JP2001226530A - Nonhalogen flame-retardant rubber composition and molded article - Google Patents
Nonhalogen flame-retardant rubber composition and molded articleInfo
- Publication number
- JP2001226530A JP2001226530A JP2000040107A JP2000040107A JP2001226530A JP 2001226530 A JP2001226530 A JP 2001226530A JP 2000040107 A JP2000040107 A JP 2000040107A JP 2000040107 A JP2000040107 A JP 2000040107A JP 2001226530 A JP2001226530 A JP 2001226530A
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- rubber
- flame
- halogen
- retardant
- odor
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、難燃性を有し、ハ
ロゲンを含まない難燃性ゴム組成物および成形物に関
し、特に最終製品におけるゴム特有の臭いおよび架橋剤
による臭いが低減されたノンハロゲン難燃性ゴム組成物
および成形物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant rubber composition having flame retardancy and containing no halogen, and more particularly to a rubber product and a molded product having reduced odor peculiar to rubber in a final product and odor due to a crosslinking agent. The present invention relates to a halogen-free flame-retardant rubber composition and a molded product.
【０００２】[0002]
【従来の技術】従来より、ゴムまたはゴムが配合された
樹脂材料に難燃剤を添加して難燃性を付与する方法が知
られており、このようにして得られる難燃性のゴム組成
物は、電線・ケーブルやその周辺部品の分野をはじめ各
種分野で使用されている。また近年では、燃焼時に有害
ガスを発生しないもの、廃棄物となったときに焼却処分
が可能なものが求められており、これに応じてゴム材
料、樹脂材料、および難燃剤等にはハロゲンを含まない
ノンハロゲン系のものが用いられるようになってきた。
ところで、殆どのゴムは、架橋されてはじめてゴム特有
の弾性を示すものであるので、通常、ゴム製品は、架橋
前の生ゴムに架橋剤等の添加剤を添加して混練したもの
を成形した後、架橋させることによって製造される。架
橋剤としては主に過酸化物や硫黄・硫黄化合物が用いら
れ、硫黄を用いた架橋は特に架硫と呼ばれる。2. Description of the Related Art A method of imparting flame retardancy by adding a flame retardant to rubber or a resin material containing rubber has been known, and a flame-retardant rubber composition thus obtained is known. Is used in various fields, including the field of electric wires and cables and their peripheral parts. In recent years, materials that do not generate harmful gases during combustion and that can be incinerated when turned into waste have been demanded, and accordingly, rubber materials, resin materials, and flame retardants contain halogens. Non-halogen-based materials that do not contain the same have come to be used.
By the way, since most rubbers show elasticity peculiar to rubber only after being crosslinked, usually, rubber products are obtained by adding and kneading additives such as a crosslinking agent to raw rubber before crosslinking. , Manufactured by crosslinking. As the crosslinking agent, peroxides and sulfur-sulfur compounds are mainly used, and crosslinking using sulfur is particularly called cross-linking.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、従来の
方法で得られるゴム製品には、ゴムが本来有している特
有のゴム臭、および架橋剤の分解残渣に起因する臭いが
あるため、臭いを有することが好ましくない環境では使
用できないという欠点があった。However, the rubber product obtained by the conventional method has a peculiar rubber odor inherent in rubber and an odor caused by a decomposition residue of a crosslinking agent. There is a disadvantage that it cannot be used in an environment where it is not desirable to have it.
【０００４】本発明は前記事情に鑑みてなされたもの
で、ゴム特有の臭いおよび架橋剤による臭いを抑えたノ
ンハロゲン難燃性ゴム組成物および成形物を提供するこ
とを目的とする。The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a halogen-free flame-retardant rubber composition and a molded article in which odor peculiar to rubber and odor due to a crosslinking agent are suppressed.
【０００５】[0005]
【課題を解決するための手段】前記課題は、ハロゲンを
含まないゴムを含有してなるベース樹脂に、ハロゲンを
含まない難燃剤、架橋剤、およびゼオライトを添加した
ノンハロゲン難燃性ゴム組成物によって解決できる。こ
のノンハロゲン難燃性ゴム組成物を、成形後、架橋させ
ることによりノンハロゲン難燃性ゴム成形物が得られ
る。あるいは、前記課題は、ハロゲンを含まないゴムを
含有してなるベース樹脂に、ハロゲンを含まない難燃
剤、および架橋剤を添加したノンハロゲン難燃性ゴム組
成物を、成形して架橋せしめた後、加熱処理してなるこ
とを特徴とするノンハロゲン難燃性ゴム成形物によって
も解決できる。本発明のノンハロゲン難燃性ゴム成形物
は、特に電線・ケーブルまたはその周辺部品に好適であ
る。An object of the present invention is to provide a non-halogen flame-retardant rubber composition obtained by adding a halogen-free flame retardant, a crosslinking agent, and a zeolite to a base resin containing a halogen-free rubber. Solvable. This non-halogen flame-retardant rubber composition is molded and then crosslinked to obtain a non-halogen flame-retardant rubber molded product. Alternatively, the problem is that a non-halogen flame-retardant rubber composition obtained by adding a halogen-free flame retardant and a crosslinking agent to a base resin containing a rubber containing no halogen is molded and cross-linked, The problem can also be solved by a non-halogen flame-retardant rubber molded product characterized by being subjected to a heat treatment. The halogen-free flame-retardant rubber molded product of the present invention is particularly suitable for electric wires and cables or peripheral parts thereof.
