy mechanical strength such as initial breaking tensile strength have not been known so far. Electric wires have been developed (Japanese Patent Nos. 2525982 and 2525968).
issue). This insulated wire satisfies the fire extinguishing within 60 seconds, which is the standard of the VW-1 test, but may continue to burn for 20 seconds or more, and it has been desired to develop a non-halogen flame-retardant wire having higher flame retardancy.

【０００７】一方、直流用高圧電線に関しては、耐トラ
ッキング性を活かすためにポリエチレン等のエチレン−
αオレフィン共重合体が導体上に被覆されるが、ポリエ
チレンの欠点である易燃性を塩化ビニル単量体やハロゲ
ンを含む単量体を繰返単位として含有する重合体を主体
とする難燃性樹脂組成物を被覆することによって電線全
体の難燃性を確保していた。しかし、やはりポリ塩化ビ
ニルを用いた樹脂組成物は一旦着火すると、塩化水素ガ
ス等の人体に有害な燃焼ガスを発生するだけでなく、樹
脂組成物中に加工安定性の点から鉛系化合物等の重金属
物質を配合したものが多く、環境にとって必ずしも好ま
しくない側面を有しているためノンハロゲンの直流用高
圧電線が望まれていた。On the other hand, with respect to DC high-voltage electric wires, ethylene-based materials such as polyethylene are used in order to take advantage of tracking resistance.
Although the α-olefin copolymer is coated on the conductor, the flame retardancy, which is a drawback of polyethylene, is mainly based on a polymer containing a vinyl chloride monomer or a monomer containing halogen as a repeating unit. By coating the conductive resin composition, the flame resistance of the entire electric wire was ensured. However, once ignited, a resin composition using polyvinyl chloride not only generates a combustion gas harmful to the human body such as hydrogen chloride gas, but also generates a lead-based compound or the like in the resin composition from the viewpoint of processing stability. Many heavy metal substances are blended, and they have aspects that are not necessarily favorable to the environment. Therefore, non-halogen DC high-voltage electric wires have been desired.

【０００８】[0008]

【課題を解決するための手段】本発明者は上記課題につ
いて種々検討した結果、熱可塑性樹脂１００重量部に対
して、金属水酸化物１００〜２５０重量部、酢酸塩５〜
５０重量部或いは炭酸カルシウム５〜８０重量部を配合
することにより、燃焼時に塩化水素ガスのようなハロゲ
ン化水素等の有害な燃焼ガスの発生がなく、しかも、こ
の酢酸塩或いは炭酸カルシウムを配合してなる難燃性樹
脂組成物は、酢酸塩或いは炭酸カルシウムを配合しない
難燃性樹脂組成物と比較してその限界酸素指数（ＬＯ
Ｉ）に大差は見られないが、ＵＬ規格のＶＷ−１試験で
ＰＶＣと同等以上の難燃性を示し、機械的強度にも優れ
た難燃性樹脂組成物と、それを用いた絶縁電線及びチュ
ーブ、熱収縮チューブ、フラットケーブル、及び直流用
高圧電線を提供できることを見出し、本発明を完成する
に至った。As a result of various studies on the above problems, the present inventors have found that 100 to 250 parts by weight of a metal hydroxide, 100 to 250 parts by weight of a metal hydroxide,
By mixing 50 parts by weight or 5 to 80 parts by weight of calcium carbonate, there is no generation of harmful combustion gas such as hydrogen halide gas such as hydrogen chloride gas at the time of combustion. The flame retardant resin composition of the present invention has a lower oxygen index (LO) than that of the flame retardant resin composition containing no acetate or calcium carbonate.
Although there is no significant difference in I), a flame-retardant resin composition exhibiting flame retardancy equal to or higher than that of PVC in a VW-1 test of UL standard and excellent in mechanical strength, and an insulated wire using the same The present inventors have found that a tube, a heat-shrinkable tube, a flat cable, and a high-voltage electric wire for direct current can be provided, and have completed the present invention.

【０００９】即ち、本発明は： 〔Ｉ〕難燃性樹脂組成物： 熱可塑性樹脂１００重量部に対して、金属水酸化物
１００〜２５０重量部、酢酸塩５〜５０重量部或いは炭
酸カルシウム５〜８０重量部を配合してなる、難燃性樹
脂組成物を提供する。また、 炭酸カルシウムが５〜３０重量部配合する点にも特
徴を有する。また、 熱可塑性樹脂がエチレン−酢酸ビニル共重合体、エ
チレン−アクリル酸エチル共重合体、エチレン−メタク
リル酸メチル共重合体、エチレン−メタクリル酸共重合
体、エチレン−アクリル酸メチル共重合体から選択され
た１種のエチレン−αオレフィン共重合体或いはこれら
２種以上の混合物であることを特徴とする。また、 エチレン−αオレフィン共重合体が、酢酸ビニル成
分含有率６〜５０％でかつメルトフロレート（１９０
℃、２．１６ｋｇ荷重下）０．５〜３０であるエチレン
−酢酸ビニル共重合体である点にも特徴を有する。ま
た、That is, the present invention provides: [I] Flame-retardant resin composition: 100 to 250 parts by weight of metal hydroxide, 5 to 50 parts by weight of acetate, or 5 parts by weight of calcium carbonate per 100 parts by weight of thermoplastic resin Provided is a flame-retardant resin composition, which is blended with ８０80 parts by weight. It is also characterized in that 5 to 30 parts by weight of calcium carbonate is blended. In addition, the thermoplastic resin is selected from ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer Or a mixture of two or more of these ethylene-α-olefin copolymers. The ethylene-α-olefin copolymer has a vinyl acetate component content of 6 to 50% and a melt flow rate of 190 to 190%.
It is also characterized in that it is an ethylene-vinyl acetate copolymer having a temperature of 0.5 to 30 under a load of 2.16 kg at a temperature of 2.degree. Also,

【００１０】 更に一般式〔Ｉ〕：カーボネートFurther, a general formula [I]: carbonate

【化２】 （ただし、Ｒはアクリル基、メタクリル基又はアリル基
を含有するアルキル基であり、Ｙ1 、Ｙ2 、Ｙ3 はアル
キル基、アルコキシ基、ハロゲン基からなる群より選ば
れた原子団を表す。）の有機ケイ素化合物カップリング
剤が、エチレン−αオレフィン共重合体１００重量部に
対して０．１〜１０重量部添加されていることを特徴と
する。また、 酢酸塩が、粒径０．５〜５μｍの酢酸マグネシウ
ム、酢酸ナトリウム、酢酸カリウム、酢酸亜鉛、酢酸
銅、酢酸鉄、酢酸カルシウム、酢酸アルミニウム、酢酸
ニッケル、酢酸コバルト、酢酸ガリウム、酢酸銀、酢酸
錫、酢酸バリウム、、酢酸セリウム、酢酸鉛、酢酸ベリ
リウムから選択された１種或いはこれら２種以上の混合
物である点にも特徴を有する。また、 炭酸カルシウムの一次粒子径が４μｍ以下である
点にも特徴を有する。また、 炭酸カルシウムが脂肪酸系、油脂系、界面活性剤
系、ワックス系等の表面処理剤によって処理された炭酸
カルシウム、或いはシラン系、チタネート系、アルミニ
ウム系、ジルコアルミニウム系、カルボン酸系、リン酸
系等のカップリング剤で処理された炭酸カルシウムから
選択された１種或いはこれら２種以上の混合物である点
にも特徴を有する。Embedded image (However, R is an alkyl group containing an acryl group, a methacryl group, or an allyl group, and Y 1 , Y 2 , and Y 3 represent an atomic group selected from the group consisting of an alkyl group, an alkoxy group, and a halogen group. Wherein the organic silicon compound coupling agent is added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the ethylene-α-olefin copolymer. In addition, the acetate has a particle size of 0.5 to 5 μm, such as magnesium acetate, sodium acetate, potassium acetate, zinc acetate, copper acetate, iron acetate, calcium acetate, aluminum acetate, nickel acetate, cobalt acetate, gallium acetate, silver acetate, It is also characterized in that it is one selected from tin acetate, barium acetate, cerium acetate, lead acetate, and beryllium acetate, or a mixture of two or more thereof. Another feature is that the primary particle size of calcium carbonate is 4 μm or less. Further, calcium carbonate obtained by treating calcium carbonate with a surface treatment agent such as a fatty acid type, oil type, surfactant type, wax type, or silane type, titanate type, aluminum type, zircon aluminum type, carboxylic acid type, phosphoric acid type It is also characterized in that it is one kind selected from calcium carbonate treated with a coupling agent such as a system or a mixture of two or more kinds thereof.

【００１１】〔ＩＩ〕絶縁電線 〔Ｉ〕の〜のいずれかに記載の難燃性樹脂組成
物の被覆層を具えた絶縁電線を提供する。また、 該被覆層が架橋されてなる点に特徴を有する。ま
た、 導体外径が１．０ｍｍ以下の導体に、〔Ｉ〕の〜
のいずれかに記載の難燃性樹脂組成物が０．１ｍｍ以
上１．０ｍｍ以下の厚みで被覆されており、該被覆層が
架橋されている薄肉高強度絶縁電線を提供する。 〔ＩＩＩ〕絶縁チューブ等 〔Ｉ〕の〜のいずれかに記載の難燃性樹脂組成
物でチューブ状に成形した絶縁チューブを提供する。ま
た、 該チューブ層が架橋されている点に特徴を有する。
また、 〔Ｉ〕の〜のいずれかに記載の難燃性樹脂組成
物のチューブ状成形物が架橋された後、加熱下で径方向
に膨張され、その形状を冷却固定した熱収縮チューブを
提供する。[II] An insulated electric wire An insulated electric wire provided with a coating layer of the flame-retardant resin composition according to any one of [I] to [1]. It is also characterized in that the coating layer is crosslinked. In addition, for conductors with a conductor outer diameter of 1.0 mm or less,
The present invention provides a thin high-strength insulated wire in which the flame-retardant resin composition according to any one of the above is coated with a thickness of 0.1 mm or more and 1.0 mm or less, and the coating layer is crosslinked. [III] Insulating tube, etc. Provided is an insulating tube formed into a tubular shape with the flame-retardant resin composition according to any one of [I] to [1]. It is also characterized in that the tube layer is crosslinked.
In addition, the present invention provides a heat-shrinkable tube in which, after a tubular molded product of the flame-retardant resin composition according to any one of the above [I] is crosslinked, it is expanded in a radial direction under heating, and its shape is fixed by cooling. I do.

【００１２】〔ＩＶ〕フラットケーブル 絶縁被覆内に複数本の導体を間隔をおいて並列に配
置したフラットケーブルであって、上記絶縁被覆が
〔Ｉ〕の〜のいずれかに記載の難燃性樹脂組成物か
らなるフラットケーブルを提供する。また、 該絶縁被覆が架橋されている点に特徴を有する。ま
た、 上記絶縁被覆の少なくとも一方の面に高分子材料の
フィルムを貼合せてなる点にも特徴を有する。また、 該絶縁被覆に電離放射線の照射が施されている点に
も特徴を有する。[IV] Flat cable A flat cable in which a plurality of conductors are arranged in parallel in an insulating coating with an interval therebetween, wherein the insulating coating is any of the flame-retardant resin according to any one of [I] to [6]. A flat cable comprising the composition is provided. It is also characterized in that the insulating coating is crosslinked. Another characteristic is that a film of a polymer material is attached to at least one surface of the insulating coating. Another characteristic is that the insulating coating is irradiated with ionizing radiation.

【００１３】〔Ｖ〕直流用高圧電線 絶縁層としてエチレン−αオレフィン共重合体樹脂
組成物が導体上に被覆され、その外層に〜のいずれ
かに記載の難燃性樹脂組成物の被覆層を備えた直流用高
圧電線を提供する。また、 該絶縁層及び被覆層が架橋されている点に特徴を有
する。[V] A high-voltage electric wire for direct current is coated on a conductor with an ethylene-α-olefin copolymer resin composition as an insulating layer, and the outer layer is coated with a coating layer of the flame-retardant resin composition described in any of the above. To provide a high-voltage electric wire for direct current. Further, it is characterized in that the insulating layer and the coating layer are crosslinked.

【００１４】[0014]

【作用】上記の態様による作用をまとめると、以下の通
りになる。 (i) 難燃性樹脂組成物 熱可塑性樹脂１００重量部に対して、金属水酸化物１０
０〜２５０重量部、酢酸塩５〜５０重量部或いは炭酸カ
ルシウム５〜８０重量部を配合した難燃性樹脂組成物は
（請求項１）、燃焼時に塩化水素ガスのようなハロゲン
化水素等の有害な燃焼ガスの発生がなく、しかもＵＬ規
格のＶＷ−１試験でＰＶＣと同等以上の難燃性を示し、
更に機械的強度にも優れた作用を示し、難燃性の絶縁電
線やフラットケーブル、直流用高圧電線として使用可能
である。 (ii)絶縁電線等 ・該難燃性樹脂組成物を導体上に被覆すれば（請求項
９）、難燃性で機械的強度に優れる絶縁電線を得ること
ができる。 ・該絶縁電線を架橋させ、特に電離放射線を照射すれば
（請求項１０）、難燃性及び機械的強度と共に、耐熱
性、耐熱変形性、耐薬品性等にも優れた絶縁電線やフラ
ットケーブルが得られる。 ・該絶縁電線は架橋されていると、極細導体に薄肉絶縁
被覆を設けても高強度で高い難燃性を示すノンハロゲン
絶縁電線が得られる（請求項１１）。The following is a summary of the operation according to the above embodiment. (i) Flame retardant resin composition Metal hydroxide 10 per 100 parts by weight of thermoplastic resin
The flame-retardant resin composition containing 0 to 250 parts by weight, 5 to 50 parts by weight of acetate, or 5 to 80 parts by weight of calcium carbonate (Claim 1) is characterized in that it contains hydrogen chloride such as hydrogen chloride gas during combustion. There is no generation of harmful combustion gas, and it shows the same or higher flame retardancy as PVC in VW-1 test of UL standard,
Furthermore, it exhibits an excellent action in mechanical strength and can be used as a flame-retardant insulated wire, flat cable, or DC high-voltage wire. (ii) Insulated wire, etc. If the flame-retardant resin composition is coated on a conductor (claim 9), an insulated wire having flame retardancy and excellent mechanical strength can be obtained. -If the insulated wire is cross-linked and irradiated with ionizing radiation (claim 10), the insulated wire or flat cable has excellent flame resistance, mechanical strength, heat resistance, heat deformation resistance, chemical resistance, etc. Is obtained. If the insulated wire is crosslinked, a non-halogen insulated wire having high strength and high flame retardancy can be obtained even if a very thin conductor is provided with a thin insulating coating (claim 11).

【００１５】(iii) 絶縁チューブ等 ・該難燃性樹脂組成物をチューブ状に成形したチューブ
とすることができる（請求項１２）。 ・該チューブ層が架橋されていると（請求項１３）、難
燃性及び機械的強度と共に、耐熱性、耐熱変形性、耐薬
品性にも優れた絶縁チューブが得られる。 ・該チューブ状成形物を架橋させ、特に電離放射線を照
射した後、拡径固定すれば（請求項１４）、難燃性及び
機械的強度に優れた熱収縮チューブとすることが可能で
ある。(Iii) Insulating tube, etc. The tube can be formed by molding the flame-retardant resin composition into a tube. When the tube layer is crosslinked (claim 13), an insulating tube having excellent heat resistance, heat deformation resistance and chemical resistance as well as flame retardancy and mechanical strength can be obtained. If the tube-shaped molded product is cross-linked and, in particular, irradiated with ionizing radiation and then fixed in diameter (claim 14), a heat-shrinkable tube excellent in flame retardancy and mechanical strength can be obtained.

