JP2007070483A - Flame-retardant composition for coating of electric wire/cable and flame-retardant electric wire/cable - Google Patents
Flame-retardant composition for coating of electric wire/cable and flame-retardant electric wire/cable Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 69
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- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 238000000576 coating method Methods 0.000 title claims abstract description 12
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- 229920010346 Very Low Density Polyethylene (VLDPE) Polymers 0.000 description 1
- OKZJGWWKRGIIRL-UHFFFAOYSA-N [N].NC1=NC(N)=NC(N)=N1 Chemical compound [N].NC1=NC(N)=NC(N)=N1 OKZJGWWKRGIIRL-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical compound P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、ノンハロゲンの電線・ケーブル被覆用難燃性組成物およびこれを用いた環境保全性の高い難燃電線・ケーブルに関する。 TECHNICAL FIELD The present invention relates to a non-halogen flame retardant composition for covering electric wires and cables and a flame retardant electric wire and cable having high environmental conservation using the same.
ポリ塩化ビニル（ＰＶＣ）は、絶縁特性が比較的良好なうえ、分子中にハロゲン（Ｃｌ）を含むため難燃性に優れており、さらに、耐油性、耐オゾン性、耐薬品性、耐水性なども良好であることから、電線・ケーブルの絶縁体やシース材料として広く用いられている。 Polyvinyl chloride (PVC) has relatively good insulation properties and is excellent in flame retardancy because it contains halogen (Cl) in the molecule. Furthermore, it has oil resistance, ozone resistance, chemical resistance, and water resistance. Etc., it is widely used as an insulator and sheath material for electric wires and cables.
一方、近年、地球環境保護に対する意識が高まるなか、環境負荷の大きい材料の使用を規制しようとする動きが強まっており、上記ＰＶＣについても、火災時や焼却処理の際にハロゲンに起因する有害なハロゲンガスやダイオキシンを発生することから、その使用が制限されつつある。 On the other hand, in recent years, as awareness of global environmental protection has increased, there has been an increasing movement to regulate the use of materials with a large environmental load, and the above-mentioned PVC is also harmful due to halogens in the event of a fire or incineration. The use of halogen gas and dioxin is being limited due to the generation of halogen gas and dioxin.
このため、ＰＶＣに代わる環境保全性の高い電線・ケーブル被覆用難燃材料、すなわち、ハロゲンを含有せず、燃焼時にハロゲンガスやダイオキシンなどの有害な物質が発生するおそれのないノンハロゲン難燃材料が強く求められている。 For this reason, a highly environmentally friendly flame retardant material for covering wires and cables that replaces PVC, that is, a non-halogen flame retardant material that does not contain halogen and does not generate harmful substances such as halogen gas or dioxin during combustion. There is a strong demand.
このような電線・ケーブル被覆用ノンハロゲン難燃材料としては、可燃性のエチレン系ポリマー、例えばポリエチレンに、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を多量に添加して難燃化したものが知られている（例えば、特許文献１参照。）。 As such non-halogen flame retardant materials for covering electric wires and cables, flame retardant ethylene polymers, for example, flame retardant by adding a large amount of metal hydroxide such as magnesium hydroxide or aluminum hydroxide to polyethylene Is known (for example, see Patent Document 1).
しかしながら、この組成物は、金属水酸化物の多量の添加によって、エチレン系ポリマー本来の優れた特性、特に機械的特性（例えば、引張強さ、伸びなど）が損なわれ、これを用いた電線・ケーブルは十分な要求特性を具備することができないという問題があった。
上述したように、ＰＶＣに代わる環境保全性の高いノンハロゲンの電線・ケーブル被覆用難燃材料が求められているが、従来の可燃性のエチレン系ポリマーに、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を添加して難燃化したものは、特に機械的特性が低下するという問題があった。 As described above, there is a demand for a non-halogen non-halogen wire / cable flame retardant material that replaces PVC, but metals such as magnesium hydroxide and aluminum hydroxide have been added to conventional flammable ethylene polymers. The flame retardant added with a hydroxide has a problem that the mechanical properties are particularly deteriorated.
