JP4406942B2 - Non-halogen flame retardant cable - Google Patents
Non-halogen flame retardant cable Download PDFInfo
- Publication number
- JP4406942B2 JP4406942B2 JP17449098A JP17449098A JP4406942B2 JP 4406942 B2 JP4406942 B2 JP 4406942B2 JP 17449098 A JP17449098 A JP 17449098A JP 17449098 A JP17449098 A JP 17449098A JP 4406942 B2 JP4406942 B2 JP 4406942B2
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- JP
- Japan
- Prior art keywords
- ethylene
- flame retardant
- halogen
- retardant cable
- copolymer
- 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.)
- Expired - Fee Related
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Description
【0001】
【発明の属する技術分野】
本発明は、燃焼時にハロゲン系ガスを発生せず、かつ高度の難燃性を有すると共に機械強度を低下させることなく可撓性を付与したノンハロゲン難燃絶縁電線に関するものである。
【0002】
【従来の技術】
電線・ケーブルの絶縁材料やシース材料としては電気絶縁性の優れたポリオレフィンが多く用いられてきている。
【0003】
最近のすう勢としては原子力発電所用電線・ケーブル、車両用電線及び盤内・機内配線用電線等に難燃性が強く要望されるようになってきた。ポリオレフィンを難燃化する方法としてはハロゲン含有化合物、リン含有化合物等を混和する方法が一般に採用されてきている。
【0004】
しかし、これらは難燃時多量の煙を発生し機器への腐食性、人体への有害性等が問題になってきている。特に最近は安全面からこのようなハロゲン系ガスを発生しないことが強く要望されるようになってきている。
【0005】
このような情勢を踏まえ、発煙性、有毒性の非常に少ない無機系難燃剤が注目されるようになってきた。
【0006】
【発明が解決しようとする課題】
しかし高度の難燃性を付与するためには無機系難燃剤を多量に加える必要があり、そのため引張強さや可撓性等の機械特性が大幅に低下する問題がある。
【0007】
引張強さを保持するため高強度のポリマを使用する技術もあるが、これは一般に硬いものが多く可撓性が足りない。
【0008】
本発明の目的は、前記した課題を解消し、難燃時にハロゲン系ガスを発生せず、かつ高度の難燃性を有すると共に機械強度を低下させることなく可撓性を付与したノンハロゲン難燃絶縁電線を提供することにある。
【0009】
【課題を解決するための手段】
上記課題を解決するため、請求項1の発明は、直鎖状低密度ポリエチレン又は超低密度ポリエチレン50〜95重量%、メタロセン触媒により重合されたエチレン系コポリマ5〜50重量%からなるブレンドポリマ100重量部に対し、金属水酸化物を50〜200重量部混和してなる組成物を、電線コア外周に押出被覆してなることを特徴とするノンハロゲン難燃ケーブルである。
【0010】
また、請求項2は、上記ケーブルが架橋していないことを特徴とする請求項1に記載のノンハロゲン難燃ケーブルである。
【0011】
請求項3は、上記メタロセン触媒により重合されたエチレン系コポリマが、エチレン−プロピレンコポリマ、エチレン−ブテンコポリマ、エチレン−オクテンコポリマの内、少なくとも1種であることを特徴とする請求項1又は2に記載のノンハロゲン難燃ケーブルである。
【0012】
【発明の実施の形態】
本発明は、非架橋ケーブルでありながら、優れた引張強さを有し、さらに可撓性と耐油性を兼備したこれまでにない新規なノンハロゲン難燃ケーブルである。
【0013】
本発明において、エチレン−α−オレフィンコポリマにおけるエチレンと共重合するα−オレフィンが、例えばプロピレン、1−ブテン、1−ヘキセン、4−メチル−1−ペンテン、1−オクテン等が挙げられる。α−オレフィンとエチレンとを共重合すると、ポリエチレンに短鎖分岐ができ、これが結晶化を阻害するため、非晶部が多くなり、フィラーの受容性が増す。シングルサイト触媒の代表であるメタロセン触媒によって重合したエチレン系コポリマとしては、エチレン−プロピレンコポリマ、直鎖状低密度ポリエチレン、超低密度ポリエチレン、エチレン−ブテンコポリマ、エチレン−オクテンコポリマ等が挙げられるが、可撓性に富んだエチレン−プロピレン、エチレン−ブテン及びエチレン−オクテンコポリマが好ましい。エチレン−α−オレフィン共重合体とメタロセン系エチレン系コポリマの比を各々50/50〜95/5の範囲に規定したのは、エチレン−α−オレフィンコポリマが少ないと引張強さや耐油性、耐熱性が大幅に低下し、反対に多すぎると可撓性が損われてしまう。