【００１６】(iv)フラットケーブル ・導体を並列に配置した並列導体の両面に、該難燃性樹
脂組成物を押出被覆すると（請求項１５）、難燃性で且
つ機械的強度に優れるフラットケーブルを得ることがで
きる。 ・該フラットケーブルの絶縁被覆を架橋させ、特に電離
放射線を照射すれば（請求項１６）、難燃性で且つ機械
的強度に優れると共に、耐熱変形性、耐薬品性にも優れ
たフラットケーブルが得られる。 ・該難燃性樹脂組成物を溶融押出法等により、二軸延伸
ポリエステルフィルム等に貼合せテープを得た後、並列
導体の両面にポリエステルフィルムが外面となるよう
に、２枚のテープを配置して熱ラミネータを用いて絶縁
被覆すれば（請求項１７）、難燃性で且つ機械的強度に
優れるフラットケーブルを得ることができる。 ・この場合、該フラットケーブルに架橋させ、特に電離
放射線を照射すれば（請求項１８）、難燃性で且つ機械
的強度に優れると共に、耐熱変形性、耐薬品性にも優れ
たフラットケーブルが得られる。(Iv) Flat cable When the flame-retardant resin composition is extrusion-coated on both surfaces of a parallel conductor in which conductors are arranged in parallel (claim 15), a flat cable having flame retardancy and excellent mechanical strength Can be obtained. If the insulating coating of the flat cable is cross-linked, and particularly when irradiated with ionizing radiation (claim 16), the flat cable which is flame-retardant, has excellent mechanical strength, and has excellent heat deformation resistance and chemical resistance. can get. After the flame retardant resin composition is obtained by laminating a biaxially stretched polyester film or the like by a melt extrusion method or the like, two tapes are arranged so that the polyester film is on the outer surface on both surfaces of the parallel conductor. Then, if a thermal laminator is used to perform insulation coating (claim 17), a flat cable that is flame-retardant and has excellent mechanical strength can be obtained. In this case, if the flat cable is cross-linked and irradiated with ionizing radiation (claim 18), a flat cable which is flame-retardant, has excellent mechanical strength, and has excellent heat deformation resistance and chemical resistance. can get.

【００１７】（v)直流用高圧電線 ・絶縁層としてエチレン−αオレフィン共重合体樹脂組
成物が導体上に被覆され、その外層に該難燃性樹脂組成
物を押出被覆すると（請求項１９）、難燃性で、機械的
強度に優れ且つ環境に優しい直流用高圧電線を得ること
ができる。 ・該直流用高圧電線の絶縁層及び被覆層を架橋させい、
特に電離放射線を照射すれば（請求項２０）、難燃性で
且つ機械的強度に優れると共に、耐熱変形性、耐薬品性
にも優れた直流用高圧電線が得られる。(V) High-voltage electric wire for direct current • An ethylene-α-olefin copolymer resin composition is coated on a conductor as an insulating layer, and the outer layer is extrusion-coated with the flame-retardant resin composition. A high-voltage electric wire for direct current, which is flame-retardant, has excellent mechanical strength and is environmentally friendly. Cross-linking the insulating layer and the coating layer of the DC high-voltage electric wire,
In particular, when ionizing radiation is applied (claim 20), a DC high-voltage electric wire that is flame-retardant, has excellent mechanical strength, and is excellent in heat deformation resistance and chemical resistance can be obtained.

【００１８】以下、本発明を詳細に説明する。 (A) 難燃性樹脂組成物 本発明の難燃性樹脂組成物は、基本的に、熱可塑性樹脂
１００重量部に対して、金属水酸化物１００〜２５０重
量部、酢酸塩５〜５０重量部或いは炭酸カルシウム５〜
８０重量部を配合してなるものである（請求項１）。 （1) 熱可塑性樹脂 難燃性樹脂組成物を構成する熱可塑性樹脂としては特に
制限されないが、例えばポリエチレン、ポリプロピレン
等のポリオレフィン、エチレン−酢酸ビニル共重合体、
エチレン−アクリル酸エチル共重合体、エチレン−メタ
クリル酸メチル共重合体、エチレン−メタクリル酸共重
合体、エチレン−アクリル酸メチル共重合体等のエチレ
ン−αオレフィン共重合体；ポリウレタンエラストマ
ー、ポリエステルエラストマー、エチレン−プロピレン
共重合体エラストマーのようなポリオレフィンエラスト
マー、ポリアミドエラストマー等の熱可塑性エラストマ
ー；ポリエチレンテレフタレート、ポリブチレンテレフ
タレート等のポリエステル等が挙げられる。これら熱可
塑性樹脂を単独に或いは２種類以上併用しても良い。こ
の中でも、エチレン−酢酸ビニル共重合体、エチレン−
アクリル酸エチル共重合体、エチレン−メタクリル酸メ
チル共重合体、エチレン−メタクリル酸共重合体、エチ
レン−アクリル酸メチル共重合体から選択された１種の
エチレン−αオレフィン共重合体単一或いはこれら２種
以上の混合物が難燃性や柔軟性等の観点から好ましく使
用でき、特にエチレン−酢酸ビニル共重合体が難燃性等
の観点から好ましい結果が得られる（請求項３）。Hereinafter, the present invention will be described in detail. (A) Flame retardant resin composition The flame retardant resin composition of the present invention basically comprises 100 to 250 parts by weight of a metal hydroxide and 5 to 50 parts by weight of an acetate with respect to 100 parts by weight of a thermoplastic resin. Part or calcium carbonate 5
80 parts by weight are blended (claim 1). (1) Thermoplastic resin The thermoplastic resin constituting the flame-retardant resin composition is not particularly limited. For example, polyethylene, polyolefin such as polypropylene, ethylene-vinyl acetate copolymer,
Ethylene-α-olefin copolymers such as ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer; polyurethane elastomers, polyester elastomers, Thermoplastic elastomers such as polyolefin elastomers such as ethylene-propylene copolymer elastomers and polyamide elastomers; polyesters such as polyethylene terephthalate and polybutylene terephthalate; These thermoplastic resins may be used alone or in combination of two or more. Among them, ethylene-vinyl acetate copolymer, ethylene-
One kind of ethylene-α-olefin copolymer selected from ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer or a mixture thereof A mixture of two or more types can be preferably used from the viewpoint of flame retardancy, flexibility, and the like, and particularly, an ethylene-vinyl acetate copolymer can obtain favorable results from the viewpoint of flame retardancy (claim 3).

【００１９】エチレン−酢酸ビニル共重合体の場合、酢
酸ビニル成分の含有量としては、６〜５０重量％、好ま
しくは１０〜４８重量％のものが機械的強度と難燃性の
バランス等の観点から好ましく使用でき、溶融流動性に
関してはメルトフロレート（１９０℃、２．１６ｋｇ荷
重下）で０．５〜３０、好ましくは０．５〜２０の範囲
に選定すれば（請求項４）、押出加工性等の点で好まし
い結果が得られる。酢酸ビニル含量が６重量％未満では
難燃性の低下となるし、５０重量％を越えると機械的強
度の低下となる。また、エチレン−酢酸ビニル共重合体
のメルトフロレートは０．５未満では押出成形品の表面
が荒れやすくなり、３０を超えると機械的強度が低下な
る傾向がある。なお、他のエチレン−αオレフィン共重
合体についても、αオレフィン含量、メルトフロレート
はエチレン−酢酸ビニル共重合体の場合に準ずる。上記
エチレン−αオレフィン共重合体において、例示のαオ
レフィン以外のエチレン性不飽和化合物を必要に応じて
共重合させても良い。In the case of the ethylene-vinyl acetate copolymer, the content of the vinyl acetate component is from 6 to 50% by weight, preferably from 10 to 48% by weight, from the viewpoint of balance between mechanical strength and flame retardancy. If the melt fluidity is selected in the range of 0.5 to 30, preferably 0.5 to 20 at a melt flow rate (at 190 ° C. under a load of 2.16 kg) (claim 4), Preferred results are obtained in terms of workability and the like. If the vinyl acetate content is less than 6% by weight, the flame retardancy will decrease, and if it exceeds 50% by weight, the mechanical strength will decrease. If the melt flow rate of the ethylene-vinyl acetate copolymer is less than 0.5, the surface of the extruded product tends to be rough, and if it exceeds 30, the mechanical strength tends to decrease. The α-olefin content and melt flow rate of other ethylene-α-olefin copolymers are the same as those of the ethylene-vinyl acetate copolymer. In the ethylene-α-olefin copolymer, an ethylenically unsaturated compound other than the exemplified α-olefin may be copolymerized as necessary.

【００２０】（2) 配合剤 (i) 有機ケイ素化合物カップリング剤 １）一般式〔Ｉ〕：(2) Compounding agent (i) Coupling agent of organosilicon compound 1) General formula [I]:

【化３】 （ただし、Ｒはアクリル基、メタクリル基又はアリル基
を含有するアルキル基であり、Ｙ1 、Ｙ2 、Ｙ3 はアル
キル基、アルコキシ基、ハロゲン基からなる群より選ば
れた原子団を表す。）で示される有機ケイ素化合物カッ
プリング剤が、熱可塑性樹脂１００重量部に対して０．
１〜１０重量部添加すれば（請求項５）、機械物性の点
で好ましい結果が得られる。Embedded image (However, R is an alkyl group containing an acryl group, a methacryl group, or an allyl group, and Y 1 , Y 2 , and Y 3 represent an atomic group selected from the group consisting of an alkyl group, an alkoxy group, and a halogen group. ) Is used in an amount of 0.1 parts by weight based on 100 parts by weight of the thermoplastic resin.
When 1 to 10 parts by weight is added (claim 5), favorable results can be obtained in terms of mechanical properties.

【００２１】２）一般式〔１〕で表されるシラン系カッ
プリング剤としては、γ−メタクリロキシプロピルトリ
メトキシシラン、γ−メタクリロキシプロピルトリエト
キシシラン、γ−アクリロキシプロピルトリメトキシシ
ラン、γ−メタクリロキシプロピルジメトキシメチルシ
ラン、γ−メタクリロキシプロピルジメチルクロロシラ
ンなどを例示でき、その単一または混合物を使用でき
る。2) The silane coupling agent represented by the general formula [1] includes γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ Methacryloxypropyldimethoxymethylsilane, γ-methacryloxypropyldimethylchlorosilane, etc., and a single or a mixture thereof can be used.

【００２２】(ii) 金属水酸化物(a) １）金属水酸化物(a) としては、水酸化マグネシウム、
水酸化カルシウム、水酸化アルミニウム等が例示でき
る。樹脂組成物の押出加工温度等の観点から水酸化マグ
ネシウム、水酸化カルシウムが特に好ましく使用でき
る。使用する金属水酸化物(a) の粒径として０．３〜３
０μｍ、好ましくは０．５〜２５μｍ、比表面積がＢＥ
Ｔ法で３〜３０ｍ2 ／ｇ、好ましくは５〜２８ｍ2／ｇ
程度のものを選定すれば、難燃性、混練性、押出加工
性、機械的強度等の点で好ましい結果が得られる。該金
属水酸化物(a) の粒径が０．３μｍ未満では粒子同士が
凝集し易く混練時間がかかるし、３０μｍを越えると機
械的強度の低下を招くことになる。該金属水酸化物(a)
の比表面積が３ｍ2 ／ｇ未満では難燃性低下となるし、
３０ｍ2 ／ｇを越えると粒子同士が凝集し易く混練時間
がかかる傾向となる。 ２）また、金属水酸化物(a) の表面は、表面処理剤によ
り処理すれば、樹脂組成物の混練性や伸びの点で好まし
い結果が得られる。該表面処理剤としては、例えばステ
アリン酸等の脂肪酸やステアリン酸ナトリウムやオレイ
ン酸ナトリウム等の脂肪酸金属塩等のアニオン系界面活
性剤を挙げることができる。 ３）また、該金属水酸化物は、上記一般式〔１〕で示さ
れる有機ケイ素化合物カップリング剤で表面処理されて
いても機械物性の点で好ましい結果が得られる。(Ii) Metal hydroxide (a) 1) As the metal hydroxide (a), magnesium hydroxide,
Examples thereof include calcium hydroxide and aluminum hydroxide. Magnesium hydroxide and calcium hydroxide can be particularly preferably used from the viewpoint of the extrusion temperature of the resin composition and the like. The particle size of the metal hydroxide (a) used is 0.3 to 3
0 μm, preferably 0.5 to 25 μm, having a specific surface area of BE
3~30m 2 / g at T method, preferably 5~28m 2 / g
If a material having such a degree is selected, favorable results can be obtained in terms of flame retardancy, kneading properties, extrudability, mechanical strength and the like. If the particle size of the metal hydroxide (a) is less than 0.3 μm, the particles are likely to aggregate with each other and it takes a kneading time, and if it exceeds 30 μm, the mechanical strength is reduced. The metal hydroxide (a)
If the specific surface area is less than 3 m 2 / g, the flame retardancy decreases,
If it exceeds 30 m 2 / g, the particles tend to agglomerate and tend to require a kneading time. 2) If the surface of the metal hydroxide (a) is treated with a surface treating agent, favorable results can be obtained in terms of kneading properties and elongation of the resin composition. Examples of the surface treating agent include anionic surfactants such as fatty acids such as stearic acid and metal salts of fatty acids such as sodium stearate and sodium oleate. 3) Even if the metal hydroxide is surface-treated with the organosilicon compound coupling agent represented by the general formula [1], favorable results can be obtained in terms of mechanical properties.

【００２３】(iii) 酢酸塩(b1) 本発明で金属水酸化物(a) と併用される酢酸塩(b1)は、
基本的に、一般式Ｍn 〔ＣＨ3 ＣＯＯ〕n （Ｍn はｎ価
の陽イオンである）で示される化合物である。例えば、
酢酸マグネシウム、酢酸ナトリウム、酢酸カリウム、酢
酸亜鉛、酢酸銅、酢酸鉄、酢酸カルシウム、酢酸アルミ
ニウム、酢酸ニッケル、酢酸コバルト、酢酸ガリウム、
酢酸銀、酢酸錫、酢酸バリウム、酢酸セリウム、酢酸
鉛、酢酸ベリリウム等を挙げることができる。それら酢
酸塩(b1)の塩の形態としては、正塩、酸性塩、塩基性
塩、多核金属錯塩があり、中には結晶水を有するものも
使用できる。この中で、樹脂組成物の押出加工温度等の
観点から酢酸マグネシウム、酢酸ナトリウム、酢酸亜
鉛、酢酸銅、酢酸鉄、酢酸カルシウム、酢酸アルミニウ
ム、酢酸ニッケル、酢酸バリウムが好ましく使用でき
る。これら酢酸塩(b1)の粒径としては、０．５〜５μ
ｍ、好ましくは０．５〜３μｍ程度のものを選定すれば
（請求項６）、ベース樹脂との混練性や樹脂組成物とし
た場合の溶融押出加工性等の点においても好ましい結果
が得られ、金属水酸化物の場合と同様に表面をアニオン
系界面活性剤で表面処理すれば、ベース樹脂との混練性
や樹脂組成物とした場合の溶融押出加工性等の特性を向
上せしめることができる。(Iii) Acetate (b1) The acetate (b1) used in combination with the metal hydroxide (a) in the present invention is:
Basically, it is a compound represented by the general formula M n [CH 3 COO] n (M n is an n-valent cation). For example,
Magnesium acetate, sodium acetate, potassium acetate, zinc acetate, copper acetate, iron acetate, calcium acetate, aluminum acetate, nickel acetate, cobalt acetate, gallium acetate,
Silver acetate, tin acetate, barium acetate, cerium acetate, lead acetate, beryllium acetate and the like can be mentioned. The salt forms of these acetates (b1) include normal salts, acidic salts, basic salts, and polynuclear metal complex salts, some of which include water of crystallization. Among them, magnesium acetate, sodium acetate, zinc acetate, copper acetate, iron acetate, calcium acetate, aluminum acetate, nickel acetate, and barium acetate can be preferably used from the viewpoint of the extrusion temperature of the resin composition. The particle size of these acetates (b1) is 0.5 to 5 μm.
m, preferably about 0.5 to 3 μm (claim 6), favorable results can be obtained in terms of kneadability with the base resin and melt extrusion processability when the resin composition is used. By treating the surface with an anionic surfactant in the same manner as in the case of the metal hydroxide, it is possible to improve properties such as kneadability with a base resin and melt extrusion processability when a resin composition is formed. .