【０００６】[0006]
【発明の実施の形態】以下、本発明を詳しく説明する。
本明細書において、ノンハロゲン難燃性ゴム組成物とは
架橋前の組成物をいう。本発明におけるベース樹脂は、
ゴム単独でもよく、ゴムと他のノンハロゲン系の樹脂と
の混合物でもよい。本発明で用いられるゴムとしては、
ハロゲンを含まないものであればよいが、製造に架橋工
程を必要とするものを用いた場合に本発明による効果が
大きい。具体的には、エチレン−プロピレンゴム（ＥＰ
ゴム）、ブチルゴム、シリコーンゴム、スチレン−ブタ
ジエンゴム、アクリルゴム等が挙げられる。またこれら
のゴムと他の樹脂を混合して用いる場合、他の樹脂とし
てはハロゲンを含まないオレフィン系樹脂が好適に用い
られる。具体的には、エチレン−酢酸ビニル共重合体
（ＥＶＡ）、エチレン−エチルアクリレート共重合体
（ＥＥＡ）、エチレン−ブチルアクリレート共重合体
（ＥＢＡ）、エチレン−メチルアクリレート共重合体
（ＥＭＡ）等が挙げられる。また、これらのポリオレフ
ィン樹脂の重合時または重合後に、無水マレイン酸やア
クリル酸等の不飽和カルボン酸、あるいはこれらの誘導
体を反応させて、変性させた酸変性ポリオレフィンも使
用可能である。これらのオレフィン系樹脂は１種を用い
てもよく、２種以上を併用してもよい。ゴムとオレフィ
ン系樹脂を混合して用いる場合、オレフィン系樹脂の配
合量は、多すぎるとゴム弾性を損なうおそれがあり、少
なすぎると高難燃性が得られないので、ゴム１００重量
部に対して５〜１５０重量部の範囲が好ましく、より好
ましくは５〜１００重量部の範囲である。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the present specification, the non-halogen flame-retardant rubber composition refers to a composition before crosslinking. Base resin in the present invention,
The rubber alone may be used, or a mixture of the rubber and another non-halogen resin. As the rubber used in the present invention,
Any material that does not contain halogen may be used, but the effect of the present invention is great when a material that requires a crosslinking step for production is used. Specifically, ethylene-propylene rubber (EP
Rubber), butyl rubber, silicone rubber, styrene-butadiene rubber, acrylic rubber and the like. When these rubbers and other resins are used as a mixture, an olefin resin containing no halogen is preferably used as the other resin. Specifically, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer (EBA), ethylene-methyl acrylate copolymer (EMA), etc. No. Further, an acid-modified polyolefin modified by reacting an unsaturated carboxylic acid such as maleic anhydride or acrylic acid or a derivative thereof at the time of or after the polymerization of these polyolefin resins can also be used. One of these olefin resins may be used, or two or more of them may be used in combination. When a rubber and an olefin-based resin are used in a mixture, the amount of the olefin-based resin is too large, the rubber elasticity may be impaired. If the amount is too small, high flame retardancy cannot be obtained. The range is preferably 5 to 150 parts by weight, more preferably 5 to 100 parts by weight.
【０００７】特にノンハロゲン難燃性ゴム組成物を用い
て電線・ケーブルおよびその周辺部品を製造する場合、
ゴムは可撓性に優れており電気絶縁性も良いが難燃性が
比較的低いので、難燃性が比較的高い樹脂と混合して用
いることが好ましい。上記に挙げたポリオレフィン系樹
脂の中でも、特にＥＥＡおよびＥＶＡは酸素指数が比較
的高いので、これをゴムと混合して用いることが高難燃
性を達成するうえで好ましい。この電線・ケーブルおよ
びその周辺部品用途において、ベース樹脂中のゴムの含
有比率は４０重量％以上９０重量％が好ましく、より好
ましくは４５重量％以上６５重量％以下である。ゴムの
含有比率が大きいと、他のポリオレフィン系樹脂と混合
することによる難燃性向上効果が小さくなり、反対に、
ゴムの含有比率が小さくて他のポリオレフィン系樹脂の
含有割合が大きいと、難燃性は高くなるが電気絶縁性の
劣化が大きくなる。ゴムとしてはＥＰゴムが好ましく用
いられる。[0007] In particular, when an electric wire / cable and its peripheral parts are manufactured using a non-halogen flame-retardant rubber composition,
Rubber is excellent in flexibility and good in electrical insulation, but has relatively low flame retardancy. Therefore, it is preferable to use a rubber mixed with a resin having relatively high flame retardancy. Among the polyolefin-based resins mentioned above, EEA and EVA in particular have a relatively high oxygen index, and therefore it is preferable to use them in combination with rubber in order to achieve high flame retardancy. In this electric wire / cable and peripheral component applications, the content ratio of rubber in the base resin is preferably from 40% by weight to 90% by weight, more preferably from 45% by weight to 65% by weight. If the content ratio of rubber is large, the effect of improving the flame retardancy by mixing with other polyolefin-based resin is reduced, and conversely,
When the content ratio of rubber is small and the content ratio of other polyolefin-based resin is large, flame retardancy is increased but electrical insulation is greatly deteriorated. EP rubber is preferably used as the rubber.