本発明はこのような従来技術の課題を解決するためになされたもので、燃焼時にハロゲンガスやダイオキシンなどの有害なガスを発生することがないノンハロゲンの難燃性組成物であって、優れた難燃性を有し、かつ、引張強さなどの機械的特性も良好な電線・ケーブル被覆用難燃性組成物、およびこのような難燃性組成物を用いた難燃電線・ケーブルを提供することを目的とする。 The present invention has been made in order to solve such problems of the prior art, and is a non-halogen flame retardant composition that does not generate harmful gases such as halogen gas and dioxin during combustion, and is excellent. Providing flame retardant compositions for wire and cable coatings that have flame retardancy and good mechanical properties such as tensile strength, and flame retardant wires and cables using such flame retardant compositions The purpose is to do.
本発明者らは、上記の目的を達成するため鋭意研究を重ねた結果、金属水酸化物に難燃助剤としてナノクレイを併用することにより、良好な難燃性と機械的特性を併せ持つノンハロゲンの難燃性組成物が得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have used non-halogen having both good flame retardancy and mechanical properties by using nanoclay as a flame retardant aid in combination with metal hydroxides. The inventors have found that a flame retardant composition can be obtained, and have completed the present invention.
すなわち、本願の第１の発明は、エチレン系ポリマーを主成分とするノンハロゲン難燃性組成物であって、エチレン系ポリマー１００重量部あたり、（ａ）金属水酸化物３０〜１００重量部と、（ｂ）ナノクレイ１〜１０重量部とを含有することを特徴とする電線・ケーブル被覆用難燃性組成物である。 That is, the first invention of the present application is a non-halogen flame retardant composition mainly composed of an ethylene-based polymer, and (a) 30 to 100 parts by weight of a metal hydroxide per 100 parts by weight of the ethylene-based polymer, (B) A flame retardant composition for covering electric wires and cables, which contains 1 to 10 parts by weight of nanoclay.
上記電線・ケーブル被覆用難燃性組成物において、エチレン系ポリマー１００重量部あたり、（ａ）金属水酸化物５０〜８０重量部と、（ｂ）ナノクレイ３〜８重量部とを含有するものであってもよい。 In the flame retardant composition for covering an electric wire / cable, the composition contains (a) 50 to 80 parts by weight of metal hydroxide and (b) 3 to 8 parts by weight of nanoclay per 100 parts by weight of the ethylene polymer. There may be.
上記電線・ケーブル被覆用難燃性組成物において、エチレン系ポリマーは、エチレン・酢酸ビニル共重合体を含むものであってもよい。 In the flame retardant composition for covering an electric wire / cable, the ethylene-based polymer may contain an ethylene / vinyl acetate copolymer.
上記電線・ケーブル被覆用難燃性組成物において、金属水酸化物は、水酸化アルミニウムを含むものであってもよい。 In the flame retardant composition for covering an electric wire / cable, the metal hydroxide may contain aluminum hydroxide.
上記電線・ケーブル被覆用難燃性組成物において、（ｂ）のナノクレイは、厚さが１０ｎｍ以下で、アスペクト比が１００〜５００であってもよく、また、層状のクレイ粒子をジステアリルジメチルアンモニウムクロライドで処理して得られたものであってもよい。なお、ここで、アスペクト比とは、粒子の最大厚さに対する最大長さの比をいう。 In the flame retardant composition for covering an electric wire / cable, the nanoclay (b) may have a thickness of 10 nm or less and an aspect ratio of 100 to 500. The layered clay particles may be distearyldimethylammonium. It may be obtained by treatment with chloride. Here, the aspect ratio refers to the ratio of the maximum length to the maximum thickness of the particles.