【００２４】（iv) 炭酸カルシウム(b2) １）本発明で金属水酸化物(a) と併用される炭酸カルシ
ウム(b2)としては、ホウカイ石、ヒョウシュウ石、アラ
レ石、石灰石、大理石、ホワイチング等の鉱石を粉砕し
た重質炭酸カルシウムや合成石である沈降性炭酸カルシ
ウム或いは軽質炭酸カルシウム等を挙げることができ
る。その炭酸カルシウム(b2)の結晶構造は、六方晶系の
リョウ面体ホウカイ石構造や斜方晶系のアラレ石型構造
を取る。この中で、押出加工性や物性の点からは、粒度
分布が均一な合成品の炭酸カルシウムが好ましく使用で
きる。炭酸カルシウム(b2)の一次粒径としては４μｍ以
下、好ましくは３μｍ以下、より好ましくは１μｍ以下
のものを選定すれば（請求項７）、難燃性やベース樹脂
との混練性等の点から好ましい結果が得られる。 ２）また、炭酸カルシウム(b2)は、表面を脂肪酸系、油
脂系、界面活性剤系、ワックス系等の表面処理剤によっ
て表面処理されたもの、或いはシラン系、チタネート
系、アルミニウム系、ジルコアルミニウム系、カルボン
酸系、リン酸系等のカップリング剤で表面処理されたも
のからなる群より選択された１種又はこれら２種以上の
混合物を用いると（請求項８）、ベース樹脂との混練性
や樹脂組成物とした場合の溶融押出加工性等の特性を向
上せしめることが可能である。(Iv) Calcium carbonate (b2) 1) As the calcium carbonate (b2) used in combination with the metal hydroxide (a) in the present invention, dolomite, leopardite, aragonite, limestone, marble, whileing Heavy calcium carbonate obtained by pulverizing ores such as precipitated calcium carbonate or light calcium carbonate which is a synthetic stone. The crystal structure of the calcium carbonate (b2) has a hexagonal rhyohedral borolite structure and an orthorhombic aragonite structure. Among them, from the viewpoint of extrudability and physical properties, synthetic calcium carbonate having a uniform particle size distribution can be preferably used. If the primary particle size of calcium carbonate (b2) is selected to be 4 μm or less, preferably 3 μm or less, more preferably 1 μm or less (claim 7), from the viewpoint of flame retardancy and kneading with the base resin, etc. Good results are obtained. 2) In addition, calcium carbonate (b2) whose surface is surface-treated with a fatty acid-based, oil-based, surfactant-based, or wax-based surface treatment agent, or silane-based, titanate-based, aluminum-based, or zirconium-aluminum When one or a mixture of two or more selected from the group consisting of those surface-treated with a coupling agent such as a carboxylic acid type, a phosphoric acid type or the like is used (claim 8), kneading with the base resin is performed. It is possible to improve the properties such as the meltability and processability of the resin composition when it is used as a resin composition.

【００２５】（v) 配合量等 １）熱可塑性樹脂に配合する金属水酸化物(a) と酢酸塩
(b1)或いは炭酸カルシウム(b2)の配合量としては、難燃
性と機械的強度の観点から、熱可塑性樹脂１００重量部
に対して、金属水酸化物１００〜２５０重量部、好まし
くは１００〜２００重量部、酢酸塩５〜５０重量部、好
ましくは１０〜４０重量部或いは炭酸カルシウム５〜８
０重量部、好ましくは５〜３０重量部の範囲で併用する
ことが好ましい。金属水酸化物(a) の配合量が１００重
量部未満では、酢酸塩(b1)或いは炭酸カルシウム(b2)の
配合量に係わらず難燃性が不足し、また、金属水酸化物
(a) の配合量が２５０重量部を越えると、機械的強度が
低下する傾向になる。また、金属水酸化物(a) の配合量
が１００〜２５０重量部の範囲でも、酢酸塩(b1)の配合
量が５重量部未満或いは炭酸カルシウム(b2)の配合量が
５重量部未満では難燃性が不足し、酢酸塩(b1)の配合量
が５０重量部を越えると或いは炭酸カルシウム(b2)の配
合量が８０重量部を越えると機械的強度が低下するとい
う問題がある。(V) Incorporation amount, etc. 1) Metal hydroxide (a) and acetate compounded in thermoplastic resin
(b1) or the amount of calcium carbonate (b2), from the viewpoint of flame retardancy and mechanical strength, based on 100 parts by weight of the thermoplastic resin, 100 to 250 parts by weight of metal hydroxide, preferably 100 to 100 parts by weight 200 parts by weight, acetate 5 to 50 parts by weight, preferably 10 to 40 parts by weight or calcium carbonate 5 to 8
It is preferable to use 0 part by weight, preferably 5 to 30 parts by weight. If the amount of the metal hydroxide (a) is less than 100 parts by weight, the flame retardancy is insufficient irrespective of the amount of the acetate (b1) or calcium carbonate (b2).
If the amount of (a) exceeds 250 parts by weight, the mechanical strength tends to decrease. Further, even when the amount of the metal hydroxide (a) is in the range of 100 to 250 parts by weight, the amount of the acetate (b1) is less than 5 parts by weight or the amount of the calcium carbonate (b2) is less than 5 parts by weight. When the flame retardancy is insufficient and the amount of the acetate (b1) exceeds 50 parts by weight or the amount of the calcium carbonate (b2) exceeds 80 parts by weight, there is a problem that the mechanical strength is reduced.

【００２６】２）本発明の難燃性樹脂組成物において
は、熱可塑性樹脂に対して、金属水酸化物(a) に加え
て、特定範囲量の酢酸塩(b1)或いは炭酸カルシウム(b2)
を混合することによって、従来の薄肉高強度ノンハロゲ
ン絶縁電線やチューブ、熱収縮チューブ、フラットケー
ブルで課題であった２０秒以上燃え続ける点が解決でき
るに至った。また、該難燃性樹脂組成物を直流用高圧電
線のシースに適用すれば垂直燃焼試験に合格できること
が分かった。 ３）混合・成形 熱可塑性樹脂と金属水酸化物、酢酸塩或いは炭酸カルシ
ウム等との混合は、オープンロールミキサー、バンバリ
ーミキサー、加圧型ニーダー、二軸混合機等の既知の混
合装置を使用することができる。得られた樹脂組成物
は、溶融押出機や射出成形機等の既知の樹脂成形装置を
使用すれば、絶縁電線、チューブ、熱収縮チューブ、フ
ラットケーブル、直流用高圧電線等の種々の成形物を容
易に製造できる。2) In the flame-retardant resin composition of the present invention, a specific amount of acetate (b1) or calcium carbonate (b2) is added to the thermoplastic resin in addition to the metal hydroxide (a).
Can solve the problem of the conventional thin-walled high-strength non-halogen insulated wires, tubes, heat-shrinkable tubes, and flat cables that keep burning for 20 seconds or more. In addition, it was found that if the flame-retardant resin composition was applied to the sheath of a high-voltage electric wire for direct current, it could pass the vertical combustion test. 3) Mixing / Molding The mixing of the thermoplastic resin with metal hydroxide, acetate or calcium carbonate should use a known mixing device such as an open roll mixer, a Banbury mixer, a pressurized kneader or a twin screw mixer. Can be. The obtained resin composition can be used to form various molded products such as insulated wires, tubes, heat-shrinkable tubes, flat cables, high-voltage wires for direct current, etc., using known resin molding devices such as melt extruders and injection molding machines. Can be easily manufactured.

【００２７】（v) その他の樹脂成分、添加剤 １）本発明の樹脂組成物には、難燃性や機械的強度等の
特性を損なわない範囲で、各種特性改良の目的で、ＥＰ
ＤＭ、エチレンアクリルゴム等の各種ポリマーを配合で
きる。 ２）また、各種の熱安定剤、酸化防止剤、紫外線吸収
剤、滑剤、加工安定助剤、着色剤、発泡剤、補強剤、有
機性又は無機性の充填剤、多官能モノマー等の各種添加
剤を配合することができる。(V) Other Resin Components and Additives 1) The resin composition of the present invention is used in order to improve various properties within a range that does not impair properties such as flame retardancy and mechanical strength.
Various polymers such as DM and ethylene acrylic rubber can be blended. 2) Addition of various heat stabilizers, antioxidants, ultraviolet absorbers, lubricants, processing stabilizing aids, coloring agents, foaming agents, reinforcing agents, organic or inorganic fillers, polyfunctional monomers, etc. An agent can be compounded.

【００２８】３）特に、上記多官能モノマーは、架橋助
剤の作用を果たし、特に電離放射線の照射時に、架橋効
率を高めるため、必要に応じて樹脂成分に添加しても良
い。例えば、多官能モノマーとしては、トリメチロール
プロパントリメタクリレート、ペンタエリスリトールト
リアクリレート、エチレングリコールジメタクリレー
ト、トリアリルシアヌレート、トリアリルイソシアヌレ
ート等の分子内に複数個の不飽和結合部分を有するモノ
マーを挙げることができる。3) In particular, the above-mentioned polyfunctional monomer may be added to the resin component as needed in order to fulfill the function of a crosslinking aid and to increase the crosslinking efficiency, especially during irradiation with ionizing radiation. For example, examples of the polyfunctional monomer include monomers having a plurality of unsaturated bond portions in a molecule such as trimethylolpropane trimethacrylate, pentaerythritol triacrylate, ethylene glycol dimethacrylate, triallyl cyanurate, and triallyl isocyanurate. be able to.

【００２９】(B) 各種成形物及びその製造 (i) 絶縁電線、フラットケーブルの製造 ・本発明の難燃性樹脂組成物は、溶融押出機等を使用し
て導体上に押出被覆すると、そのままの状態でも燃焼時
に有害ガスの発生する問題のない難燃性の絶縁電線やフ
ラットケーブルとして使用可能である（請求項１５）。 ・また、得られたフラットケーブルを２枚のポリエステ
ルフィルム等の絶縁性高分子フィルムで挟み込んでも、
燃焼時に有害ガスの発生する問題のない難燃性フラット
ケーブルとして使用可能である（請求項１７）。 ・この絶縁電線やフラットケーブルに電離放射線の照射
等の方法により被覆層を架橋すれば、機械的強度や耐熱
性、加熱変形性等の特性に優れた絶縁電線やフラットケ
ーブルとすることができる（請求項１６、１８）。(B) Various molded articles and production thereof (i) Production of insulated wires and flat cables The flame-retardant resin composition of the present invention is extruded and coated on a conductor using a melt extruder or the like. It can be used as a flame-retardant insulated wire or flat cable that has no problem of generating harmful gas during combustion even in the above condition (claim 15). Also, even if the obtained flat cable is sandwiched between two insulating polymer films such as polyester films,
It can be used as a flame-retardant flat cable having no problem of generating harmful gas during combustion (claim 17). -By cross-linking the insulated wire or flat cable with a coating layer by a method such as irradiation with ionizing radiation, an insulated wire or flat cable having excellent properties such as mechanical strength, heat resistance, and heat deformability can be obtained ( Claims 16 and 18).

【００３０】(ii)薄肉高強度絶縁電線 １）従来、ポリオレフィン等の熱可塑性樹脂に非ハロゲ
ン系難燃剤である水酸化マグネシウムを多量に添加して
難燃化した樹脂組成物は、良好な難燃性を付与できるも
のの、熱可塑性樹脂との相溶性が悪いために絶縁電線に
応用した場合、初期抗張力が小さく、しかも熱老化後の
物性が著しく低下する等の問題があったが、本発明はそ
の問題をより解決するものである。 ２）本発明者により、ＵＬ規格を満たした薄肉高強度ノ
ンハロゲン絶縁電線が開発されているが、この絶縁電線
はＶＷ−１試験の規格である６０秒以内の消火は満たす
が、２０秒以上燃え続ける場合があり、薄肉高強度ノン
ハロゲン絶縁電線として十分なものではなく、更に難燃
性の高いノンハロゲン難燃電線の開発が望まれていた。
本発明は、更にその問題をも解決するものである。(Ii) Thin-walled high-strength insulated wires 1) Conventionally, a resin composition obtained by adding a large amount of magnesium hydroxide as a non-halogen flame retardant to a thermoplastic resin such as polyolefin to make it flame-retardant has a good difficulty. Although it can impart flammability, when applied to insulated wires due to poor compatibility with the thermoplastic resin, there are problems such as a low initial tensile strength and a significant decrease in physical properties after thermal aging. Is the solution to that problem. 2) The inventor has developed a thin high-strength non-halogen insulated wire satisfying the UL standard. This insulated wire satisfies the fire extinguishing within 60 seconds, which is the standard of the VW-1 test, but burns for 20 seconds or more. In some cases, it is not sufficient as a thin-walled high-strength non-halogen insulated wire, and there has been a demand for the development of a non-halogen flame-retardant wire having higher flame retardancy.
The present invention further solves that problem.

【００３１】３）本発明の難燃性樹脂組成物は、その組
成上の特徴から薄肉高強度で高い難燃性を有するノンハ
ロゲン絶縁電線にすることができる。即ち、導体外径が
１．０ｍｍ以下、好ましくは０．１〜１．０ｍｍの導体
に、請求項１〜８のいずれかに記載の難燃性樹脂組成物
が０．１ｍｍ以上１．０ｍｍ以下の厚みで被覆されてお
り、該被覆層が架橋、特に電離性放射線の照射されてい
る薄肉高強度絶縁電線を提供する（請求項１１）。この
絶縁厚みが０．１ｍｍ未満の厚みでは薄すぎて通常耐電
圧が実用に耐えず、また厚みが１．０ｍｍを越えて厚す
ぎると、導体径の細い機器配線用電線の場合に、難燃性
に問題を生じるようになる。 ４）この薄肉高強度絶縁電線は、各種ＵＬ規格等の安全
規格を満たす機器内配線用絶縁電線として好適であっ
て、火災防止等の安全性を確保しながら無公害を達成で
きる利点がある。3) The flame-retardant resin composition of the present invention can be made into a thin, high-strength, non-halogen insulated wire having high flame retardancy due to its compositional characteristics. That is, the outer diameter of the conductor is 1.0 mm or less, preferably 0.1 to 1.0 mm, and the flame-retardant resin composition according to any one of claims 1 to 8 is 0.1 mm or more and 1.0 mm or less. The present invention provides a thin high-strength insulated wire which is coated with a crosslinking layer, in particular, ionizing radiation. If the insulation thickness is less than 0.1 mm, it is too thin to withstand the normal withstand voltage, and if it exceeds 1.0 mm, the flame resistance is low when the conductor diameter is too small. This causes problems in sex. 4) This thin high-strength insulated wire is suitable as an insulated wire for wiring in equipment that meets safety standards such as various UL standards, and has the advantage of achieving zero pollution while ensuring safety such as fire prevention.

【００３２】(iii) 絶縁チューブ等の製造 ・本発明の難燃性樹脂組成物を溶融押出等の方法により
絶縁チューブとすることができる（請求項１２）。 ・本発明の難燃性樹脂組成物のチューブ状成形物は、特
に電離放射線を照射して樹脂層を架橋後に、高温下でチ
ューブの内部に圧縮空気を送り込む等の方法で径方向に
拡径して冷却し、その形状を固定すれば熱収縮チューブ
とすることができる（請求項１４）。(Iii) Production of Insulating Tube, etc. The flame-retardant resin composition of the present invention can be made into an insulating tube by a method such as melt extrusion. The tubular molded product of the flame-retardant resin composition of the present invention, particularly after cross-linking the resin layer by irradiating with ionizing radiation, is radially expanded by a method such as blowing compressed air into the inside of the tube at a high temperature. Then, if the shape is fixed, the heat-shrinkable tube can be obtained (claim 14).

【００３３】（iv) 流用高圧電線の製造 ・溶融押出機等を使用して導体上にエチレン−αオレフ
ィン共重合体樹脂組成物を導体上に被覆し、更にその外
層に本発明の難燃性樹脂組成物の被覆層（シース）を備
え電離性放射線の照射等の方法により夫々の被覆層を架
橋すれば、或いは絶縁層と被覆層を夫々照射架橋するの
でなく、被覆層を設けた後に絶縁層と被覆層の両方を一
括照射することによって架橋すれば、もちろん絶縁層及
び被覆層中に有機過酸化物等の化学架橋剤を予め配合し
ておき架橋させれば、機械的強度や耐熱性、加熱変形性
等の特性に優れた直流用高圧電線とすることができる
（請求項１９、２０）。(Iv) Manufacture of a high-voltage electric wire to be diverted ・ The conductor is coated with the ethylene-α-olefin copolymer resin composition on the conductor using a melt extruder or the like, and the outer layer is further provided with the flame retardancy of the present invention. If a coating layer (sheath) of a resin composition is provided and each of the coating layers is cross-linked by a method such as irradiation with ionizing radiation or the like, the insulating layer and the coating layer are not cross-linked by irradiation, but after the coating layer is provided, the insulation is performed. If both the layer and the coating layer are cross-linked by irradiating them together, of course, if a chemical cross-linking agent such as an organic peroxide is blended in advance in the insulating layer and the coating layer and then cross-linked, mechanical strength and heat resistance A high voltage electric wire for direct current having excellent properties such as heat deformability can be obtained (claims 19 and 20).