【0014】
金属水酸化物としては、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム、ハイドロタルサイト類等が挙げられ、これらは1種または2種以上の使用が可能である。また、これらの金属水酸化物は例えば、シランカップリング剤やステアリン酸等を用いて周知の方法で表面処理しても差し支えない。
【0015】
また、金属水酸化物を50〜200重量部としたのは、50重量部未満では十分な難燃効果が得られず、200重量部を越えると引張強さが大幅に低下するからである。
【0016】
尚、本発明においては、前記成分に加えてカーボンブラック、難燃助剤、酸化防止剤、滑剤、安定剤、シリコーンゴム等を適当量添加してもよい。
【0017】
【実施例】
以下、本発明の実施例を比較例と共に詳述する。
【0018】
先ず、表1の各例(実施例1〜5及び比較例1〜6)に示すような配合成分の各種組成物を、100〜130℃に保持された8インチロールに投入してロール混練を行い、混練後、150℃に保持された40mm押出機(L/D=24)を用い、図1に示すように、銅撚線(導体)2とノンハロゲン絶縁被覆3とからなる外径1.8mmのノンハロゲン絶縁電線4を2本撚合せ、これに介在5を設けた電線コア上に厚さ1.0mmのシース6として押出被覆し、ケーブルを作製した。
【0019】
次に、このようにして作製した各種ケーブルからシースをはぎ取り、電線コアと接触していた面を研磨して0.8mmのシースを作製し、評価(引張特性、可撓性、難燃性及び耐熱性)を下記に基づいて行った。各例における評価結果は表1の下欄に示す通りである。
【0020】
引張特性:JIS C−3004に準じて行った。
【0021】
可撓性:テンシロン(オリエンテック社製)を用いて5%モジュラスを測定した。
【0022】
耐熱性:100℃に保持した老化試験機に48時間放置した後、上記引張試験により残率を評価する。
【0023】
難燃性:ASTM−D2863に準じ、酸素指数により評価した。
【0024】
耐油性:70℃に保持した油(JIS2号)に4時間浸漬した後、上記引張試験を行い残率を求める。
【0025】
表1からも明らかなように、本発明に係わる実施例1〜5ではいずれの特性も優れていることがわかる。即ち、引張特性は、実用上10MPa 以上必要であり、実施例1〜5は全てこの値を越えている。また、5%モジュラスも低く、ケーブルを実際に手で曲げた時の感触は柔軟である。耐熱性、耐油性ともに非架橋でありながら優れた特性を示している。難燃性の目安となる酸素指数30を越えており、良好である。
【0026】
これに対し、比較例1は、メタロセン触媒エチレン−オクテンコポリマの比率が規定より多い例であるが、引張強さがやや低く、耐油性が大幅に劣っている。比較例2は、直鎖状ポリエチレンが規定より多い例であるが、可撓性の目安である5%モジュラスが高く、硬いことがわかる。また比較例3及び4は、規定外のポリマを用いた例で、これらは引張特性が低いことと、特に比較例4は、耐油性も大幅に低下している。比較例5及び6は、難燃剤が規定範囲外のものであり、難燃剤が多過ぎると引張特性や耐熱性を低下させ、逆に少ないと酸素係数が小さく、難燃性が著しく低いことがわかる。
【0027】
【表1】
【0028】
【発明の効果】
以上説明してきたとおり本発明によれば、難燃時にハロゲン系ガスを発生せず、かつ高度の難燃性を有すると共に耐熱性や耐油性、機械強度、可撓性に優れたノンハロゲン難燃ケーブルが得られる。
【図面の簡単な説明】
【図1】本発明のノンハロゲン難燃ケーブルの横断面を示す図である。
【符号の説明】
1 ノンハロゲン難燃ケーブル
2 銅撚線(導体)
3 ノンハロゲン絶縁被覆
4 ノンハロゲン絶縁電線
5 介在
6 シース[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a non-halogen flame-retardant insulated electric wire that does not generate a halogen-based gas at the time of combustion, has a high degree of flame retardancy, and imparts flexibility without reducing mechanical strength.