また、本願の第２の発明は、上記電線・ケーブル被覆用難燃性組成物からなる被覆を有することを特徴とする難燃電線・ケーブルである。 Moreover, 2nd invention of this application is a flame-retardant electric wire and cable characterized by having the coating | cover consisting of the said flame-retardant composition for electric wire and cable coating | cover.
本発明の電線・ケーブル被覆用難燃性組成物は、ノンハロゲンであって、従来のＰＶＣをベースとしたハロゲン系難燃材料に匹敵する優れた難燃性を有するとともに、機械的特性も良好である。 The flame retardant composition for covering electric wires and cables of the present invention is non-halogen, has excellent flame retardancy comparable to conventional flame retardant materials based on PVC, and also has good mechanical properties. is there.
また、本発明の難燃電線・ケーブルは、このような特性を有する被覆を有するので、環境保全性が高い難燃電線・ケーブルとして、高い信頼性を有することができる。 Moreover, since the flame-retardant electric wire / cable of this invention has the coating | cover which has such a characteristic, it can have high reliability as a flame-retardant electric wire / cable with high environmental conservation.
以下、本発明を詳細に説明する。
本発明の電線・ケーブル被覆用難燃性組成物において使用されるエチレン系ポリマーとしては、低密度ポリエチレン（ＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、超低密度ポリエチレン（ＶＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）などのポリエチレン、ポリプロピレン（ＰＰ）、エチレン・アクリル酸エチル共重合体（ＥＥＡ）、エチレン・アクリル酸メチル共重合体（ＥＭＡ）、エチレン・メタクリル酸エチル共重合体、エチレン・酢酸ビニル共重合体（ＥＶＡ）、エチレン・プロピレン共重合体（ＥＰ）、エチレン・プロピレン・ジエン共重合体（ＥＰＤＭ）、ポリイソプチレンなどが例示される。また、メタロセン触媒によりエチレンにプロピレン、ブテン、ペンテン、ヘキセン、オクテンなどのα−オレフィンや環状オレフィンなどを共重合させたものなども使用することができる。これらは単独または混合して使用される。本発明においては、なかでも、エチレン・酢酸ビニル共重合体が好ましく、他のエチレン系ポリマーは、エチレン・酢酸ビニル共重合体の併用成分として使用することが好ましい。この場合、エチレン・酢酸ビニル共重合体以外のエチレン系ポリマーは、エチレン系ポリマー全体の５０重量％以下とすることが好ましく、５０重量％を超えると機械的特性が低下する。
Hereinafter, the present invention will be described in detail.
Examples of the ethylene polymer used in the flame retardant composition for covering electric wires and cables of the present invention include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and very low density polyethylene (VLDPE). ), Polyethylene such as linear low density polyethylene (LLDPE), polypropylene (PP), ethylene / ethyl acrylate copolymer (EEA), ethylene / methyl acrylate copolymer (EMA), ethylene / ethyl methacrylate copolymer Examples thereof include a polymer, an ethylene / vinyl acetate copolymer (EVA), an ethylene / propylene copolymer (EP), an ethylene / propylene / diene copolymer (EPDM), and polyisobutylene. Moreover, what copolymerized alpha-olefin, cyclic olefins, etc., such as propylene, butene, pentene, hexene, and octene, can be used for the metallocene catalyst. These are used alone or in combination. In the present invention, an ethylene / vinyl acetate copolymer is preferable, and the other ethylene-based polymer is preferably used as a combined component of the ethylene / vinyl acetate copolymer. In this case, the ethylene-based polymer other than the ethylene / vinyl acetate copolymer is preferably 50% by weight or less of the entire ethylene-based polymer, and if it exceeds 50% by weight, the mechanical properties are deteriorated.
また、本発明の電線・ケーブル被覆用難燃性組成物において使用される（ａ）金属水酸化物としては、水酸化マグネシウム、水酸化アルミニウム、塩基性炭酸マグネシウム、ハイドロタルサイト類などが挙げられる。これらは単独または混合して使用することができる。 In addition, examples of the (a) metal hydroxide used in the flame retardant composition for covering electric wires and cables of the present invention include magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, hydrotalcite and the like. . These can be used alone or in combination.