【００３４】（v)架橋等 １）電離放射線としては、電子線、加速電子線やガンマ
線、β線、Ｘ線、α線、紫外線等が例示できるが、線源
の簡便さや電離放射線の透過厚み、架橋処理の速度など
工業的利用の観点から加速電子線が最も好ましく利用で
きる。電離放射線の照射線量は、例えば電子線の場合、
３〜５０Ｍｒａｄ、好ましくは５〜２５Ｍｒａｄの照射
線量に設定すれば良い。この照射線量が３Ｍｒａｄ未満
では抗張力の改善効果が小さく、５０Ｍｒａｄを越える
と伸びが却って低下する。 ２）電離放射線の照射の代わりに、予め難燃性樹脂組成
物に有機過酸化物等を配合・成形後に、加熱処理する化
学架橋も採用できる。有機過酸化物としては、例えばジ
クミルパーオキサイド、ビス（ｔ−ブチルパーオキシイ
ソプロピル）パーオキシド等を挙げることができる。し
かしながら、電離放射線照射が初期機械的強度と難燃性
の両立にとって好ましい。(V) Crosslinking etc. 1) Examples of ionizing radiation include electron beam, accelerating electron beam, gamma ray, β-ray, X-ray, α-ray, ultraviolet ray and the like. From the viewpoint of industrial use such as the speed of crosslinking treatment, an accelerated electron beam can be most preferably used. The irradiation dose of ionizing radiation, for example, in the case of an electron beam,
The irradiation dose may be set to 3 to 50 Mrad, preferably 5 to 25 Mrad. If the irradiation dose is less than 3 Mrad, the effect of improving tensile strength is small, and if it exceeds 50 Mrad, the elongation is rather reduced. 2) Instead of irradiating with ionizing radiation, chemical crosslinking in which an organic peroxide or the like is blended in advance with the flame-retardant resin composition and then molded, followed by heat treatment can be employed. Examples of the organic peroxide include dicumyl peroxide and bis (t-butylperoxyisopropyl) peroxide. However, ionizing radiation irradiation is preferred for achieving both initial mechanical strength and flame retardancy.

【００３５】[0035]

【実施例】以下、実施例により本発明を説明するが、こ
れらは本発明の範囲を制限しない。 ＜物性等の測定＞ 絶縁電線について １) 絶縁電線のＵＬ規格の難燃性 難燃性を調べるために、ＵＬ規格のＶＷ−１試験を各１
０点の試料について行った。判定は、１０点中１点でも
６０秒以上燃焼したり、下部に敷いた脱脂綿が燃焼落下
物によって燃焼したり、試料の上部に取り付けたクラフ
ト紙が燃えたり、焦げたりしたものを不合格とした。 ２）燃焼時間 試験点数１０点の燃焼時間の範囲を０秒〜２０秒未満、
２０秒〜４０秒未満、４０秒〜６０秒未満、６０秒以上
に分類し、４０秒未満ですべてが消えるものを良好とし
た。 ３）機械特性 ＪＩＳ Ｃ３００５法に準じた測定法により、初期破断
抗張力、初期破断伸び（標線間距離５０ｍｍ）を各３点
で測定し平均値を求めた。 ４）引張試験 押出被覆材料の引張試験（引張速度５００ｍｍ／分）を
行い、初期破断抗張力、初期破断伸び（標間距離２０ｍ
ｍ）を各３点で測定し平均値を求めた。The present invention will be described below by way of examples, which do not limit the scope of the present invention. <Measurement of physical properties, etc.> About insulated wires 1) UL standard flame retardancy of insulated wires To investigate the flame retardancy, UL standard VW-1 test was performed for each one.
The test was performed on the sample of 0 point. Judgment was made that even if one of the 10 points burned for 60 seconds or more, the cotton wool laid at the bottom was burned by burning falling objects, or the kraft paper attached to the top of the sample was burned or burned, it was judged as a failure. did. 2) Burning time The range of burning time for 10 test points is 0 seconds to less than 20 seconds,
The classification was made from 20 seconds to less than 40 seconds, from 40 seconds to less than 60 seconds, and more than 60 seconds. 3) Mechanical properties The initial breaking tensile strength and the initial breaking elongation (distance between marked lines: 50 mm) were measured at three points by a measuring method according to the JIS C3005 method, and the average value was obtained. 4) Tensile test The extruded coating material was subjected to a tensile test (tensile speed: 500 mm / min) to obtain an initial tensile strength at break and an initial elongation at break (interval distance of 20 m).
m) was measured at each of three points, and the average value was determined.

【００３６】 絶縁チューブについて １）難燃性試験 チューブの内部にチューブ内径と同じサイズ６．４ｍｍ
φの鉄棒を挿入し、オールチュービング燃焼試験で夫々
１０点試験し、１０点中１点でも６０秒以上燃焼やクラ
フト紙燃え、脱脂綿燃えを起こして合格しないものは不
合格と判断した。 ２）試験点数１０点の燃焼時間の範囲を０秒〜２０秒未
満、２０秒〜４０秒未満、４０秒〜６０秒未満に分類
し、４０秒未満ですべてが消えるものを良好とした。
３）引張試験 このチューブの機械的強度を調べるため、ＪＩＳ Ｃ３
００５法に準じて、引張試験（引張速度５００ｍｍ／
分）を行い、破断時の抗張力と伸び（標間距離２０ｍ
ｍ）を各３点で測定し平均値を求めた。Insulation Tube 1) Flame Retardancy Test Inside the tube, the same size as the tube inner diameter, 6.4 mm
An iron rod of φ was inserted, and 10 points were tested in the all tubing combustion test, and even one point out of the ten points, which did not pass because of burning for 60 seconds or more, burning kraft paper, or burning absorbent cotton, was judged to be rejected. 2) The range of the burning time for the ten test points was classified into 0 to less than 20 seconds, 20 to less than 40 seconds, and 40 to less than 60 seconds, and those that disappeared in less than 40 seconds were regarded as good.
3) Tensile test To check the mechanical strength of this tube, JIS C3
A tensile test (a tensile speed of 500 mm /
Min), and the tensile strength and elongation at break (intermark distance 20m)
m) was measured at each of three points, and the average value was determined.

【００３７】 熱収縮チューブについて １）燃焼試験 内径７ｍｍの拡径した熱収縮チューブ内に外径３．３ｍ
ｍφの鉄棒を挿入し、１５０℃の恒温槽に３分間放置
し、熱収縮チューブが鉄棒の周囲にフィットする状態で
熱収縮させ、オールチュービング燃焼試験で夫々１０点
試験し、１０点中１点でも６０秒以上燃焼やクラフト紙
燃え、脱脂綿燃えを起こして合格しないものは不合格と
判断した。 ２） この熱収縮チューブの機械的強度を調べるため、
熱収縮チューブを１５０℃に設定した恒温槽に３分間放
置して熱収縮させた試料について、ＪＩＳ Ｃ３００５
に準じて、引張試験（引張速度５００ｍｍ／分）を行
い、破断時の抗張力と伸び（標間距離２０ｍｍ）を各３
点で測定し平均値を求めた。About Heat Shrink Tubing 1) Combustion Test An outer diameter of 3.3 m is placed in an expanded heat shrink tube having an inner diameter of 7 mm.
Insert an iron rod of mφ, leave it in a thermostat at 150 ° C. for 3 minutes, heat-shrink it while the heat-shrinkable tube fits around the iron rod, test 10 points each in the all tubing combustion test, and 1 point out of 10 points However, those that did not pass due to burning, kraft paper burning, and absorbent cotton burning for 60 seconds or more were judged to be rejected. 2) To check the mechanical strength of this heat shrink tube,
The heat-shrinkable tube was left in a thermostat set at 150 ° C. for 3 minutes and heat-shrinked.
A tensile test (tensile speed: 500 mm / min) was performed in accordance with the above.
It measured at the point and calculated | required the average value.

【００３８】 直流用高圧電線について １）直流用高圧電線のＵＬ規格の難燃性 難燃性を調べるために、ＵＬ規格のＶＷ−１試験を各１
０点の試料について行った。判定は、１０点中１点でも
６０秒以上燃焼したり、下部に敷いた脱脂綿が燃焼落下
物によって類焼したり、試料の上部に取り付けたクラフ
ト紙が燃えたり、焦げたりしたものを不合格とした。 ２）機械的物性 押出被覆層の引張試験（引張速度５００ｍｍ／分）を行
い、初期破断抗張力、初期破断伸び（標線間距離２０ｍ
ｍ）を各３点で測定し平均値を求めた。 ３）熱老化物性 電線試料を１５８℃のギアオーブンで７日間熱老化した
後の被覆層の伸び残率を評価した。ここで、伸び残率
（％）＝（熱老化試料の伸び／初期伸び）×１００であ
り、伸び残率６５％以上を合格の目安とした。Regarding DC High Voltage Wires 1) UL Standard Flame Retardancy of DC High Voltage Wires In order to investigate the flame retardancy, a UL standard VW-1 test was performed for each one.
The test was performed on the sample of 0 point. Judgment was made that even if one of the 10 points burned for 60 seconds or more, the cotton wool laid at the bottom was burned down by burning and falling objects, or the kraft paper attached to the top of the sample was burned or burned, it was rejected. did. 2) Mechanical properties The extruded coating layer was subjected to a tensile test (tensile speed: 500 mm / min) to obtain an initial breaking tensile strength and an initial breaking elongation (a distance between marked lines of 20 m).
m) was measured at each of three points, and the average value was determined. 3) Heat Aging Property After the wire sample was heat-aged for 7 days in a gear oven at 158 ° C., the residual elongation of the coating layer was evaluated. Here, the residual elongation rate (%) = (elongation of heat-aged sample / initial elongation) × 100, and a residual elongation rate of 65% or more was used as a measure of acceptance.

【００３９】４）高圧カットスルー試験 図２はＵＬ規格Subject758による高圧カットスルー試験
を説明する模式図である。図２に示すように、１２５℃
に設定した槽内で２本の平行に配置した１／３２”のド
リルロッド１１を介して電線１３の両端に１ポンドの荷
重１０をかけ、直流電源１２より定格電圧の１．５倍の
電圧を印加した場合に７時間以内に絶縁破壊を起こした
時に不合格とした。ｎ＝３で評価した。 ５）耐電圧試験(MethodII) 図３は、前記ＵＬ規格による耐電圧試験(MethodII)を説
明する模式図である。電線試料を１５８℃のギアオーブ
ンで７日間熱老化した後、図３に示すように、電線２１
を外径０．５インチのマンドレル１９に７回巻き付け、
１２５℃のギアオーブン内で定格電圧１．２５倍の電圧
を印加した場合に７時間以内に絶縁破壊を起こした時に
不合格とした。ｎ＝３で評価した。4) High-pressure cut-through test FIG. 2 is a schematic diagram illustrating a high-pressure cut-through test according to UL Standard Subject758. As shown in FIG.
A 1 lb load 10 is applied to both ends of the electric wire 13 via two 1/32 "drill rods 11 arranged in parallel in a tank set at a voltage of 1.5 times the rated voltage from the DC power supply 12. Was rejected when dielectric breakdown occurred within 7 hours when a voltage was applied.Evaluated at n = 3 5) Withstand voltage test (Method II) FIG. 3 shows the withstand voltage test (Method II) according to the UL standard. After the wire sample was heat-aged for 7 days in a gear oven at 158 ° C., as shown in FIG.
Is wound around a mandrel 19 having an outer diameter of 0.5 inch seven times,
When a voltage of 1.25 times the rated voltage was applied in a gear oven at 125 ° C., failure was caused when dielectric breakdown occurred within 7 hours. Evaluation was made at n = 3.

【００４０】＜難燃性樹脂組成物の調製＞表１〜１４に
記載の樹脂組成物を１４０℃に設定した加圧ニーダーで
混練し、得られた混練物をフィーダールーダーを用いて
ペレット状にした。なお、表１〜１９記載の配合組成物
には、各ベースポリマー１００重量部に対してオレイン
酸アミドを０．５重量部、ペンタエリスリトール−テト
ラキス〔３−（３，５−ｔブチル−４−ヒドロキシフェ
ニル）プロピオネート〕１重量部を共通に配合した。<Preparation of Flame-Retardant Resin Composition> The resin compositions shown in Tables 1 to 14 were kneaded in a pressure kneader set at 140 ° C., and the obtained kneaded material was formed into pellets using a feeder ruder. did. In addition, in the compounding compositions described in Tables 1 to 19, 0.5 parts by weight of oleamide was added to 100 parts by weight of each base polymer, and pentaerythritol-tetrakis [3- (3,5-tbutyl-4-) was used. [Hydroxyphenyl) propionate] was added in common.

【００４１】（A) 絶縁電線−１： （実施例１〜１４）表１〜３のペレットを溶融押出機
（４５ｍｍφ、Ｌ／Ｄ＝２４、圧縮比＝２．５のフルフ
ライトタイプ）を使用し、導体（０．８ｍｍφ厚みの錫
メッキ軟銅線）上に肉厚が０．４０ｍｍになるように押
出被覆し、加速電圧２ＭｅＶの電子線を２００ｋＧｙ照
射して試料を作製した。なお、表１の実施例７及び表２
の実施例１４、表３の比較例５に関しては電子線照射工
程を省いた。表１の実施例１〜７は、エチレン−酢酸ビ
ニル共重合体樹脂１００重量部に対し、金属水酸化物で
ある水酸化マグネシウム１５０〜１９０重量部、酢酸塩
である酢酸マグネシウム或いは酢酸カルシウムを１０〜
５０重量部の範囲で配合した樹脂組成物を使用した絶縁
電線である。(A) Insulated wire-1: (Examples 1 to 14) The pellets shown in Tables 1 to 3 were melt-extruded (45 mmφ, L / D = 24, compression ratio = 2.5, full flight type). Then, a conductor (tin-plated soft copper wire having a thickness of 0.8 mmφ) was extrusion-coated so as to have a thickness of 0.40 mm, and an electron beam having an acceleration voltage of 2 MeV was irradiated at 200 kGy to prepare a sample. In addition, Example 7 of Table 1 and Table 2
In Example 14 of Comparative Example 5 and Table 3, the electron beam irradiation step was omitted. In Examples 1 to 7 of Table 1, 150 to 190 parts by weight of magnesium hydroxide as a metal hydroxide and magnesium acetate or calcium acetate as an acetate were added to 100 parts by weight of an ethylene-vinyl acetate copolymer resin. ~
It is an insulated wire using a resin composition blended in a range of 50 parts by weight.

【００４２】また、表２の実施例８〜１４は、エチレン
−酢酸ビニル共重合体樹脂１００重量部に対し、金属水
酸化物である水酸化マグネシウム１５０〜１９０重量
部、炭酸カルシウムを１０〜５０重量部の範囲で配合し
た樹脂組成物を使用した絶縁電線である。これらのＶＷ
−１試験を行ったところ、全て合格し、燃焼時間の分布
は０〜２０秒に入るものが多く、長くても４０秒以内に
消火することが分かった。また、シラン系カップリング
剤としてγ−メタクリロキシプロピルトリメトキシシラ
ンを添加した実施例３〜６、１０〜１３の樹脂組成物を
用いた試料では、初期抗張力１．０６ｋｇ／ｍｍ2 以
上、伸び１００％以上というＵＬ規格を上回る機械的強
度を示すことが分かった。Examples 8 to 14 in Table 2 show that, with respect to 100 parts by weight of the ethylene-vinyl acetate copolymer resin, 150 to 190 parts by weight of magnesium hydroxide, which is a metal hydroxide, and 10 to 50 parts by weight of calcium carbonate. It is an insulated wire using a resin composition compounded in a range of parts by weight. These VW
When the -1 test was conducted, all passed, and the distribution of the burning time was often in the range of 0 to 20 seconds, and it was found that the fire was extinguished within at most 40 seconds. In the samples using the resin compositions of Examples 3 to 6 and 10 to 13 to which γ-methacryloxypropyltrimethoxysilane was added as a silane coupling agent, the initial tensile strength was 1.06 kg / mm 2 or more, and the elongation was 100%. % Or more of the mechanical strength exceeding the UL standard.

【００４３】（比較例１〜７）表３に示した比較例１〜
６は、エチレン−酢酸ビニル共重合体樹脂１００重量部
に対し、金属水酸化物である水酸化マグネシウム１８０
〜２５０重量部の範囲で配合した樹脂組成物を使用した
絶縁電線である。表３の比較例１〜５の樹脂組成物を使
用した絶縁電線のＶＷ−１試験を行ったところ全て合格
するが、燃焼時間は２０〜４０秒乃至４０〜６０秒に多
く分布しており、酢酸塩を添加した表１の実施例１〜７
或いは表２の炭酸カルシウムを添加した実施例８〜１４
に比べて難燃性に劣ることが分かった。表３の比較例６
に関してはＶＷ−１試験に合格し、その燃焼時間も０〜
２０秒以内に多く分布し難燃性に優れるが、初期抗張力
はＵＬ規格を満足せず、伸びも１００％を下回った。表
３の比較例７はＰＶＣ組成物の絶縁電線であり、ＶＷ−
１試験の燃焼時間は２０秒以内で全て消火することが分
かる。(Comparative Examples 1 to 7) Comparative Examples 1 to 7 shown in Table 3
6 is a metal hydroxide of magnesium hydroxide 180 per 100 parts by weight of the ethylene-vinyl acetate copolymer resin.
It is an insulated wire using a resin composition blended in a range of up to 250 parts by weight. When the VW-1 test was performed on the insulated wires using the resin compositions of Comparative Examples 1 to 5 in Table 3, all passed, but the burning time is widely distributed in 20 to 40 seconds to 40 to 60 seconds, Examples 1 to 7 of Table 1 with addition of acetate
Alternatively, Examples 8 to 14 in which the calcium carbonate shown in Table 2 was added
It turned out that it was inferior to flame retardancy compared with. Comparative Example 6 in Table 3
Passed the VW-1 test and the combustion time was
It was distributed in a large amount within 20 seconds and was excellent in flame retardancy, but the initial tensile strength did not satisfy the UL standard, and the elongation was less than 100%. Comparative Example 7 in Table 3 is an insulated wire of a PVC composition, and VW-
It can be seen that all the fires were extinguished within 20 seconds in one test.