【０００８】本発明で用いられる難燃剤としてはノンハ
ロゲン系のものが用いられ、例えば水酸化マグネシウム
や水酸化アルミニウムなどの金属水酸化物、例えば三酸
化モリブデン等の酸化物、二硫化モリブデン等の硫化
物、ジモリブデン酸アンモニウム、モリブデン酸カルシ
ウム、モリブデン酸亜鉛、モリブデン酸カリウム、モリ
ブデン酸ナトリウムなどのモリブデン化合物が好ましく
用いられる。これらは１種単独で用いてもよく、２種以
上を併用してもよい。これらの難燃剤の添加量は多いほ
ど樹脂の難燃性は高くなるが、多すぎると樹脂組成物の
機械的特性等の低下や絶縁抵抗の低下が著しくなるの
で、概ね、ベース樹脂１００重量部に対して、金属水酸
化物の添加量は１００〜２００重量部の範囲内、モリブ
デン化合物の添加量は１〜１０重量部の範囲内で好まし
く設定される。また金属水酸化物をシランカップリング
剤、ステアリン酸などの高級脂肪酸、シュウ酸アニオン
等によって表面処理したものを用いると、ベース樹脂と
の親和性向上、樹脂組成物の機械特性の低下防止、耐水
性、耐酸性の向上等の効果が得られる。また上記に挙げ
たモリブデン化合物でコーティングされた金属水酸化物
は、燃焼時に分解し難いので高難燃性を達成するうえで
好ましい。また、上記に例示した難燃剤以外の難燃剤を
用いてもよく、例えば炭酸カルシウム、ガム状シリコー
ンオイル、シリコーンパウダー、ホウ酸亜鉛、スズ酸亜
鉛、赤リン、ポリリン酸アンモニウム等を用いてもよ
い。As the flame retardant used in the present invention, non-halogen type flame retardants are used, for example, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, for example, oxides such as molybdenum trioxide, and sulfides such as molybdenum disulfide. And molybdenum compounds such as ammonium dimolybdate, calcium molybdate, zinc molybdate, potassium molybdate and sodium molybdate are preferably used. These may be used alone or in combination of two or more. The greater the amount of these flame retardants added, the higher the flame retardancy of the resin. However, if the amount is too large, the mechanical properties of the resin composition and the like and the insulation resistance are significantly reduced. On the other hand, the addition amount of the metal hydroxide is preferably set in the range of 100 to 200 parts by weight, and the addition amount of the molybdenum compound is preferably set in the range of 1 to 10 parts by weight. When a metal hydroxide is used which has been surface-treated with a silane coupling agent, a higher fatty acid such as stearic acid, or an oxalate anion, the affinity with the base resin is improved, the mechanical properties of the resin composition are prevented from lowering, and the water resistance is improved. Effects such as improvement of the properties and acid resistance can be obtained. The above-mentioned metal hydroxide coated with a molybdenum compound is preferable for achieving high flame retardancy because it is difficult to be decomposed during combustion. Further, a flame retardant other than the flame retardants exemplified above may be used, and for example, calcium carbonate, gum-like silicone oil, silicone powder, zinc borate, zinc stannate, red phosphorus, ammonium polyphosphate and the like may be used. .
【０００９】本発明における架橋剤は、ゴムを架橋させ
るために添加されるもので、硫黄、硫黄化合物等の架硫
剤や過酸化物系架橋剤など、周知の架硫剤および架橋剤
の中からゴムの種類、好ましい架橋の形態に応じて適宜
選択して用いられる。なお、硫黄や硫黄化合物を用いた
架橋、すなわち架硫も本発明における架橋に含まれ、し
たがって架硫剤も本発明における架橋剤に含まれる。ま
た必要に応じて周知の架橋助剤を適宜添加することが好
ましい。例えば、ＥＰゴムを用いる場合は、架橋剤とし
てジクミルパーオキサイドを添加し、架橋助剤としてメ
タクリル酸亜鉛を添加することが好ましい。The cross-linking agent in the present invention is added to cross-link rubber. Among the well-known cross-linking agents and cross-linking agents, such as sulfur-containing agents such as sulfur and sulfur compounds and peroxide-based cross-linking agents. The rubber is appropriately selected and used depending on the type of rubber and the preferred form of crosslinking. Crosslinking using sulfur or a sulfur compound, that is, crosslinking, is also included in the crosslinking of the present invention, and therefore, a crosslinking agent is also included in the crosslinking agent of the present invention. It is also preferable to add a known crosslinking aid as needed. For example, when using EP rubber, it is preferable to add dicumyl peroxide as a crosslinking agent and zinc methacrylate as a crosslinking aid.