この（ａ）の金属水酸化物の配合量は、前述したエチレン系ポリマー１００重量部に対し、３０〜１００重量部、好ましくは５０〜８０重量部の範囲である。配合量が３０重量部未満では十分な難燃性が得られず、また、逆に１００重量部を超えると、機械的特性が低下する。 The compounding amount of the metal hydroxide (a) is in the range of 30 to 100 parts by weight, preferably 50 to 80 parts by weight, with respect to 100 parts by weight of the above-mentioned ethylene polymer. If the blending amount is less than 30 parts by weight, sufficient flame retardancy cannot be obtained, and conversely if it exceeds 100 parts by weight, the mechanical properties are deteriorated.
さらに、本発明の電線・ケーブル被覆用難燃性組成物において使用される（ｂ）ナノクレイは、モンモリロナイトやモンモリロナイトを主成分とするベントナイトやヘクトライトなどの層状、すなわち、アスペクト比の高い鱗片状の無機鉱物を有機材料で処理することによって得られるナノサイズのプレート状の粒子である。本発明の効果を得る上では、特に、粒子径（Ｘ−Ｙ寸法）が１０００ｎｍ以下、厚さ（Ｚ方向の寸法）が１０ｎｍ以下で、アスペクト比が１００〜５００のものが好ましく使用される。粒子径（Ｘ−Ｙ寸法）は１００〜５００ｎｍであることがより好ましく、厚さ（Ｚ方向の寸法）は３ｎｍ以下であることがより好ましい。なお、層状のクレイ粒子をジステアリルジメチルアンモニウムクロライドで処理したもの、すなわち、表面がジステアリルジメチルアンモニウムクロライドで改質されているナノクレイは、本発明において（ｂ）ナノクレイとして好ましく使用されるものの１つであるが、エチレン系ポリマー成分としてエチレン・酢酸ビニル共重合体を使用した場合には、難燃性を改善する効果が大きいことから、特に好ましい。 Furthermore, the (b) nanoclay used in the flame retardant composition for covering electric wires and cables of the present invention is a layered layer of montmorillonite, bentonite or hectorite mainly composed of montmorillonite, that is, a scaly shape having a high aspect ratio. Nano-sized plate-like particles obtained by treating inorganic minerals with organic materials. In order to obtain the effects of the present invention, those having a particle diameter (XY dimension) of 1000 nm or less, a thickness (dimension in the Z direction) of 10 nm or less, and an aspect ratio of 100 to 500 are preferably used. The particle diameter (XY dimension) is more preferably 100 to 500 nm, and the thickness (dimension in the Z direction) is more preferably 3 nm or less. In addition, one obtained by treating layered clay particles with distearyldimethylammonium chloride, that is, a nanoclay whose surface is modified with distearyldimethylammonium chloride is one of those preferably used as (b) nanoclay in the present invention. However, when an ethylene / vinyl acetate copolymer is used as the ethylene polymer component, the effect of improving flame retardancy is great, which is particularly preferable.
この（ｂ）のナノクレイは、（ａ）の金属水酸化物の難燃助剤として作用し、その使用量を減らし、（ａ）の金属水酸化物の配合にともなう機械的特性の低下を防止する効果を有する。この（ｂ）のナノクレイの配合量は、前述したエチレン系ポリマー１００重量部に対し、１〜１０重量部、好ましくは３〜８重量部の範囲である。配合量が１重量部未満では添加による効果が得られず、また、逆に１０重量部を超えると、機械的強度が低下する。 The nanoclay of (b) acts as a flame retardant aid for the metal hydroxide of (a), reduces the amount used, and prevents the mechanical properties from deteriorating due to the blending of the metal hydroxide of (a). Has the effect of The amount of nanoclay (b) is 1 to 10 parts by weight, preferably 3 to 8 parts by weight, based on 100 parts by weight of the above-described ethylene-based polymer. If the blending amount is less than 1 part by weight, the effect due to addition cannot be obtained. Conversely, if the blending amount exceeds 10 parts by weight, the mechanical strength decreases.