【００４４】[0044]

【表１】 [Table 1]

【００４５】（注） ＊１：酢酸ビニル含有率＝２５％、メルトフロレート＝
３ ＊２：酢酸ビニル含有率＝４５％、メルトフロレート＝
１ ＊３：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、ステアリン酸表面処理品 ＊４：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、表面処理なし ＊５：和光純薬（株）製 平均粒子径＝３μｍ ＊６：和光純薬（株）製 平均粒子径＝３μｍ(Note) * 1: Vinyl acetate content = 25%, melt flow rate =
3 * 2: vinyl acetate content = 45%, melt flow rate =
1 * 3: Average particle size = 0.7 µm, BET specific surface area = 7 m
2 / g, stearic acid surface-treated product * 4: Average particle size = 0.7 μm, BET specific surface area = 7 m
2 / g, no surface treatment * 5: Wako Pure Chemical Industries, Ltd. average particle size = 3 μm * 6: Wako Pure Chemical Co., Ltd. average particle size = 3 μm

【００４６】[0046]

【表２】 [Table 2]

【００４７】（注） ＊１：酢酸ビニル含有率＝２５％、メルトフロレート＝
３ ＊２：酢酸ビニル含有率＝４５％、メルトフロレート＝
１ ＊３：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、ステアリン酸表面処理品 ＊４：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、表面処理なし ＊５：一次粒子径＝０．０４μｍ、ステアリン酸表面処
理品 ＊６：一次粒子径＝１．５μｍ、表面処理なし(Note) * 1: Vinyl acetate content = 25%, melt flow rate =
3 * 2: vinyl acetate content = 45%, melt flow rate =
1 * 3: Average particle size = 0.7 µm, BET specific surface area = 7 m
2 / g, stearic acid surface-treated product * 4: Average particle size = 0.7 μm, BET specific surface area = 7 m
2 / g, no surface treatment * 5: Primary particle size = 0.04 µm, stearic acid surface-treated product * 6: Primary particle size = 1.5 µm, no surface treatment

【００４８】[0048]

【表３】 [Table 3]

【００４９】（注） ＊１：酢酸ビニル含有率＝２５％、メルトフロレート＝
３ ＊２：酢酸ビニル含有率＝４５％、メルトフロレート＝
１ ＊３：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、ステアリン酸表面処理品 ＊４：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、表面処理なし(Note) * 1: Vinyl acetate content = 25%, melt flow rate =
3 * 2: vinyl acetate content = 45%, melt flow rate =
1 * 3: Average particle size = 0.7 µm, BET specific surface area = 7 m
2 / g, stearic acid surface-treated product * 4: Average particle size = 0.7 μm, BET specific surface area = 7 m
2 / g, no surface treatment

【００５０】(B) 絶縁電線−２ （実施例１５〜２２）次に、表４〜５に示した難燃性樹
脂組成物を溶融押出機（４５ｍｍφ、Ｌ／Ｄ＝２４、圧
縮比＝２．５のフルフライトタイプ）を使用し、導体
（０．８ｍｍφ厚みの錫メッキ軟銅線）上に肉厚が０．
８０ｍｍになるように押出被覆し、加速電圧２ＭｅＶの
電子線を２００ｋＧｙ照射して試料を作製した。この絶
縁電線の物性を実施例１〜１４と同様の方法で評価し
た。(B) Insulated Wire-2 (Examples 15 to 22) Next, the flame-retardant resin compositions shown in Tables 4 to 5 were melt extruded (45 mmφ, L / D = 24, compression ratio = 2). 0.5 full-flight type) and a thickness of 0.5 mm on the conductor (0.8 mmφ thick tinned annealed copper wire).
Extrusion coating was performed so that the thickness became 80 mm, and an electron beam having an acceleration voltage of 2 MeV was irradiated with 200 kGy to prepare a sample. The physical properties of this insulated wire were evaluated in the same manner as in Examples 1 to 14.

【００５１】表４の実施例１５〜２２は、エチレン−酢
酸ビニル共重合体樹脂１００重量部に対し、金属水酸化
物である水酸化マグネシウム１５０〜１９０重量部、酢
酸塩である酢酸マグネシウム或いは酢酸カルシウムを１
０〜５０重量部の範囲で配合した樹脂組成物を使用した
絶縁電線であり、且つエチレン−酢酸ビニル共重合体樹
脂１００重量部に対し、金属水酸化物である水酸化マグ
ネシウム１５０〜１９０重量部、炭酸カルシウムを１０
〜５０重量部の範囲で配合した樹脂組成物を使用した絶
縁電線である。これらのＶＷ−１試験を行ったところ、
全て合格し、２０秒以内に消火するものが多くを占め、
優れた難燃性を示すことが分かった。また、シラン系カ
ップリング剤としてγ−メタクリロキシプロピルトリメ
トキシシランを添加した樹脂組成物を用いた表４の実施
例１７、１８及び実施例２１、２２では、初期抗張力
１．０６ｋｇ／ｍｍ2 以上、伸び１００％以上というＵ
Ｌ規格を上回る機械的強度を示すことが分かった。Examples 15 to 22 in Table 4 show that, relative to 100 parts by weight of the ethylene-vinyl acetate copolymer resin, 150 to 190 parts by weight of magnesium hydroxide as a metal hydroxide, magnesium acetate or acetate as an acetate. One calcium
It is an insulated wire using the resin composition blended in the range of 0 to 50 parts by weight, and 150 to 190 parts by weight of magnesium hydroxide which is a metal hydroxide based on 100 parts by weight of the ethylene-vinyl acetate copolymer resin. , Calcium carbonate 10
It is an insulated wire using a resin composition blended in a range of ５０50 parts by weight. When these VW-1 tests were performed,
Most passed and fire extinguished within 20 seconds.
It was found to show excellent flame retardancy. Further, in Examples 17 and 18 and Examples 21 and 22 of Table 4 using a resin composition to which γ-methacryloxypropyltrimethoxysilane was added as a silane coupling agent, the initial tensile strength was 1.06 kg / mm 2 or more. , U of 100% or more
It was found to exhibit mechanical strength exceeding the L standard.

【００５２】（比較例８〜１２）表５に示した比較例８
〜１１は、エチレン−酢酸ビニル共重合体樹脂１００重
量部に対し、金属水酸化物である水酸化マグネシウム１
８０〜２００重量部の範囲で配合した樹脂組成物を使用
した絶縁電線である。比較例８〜１１の樹脂組成物を使
用した絶縁電線のＶＷ−１試験を行ったところ全て合格
するが、燃焼時間は２０〜４０秒乃至４０〜６０秒に多
く分布しており、酢酸塩を添加した表４の実施例１５〜
１８或いは炭酸カルシウムを添加した実施例１９〜２２
の絶縁電線よりも難燃性が劣ることが分かった。比較例
１２はＰＶＣ組成物の絶縁電線であり、ＶＷ−１試験の
燃焼時間は２０秒以内で全て消火することが分かる。(Comparative Examples 8 to 12) Comparative Example 8 shown in Table 5
Nos. 11 to 11 are magnesium hydroxide 1 which is a metal hydroxide with respect to 100 parts by weight of an ethylene-vinyl acetate copolymer resin.
It is an insulated wire using a resin composition blended in the range of 80 to 200 parts by weight. When the insulated wires using the resin compositions of Comparative Examples 8 to 11 were subjected to the VW-1 test, they all passed, but the burning time was widely distributed in 20 to 40 seconds to 40 to 60 seconds, and acetate was added. Example 15 of Table 4 added
Examples 19 to 22 to which 18 or calcium carbonate was added
It was found that the flame retardancy was inferior to that of the insulated wire. Comparative Example 12 is an insulated electric wire of a PVC composition, and it can be seen that all the fires extinguished within a burning time of 20 seconds in the VW-1 test.

【００５３】[0053]

【表４】 [Table 4]

【００５４】（注）＊１：酢酸ビニル含有率＝２５％、
メルトフロレート＝３ ＊２：酢酸ビニル含有率＝４５％、メルトフロレート＝
１ ＊３：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、ステアリン酸表面処理品 ＊４：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、表面処理なし ＊５：和光純薬（株）製 平均粒子径＝３μｍ ＊６：和光純薬（株）製 平均粒子径＝３μｍ ＊７：一次粒子径＝０．０４μｍ、ステアリン酸表面処
理品 ＊８：一次粒子径＝１．５μｍ、表面処理なし(Note) * 1: Vinyl acetate content = 25%,
Melt flow rate = 3 * 2: Vinyl acetate content = 45%, melt flow rate =
1 * 3: Average particle size = 0.7 µm, BET specific surface area = 7 m
2 / g, stearic acid surface-treated product * 4: Average particle size = 0.7 μm, BET specific surface area = 7 m
2 / g, no surface treatment * 5: Average particle size = 3 μm, manufactured by Wako Pure Chemical Co., Ltd. * 6: Average particle size = 3 μm, manufactured by Wako Pure Chemical Co., Ltd. * 7: Primary particle size = 0.04 μm, stearic acid Surface treated product * 8: Primary particle size = 1.5 µm, no surface treatment

【００５５】[0055]

【表５】 [Table 5]

【００５６】（注） ＊１：酢酸ビニル含有率＝２５％、メルトフロレート＝
３ ＊２：酢酸ビニル含有率＝４５％、メルトフロレート＝
１ ＊３：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、ステアリン酸表面処理品 ＊４：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、表面処理なし(Note) * 1: Vinyl acetate content = 25%, melt flow rate =
3 * 2: vinyl acetate content = 45%, melt flow rate =
1 * 3: Average particle size = 0.7 µm, BET specific surface area = 7 m
2 / g, stearic acid surface-treated product * 4: Average particle size = 0.7 μm, BET specific surface area = 7 m
2 / g, no surface treatment

【００５７】(C) 絶縁チューブ−１ （実施例２３〜２８）表６、７に示した難燃性樹脂組成
物を溶融押出機（４５ｍｍφ、Ｌ／Ｄ＝２４、圧縮比＝
２．５のフルフライトタイプ）を使用して押出温度１６
０℃で内径６．４ｍｍφ、肉厚０．５ｍｍのチューブ状
成形物を成形した。このチューブ状成形物に加速電圧２
ＭｅＶの電子線を１００ｋＧｙ照射してチューブ層を架
橋した。なお、表６の実施例２５、２８及び表７の比較
例１５のチューブに関しては電子線照射工程を省いた。
得られたチューブの難燃性を調べるために、チューブの
内部にチューブ内径と同じサイズ６．４ｍｍφの鉄棒を
挿入し、オールチュービングフレームテストで夫々１０
点試験し、１０点中１点でも６０秒以上燃焼やクラフト
紙燃え、脱脂綿燃えを起こしたものは不合格と判断し
た。また、このチューブの機械的強度を調べるため、引
張試験（引張速度５００ｍｍ／分）を行い、破断時の抗
張力と伸び（標線間距離２０ｍｍ）を各３点について測
定し平均値を求めた。(C) Insulating tube-1 (Examples 23 to 28) The flame-retardant resin compositions shown in Tables 6 and 7 were melt extruded (45 mmφ, L / D = 24, compression ratio =
Extrusion temperature 16 using 2.5 full flight type)
At 0 ° C., a tubular molded product having an inner diameter of 6.4 mmφ and a thickness of 0.5 mm was formed. An acceleration voltage of 2
The tube layer was cross-linked by irradiation with an electron beam of MeV at 100 kGy. The electron beam irradiation step was omitted for the tubes of Examples 25 and 28 in Table 6 and Comparative Example 15 in Table 7.
In order to examine the flame retardancy of the obtained tubes, an iron rod having the same size as the tube inner diameter of 6.4 mmφ was inserted into the tubes, and each was subjected to an all tubing frame test by 10 times.
A point test was conducted, and even one of the ten points, which burned for 60 seconds or more, burned kraft paper, or burned absorbent cotton, was judged to be rejected. Further, in order to examine the mechanical strength of the tube, a tensile test (tensile speed: 500 mm / min) was performed, and the tensile strength and elongation at break (distance between marked lines: 20 mm) were measured for each of three points to obtain an average value.

【００５８】表６の実施例２３〜２８は、夫々酢酸塩を
添加した実施例１、３、７の樹脂組成物、及び炭酸カル
シウムを添加した実施例８、１０、１４の樹脂組成物を
使用したチューブである。これらオールチュービングフ
レームテストを行ったところ全て合格し、燃焼時間の分
布は５０％以上の確率で２０秒以内に消火することが分
かった。また、シラン系カップリング剤としてγ−メタ
クリロキシプロピルトリメトキシシランを添加した表６
の実施例２４、２７のチューブに関しては、難燃性と共
に初期抗張力１．０６ｋｇｍｍ2 以上、伸び１００％以
上とＵＬ規格の要求値を満たすことが分かった。In Examples 23 to 28 of Table 6, the resin compositions of Examples 1, 3 and 7 to which acetate was added and the resin compositions of Examples 8, 10 and 14 to which calcium carbonate was added were used. Tube. All these tubing flame tests passed, and it was found that the distribution of the burning time extinguished within 20 seconds with a probability of 50% or more. Table 6 in which γ-methacryloxypropyltrimethoxysilane was added as a silane coupling agent.
With respect to the tubes of Examples 24 and 27, it was found that the flame resistance was satisfied and the initial tensile strength was 1.06 kgmm 2 or more and the elongation was 100% or more, which satisfied the requirements of the UL standard.

【００５９】（比較例１３〜１５）表７の比較例１３〜
１５は、夫々比較例１、３、５の樹脂組成物を使用した
チューブである。これらのチューブのオールチュービン
グフレームテストを行ったところ全て合格するが、燃焼
時間の分布は５０％以上が２０秒以上と酢酸塩を添加し
た表６の実施例２３〜２５或いは炭酸カルシウムを添加
した表６の実施例２６〜２８に比べて難燃性に劣ること
が分かった。(Comparative Examples 13 to 15) Comparative Examples 13 to 15 in Table 7
Reference numeral 15 denotes tubes using the resin compositions of Comparative Examples 1, 3, and 5, respectively. All the tubing flame tests of these tubes passed, but all of them passed, but the distribution of burning time was 50 seconds or more, 20 seconds or more, and Examples 23 to 25 in Table 6 in which acetate was added or Table 23 in which calcium carbonate was added. It was found that the flame retardancy was inferior to Examples 26 to 28 of No. 6.