[0002]
[Prior art]
As an insulating material and sheath material for electric wires and cables, a polyolefin having excellent electrical insulation has been used in many cases.
[0003]
As a recent trend, there has been a strong demand for flame retardancy for electric wires and cables for nuclear power plants, electric wires for vehicles, and electric wires for in-board / in-machine wiring. As a method for flame-retarding polyolefin, a method of incorporating a halogen-containing compound, a phosphorus-containing compound, or the like has been generally employed.
[0004]
However, they generate a large amount of smoke when flame retardant, and have become a problem of corrosiveness to equipment and harmfulness to human bodies. In recent years, it has been strongly demanded not to generate such a halogen-based gas from the viewpoint of safety.
[0005]
In light of this situation, inorganic flame retardants with very little fuming and toxic properties have attracted attention.
[0006]
[Problems to be solved by the invention]
However, in order to impart a high degree of flame retardancy, it is necessary to add a large amount of an inorganic flame retardant, so that there is a problem that mechanical properties such as tensile strength and flexibility are significantly lowered.
[0007]
There is also a technique of using a high-strength polymer in order to maintain the tensile strength, but this is generally hard and lacks flexibility.
[0008]
The object of the present invention is to solve the above-mentioned problems, and to generate a halogen-free gas at the time of flame retardancy, to have a high degree of flame retardancy and to give flexibility without lowering mechanical strength, non-halogen flame retardant insulation It is to provide electric wires.
[0009]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the invention of claim 1 is a blend polymer 100 comprising 50 to 95% by weight of linear low density polyethylene or ultra low density polyethylene and 5 to 50% by weight of an ethylene copolymer polymerized by a metallocene catalyst. A non-halogen flame-retardant cable obtained by extrusion coating an outer periphery of a wire core with a composition obtained by mixing 50 to 200 parts by weight of a metal hydroxide with respect to parts by weight.
[0010]
Further, according to
[0011]
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is an unprecedented novel non-halogen flame retardant cable that has excellent tensile strength while having flexibility and oil resistance while being a non-crosslinked cable.
[0013]
In the present invention, examples of the α-olefin copolymerized with ethylene in the ethylene-α-olefin copolymer include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. When α-olefin and ethylene are copolymerized, polyethylene has short chain branching, which inhibits crystallization, increasing the amorphous part and increasing the acceptability of the filler. Examples of the ethylene copolymer polymerized by a metallocene catalyst, which is a representative single site catalyst, include ethylene-propylene copolymer, linear low density polyethylene, ultra-low density polyethylene, ethylene-butene copolymer, ethylene-octene copolymer, etc. Highly flexible ethylene-propylene, ethylene-butene and ethylene-octene copolymers are preferred. The ratio of the ethylene-α-olefin copolymer and the metallocene-based ethylene copolymer was specified in the range of 50/50 to 95/5, respectively, when the ethylene-α-olefin copolymer was small, the tensile strength, oil resistance, heat resistance However, if the amount is too large, the flexibility is impaired.
[0014]
Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and hydrotalcites, and these can be used alone or in combination of two or more. These metal hydroxides may be surface-treated by a known method using, for example, a silane coupling agent or stearic acid.
[0015]
Further, the reason why the metal hydroxide is 50 to 200 parts by weight is that if the amount is less than 50 parts by weight, a sufficient flame retarding effect cannot be obtained, and if the amount exceeds 200 parts by weight, the tensile strength is significantly reduced.
[0016]
In the present invention, an appropriate amount of carbon black, flame retardant aid, antioxidant, lubricant, stabilizer, silicone rubber, etc. may be added in addition to the above components.