【００１０】また、上記の配合剤の他に老化防止剤を添
加することが好ましく、これにより熱劣化が抑えられ
る。老化防止剤としては特に限定されないが、例えばフ
ェノール系やアミン系のもの等を好ましく用いることが
できる。老化防止剤の添加量は少なすぎると添加効果が
得られず、多すぎるとブルーミングやブリード・アウト
が生じることがあるので、ベース樹脂１００重量部に対
して０．１重量部以上５．０重量部以下の範囲内で、ベ
ース樹脂との相溶性を考慮して設定される。さらに、紫
外線吸収剤、銅害防止剤、顔料、染料その他の着色剤、
少量のタルクなどの無機物微粉末など、用途に応じて適
宜の添加剤を配合することができる。添加剤はハロゲン
を含まないものが用いられ、有害な重金属をできるだけ
含まないものが好ましい。It is preferable to add an anti-aging agent in addition to the above-mentioned compounding agents, thereby suppressing thermal deterioration. The antioxidant is not particularly limited, but for example, phenol-based or amine-based ones can be preferably used. If the amount of the antioxidant is too small, the effect of addition is not obtained, and if it is too large, blooming or bleed out may occur. Therefore, 0.1 to 5.0 parts by weight based on 100 parts by weight of the base resin. Is set in consideration of the compatibility with the base resin within the range of not more than 1 part. In addition, ultraviolet absorbers, copper damage inhibitors, pigments, dyes and other coloring agents,
An appropriate additive such as a small amount of inorganic fine powder such as talc can be blended depending on the use. As the additive, one containing no halogen is used, and one containing as little harmful heavy metal as possible is preferable.
【００１１】本発明の第１の実施形態においては、ベー
ス樹脂に必須成分としてゼオライトが添加される。ゼオ
ライトは吸着作用を有しており、これを添加することに
よりゴムや架橋剤に起因する臭いが吸着されて低減され
る。ゼオライトの添加量は、少なすぎると臭いの吸着作
用が十分でなく、多すぎると、樹脂組成物の機械的特性
が劣化するなど特性への悪影響が大きくなるので、好ま
しくはベース樹脂１００重量部に対して０．１〜２０重
量部、より好ましくは５〜１０重量部程度とされる。本
発明の第１の実施形態のノンハロゲン難燃性ゴム組成物
は、ベース樹脂に難燃剤、架橋剤、ゼオライト、および
必要に応じて架橋助剤、老化防止剤等を添加して混練す
ることによって得られる。そしてこのノンハロゲン難燃
性ゴム組成物を目的の形状に成形した後、架橋させるこ
とによってノンハロゲン難燃性ゴム成形物が得られる。
架橋は、加熱架橋、シラン架橋などゴムの架橋方法とし
て知られている手法を適宜用いることができる。本実施
形態によれば、ゴムおよび架橋剤等に起因する臭いがゼ
オライトに吸着されるので、ノンハロゲン難燃性ゴム組
成物および成形物における臭いの発生が抑えられる。In the first embodiment of the present invention, zeolite is added as an essential component to the base resin. Zeolite has an adsorptive action, and by adding it, the odor caused by rubber and the crosslinking agent is adsorbed and reduced. If the amount of zeolite is too small, the effect of adsorbing odor is not sufficient if it is too small, and if it is too large, adverse effects on the properties such as deterioration of the mechanical properties of the resin composition become large, so preferably 100 parts by weight of the base resin. It is 0.1 to 20 parts by weight, more preferably about 5 to 10 parts by weight. The non-halogen flame-retardant rubber composition of the first embodiment of the present invention is obtained by adding a flame retardant, a cross-linking agent, a zeolite, and if necessary, a cross-linking aid, an antioxidant, etc. to a base resin and kneading the mixture. can get. Then, after molding this non-halogen flame-retardant rubber composition into a desired shape, it is crosslinked to obtain a non-halogen flame-retardant rubber molded product.
As the crosslinking, a method known as a rubber crosslinking method such as heat crosslinking or silane crosslinking can be used as appropriate. According to the present embodiment, the odor caused by the rubber, the crosslinking agent, and the like is adsorbed on the zeolite, so that the generation of the odor in the halogen-free flame-retardant rubber composition and the molded product is suppressed.
【００１２】また本発明の第２の実施形態では、ベース
樹脂に難燃剤、架橋剤、および必要に応じて架橋助剤、
老化防止剤等を添加して混練することによってノンハロ
ゲン難燃性ゴム組成物を得、これを目的の形状に成形
し、架橋させた後、加熱処理を施すことによってノンハ
ロゲン難燃性ゴム成形物を得る。架橋は、加熱架橋、シ
ラン架橋などゴムの架橋方法として知られている手法を
適宜用いることができる。本実施形態において、架橋後
に行う加熱処理は、これによってゴムや架橋剤に起因す
る臭いを揮発するために行われる。この加熱処理条件
は、加熱温度が低すぎたり加熱時間が短すぎると臭いの
揮発が不十分となり、逆に加熱温度が高すぎたり加熱時
間が長すぎたりすると加熱による劣化が大きくなるの
で、７０〜１２０℃、好ましくは８０〜９０℃の温度で
１〜１０日間、好ましくは１〜７日間、より好ましくは
１〜５日間の範囲で設定される。本実施形態によれば、
成形、架橋後に加熱処理を施すことによって、ゴムに起
因する臭いや架橋剤の分解残渣に起因する臭いが揮発さ
れるので、臭いが低減された、あるいは臭いが除去され
たノンハロゲン難燃性ゴム成形物が得られる。なお本実
施形態においては、架橋後の加熱処理により臭いを除去
することができるので、ゴム組成物にゼオライトを添加
しなくても臭いが無い成形物を得ることができるが、特
性を損なわない範囲でゼオライトを添加しても構わな
い。In a second embodiment of the present invention, a flame retardant, a crosslinking agent, and, if necessary, a crosslinking aid are added to the base resin.