【００６０】[0060]

【表６】 [Table 6]

【００６１】（注） ＊１：酢酸ビニル含有率＝２５％、メルトフロレート＝
３ ＊２：酢酸ビニル含有率＝４５％、メルトフロレート＝
１ ＊３：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、ステアリン酸表面処理品 ＊４：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、表面処理なし ＊５：和光純薬（株）製 平均粒子径＝３μｍ ＊６：和光純薬（株）製 平均粒子径＝３μｍ ＊７：一次粒子径＝０．０４μｍ、ステアリン酸表面処
理品 ＊８：一次粒子径＝１．５μｍ、表面処理なし(Note) * 1: Vinyl acetate content = 25%, melt flow rate =
3 * 2: vinyl acetate content = 45%, melt flow rate =
1 * 3: Average particle size = 0.7 µm, BET specific surface area = 7 m
2 / g, stearic acid surface-treated product * 4: Average particle size = 0.7 μm, BET specific surface area = 7 m
2 / g, no surface treatment * 5: Average particle size = 3 μm, manufactured by Wako Pure Chemical Co., Ltd. * 6: Average particle size = 3 μm, manufactured by Wako Pure Chemical Co., Ltd. * 7: Primary particle size = 0.04 μm, stearic acid Surface treated product * 8: Primary particle size = 1.5 µm, no surface treatment

【００６２】[0062]

【表７】 [Table 7]

【００６３】（注） ＊１：酢酸ビニル含有率＝２５％、メルトフロレート＝
３ ＊２：酢酸ビニル含有率＝４５％、メルトフロレート＝
１ ＊３：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、ステアリン酸表面処理品 ＊４：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、表面処理なし(Note) * 1: Vinyl acetate content = 25%, melt flow rate =
3 * 2: vinyl acetate content = 45%, melt flow rate =
1 * 3: Average particle size = 0.7 µm, BET specific surface area = 7 m
2 / g, stearic acid surface-treated product * 4: Average particle size = 0.7 μm, BET specific surface area = 7 m
2 / g, no surface treatment

【００６４】(D) 熱収縮チューブ−１ （実施例２９〜３０）表８に示した難燃性樹脂組成物を
溶融押出機（４５ｍｍφ、Ｌ／Ｄ＝２４、圧縮比＝２．
５のフルフライトタイプ）を使用して押出温度１６０℃
で内径３．２ｍｍφ、肉厚０．５ｍｍのチューブ状成形
物を成形した。このチューブ状成形物に加速電圧２Ｍｅ
Ｖの電子線を１００ｋＧｙ照射してチューブ層を架橋し
た。架橋したチューブを１６０℃に設定した恒温槽内に
３分間放置し予熱し、チューブ内に圧縮空気を送り込む
方法で、内径が７ｍｍφになるまで拡径し、すぐさま恒
温槽から取り出し、水冷して形状を保持させ熱収縮チュ
ーブを得た。(D) Heat Shrink Tube-1 (Examples 29 to 30) The flame-retardant resin composition shown in Table 8 was melt extruded (45 mmφ, L / D = 24, compression ratio = 2.
Extrusion temperature 160 ° C using 5 full flight type)
To form a tubular molded product having an inner diameter of 3.2 mm and a wall thickness of 0.5 mm. An acceleration voltage of 2 Me is applied to this tubular product.
The tube layer was cross-linked by irradiating 100 kGy with an electron beam of V. Leave the crosslinked tube in a constant temperature bath set at 160 ° C for 3 minutes to preheat it, then expand the inner diameter to 7 mmφ by sending compressed air into the tube. Immediately remove the tube from the constant temperature bath and cool with water. And a heat-shrinkable tube was obtained.

【００６５】得られた熱収縮チューブの難燃性を調べる
ために、内径が７ｍｍφの拡径した熱収縮チューブ内に
外径３．３ｍｍφの鉄棒を挿入し、１５０℃の恒温槽に
３分間放置し、熱収縮チューブが鉄棒の周囲にフィット
する状態で熱収縮させ、オールチュービングテストで夫
々１０点試験し、１０点中１点でも６０秒以上燃焼やク
ラフト紙燃え、脱脂綿燃えを起こして合格しないものは
不合格と判断した。また、このチューブの機械的強度を
調べるため、熱収縮チューブを１５０℃に設定した恒温
槽に３分間放置して熱収縮させた試料について引張試験
（引張速度５００ｍｍ／分）を行い、破断時の抗張力と
伸び（標線間距離２０ｍｍ）を各３点について測定し平
均値を求めた。表８の実施例２９〜３０は、表１の実施
例１、８の樹脂組成物を使用した熱収縮チューブであ
る。このオールチュービングテストを行ったところ全て
合格し、燃焼時間は０〜２０秒に分布するものが多く、
難燃性に優れることが分かった。In order to examine the flame retardancy of the obtained heat-shrinkable tube, an iron rod having an outer diameter of 3.3 mm was inserted into an expanded heat-shrinkable tube having an inner diameter of 7 mm and left in a thermostat at 150 ° C. for 3 minutes. Then, heat shrink the heat-shrinkable tube so that it fits around the iron bar. Ten points are tested in the all tubing test, and even one of the ten points does not pass because it burns for 60 seconds or more, burns kraft paper, or burns cotton wool. Those were judged as rejected. Further, in order to examine the mechanical strength of this tube, a tensile test (tensile speed: 500 mm / min) was performed on the heat-shrinkable sample which was left in a thermostat set at 150 ° C. for 3 minutes and heat-shrinked. Tensile strength and elongation (distance between marked lines: 20 mm) were measured for each of three points, and the average value was determined. Examples 29 to 30 in Table 8 are heat-shrinkable tubes using the resin compositions of Examples 1 and 8 in Table 1. When all the tubing tests were performed, all passed, and the burning time was often distributed between 0 and 20 seconds.
It was found to be excellent in flame retardancy.

【００６６】（比較例１６）表８の比較例１６は、比較
例１の樹脂組成物を使用した熱収縮チューブである。こ
のオールチュービングテストを行ったところ全て合格す
るが、燃焼時間４０〜６０秒に分布するものが多く、酢
酸塩を添加した表８の実施例２９及び炭酸カルシウムを
添加した表８の実施例３０に比べ劣ることが分かった。Comparative Example 16 Comparative Example 16 in Table 8 is a heat-shrinkable tube using the resin composition of Comparative Example 1. When all the tubing tests were performed, all passed, but many were distributed in the combustion time of 40 to 60 seconds. In Example 29 of Table 8 to which acetate was added and Example 30 of Table 8 to which calcium carbonate was added. It turned out to be inferior.

【００６７】[0067]

【表８】 [Table 8]

【００６８】（注） ＊１：酢酸ビニル含有率＝２５％、メルトフロレート＝
３ ＊２：酢酸ビニル含有率＝４５％、メルトフロレート＝
１ ＊３：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、ステアリン酸表面処理品 ＊４：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、表面処理なし ＊５：和光純薬（株）製 平均粒子径＝３μｍ ＊６：和光純薬（株）製 平均粒子径＝３μｍ ＊７：一次粒子径＝０．０４μｍ、ステアリン酸表面処
理品 ＊８：一次粒子径＝１．５μｍ、表面処理なし(Note) * 1: Vinyl acetate content = 25%, melt flow rate =
3 * 2: vinyl acetate content = 45%, melt flow rate =
1 * 3: Average particle size = 0.7 µm, BET specific surface area = 7 m
2 / g, stearic acid surface-treated product * 4: Average particle size = 0.7 μm, BET specific surface area = 7 m
2 / g, no surface treatment * 5: Average particle size = 3 μm, manufactured by Wako Pure Chemical Co., Ltd. * 6: Average particle size = 3 μm, manufactured by Wako Pure Chemical Co., Ltd. * 7: Primary particle size = 0.04 μm, stearic acid Surface treated product * 8: Primary particle size = 1.5 µm, no surface treatment

【００６９】(E) フラットケーブル−１ （実施例３１〜３６）表９、１０に示した難燃性樹脂組
成物を混合し、導体（０．１２７ｍｍφの錫メッキ軟銅
線７本撚り）を２．０ｍｍ間隔に７本並列に配置した並
列導体の両面に被覆厚が０．３０ｍｍになるように三葉
製作所製５０ｍｍφの押出被覆装置を用いて１６０℃で
押出被覆し、加速電圧２ＭｅＶの電子線を２００ｋＧｙ
照射してフラットケーブルを作製した。なお、表９の実
施例３３、３６及び表１０の比較例１９に関しては電子
線照射工程を省いた。得られたフラットケーブルの難燃
性をＶＷ−１試験で夫々１０点試験し、１０点中１点で
も６０秒以上燃焼やクラフト紙燃え、脱脂綿燃えを起こ
したものは不合格と判断した。また、このフラットケー
ブルの機械的強度を調べるため、引張試験（引張速度５
００ｍｍ／分）を行い、破断時の抗張力と伸び（標線間
距離２０ｍｍ）を各３点について測定し平均値を求め
た。(E) Flat cable-1 (Examples 31 to 36) The flame-retardant resin compositions shown in Tables 9 and 10 were mixed, and 2 conductors (twisted 0.127 mmφ tinned soft copper wire) were used. Extrusion coating is performed at 160 ° C. using a 50 mmφ extrusion coating device manufactured by Mitsuba Seisakusho so that the coating thickness becomes 0.30 mm on both surfaces of the parallel conductors arranged in parallel at intervals of 0.0 mm, and an electron beam having an acceleration voltage of 2 MeV. 200kGy
Irradiation produced a flat cable. In Examples 33 and 36 of Table 9 and Comparative Example 19 of Table 10, the electron beam irradiation step was omitted. The flame retardancy of the obtained flat cable was tested at 10 points each in the VW-1 test, and even one point out of 10 points was judged as rejected if it burned for 60 seconds or more, burned kraft paper, or burned absorbent cotton. Further, in order to examine the mechanical strength of the flat cable, a tensile test (with a tensile speed of 5) was performed.
(00 mm / min), and the tensile strength and elongation at break (distance between marked lines: 20 mm) were measured at three points, and the average value was determined.

【００７０】表９の実施例３１〜３３は、夫々酢酸塩を
添加した表１の実施例２、５、７の樹脂組成物を使用し
たフラットケーブルであり、表９の実施例３４〜３６
は、それぞれ炭酸カルシウムを添加した表２の実施例
９、１２、１４の樹脂組成物を使用したフラットケーブ
ルである。これらのＶＷ−１試験を行ったところ全て合
格し、燃焼時間は０〜２０秒に分布するものが多く難燃
性に優れることが分かった。また、シラン系カップリン
グ剤としてγ−メタクリロキシプロピルトリメトキシシ
ランを添加した実施例３２、３５のフラットケーブルに
関しては、難燃性と共に初期抗張力１．０６ｋｇｍｍ2
以上、伸び１００％以上というＵＬ規格を上回る機械的
強度を示すことが分かった。Examples 31 to 33 of Table 9 are flat cables using the resin compositions of Examples 2, 5 and 7 of Table 1 to which acetate was added, respectively, and Examples 34 to 36 of Table 9 were used.
Is a flat cable using each of the resin compositions of Examples 9, 12, and 14 in Table 2 to which calcium carbonate was added. When these VW-1 tests were performed, all passed, and it was found that many of the combustion times were distributed in the range of 0 to 20 seconds and the flame retardancy was excellent. The flat cables of Examples 32 and 35 to which γ-methacryloxypropyltrimethoxysilane was added as a silane-based coupling agent had an initial tensile strength of 1.06 kgmm 2 together with flame retardancy.
As described above, it was found that a mechanical strength exceeding the UL standard of 100% or more was exhibited.

【００７１】（比較例１７〜１９）表１０の比較例１７
〜１９は、夫々表３の比較例２、４の樹脂組成物を使用
したフラットケーブルである。これらのフラットケーブ
ルのＶＷ−１試験を行ったところ全て合格するが、燃焼
時間は２０〜４０秒に分布するものが多く、酢酸塩を添
加した表９の実施例３１〜３３及び炭酸カルシウムを添
加した表９の実施例３４〜３６に比べ難燃性が劣ること
が分かった。(Comparative Examples 17 to 19) Comparative Example 17 in Table 10
19 to 19 are flat cables using the resin compositions of Comparative Examples 2 and 4 in Table 3, respectively. When these flat cables were subjected to the VW-1 test, they all passed, but the burning time was often distributed in 20 to 40 seconds, and Examples 31 to 33 in Table 9 to which acetate was added and calcium carbonate were added. It was found that the flame retardancy was inferior to Examples 34 to 36 shown in Table 9.

【００７２】[0072]

【表９】 [Table 9]

【００７３】（注） ＊１：酢酸ビニル含有率＝２５％、メルトフロレート＝
３ ＊２：酢酸ビニル含有率＝４５％、メルトフロレート＝
１ ＊３：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、ステアリン酸表面処理品 ＊４：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、表面処理なし ＊５：和光純薬（株）製 平均粒子径＝３μｍ ＊６：和光純薬（株）製 平均粒子径＝３μｍ ＊７：一次粒子径＝０．０４μｍ、ステアリン酸表面処
理品 ＊８：一次粒子径＝１．５μｍ、表面処理なし(Note) * 1: Vinyl acetate content = 25%, melt flow rate =
3 * 2: vinyl acetate content = 45%, melt flow rate =
1 * 3: Average particle size = 0.7 µm, BET specific surface area = 7 m
2 / g, stearic acid surface-treated product * 4: Average particle size = 0.7 μm, BET specific surface area = 7 m
2 / g, no surface treatment * 5: Average particle size = 3 μm, manufactured by Wako Pure Chemical Co., Ltd. * 6: Average particle size = 3 μm, manufactured by Wako Pure Chemical Co., Ltd. * 7: Primary particle size = 0.04 μm, stearic acid Surface treated product * 8: Primary particle size = 1.5 µm, no surface treatment

【００７４】[0074]

【表１０】 [Table 10]

【００７５】（注） ＊１：酢酸ビニル含有率＝２５％、メルトフロレート＝
３ ＊２：酢酸ビニル含有率＝４５％、メルトフロレート＝
１ ＊３：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、ステアリン酸表面処理品 ＊４：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、表面処理なし(Note) * 1: Vinyl acetate content = 25%, melt flow rate =
3 * 2: vinyl acetate content = 45%, melt flow rate =
1 * 3: Average particle size = 0.7 µm, BET specific surface area = 7 m
2 / g, stearic acid surface-treated product * 4: Average particle size = 0.7 μm, BET specific surface area = 7 m
2 / g, no surface treatment

【００７６】(F) フラットケーブル−２ （実施例３７〜４２）表１１、１２に示した難燃性樹脂
組成物を混合し、三葉製作所製５０ｍｍφのＴダイ押出
機を用いて１６０℃で二軸延伸ポリエステルフィルム上
に厚み０．３０ｍｍで押出して、ポリエステルフィルム
貼合せテープを得た後、並列導体（０．１２７ｍｍφの
錫メッキ軟銅線７本撚りを２．０ｍｍ間隔に７本並列に
配置した）の両面にポリエステルフィルムが外面になる
ように２枚のテープを配置して、１６０℃の熱ラミネー
タを用いて絶縁被覆し、加速電圧２ＭｅＶの電子線を２
００ｋＧｙ照射してフラットケーブルを作製した。な
お、表１１の実施例３９、４２及び表１２の比較例２２
に関しては電子線照射工程を省いた。得られたフラット
ケーブルの難燃性をＶＷ−１試験で夫々１０点試験し、
１０点中１点でも６０秒以上燃焼やクラフト紙燃え、脱
脂綿燃えを起こしたものは不合格と判断した。(F) Flat cable-2 (Examples 37 to 42) The flame-retardant resin compositions shown in Tables 11 and 12 were mixed, and the mixture was heated at 160 ° C. using a T-die extruder of 50 mmφ manufactured by Mitsuba Seisakusho. After extruding on a biaxially stretched polyester film at a thickness of 0.30 mm to obtain a polyester film laminating tape, parallel conductors (seven strands of tinned annealed copper wire of 0.127 mmφ are laid out in parallel at an interval of 2.0 mm, seven in a row. The two tapes were arranged so that the polyester film was on the outer surface on both sides of the film, and the insulation was applied using a 160 ° C. heat laminator.
Irradiation at 00 kGy produced a flat cable. Examples 39 and 42 in Table 11 and Comparative Example 22 in Table 12
For, the electron beam irradiation step was omitted. Each of the obtained flat cables was tested for flame retardancy by a VW-1 test at 10 points.
At least one of the ten points, which burned for 60 seconds or more, burned kraft paper, or burned absorbent cotton, was judged to be rejected.

【００７７】表１１の実施例３７〜３９は、夫々酢酸塩
を添加した実施例２、５、７の樹脂組成物を使用し、ポ
リエステルフィルムで貼り合わせたフラットケーブルで
あり、実施例４０〜４２は、それぞれ炭酸カルシウムを
添加した実施例９、１２、１４の樹脂組成物を使用し、
ポリエステルフィルムで貼り合わせたフラットケーブル
である。これらのＶＷ−１試験を行ったところ、ポリエ
ステルフィルムを貼り合わせているため、表９に示した
実施例３１〜３６のフラットケーブルより燃焼時間は若
干長くなるが、それであっても全て合格し、５０％以上
の確率で２０秒以内に消火することが分かった。Examples 37 to 39 in Table 11 are flat cables which were bonded with a polyester film using the resin compositions of Examples 2, 5 and 7, respectively, to which acetate was added, and Examples 40 to 42. Used the resin compositions of Examples 9, 12, and 14 to which calcium carbonate was added,
This is a flat cable bonded with a polyester film. When these VW-1 tests were performed, the burning time was slightly longer than that of the flat cables of Examples 31 to 36 shown in Table 9 because the polyester films were bonded, but all of them passed, It was found that the fire extinguished within 20 seconds with a probability of 50% or more.