[0017]
【Example】
Examples of the present invention will be described in detail below together with comparative examples.
[0018]
First, various compositions of blending components as shown in each example of Table 1 (Examples 1 to 5 and Comparative Examples 1 to 6) are put into 8 inch rolls maintained at 100 to 130 ° C. and roll kneaded. After the kneading and kneading, using an 40 mm extruder (L / D = 24) maintained at 150 ° C., the outer diameter of the copper stranded wire (conductor) 2 and the
[0019]
Next, the sheath was peeled off from the various cables thus prepared, and the surface that was in contact with the wire core was polished to prepare a 0.8 mm sheath, which was evaluated (tensile properties, flexibility, flame resistance and Heat resistance) was performed based on the following. The evaluation results in each example are as shown in the lower column of Table 1.
[0020]
Tensile properties: Performed according to JIS C-3004.
[0021]
Flexibility: 5% modulus was measured using Tensilon (Orientec).
[0022]
Heat resistance: After being left in an aging tester maintained at 100 ° C. for 48 hours, the residual rate is evaluated by the tensile test.
[0023]
Flame retardancy: Evaluated by oxygen index according to ASTM-D2863.
[0024]
Oil resistance: After dipping in oil (JIS No. 2) maintained at 70 ° C. for 4 hours, the tensile test is performed to determine the residual rate.
[0025]
As is clear from Table 1, it can be seen that Examples 1 to 5 according to the present invention are excellent in all characteristics. That is, the tensile property is required to be 10 MPa or more practically, and all of Examples 1 to 5 exceed this value. The 5% modulus is also low, and the feel when the cable is actually bent by hand is flexible. Both heat resistance and oil resistance show excellent characteristics while being non-crosslinked. It exceeds the oxygen index of 30, which is a measure of flame retardancy, and is good.
[0026]
On the other hand, Comparative Example 1 is an example in which the ratio of the metallocene catalyst ethylene-octene copolymer is higher than specified, but the tensile strength is slightly low and the oil resistance is significantly inferior. Comparative Example 2 is an example in which the amount of linear polyethylene is more than specified, but it can be seen that the 5% modulus, which is a measure of flexibility, is high and hard. Further, Comparative Examples 3 and 4 are examples using non-regulated polymers, and these have low tensile properties, and in particular, Comparative Example 4 has greatly reduced oil resistance. In Comparative Examples 5 and 6, the flame retardant is outside the specified range. If the amount of the flame retardant is too much, the tensile properties and the heat resistance are deteriorated. Recognize.
[0027]
[Table 1]
[0028]
【The invention's effect】
As described above, according to the present invention, a halogen-free flame retardant cable that does not generate a halogen-based gas at the time of flame retardancy, has high flame retardancy, and is excellent in heat resistance, oil resistance, mechanical strength, and flexibility. Is obtained.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a non-halogen flame retardant cable of the present invention.
[Explanation of symbols]
1 Non-halogen
3 Non-halogen insulation coating 4 Non-halogen insulation wire 5 Interposition 6 Sheath
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17449098A JP4406942B2 (en) | 1998-06-22 | 1998-06-22 | Non-halogen flame retardant cable |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17449098A JP4406942B2 (en) | 1998-06-22 | 1998-06-22 | Non-halogen flame retardant cable |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2000011765A JP2000011765A (en) | 2000-01-14 |
JP4406942B2 true JP4406942B2 (en) | 2010-02-03 |
Family
ID=15979409
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Application Number | Title | Priority Date | Filing Date |
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JP17449098A Expired - Fee Related JP4406942B2 (en) | 1998-06-22 | 1998-06-22 | Non-halogen flame retardant cable |
Country Status (1)
Country | Link |
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JP (1) | JP4406942B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005268036A (en) * | 2004-03-18 | 2005-09-29 | Hitachi Cable Ltd | Non halogen flame retardant electric wire / cable |
MX348309B (en) * | 2012-09-25 | 2017-06-06 | Dow Global Technologies Llc | Modified ethylene-based polymer compositions and methods of their production. |
-
1998
- 1998-06-22 JP JP17449098A patent/JP4406942B2/en not_active Expired - Fee Related
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