A non-halogen flame-retardant rubber composition is obtained by adding and kneading an anti-aging agent, etc., and then molding it into a desired shape, crosslinking it, and then subjecting it to a heat treatment. obtain. As the crosslinking, a method known as a rubber crosslinking method such as heat crosslinking or silane crosslinking can be used as appropriate. In the present embodiment, the heat treatment performed after the crosslinking is performed to volatilize the odor caused by the rubber and the crosslinking agent. If the heating temperature is too low or the heating time is too short, the odor will not be sufficiently volatilized. Conversely, if the heating temperature is too high or the heating time is too long, the deterioration due to heating will increase. The temperature is set in a range of 1 to 10 days, preferably 1 to 7 days, more preferably 1 to 5 days at a temperature of 120 to 120 ° C, preferably 80 to 90 ° C. According to the present embodiment,
By performing a heat treatment after molding and crosslinking, the odor caused by the rubber and the odor caused by the decomposition residue of the crosslinking agent are volatilized, so that the odor is reduced or the odor is removed. Things are obtained. In the present embodiment, since the odor can be removed by a heat treatment after crosslinking, a molded article without odor can be obtained without adding zeolite to the rubber composition, but the properties are not impaired. And zeolite may be added.
【００１３】本発明のノンハロゲン難燃性ゴム成形物の
好ましい例は、電線・ケーブルおよびその周辺部品であ
る。具体的には、例えば絶縁電線、電源コード、および
船用ケーブルなどの各種電線・ケーブルの絶縁材、シー
ス材、テープ類、および介在物、ならびにケース、プラ
グ、およびテープなどの電線・ケーブル用付属部品（具
体的には収縮チューブ、ゴムストレスリリーフコーン
等）、電線管、配線ダクト、およびバスダクトなどの電
材製品などである。特に、ＥＰゴムを用いてなるノンハ
ロゲン難燃性ゴム成形物は電線や電源コードに好適であ
り、可撓性に優れるとともに、プラグ屈曲特性が良好
で、プラグ部の耐トラッキング特性が優れた製品が得ら
れる。Preferred examples of the non-halogen flame-retardant rubber molded article of the present invention are electric wires and cables and peripheral parts thereof. Specifically, for example, insulating materials, sheath materials, tapes, and inclusions of various electric wires and cables such as insulated electric wires, power cords, and marine cables, and accessories for electric wires and cables such as cases, plugs, and tapes (Specifically, shrinkable tubes, rubber stress relief cones and the like), electrical conduits, wiring ducts, and electrical products such as bus ducts. In particular, a non-halogen flame-retardant rubber molded product using EP rubber is suitable for electric wires and power cords, and has excellent flexibility, good plug bending characteristics, and excellent plug portion tracking resistance characteristics. can get.
【００１４】[0014]
【実施例】以下、具体的な実施例を示して本発明の効果
を明らかにする。 （実施例１，２および比較例１，２）下記表１に示す配
合割合（単位：重量部）で各種成分を配合し、混練機で
混練してノンハロゲン難燃性ゴム組成物を得た。押出機
にて２ｍｍ2の導体上に混練後のゴム組成物を押出被覆
して絶縁層を形成して外径５ｍｍとした後、架橋を施し
て電線を得た。架橋は１６０℃の蒸気中で４０分間加熱
して行った。得られた電線について、ゴム臭および架橋
剤臭の有無を調べた。その結果を下記表１に示す。また
同様の製造条件で製造した試験片について、ＪＩＳ Ｋ
６７６０に準処する引張強度および伸びを測定するとと
もに、硬度（ショアＡ）も測定した。これらの測定結果
を表１に示す。またＵＬ−９４規格（Ｖ−０〜Ｖ−２）
に準処する耐炎性試験を行った。その結果、Ｖ−０、Ｖ
−１、Ｖ−２のいずれの規格を満たしたかを下記表１に
示す。これらの規格のうちＶ−０が難燃性が最も高く、
次いでＶ−１、Ｖ−２の順に難燃性が高い。EXAMPLES Hereinafter, the effects of the present invention will be clarified by showing specific examples. (Examples 1 and 2 and Comparative Examples 1 and 2) Various components were blended in the blending ratios (unit: parts by weight) shown in Table 1 below and kneaded with a kneader to obtain a halogen-free flame-retardant rubber composition. The extruder was used to extrude and coat the rubber composition after kneading on a 2 mm 2 conductor to form an insulating layer having an outer diameter of 5 mm, and then crosslinking was performed to obtain an electric wire. Crosslinking was performed by heating in steam at 160 ° C. for 40 minutes. The obtained electric wires were examined for the presence of rubber odor and crosslinking agent odor. The results are shown in Table 1 below. In addition, for test pieces manufactured under the same manufacturing conditions, JIS K
While measuring the tensile strength and elongation corresponding to 6760, the hardness (Shore A) was also measured. Table 1 shows the measurement results. UL-94 standard (V-0 to V-2)
A flame resistance test was conducted according to the above. As a result, V-0, V
Table 1 below shows which of the standards -1 and V-2 was satisfied. Of these standards, V-0 has the highest flame retardancy,
Next, the flame retardancy is higher in the order of V-1 and V-2.