【００７８】（比較例２０〜２２）表１２の比較例２０
〜２２は、夫々表３の比較例２、４の樹脂組成物を使用
し、ポリエステルフィルムで貼り合わせたフラットケー
ブルである。これらのＶＷ−１試験を行ったところ全て
合格するが、５０％以上が２０秒以上の燃焼時間であっ
た。表１２の比較例２０〜２２は、表１１の実施例３７
〜３９或いは実施例４０〜４２よりも水酸化マグネシウ
ムの配合量が多いにも係わらず、ＶＷ−１試験の燃焼時
間が２０秒以内に納まる確率が５０％以上、且つ初期抗
張力、初期伸びのＵＬ規格を同時に満たすことができな
いことが分かった。(Comparative Examples 20 to 22) Comparative Example 20 in Table 12
No. 22 to No. 22 are flat cables bonded using a polyester film using the resin compositions of Comparative Examples 2 and 4 in Table 3, respectively. These VW-1 tests all passed, but 50% or more had a burning time of 20 seconds or more. Comparative Examples 20 to 22 in Table 12 correspond to Example 37 in Table 11.
Despite the fact that the mixing amount of magnesium hydroxide is larger than that of Examples 39 to 39 or Examples 40 to 42, the probability that the burning time in the VW-1 test falls within 20 seconds is 50% or more, and the initial tensile strength and the initial elongation are UL. It turned out that the standard could not be met at the same time.

【００７９】[0079]

【表１１】 [Table 11]

【００８０】（注） ＊１：酢酸ビニル含有率＝２５％、メルトフロレート＝
３ ＊２：酢酸ビニル含有率＝４５％、メルトフロレート＝
１ ＊３：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、ステアリン酸表面処理品 ＊４：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、表面処理なし ＊５：和光純薬（株）製 平均粒子径＝３μｍ ＊６：和光純薬（株）製 平均粒子径＝３μｍ ＊７：一次粒子径＝０．０４μｍ、ステアリン酸表面処
理品 ＊８：一次粒子径＝１．５μｍ、表面処理なし(Note) * 1: Vinyl acetate content = 25%, melt flow rate =
3 * 2: vinyl acetate content = 45%, melt flow rate =
1 * 3: Average particle size = 0.7 µm, BET specific surface area = 7 m
2 / g, stearic acid surface-treated product * 4: Average particle size = 0.7 μm, BET specific surface area = 7 m
2 / g, no surface treatment * 5: Average particle size = 3 μm, manufactured by Wako Pure Chemical Co., Ltd. * 6: Average particle size = 3 μm, manufactured by Wako Pure Chemical Co., Ltd. * 7: Primary particle size = 0.04 μm, stearic acid Surface treated product * 8: Primary particle size = 1.5 µm, no surface treatment

【００８１】[0081]

【表１２】 [Table 12]

【００８２】（注） ＊１：酢酸ビニル含有率＝２５％、メルトフロレート＝
３ ＊２：酢酸ビニル含有率＝４５％、メルトフロレート＝
１ ＊３：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、ステアリン酸表面処理品 ＊４：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、表面処理なし(Note) * 1: Vinyl acetate content = 25%, melt flow rate =
3 * 2: vinyl acetate content = 45%, melt flow rate =
1 * 3: Average particle size = 0.7 µm, BET specific surface area = 7 m
2 / g, stearic acid surface-treated product * 4: Average particle size = 0.7 μm, BET specific surface area = 7 m
2 / g, no surface treatment

【００８３】（G) 直流用高圧線−１ （実施例４３〜５０）導体として、外径０．８ｍｍφ錫
メッキ軟導線を使用し、高密度ポリエチレン（密度＝
０．９５４、メルトフローレート＝０．８：ＡＳＴＭ
Ｄ１２３８）１００重量部にペンタエリスリチルテトラ
キス〔３−（３，５−ｔ−ブチル−４ヒドロキシフェニ
ル）プロピオネート〕を０．３重量部添加した材料を溶
融押出機（４５ｍｍφ、Ｌ／Ｄ＝２４、圧縮比＝２．５
のフルフライトタイプ）を使用して、絶縁層を形成し
た。被覆層として表１３〜１４のペレットを溶融押出機
（４５ｍｍφ、Ｌ／Ｄ＝２４、圧縮比＝２．５のフルフ
ライトタイプ）を使用し、上記の絶縁層の上に外径が
４．２ｍｍφになるように溶融押出した後、加圧電圧５
ＭｅＶの電子線を１５０ｋＧｙ照射して直流用高圧電線
を得た。(G) DC high voltage line-1 (Examples 43 to 50) A 0.8 mmφ tinned soft conductive wire was used as a conductor, and a high-density polyethylene (density =
0.954, melt flow rate = 0.8: ASTM
D1238) A material prepared by adding 0.3 parts by weight of pentaerythrityltetrakis [3- (3,5-tert-butyl-4hydroxyphenyl) propionate] to 100 parts by weight of a melt extruder (45 mmφ, L / D = 24, Compression ratio = 2.5
Was used to form an insulating layer. Using a melt extruder (45 mmφ, L / D = 24, compression ratio = 2.5, full flight type) as a coating layer, the outer diameter of the pellet was 4.2 mmφ on the insulating layer. After melt extrusion so that
An electron beam of MeV was irradiated at 150 kGy to obtain a DC high-voltage electric wire.

【００８４】得られた直流用高圧電線の高圧カットスル
ー試験は、１２５℃のギアオーブンで電線試料の両端に
１ポンドの荷重をかけ、６０ｋＶの直流電圧を印加して
ｎ＝３で実施した。耐電圧試験（Method ll）は電線試
料を１５８℃のギアオーブン内で７日間熱老化した後、
外径０．５インチのマンドレルにて７回巻き付け、１２
５℃のギアオーブン内で５０ｋＶの直流電圧を印加しｎ
＝３で実施した。表１３〜１４の高圧カットスルー試験
試験及び耐電圧試験の欄には、３点中の最初の１点が破
壊した時間を記載した。熱老化試験は電線試料を１５８
℃のギアオーブンで７日間熱老化した後の試料の伸び残
率（％）を評価した。ここで、伸び残率（％）＝（熱老
化試料の伸び／初期伸び）×１００であり、伸び残率６
５％以上を合否の目安とした。燃焼試験はＶＷ−１法に
従い、ｎ＝１０で評価した。The high-voltage cut-through test of the obtained DC high-voltage electric wire was performed at n = 3 by applying a 1-lb load to both ends of the electric wire sample in a gear oven at 125 ° C. and applying a DC voltage of 60 kV. The withstand voltage test (Method ll) was performed after heat aging the wire sample in a 158 ° C gear oven for 7 days.
Wrap 7 times with a 0.5 inch outer diameter mandrel, 12
Apply a 50 kV DC voltage in a 5 ° C. gear oven
= 3. In the columns of the high pressure cut-through test and the withstand voltage test in Tables 13 and 14, the time at which the first one of the three points was broken was described. The heat aging test was conducted on 158 wire samples.
After heat aging for 7 days in a gear oven at a temperature of 7 ° C., the residual elongation (%) of the sample was evaluated. Here, residual elongation (%) = (elongation of heat-aged sample / initial elongation) × 100, and residual elongation 6
5% or more was a measure of pass / fail. The combustion test was performed at n = 10 according to the VW-1 method.

【００８５】表１３の実施例４３〜５０は、エチレン−
酢酸ビニル共重合体樹脂１００重量部に対して、金属水
酸化物である水酸化マグネシウム１５０〜１９０重量
部、酢酸塩である酢酸マグネシウム或いは酢酸カルシウ
ムを１０〜５０重量部の範囲で配合した樹脂組成物を被
覆層とした直流用高圧電線である。これらのＶＷ−１試
験を行ったところ、全て合格することが分かった。ま
た、初期抗張力１．０６ｋｇ／ｍｍ2 以上、伸び１００
％以上と言うＵＬ規格を上回る機械的強度を示し、熱老
化物性や高圧カットスルー試験、耐電圧試験にも合格す
ることが分かった。Examples 43 to 50 in Table 13 show that ethylene-
A resin composition in which 150 to 190 parts by weight of magnesium hydroxide as a metal hydroxide and 10 to 50 parts by weight of magnesium acetate or calcium acetate as an acetate are mixed with 100 parts by weight of a vinyl acetate copolymer resin. It is a high-voltage electric wire for direct current with an object as a coating layer. When these VW-1 tests were performed, it was found that all passed. Further, the initial tensile strength is 1.06 kg / mm 2 or more, and the elongation is 100
% Or more, which is higher than the UL standard, and passed heat aging properties, high-pressure cut-through test, and withstand voltage test.

【００８６】（比較例２３〜２４）表１４に示した比較
例２３〜２４は、エチレン−酢酸ビニル共重合体樹脂１
００重量部に対して、金属水酸化物である水酸化マグネ
シウムを２００重量部で配合した樹脂組成物を被覆層と
した直流用高圧電線である。表１４の比較例２３〜２４
の樹脂組成物は、初期の機械的物性や熱老化後の伸び残
率、高圧カットスルー試験、耐電圧試験には合格するも
のの、表１３の実施例４３〜５０よりも水酸化マグネシ
ウムの添加量が多いにも係わらず、これらを使用した直
流用高圧電線のＶＷ−１試験を行ったところ合格しない
ことが分かった。(Comparative Examples 23 to 24) Comparative Examples 23 to 24 shown in Table 14 show that ethylene-vinyl acetate copolymer resin 1
This is a DC high-voltage electric wire having a coating layer of a resin composition in which 200 parts by weight of magnesium hydroxide as a metal hydroxide is blended with respect to 00 parts by weight. Comparative Examples 23 to 24 in Table 14
Although the resin composition of the present invention passes the initial mechanical properties and residual elongation after heat aging, high-pressure cut-through test, and withstand voltage test, the added amount of magnesium hydroxide is higher than that of Examples 43 to 50 in Table 13. In spite of the fact that there were many VW-1 tests of DC high voltage wires using these, it was found that they did not pass.

【００８７】[0087]

【表１３】 [Table 13]

【００８８】（注） ＊１：酢酸ビニル含有率＝２５％、メルトフロレート＝
３ ＊２：酢酸ビニル含有率＝４５％、メルトフロレート＝
１ ＊３：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、ステアリン酸表面処理品 ＊４：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、表面処理なし ＊５：和光純薬製 平均粒子径＝３μｍ ＊６：和光純薬製 平均粒子径＝３μｍ ＊７：一次粒子径＝０．０４μｍ、ステアリン酸表面処
理品 ＊８：一次粒子径＝１．５μｍ、表面処理なし(Note) * 1: Vinyl acetate content = 25%, melt flow rate =
3 * 2: vinyl acetate content = 45%, melt flow rate =
1 * 3: Average particle size = 0.7 µm, BET specific surface area = 7 m
2 / g, stearic acid surface-treated product * 4: Average particle size = 0.7 μm, BET specific surface area = 7 m
2 / g, no surface treatment * 5: Wako Pure Chemicals average particle diameter = 3 μm * 6: Wako Pure Chemicals average particle diameter = 3 μm * 7: Primary particle diameter = 0.04 μm, stearic acid surface treated * 8: Primary particle size = 1.5 μm, no surface treatment

【００８９】[0089]

【表１４】 [Table 14]

【００９０】＊１：酢酸ビニル含有率＝２５％、メルト
フロレート＝３ ＊２：酢酸ビニル含有率＝４５％、メルトフロレート＝
１ ＊３：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、ステアリン酸表面処理品 ＊４：平均粒子径＝０．７μｍ、ＢＥＴ比表面積＝７ｍ
2 ／ｇ、表面処理なし* 1: Vinyl acetate content = 25%, melt flow rate = 3 * 2: Vinyl acetate content = 45%, melt flow rate =
1 * 3: Average particle size = 0.7 µm, BET specific surface area = 7 m
2 / g, stearic acid surface-treated product * 4: Average particle size = 0.7 μm, BET specific surface area = 7 m
2 / g, no surface treatment

【００９１】[0091]

【発明の効果】以上説明したように、本発明によれば、
燃焼時の有害ガスの発生の問題がなく、機械的強度に優
れ、また難燃性に極めて優れた絶縁被覆電線及びチュー
ブ或いは熱収縮チューブ、フラットケーブルを得ること
ができ、電子計算機、ＯＡ機器、オーデオ、ビデオ等の
民生用電子機器類、車輛、船舶等の内部配線や直流用高
圧電線に使用することが可能である。As described above, according to the present invention,
There is no problem of generation of harmful gas at the time of combustion, and it is possible to obtain an insulated wire and a tube or a heat-shrinkable tube and a flat cable which are excellent in mechanical strength and extremely incombustibility, and can be used in computers, OA equipment, It can be used for consumer electronic devices such as audio and video, internal wiring of vehicles, ships, etc., and high-voltage electric wires for direct current.

【図面の簡単な説明】[Brief description of the drawings]

【図１】ＵＬ規格の垂直燃焼試験（ＶＷ−１試験）を説
明する燃焼試験器具の内部の状態を示す模式図である。FIG. 1 is a schematic view showing an internal state of a combustion test apparatus for explaining a vertical combustion test (VW-1 test) of UL standard.

【図２】ＵＬ規格Subject758による高圧カットスルー試
験を説明する模式図である。FIG. 2 is a schematic diagram illustrating a high-pressure cut-through test according to UL Standard Subject758.

【図３】ＵＬ規格による耐電圧試験(MethodII)を説明す
る模式図である。FIG. 3 is a schematic diagram illustrating a withstand voltage test (Method II) according to the UL standard.

【符号の説明】[Explanation of symbols]

１ クラフト紙 ２ バーナー ３ 止め具 ４ 脱脂綿 ５ 試料 １０ 荷重 １１ ドリルロッド １２、２０ 直流電源 １３、２１ 電線 １９ マンドレル DESCRIPTION OF SYMBOLS 1 Kraft paper 2 Burner 3 Stopper 4 Absorbent cotton 5 Sample 10 Load 11 Drill rod 12, 20 DC power supply 13, 21 Electric wire 19 Mandrel

【手続補正書】[Procedure amendment]

【提出日】平成１１年４月２７日（１９９９．４．２
７）[Submission date] April 27, 1999 (1999.4.2
7)

【手続補正１】[Procedure amendment 1]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】請求項５[Correction target item name] Claim 5

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【化１】 （ただし、Ｒはアクリル基、メタクリル基又はアリル基
を含有するアルキル基であり、Ｙ1 、Ｙ2 、Ｙ3 はアル
キル基、アルコキシ基、ハロゲン基からなる群より選ば
れた原子団を表す。）の有機ケイ素化合物カップリング
剤が、エチレン−αオレフィン共重合体１００重量部に
対して０．１〜１０重量部添加されていることを特徴と
する、請求項１〜４のいずれかに記載の難燃性樹脂組成
物。Embedded image (However, R is an alkyl group containing an acryl group, a methacryl group, or an allyl group, and Y 1 , Y 2 , and Y 3 represent an atomic group selected from the group consisting of an alkyl group, an alkoxy group, and a halogen group. The organic silicon compound coupling agent of (1) is added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the ethylene-α-olefin copolymer. Flame-retardant resin composition.

【手続補正２】[Procedure amendment 2]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】００１０[Correction target item name] 0010

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【００１０】 更に一般式〔Ｉ〕：カーボネートFurther, a general formula [I]: carbonate

【化２】 （ただし、Ｒはアクリル基、メタクリル基又はアリル基
を含有するアルキル基であり、Ｙ1 、Ｙ2 、Ｙ3 はアル
キル基、アルコキシ基、ハロゲン基からなる群より選ば
れた原子団を表す。）の有機ケイ素化合物カップリング
剤が、エチレン−αオレフィン共重合体１００重量部に
対して０．１〜１０重量部添加されていることを特徴と
する。また、 酢酸塩が、粒径０．５〜５μｍの酢酸マグネシウ
ム、酢酸ナトリウム、酢酸カリウム、酢酸亜鉛、酢酸
銅、酢酸鉄、酢酸カルシウム、酢酸アルミニウム、酢酸
ニッケル、酢酸コバルト、酢酸ガリウム、酢酸銀、酢酸
錫、酢酸バリウム、、酢酸セリウム、酢酸鉛、酢酸ベリ
リウムから選択された１種或いはこれら２種以上の混合
物である点にも特徴を有する。また、 炭酸カルシウムの一次粒子径が４μｍ以下である
点にも特徴を有する。また、 炭酸カルシウムが脂肪酸系、油脂系、界面活性剤
系、ワックス系等の表面処理剤によって処理された炭酸
カルシウム、或いはシラン系、チタネート系、アルミニ
ウム系、ジルコアルミニウム系、カルボン酸系、リン酸
系等のカップリング剤で処理された炭酸カルシウムから
選択された１種或いはこれら２種以上の混合物である点
にも特徴を有する。Embedded image (However, R is an alkyl group containing an acryl group, a methacryl group, or an allyl group, and Y 1 , Y 2 , and Y 3 represent an atomic group selected from the group consisting of an alkyl group, an alkoxy group, and a halogen group. Wherein the organic silicon compound coupling agent is added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the ethylene-α-olefin copolymer. In addition, the acetate has a particle size of 0.5 to 5 μm, such as magnesium acetate, sodium acetate, potassium acetate, zinc acetate, copper acetate, iron acetate, calcium acetate, aluminum acetate, nickel acetate, cobalt acetate, gallium acetate, silver acetate, It is also characterized in that it is one selected from tin acetate, barium acetate, cerium acetate, lead acetate, and beryllium acetate, or a mixture of two or more thereof. Another feature is that the primary particle size of calcium carbonate is 4 μm or less. Further, calcium carbonate obtained by treating calcium carbonate with a surface treatment agent such as a fatty acid type, oil type, surfactant type, wax type, or silane type, titanate type, aluminum type, zircon aluminum type, carboxylic acid type, phosphoric acid type It is also characterized in that it is one kind selected from calcium carbonate treated with a coupling agent such as a system or a mixture of two or more kinds thereof.