なお、（ｂ）のナノクレイは、上記効果とともに、組成物に優れた燃焼時の滴下防止性を付与する効果を併せ有する。但し、この効果は（ａ）の金属水酸化物に水酸化アルミニウムを使用した場合に顕著であるものの、水酸化マグネシウムを使用した場合にはほとんど認められないことから、良好な燃焼時の滴下防止性を得るためには、（ａ）の金属水酸化物に水酸化アルミニウムを使用することが好ましい。 In addition, the nano clay of (b) has the effect which provides the dripping prevention property at the time of the combustion which was excellent in the composition with the said effect. However, although this effect is remarkable when aluminum hydroxide is used for the metal hydroxide of (a), it is hardly recognized when magnesium hydroxide is used. In order to obtain the properties, it is preferable to use aluminum hydroxide for the metal hydroxide of (a).
本発明の電線・ケーブル被覆用難燃性組成物には、以上の各成分のほか、必要に応じて、本発明の効果を阻害しない範囲で、可塑剤、軟化剤、酸化防止剤、紫外線吸収剤、熱老化防止剤、充填剤、加工助剤、架橋剤、架橋助剤、滑剤、着色剤、安定剤などの添加剤を配合することができる。例えば、可塑剤としては、ステアリン酸、オレイン酸などの脂肪酸およびそれらの金属塩などが挙げられる。また、軟化剤としては、鉱物油、ワックス、パラフィン類などが挙げられる。さらに、上述した金属水酸化物やナノクレイ以外の他のノンハロゲン系難燃剤や難燃助剤も、本発明の効果を阻害しない範囲で配合することができる。そのようなノンハロゲン系難燃剤および難燃助剤としては、グアニジン系、メラミン系などの窒素系難燃剤、リン酸アンモニウム、赤燐などのリン系難燃剤、リン−窒素系難燃剤、ホウ酸亜鉛などのホウ酸化合物、炭酸カルシウム、シリコーン系難燃助剤などが例示される。 The flame retardant composition for covering electric wires and cables of the present invention includes, in addition to the above components, a plasticizer, a softener, an antioxidant, and an ultraviolet absorber as long as they do not impair the effects of the present invention. Additives such as an agent, a heat aging inhibitor, a filler, a processing aid, a crosslinking agent, a crosslinking aid, a lubricant, a colorant, and a stabilizer can be blended. For example, examples of the plasticizer include fatty acids such as stearic acid and oleic acid, and metal salts thereof. Examples of the softener include mineral oil, wax, paraffins and the like. Furthermore, non-halogen flame retardants and flame retardant aids other than the metal hydroxides and nano clays described above can also be blended within a range that does not impair the effects of the present invention. Examples of such non-halogen flame retardants and flame retardant aids include guanidine and melamine nitrogen flame retardants, phosphorus phosphate flame retardants such as ammonium phosphate and red phosphorus, phosphorus-nitrogen flame retardants, and zinc borate. Examples thereof include boric acid compounds such as calcium carbonate, and silicone flame retardant aids.
本発明の電線・ケーブル被覆用難燃性組成物は、以上の各成分をバンバリーミキサ、タンブラー、加圧ニーダ、混練押出機、ミキシングローラなどの通常の混練機を用いて均一に混合することにより容易に製造することができる。 The flame retardant composition for covering an electric wire / cable of the present invention is obtained by uniformly mixing the above components using a conventional kneader such as a Banbury mixer, a tumbler, a pressure kneader, a kneading extruder, or a mixing roller. It can be manufactured easily.