【００１５】[0015]
【表１】 [Table 1]
【００１６】上記表１において、各配合材料は次のもの
を用いた。 ＥＰゴム：第３成分としてＥＮＢ（エチリデンオルボル
ネン）を含むエチレン−プロピレンゴム、中ヨウ素価＝
１０〜２０、ムーニー粘度ＭＬ（１００℃）＝４０ ＥＶＡ：エチレン−酢酸ビニル共重合体、ＶＡ含有量＝
２８％ 架橋剤：ジクミルパーオキサイド 架橋助剤：メタクリル酸亜鉛 老化防止剤：４、４’−チオビス−（６−第３−ブチル
−３−メチルフェノール）In Table 1, the following ingredients were used. EP rubber: ethylene-propylene rubber containing ENB (ethylideneorbornene) as a third component, medium iodine value =
10-20, Mooney viscosity ML (100 ° C.) = 40 EVA: ethylene-vinyl acetate copolymer, VA content =
28% Crosslinking agent: Dicumyl peroxide Crosslinking aid: Zinc methacrylate Antioxidant: 4,4'-thiobis- (6-tert-butyl-3-methylphenol)
【００１７】表１の結果より、ゼオライトを添加しなか
った比較例１ではゴム臭および架橋剤臭が明らかに認め
られたのに対して、ゼオライトを５重量部添加した実施
例１ではゴム臭および架橋剤臭が大幅に低減されてお
り、ゼオライトを１０重量部添加した実施例２ではゴム
臭および架橋剤臭が除去されていた。また実施例１、２
において、ゼオライトを添加したことによる機械特性お
よび難燃性の低下はわずかであった。一方、ゼオライト
を３０重量部添加した比較例２では、ゴム臭および架橋
剤臭は除去されたが、機械特性および難燃性が大きく低
下した。From the results shown in Table 1, in Comparative Example 1 in which zeolite was not added, a rubber odor and a crosslinking agent odor were clearly observed, whereas in Example 1 in which 5 parts by weight of zeolite was added, the rubber odor and the odor were found. The odor of the crosslinking agent was significantly reduced, and in Example 2 in which 10 parts by weight of zeolite was added, the rubber odor and the odor of the crosslinking agent were removed. Examples 1 and 2
In Table 1, the decrease in mechanical properties and flame retardancy due to the addition of zeolite was slight. On the other hand, in Comparative Example 2 in which 30 parts by weight of zeolite was added, the rubber odor and the odor of the crosslinking agent were removed, but the mechanical properties and the flame retardancy were greatly reduced.
【００１８】（実施例３〜５および比較例３）下記表２
に示す配合割合（単位：重量部）で各種成分を配合し、
混練機で混練してノンハロゲン難燃性ゴム組成物を得
た。表２における各配合材料は上記表１と同じものを用
い、いずれの例も配合は共通とした。そして、押出機に
て２ｍｍ 2の導体上に混練後のゴム組成物を押出被覆し
て絶縁層を形成して外径５ｍｍとした後、架橋を施し
た。架橋は１６０℃の蒸気中で４０分間加熱して行っ
た。この後、さらに下記表２に示す条件で加熱処理を施
して最終製品としての電線を得た。得られた電線につい
て、ゴム臭および架橋剤臭の有無を調べた。また同様の
製造条件で製造した試験片について、上記実施例１と同
様にして特性を調べた。その結果を下記表２に示す。さ
らに、得られた電線の被覆層の加熱老化試験を行った。
試験は電気用品取締法に準処する方法により、温度１０
０℃、４日間の条件で行い、引張り強さ（ＴＳ）の残存
率、および伸び（ＥＬ）の残率を測定した。その結果を
表２に示す。いずれの値も８０％以上が目標とされる。(Examples 3 to 5 and Comparative Example 3)
Various components are blended in the blending ratio (unit: parts by weight) shown in
Kneading with a kneading machine to obtain a halogen-free flame-retardant rubber composition
Was. Table 2 uses the same ingredients as in Table 1 above.
In each case, the formulation was common. And to the extruder
2mm TwoExtrusion coating of the rubber composition after kneading on the conductor of
After forming an insulating layer with an outer diameter of 5 mm,
Was. Crosslinking is performed by heating in steam at 160 ° C for 40 minutes.
Was. Thereafter, a heat treatment is further performed under the conditions shown in Table 2 below.