【手続補正３】[Procedure amendment 3]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】００２０[Correction target item name] 0020

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【００２０】（２） 配合剤 （ｉ） 有機ケイ素化合物カップリング剤 １）一般式〔Ｉ〕：(2) Compounding agent (i) Coupling agent of organosilicon compound 1) General formula [I]:

【化３】 （ただし、Ｒはアクリル基、メタクリル基又はアリル基
を含有するアルキル基であり、Ｙ1 、Ｙ2 、Ｙ3 はアル
キル基、アルコキシ基、ハロゲン基からなる群より選ば
れた原子団を表す。）で示される有機ケイ素化合物カッ
プリング剤が、熱可塑性樹脂１００重量部に対して０．
１〜１０重量部添加すれば（請求項５）、機械物性の点
で好ましい結果が得られる。Embedded image (However, R is an alkyl group containing an acryl group, a methacryl group, or an allyl group, and Y 1 , Y 2 , and Y 3 represent an atomic group selected from the group consisting of an alkyl group, an alkoxy group, and a halogen group. ) Is used in an amount of 0.1 parts by weight based on 100 parts by weight of the thermoplastic resin.
When 1 to 10 parts by weight is added (claim 5), favorable results can be obtained in terms of mechanical properties.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｌ 23/08 Ｃ０８Ｌ 23/08 ５Ｇ３１５ 31/04 31/04 33/00 33/00 Ｈ０１Ｂ 3/00 Ｈ０１Ｂ 3/00 Ａ 3/44 3/44 Ｍ Ｆ 7/08 7/08 7/28 7/28 7/295 7/34 Ｂ (72)発明者 宿島 悟志 大阪府大阪市此花区島屋一丁目１番３号 住友電気工業株式会社大阪製作所内 Ｆターム(参考） 4J002 BB031 BB061 BB071 BB081 BB121 BB151 CF061 CF071 CF101 CK021 CL071 DE046 DE076 DE086 DE146 DE237 EG027 EG037 EG047 EX018 EX028 EX038 FB096 FB097 FB167 FB236 FB237 FB267 FD148 FD150 GQ01 5G303 AA06 AA10 AB12 AB20 CA01 CA09 CB06 CB17 5G305 AA02 AA14 AB15 AB25 AB35 BA15 BA22 BA24 BA26 CA01 CA04 CA07 CA45 CA51 CA54 CB26 CB27 CC03 CC11 CD01 CD06 CD13 DA01 5G311 CA01 CB01 CC01 CD03 CD05 5G313 FA09 FB02 FC04 FD04 FD15 5G315 CA03 CB01 CC08 CD04 CD14 CD15 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int. Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C08L 23/08 C08L 23/08 5G315 31/04 31/04 33/00 33/00 H01B 3/00 H01B 3 / 00 A 3/44 3/44 MF 7/08 7/08 7/28 7/28 7/295 7/34 B (72) Inventor Satoshi Sukushima 1-3-1 Shimaya, Konohana-ku, Osaka-shi, Osaka No. Sumitomo Electric Industries, Ltd. Osaka Works F term (reference) 4J002 BB031 BB061 BB071 BB081 BB121 BB151 CF061 CF071 CF101 CK021 CL071 DE046 DE076 DE086 DE146 DE237 EG027 EG037 EG047 EX018 EX028 EX038 FB096 FB0A FB096 FB09 AFB10 FB096 AB20 CA01 CA09 CB06 CB17 5G305 AA02 AA14 AB15 AB25 AB35 BA15 BA22 BA24 BA26 CA01 CA04 CA07 CA45 CA51 CA54 CB26 CB27 CC03 CC11 CD01 CD06 CD13 DA01 5G311 CA01 CB01 CC01 CD03 CD05 5G313 FA09 FB02 FC04 FD04 FD1 5 5G315 CA03 CB01 CC08 CD04 CD14 CD15

Claims (20)

【特許請求の範囲】[Claims] 【請求項１】 熱可塑性樹脂１００重量部に対して、金
属水酸化物１００〜２５０重量部、酢酸塩５〜５０重量
部或いは炭酸カルシウム５〜８０重量部を配合してなる
ことを特徴とする、難燃性樹脂組成物。1. A thermoplastic resin comprising 100 to 250 parts by weight of a metal hydroxide, 100 to 250 parts by weight of a metal hydroxide, 5 to 50 parts by weight of an acetate or 5 to 80 parts by weight of calcium carbonate. , A flame-retardant resin composition. 【請求項２】 炭酸カルシウムが５〜３０重量部配合す
ることを特徴とする請求項１記載難燃性樹脂組成物。2. The flame-retardant resin composition according to claim 1, wherein 5 to 30 parts by weight of calcium carbonate is blended. 【請求項３】 熱可塑性樹脂がエチレン−酢酸ビニル共
重合体、エチレン−アクリル酸エチル共重合体、エチレ
ン−メタクリル酸メチル共重合体、エチレン−メタクリ
ル酸共重合体、エチレン−アクリル酸メチル共重合体か
ら選択された１種のエチレン−αオレフィン共重合体或
いはこれら２種以上の混合物であることを特徴とする、
請求項１〜２記載の難燃性樹脂組成物。3. The thermoplastic resin is ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer. Characterized in that it is one kind of ethylene-α-olefin copolymer selected from coalescing or a mixture of two or more kinds thereof.
The flame-retardant resin composition according to claim 1. 【請求項４】 エチレン−αオレフィン共重合体が、酢
酸ビニル成分含有率６〜５０％でかつメルトフロレート
（１９０℃、２．１６ｋｇ荷重下）０．５〜３０である
エチレン−酢酸ビニル共重合体であることを特徴とす
る、請求項３記載の難燃性樹脂組成物。4. An ethylene-vinyl acetate copolymer having a vinyl acetate component content of 6 to 50% and a melt flow rate (at 190 ° C. under a load of 2.16 kg) of 0.5 to 30. The flame-retardant resin composition according to claim 3, which is a polymer. 【請求項５】 更に一般式〔Ｉ〕： 【化１】 （ただし、Ｒはアクリル基、メタクリル基又はアリル基
を含有するアルキル基であり、Ｙ1 、Ｙ2 、Ｙ3 はアル
キル基、アルコキシ基、ハロゲン基からなる群より選ば
れた原子団を表す。）の有機ケイ素化合物カップリング
剤が、エチレン−αオレフィン共重合体１００重量部に
対して０．１〜１０重量部添加されていることを特徴と
する、請求項１〜４のいずれかに記載の難燃性樹脂組成
物。5. A compound of the general formula [I]: (However, R is an alkyl group containing an acryl group, a methacryl group, or an allyl group, and Y 1 , Y 2 , and Y 3 represent an atomic group selected from the group consisting of an alkyl group, an alkoxy group, and a halogen group. The organic silicon compound coupling agent of (1) is added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the ethylene-α-olefin copolymer. Flame-retardant resin composition. 【請求項６】 酢酸塩が、粒径０．５〜５μｍの酢酸マ
グネシウム、酢酸ナトリウム、酢酸カリウム、酢酸亜
鉛、酢酸銅、酢酸鉄、酢酸カルシウム、酢酸アルミニウ
ム、酢酸ニッケル、酢酸コバルト、酢酸ガリウム、酢酸
銀、酢酸錫、酢酸バリウム、、酢酸セリウム、酢酸鉛、
酢酸ベリリウムから選択された１種或いはこれら２種以
上の混合物であることを特徴とする、請求項１〜４のい
ずれかに記載の難燃性樹脂組成物。6. An acetate having a particle size of 0.5 to 5 μm, wherein magnesium acetate, sodium acetate, potassium acetate, zinc acetate, copper acetate, iron acetate, calcium acetate, aluminum acetate, nickel acetate, cobalt acetate, gallium acetate, Silver acetate, tin acetate, barium acetate, cerium acetate, lead acetate,
The flame-retardant resin composition according to any one of claims 1 to 4, wherein the composition is one selected from beryllium acetate or a mixture of two or more thereof. 【請求項７】 炭酸カルシウムの一次粒子径が４μｍ以
下であることを特徴とする、請求項１〜６のいずれかに
記載の難燃性樹脂組成物。7. The flame-retardant resin composition according to claim 1, wherein the primary particle diameter of calcium carbonate is 4 μm or less. 【請求項８】 炭酸カルシウムが脂肪酸系、油脂系、界
面活性剤系、ワックス系等の表面処理剤によって処理さ
れた炭酸カルシウム、或いはシラン系、チタネート系、
アルミニウム系、ジルコアルミニウム系、カルボン酸
系、リン酸系等のカップリング剤で処理された炭酸カル
シウムから選択された１種或いはこれら２種以上の混合
物であることを特徴とする、請求項１〜５、７のいずれ
かに記載の難燃性樹脂組成物。8. Calcium carbonate treated with a fatty acid-based, oil-based, surfactant-based or wax-based surface treatment agent, or calcium carbonate, silane-based, titanate-based, or the like.
It is one selected from calcium carbonate treated with a coupling agent such as an aluminum type, a zirconium type, a carboxylic acid type, a phosphoric acid type, or a mixture of two or more thereof. The flame-retardant resin composition according to any one of items 5 and 7. 【請求項９】 請求項１〜８のいずれかに記載の難燃性
樹脂組成物の被覆層を備えたことを特徴とする絶縁電
線。9. An insulated wire comprising a coating layer of the flame-retardant resin composition according to any one of claims 1 to 8. 【請求項１０】 該被覆層が架橋されてなることを特徴
とする請求項８記載の絶縁電線。10. The insulated wire according to claim 8, wherein said coating layer is cross-linked. 【請求項１１】 導体外径が１．０ｍｍ以下の導体に、
請求項１〜７のいずれかに記載の難燃性樹脂組成物が
０．１ｍｍ以上１．０ｍｍ以下の厚みで被覆されてお
り、該被覆層が架橋されていることを特徴とする薄肉高
強度絶縁電線。11. A conductor having a conductor outer diameter of 1.0 mm or less,
The flame-retardant resin composition according to any one of claims 1 to 7, which is coated with a thickness of 0.1 mm or more and 1.0 mm or less, and wherein the coating layer is cross-linked. Insulated wires. 【請求項１２】 請求項１〜８のいずれかに記載の難燃
性樹脂組成物をチューブ状に成形したことを特徴とする
絶縁チューブ。12. An insulating tube formed by molding the flame-retardant resin composition according to claim 1 into a tube. 【請求項１３】 該チューブ層が架橋されていることを
特徴とする請求項１２記載の絶縁チューブ。13. The insulating tube according to claim 12, wherein said tube layer is cross-linked. 【請求項１４】 請求項１〜８のいずれかに記載の難燃
性樹脂組成物のチューブ状成形物が架橋された後、加熱
下で径方向に膨張され、その形状を冷却固定したことを
特徴とする熱収縮チューブ。14. After the cross-linking of the tubular molded product of the flame-retardant resin composition according to any one of claims 1 to 8, it is expanded radially under heating to cool and fix the shape. Characterized heat shrink tube. 【請求項１５】 絶縁被覆内に複数本の導体を間隔をお
いて並列に配置したフラットケーブルであって、上記絶
縁被覆が請求項１〜８のいずれかに記載の難燃性樹脂組
成物からなることを特徴とするフラットケーブル。15. A flat cable in which a plurality of conductors are arranged in parallel at intervals in an insulating coating, wherein the insulating coating is formed from the flame-retardant resin composition according to any one of claims 1 to 8. Flat cable characterized by becoming. 【請求項１６】 該絶縁被覆が架橋されていることを特
徴とする、請求項１５記載のフラットケーブル。16. The flat cable according to claim 15, wherein the insulating coating is cross-linked. 【請求項１７】 上記絶縁被覆の少なくとも一方の面に
高分子材料のフィルムを貼合せてなることを特徴とする
請求項１５又は１６記載のフラットケーブル。17. The flat cable according to claim 15, wherein a polymer film is attached to at least one surface of the insulating coating. 【請求項１８】 該絶縁被覆に電離放射線の照射が施さ
れていることを特徴とする請求項１７記載のフラットケ
ーブル。18. The flat cable according to claim 17, wherein the insulating coating is irradiated with ionizing radiation. 【請求項１９】 絶縁層としてエチレン−αオレフィン
共重合体樹脂組成物が導体上に被覆され、その外層に請
求項１〜８のいずれかに記載の難燃性樹脂組成物の被覆
層を備えていることを特徴とする直流用高圧電線。19. An insulating layer in which an ethylene-α-olefin copolymer resin composition is coated on a conductor, and the outer layer of which is provided with a coating layer of the flame-retardant resin composition according to any one of claims 1 to 8. A high-voltage electric wire for direct current. 【請求項２０】 該絶縁層及び被覆層が架橋されている
ことを特徴とする請求項１９記載の直流用高圧電線。20. The DC high-voltage electric wire according to claim 19, wherein the insulating layer and the coating layer are cross-linked.
JP11755999A 1998-05-29 1999-04-26 Flame-retardant resin composition and its insulated wires, tubes, heat-shrinkable tubes, flat cables, and high-voltage wires for direct current Expired - Fee Related JP4379947B2 (en)

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JP16445398 1998-05-29
JP22751498 1998-07-29
JP10-227514 1998-11-24
JP10-333174 1998-11-24
JP33317498 1998-11-24
JP10-164453 1998-11-24
JP11755999A JP4379947B2 (en) 1998-05-29 1999-04-26 Flame-retardant resin composition and its insulated wires, tubes, heat-shrinkable tubes, flat cables, and high-voltage wires for direct current

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005013291A1 (en) * 2003-07-30 2005-02-10 Sumitomo Electric Industries, Limited Nonhalogenated flame resistant cable
JP2006321944A (en) * 2005-05-20 2006-11-30 Sumitomo Electric Ind Ltd Electrically insulating resin composition
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US7518064B2 (en) 2003-07-30 2009-04-14 Sumitomo Electric Industries, Ltd. Halogen free flame retardant cable
JP2006321944A (en) * 2005-05-20 2006-11-30 Sumitomo Electric Ind Ltd Electrically insulating resin composition
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CN100351952C (en) * 2005-09-28 2007-11-28 江苏宝源电缆料有限公司 Cross-linked fire-resistant cable material with 125 degree radiation
JP2007161927A (en) * 2005-12-15 2007-06-28 Nippon Unicar Co Ltd Flame-retardant resin composition, its extruded molding and electric wire or cable having coated layer obtained by extrusion molding the composition
JP4495130B2 (en) * 2006-10-05 2010-06-30 古河電気工業株式会社 Wire covering resin composition and insulated wire
JP2007073530A (en) * 2006-10-05 2007-03-22 Furukawa Electric Co Ltd:The Resin composite for covering cable and insulated cable
JP2009093900A (en) * 2007-10-05 2009-04-30 Sumitomo Electric Ind Ltd Multi-core flat insulated wire and manufacturing method therefor
JP2009120694A (en) * 2007-11-14 2009-06-04 Furukawa Electric Co Ltd:The Thermoplastic resin foam
JP2011137184A (en) * 2011-04-15 2011-07-14 Nippon Unicar Co Ltd Blooming restraining method for flame-retardant resin composition
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JPWO2014046165A1 (en) * 2012-09-20 2016-08-18 住友電気工業株式会社 Flame retardant resin composition, flame retardant heat shrinkable tube, and flame retardant insulated wire
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JP2014182053A (en) * 2013-03-21 2014-09-29 Hitachi Metals Ltd Device and method for inspecting insulation characteristic, and method for manufacturing insulated electric wire
KR20200013569A (en) * 2018-07-30 2020-02-07 주식회사 포스코 Insulating coating composition for electrical steel sheet and electrical steel sheet comprising insulating coating
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