また、このようにして得られた本発明の電線・ケーブル被覆用難燃性組成物を、導体外周に直接もしくは他の被覆を介して押出被覆するか、あるいはテープ状に成形したものを巻き付けることにより、本発明の難燃電線・ケーブルが製造される。組成物は、被覆後もしくは成形後、必要に応じて常法により架橋される。 In addition, the flame retardant composition for covering an electric wire / cable of the present invention obtained as described above may be extrusion-coated on the outer periphery of a conductor directly or through another coating, or wound in a tape shape. Thus, the flame-retardant electric wire / cable of the present invention is manufactured. The composition is crosslinked by a conventional method after coating or molding, if necessary.
図１に、本発明に係る難燃ケーブルの一例を示す。
図１に示すように、このケーブルは、銅やアルミなどからなる導体１上にポリエチレンや架橋ポリエチレンなどの絶縁層２を被覆した絶縁線心３を複数本（図面の例では３本）撚り合わせてケーブルコア４を形成するとともに、このケーブルコア４上に難燃シース５を設けた構造となっている。そして、この難燃シース５は、前述した電線・ケーブル被覆用難燃性組成物の押出しにより形成されている。
FIG. 1 shows an example of a flame retardant cable according to the present invention.
As shown in FIG. 1, this cable is formed by twisting a plurality of insulated wire cores 3 (three in the example of the drawing) in which an insulating
このような難燃ケーブルにおいては、難燃シース５が、優れた難燃性と良好な機械的特性を併せ持つノンハロゲンの電線・ケーブル被覆用難燃性組成物で形成されているので、ノンハロゲンの難燃ケーブルとして高い信頼性を有している。
In such a flame retardant cable, the
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの実施例に何ら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all.
実施例１
エチレン・酢酸ビニル共重合体（ＥＶＡ；三井・デュポンポリケミカル社製 商品名 ＥＶ１８０）１００重量部と、水酸化アルミニウム（昭和電工社製 商品名 ハイジライトＨ−４２）３０重量部と、ナノクレイ（ズードケミー社製 商品名 Ｎａｎｏｆｉｌ ＳＥ３０００）５重量部とを加圧ニーダを用いて均一に混練して樹脂組成物を得た。
Example 1
100 parts by weight of ethylene / vinyl acetate copolymer (EVA; trade name EV180 manufactured by Mitsui DuPont Polychemical Co., Ltd.), 30 parts by weight of aluminum hydroxide (trade name Heidilite H-42 manufactured by Showa Denko KK), and nanoclay (Zud Chemie) A resin composition was obtained by uniformly kneading 5 parts by weight of a product name “Nanofil SE3000” manufactured by a company using a pressure kneader.
次いで、０．８ｍｍφの銅導体上に０．４ｍｍ厚のポリエチレン絶縁層を設けた絶縁線心を４本撚り合わせつつ、その外周に上記樹脂組成物を押出被覆して約１ｍｍ厚のシースを形成し、外径約６．５ｍｍのケーブルを製造した。 Next, while twisting four insulated wire cores having a 0.4 mm thick polyethylene insulation layer on a 0.8 mmφ copper conductor, the resin composition is extrusion coated on the outer periphery to form a sheath of about 1 mm thickness Thus, a cable having an outer diameter of about 6.5 mm was manufactured.
実施例２〜５、比較例１〜４
配合成分および配合量を表１に示すように変えた以外は、実施例１と同様にして樹脂組成物を得、さらに、得られた樹脂組成物を用いて実施例１と同様にしてケーブルを製造した。なお、実施例４、５において使用した水酸化マグネシウムは、協和化学工業社製のキスマ５Ａ（商品名）である。
Examples 2-5, Comparative Examples 1-4
A resin composition was obtained in the same manner as in Example 1 except that the blending components and blending amounts were changed as shown in Table 1, and a cable was obtained in the same manner as in Example 1 by using the obtained resin composition. Manufactured. In addition, the magnesium hydroxide used in Examples 4 and 5 is Kisuma 5A (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.