Thus, an electric wire was obtained as a final product. About the obtained electric wire
Then, the presence or absence of a rubber odor and a crosslinking agent odor was examined. Also similar
Specimens manufactured under the manufacturing conditions were the same as in Example 1 above.
The characteristics were examined as described above. The results are shown in Table 2 below. Sa
Further, a heat aging test was performed on the coating layer of the obtained electric wire.
The test was performed at a temperature of 10
Performed at 0 ° C for 4 days, remaining tensile strength (TS)
And the residual rate of elongation (EL) were measured. The result
It is shown in Table 2. In each case, 80% or more is targeted.
【００１９】[0019]
【表２】 [Table 2]
【００２０】表２の結果より、架橋後に加熱処理をしな
かった比較例３ではゴム臭および架橋剤臭が明らかに認
められたのに対して、加熱処理を施した実施例３〜５で
はゴム臭および架橋剤臭が大幅に低減され、あるいは除
去されていた。また実施例３、４において、加熱処理を
施したことによる特性の変化はほとんど認められなかっ
た。加熱時間が１０日と長い実施例５でも加熱老化試験
において若干の特性低下が認められる程度で、大きな悪
影響はなかった。From the results in Table 2, the rubber odor and the odor of the crosslinking agent were clearly observed in Comparative Example 3 in which the heat treatment was not performed after the crosslinking, whereas the rubber odor was observed in Examples 3 to 5 in which the heat treatment was performed. The odor and cross-linking agent odor have been greatly reduced or eliminated. In Examples 3 and 4, almost no change in the characteristics due to the heat treatment was observed. Even in Example 5 in which the heating time was as long as 10 days, a slight deterioration in properties was observed in the heat aging test, and there was no significant adverse effect.
【００２１】[0021]
【発明の効果】以上説明したように本発明によれば、ノ
ンハロゲン難燃性ゴム組成物および成形物におけるゴム
特有の臭いおよび架橋剤による臭いを大幅に低減させる
ことができ、嗅覚的に認められない程度に除去すること
が可能である。したがって、本発明のノンハロゲン難燃
性ゴム組成物および成形物は、従来のゴム組成物では臭
いがあるために使用できなかった場所や用途にも使用す
ることでき、ゴム組成物およびゴム製品の適用範囲を大
幅に拡大することができる。また、本発明のノンハロゲ
ン難燃性ゴム組成物および成形物は優れた難燃性を有
し、かつハロゲンを含まないので焼却処分が可能である
ので、難燃性を要求される用途にも適用することがで
き、環境的にも好ましい。また本発明によれば、難燃性
を有するとともに電気絶縁性が良好であり、焼却処分も
可能であり実用性が高い難燃性電線・ケーブルおよびそ
の周辺部品が得られる。As described above, according to the present invention, the odor peculiar to rubber and the odor due to the cross-linking agent in the non-halogen flame-retardant rubber composition and molded product can be greatly reduced, and the odor is recognized. It is possible to remove it to an extent. Therefore, the non-halogen flame-retardant rubber composition and the molded product of the present invention can be used in places and applications where conventional rubber compositions cannot be used due to odor. The range can be greatly expanded. In addition, the non-halogen flame-retardant rubber composition and molded article of the present invention have excellent flame retardancy, and can be incinerated because they do not contain halogen, so that they can be applied to applications requiring flame retardancy. And environmentally friendly. Further, according to the present invention, it is possible to obtain a flame-retardant electric wire / cable and its peripheral parts, which have high flame retardancy and good electrical insulation, can be incinerated, and have high practicality.
───────────────────────────────────────────────────── 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） Ｃ０８Ｋ 3/30 Ｃ０８Ｋ 3/30 3/34 3/34 5/14 5/14 // Ｈ０１Ｂ 7/295 Ｈ０１Ｂ 7/34 Ｂ Ｆターム(参考） 4F070 AA08 AA12 AA13 AA16 AA28 AA32 AA60 AB03 AB08 AB09 AB11 AB16 AC05 AC13 AC14 AC16 AC18 AC20 AC22 AC42 AC52 AC56 AE07 AE08 AE30 GA05 GA08 GA10 GB02 GC05 4J002 AC001 DJ008 FD136 FD147 GQ01 5G315 CA03 CB02 CB06 CC08 CD01 CD04 CD06 CD13 CD14 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C08K 3/30 C08K 3/30 3/34 3/34 5/14 5/14 // H01B 7/295 H01B 7/34 BF term (reference) 4F070 AA08 AA12 AA13 AA16 AA28 AA32 AA60 AB03 AB08 AB09 AB11 AB16 AC05 AC13 AC14 AC16 AC18 AC20 AC22 AC42 AC52 AC56 AE07 AE08 AE30 GA05 GA08 GA10 GB02 GC05 4J002 AC001 DJ008 GFD CB 136 315 CC08 CD01 CD04 CD06 CD13 CD14
Claims (4)
ベース樹脂に、ハロゲンを含まない難燃剤、架橋剤、お
よびゼオライトを添加してなるノンハロゲン難燃性ゴム
組成物。1. A non-halogen flame-retardant rubber composition comprising a halogen-free rubber-containing base resin and a halogen-free flame retardant, a crosslinking agent, and a zeolite.
組成物を成形後、架橋せしめてなることを特徴とするノ
ンハロゲン難燃性ゴム成形物。2. A non-halogen, flame-retardant rubber molded product obtained by molding the non-halogen, flame-retardant rubber composition according to claim 1.
ベース樹脂に、ハロゲンを含まない難燃剤、および架橋
剤を添加してなるノンハロゲン難燃性ゴム組成物を、成
形して架橋せしめた後、加熱処理してなることを特徴と
するノンハロゲン難燃性ゴム成形物。3. A non-halogen flame-retardant rubber composition obtained by adding a halogen-free flame retardant and a cross-linking agent to a base resin containing a halogen-free rubber, followed by molding and crosslinking. And a non-halogen flame-retardant rubber molded product obtained by heat treatment.
ンハロゲン難燃性ゴム成形物からなる電線・ケーブルま
たはその周辺部品。4. An electric wire or cable comprising the non-halogen flame-retardant rubber molded product according to claim 2 or a peripheral part thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000040107A JP2001226530A (en) | 2000-02-17 | 2000-02-17 | Nonhalogen flame-retardant rubber composition and molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000040107A JP2001226530A (en) | 2000-02-17 | 2000-02-17 | Nonhalogen flame-retardant rubber composition and molded article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001226530A true JP2001226530A (en) | 2001-08-21 |
Family
ID=18563552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000040107A Withdrawn JP2001226530A (en) | 2000-02-17 | 2000-02-17 | Nonhalogen flame-retardant rubber composition and molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001226530A (en) |
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| JP2007070602A (en) * | 2005-08-10 | 2007-03-22 | Hitachi Cable Ltd | Non-halogen flame retardant thermoplastic elastomer composition, its production method and electric wire/cable using the same |
| WO2008143129A1 (en) * | 2007-05-15 | 2008-11-27 | Sun Allomer Ltd. | Flame retardant, flame-retardant composition using the same, molded article of the composition, and coated electric wire |
| WO2012137961A1 (en) * | 2011-04-05 | 2012-10-11 | 株式会社オートネットワーク技術研究所 | Insulated cable |
| WO2013008498A1 (en) * | 2011-07-11 | 2013-01-17 | 株式会社オートネットワーク技術研究所 | Insulated wire |
| WO2013065768A1 (en) * | 2011-11-01 | 2013-05-10 | 住友化学株式会社 | Rubber anti-aging agent |
| WO2013065769A1 (en) * | 2011-11-01 | 2013-05-10 | 住友化学株式会社 | Rubber composition and use therefor |
| KR20160099564A (en) * | 2013-12-17 | 2016-08-22 | 아란세오 네덜란즈 비.브이. | A vulcanizable polymer composition |
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2000
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|---|---|---|---|---|
| JP4692372B2 (en) * | 2005-08-10 | 2011-06-01 | 日立電線株式会社 | Non-halogen flame retardant thermoplastic elastomer composition, method for producing the same, and electric wire / cable using the same |
| JP2007070602A (en) * | 2005-08-10 | 2007-03-22 | Hitachi Cable Ltd | Non-halogen flame retardant thermoplastic elastomer composition, its production method and electric wire/cable using the same |
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| JP2008308674A (en) * | 2007-05-15 | 2008-12-25 | Sunallomer Ltd | Flame retardant, flame-retardant composition using the same, molding of the same, and electric wire coated with the same |
| EP2151487A4 (en) * | 2007-05-15 | 2012-01-04 | Sun Allomer Ltd | Flame retardant, flame-retardant composition using the same, molded article of the composition, and coated electric wire |
| EP2151487A1 (en) * | 2007-05-15 | 2010-02-10 | Sun Allomer Ltd | Flame retardant, flame-retardant composition using the same, molded article of the composition, and coated electric wire |
| WO2012137961A1 (en) * | 2011-04-05 | 2012-10-11 | 株式会社オートネットワーク技術研究所 | Insulated cable |
| WO2013008498A1 (en) * | 2011-07-11 | 2013-01-17 | 株式会社オートネットワーク技術研究所 | Insulated wire |
| WO2013065768A1 (en) * | 2011-11-01 | 2013-05-10 | 住友化学株式会社 | Rubber anti-aging agent |
| WO2013065769A1 (en) * | 2011-11-01 | 2013-05-10 | 住友化学株式会社 | Rubber composition and use therefor |
| JP2013095857A (en) * | 2011-11-01 | 2013-05-20 | Sumitomo Chemical Co Ltd | Rubber composition and use therefor |
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| KR20160099564A (en) * | 2013-12-17 | 2016-08-22 | 아란세오 네덜란즈 비.브이. | A vulcanizable polymer composition |
| JP2016540097A (en) * | 2013-12-17 | 2016-12-22 | アランセオ・ネザーランズ・ベー・フェー | Vulcanizable polymer composition |
| US10465050B2 (en) | 2013-12-17 | 2019-11-05 | Lanxess Deutschland Gmbh | Vulcanizable polymer composition |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20070501 |