上記各実施例および各比較例で得られた樹脂組成物について、下記に示す方法で各種特性を評価した。
［引張強さおよび伸び］
難燃性組成物をプレス機にて１８０℃×５分間、圧力２０ＭＰａの条件で加熱加圧成型して試験用シートを作成し、ＪＩＳ Ｋ ６２５１に準拠して引張強さおよび伸びを測定した。
［酸素指数］
上記と同様にして試験用シートを作成し、ＪＩＳ Ｋ ７２０１に準拠して酸素指数を測定した。
［燃焼時の滴下防止性］
上記と同様にして６．５ｍｍ×１５０ｍｍ×１ｍｍの試験片を作成し、これを垂直に保持するとともにその下方に脱脂綿を敷き、チリルバーナ（炎高さ１９ｍｍ）を５秒間接炎して燃焼状況を調べた。評価は、試験片からの脱脂綿を着火させるような有害な溶融滴下物の発生の有無により行った。
これらの結果を表１下欄に示す。
About the resin composition obtained by each said Example and each comparative example, various characteristics were evaluated by the method shown below.
[Tensile strength and elongation]
The flame retardant composition was heat-press molded under conditions of 180 ° C. × 5 minutes and a pressure of 20 MPa with a press machine to prepare a test sheet, and tensile strength and elongation were measured according to JIS K 6251.
[Oxygen index]
A test sheet was prepared in the same manner as described above, and the oxygen index was measured according to JIS K7201.
[Drip prevention during combustion]
Make a test piece of 6.5mm x 150mm x 1mm in the same way as above, hold it vertically and lay absorbent cotton underneath it, and indirect flame with a tyryl burner (flame height 19mm) for 5 seconds. Examined. Evaluation was performed by the presence or absence of generation | occurrence | production of the harmful molten dripping which ignites the absorbent cotton from a test piece.
These results are shown in the lower column of Table 1.
表１から明らかなように、ナノクレイを添加した実施例の樹脂組成物では、ナノクレイ未添加の比較例に比べ、機械的特性の改善が認められ、特に、ナノクレイと水酸化アルミニウムを併用した実施例１〜３では、さらに良好な燃焼時の滴下防止性を有していた。 As is clear from Table 1, the resin compositions of the examples to which nanoclay was added showed improvement in mechanical properties as compared with the comparative examples to which no nanoclay was added, and in particular, examples in which nanoclay and aluminum hydroxide were used in combination. In 1-3, it had the dripping prevention property at the time of combustion more favorable.
１…導体、２…絶縁層、３…絶縁線心、４…ケーブルコア、５…難燃シース DESCRIPTION OF SYMBOLS 1 ... Conductor, 2 ... Insulating layer, 3 ... Insulated wire core, 4 ... Cable core, 5 ... Flame-retardant sheath
Claims (7)
エチレン系ポリマー１００重量部あたり、（ａ）金属水酸化物３０〜１００重量部と、（ｂ）ナノクレイ１〜１０重量部とを含有することを特徴とする電線・ケーブル被覆用難燃性組成物。 A non-halogen flame retardant composition mainly composed of an ethylene polymer,
A flame retardant composition for covering electric wires and cables, comprising (a) 30 to 100 parts by weight of a metal hydroxide and (b) 1 to 10 parts by weight of nanoclay per 100 parts by weight of an ethylene-based polymer. .
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| EP4002395A1 (en) | 2020-11-11 | 2022-05-25 | Prysmian S.p.A. | Flame-retardant cable with self-extinguishing coating layer |
| EP4207218A1 (en) | 2021-12-30 | 2023-07-05 | Prysmian S.p.A. | Flame-retardant cable with self-extinguishing coating layer |
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| JP2003138072A (en) * | 2001-08-23 | 2003-05-14 | Kansai Research Institute | Flame-retardant resin composition and resin composite material using the same |
| JP2003197043A (en) * | 2001-12-27 | 2003-07-11 | Furukawa Electric Co Ltd:The | Insulated wire |
| JP2005181868A (en) * | 2003-12-22 | 2005-07-07 | Sekisui Chem Co Ltd | Noncombustible display material or noncombustible sign |
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| JP2011111564A (en) * | 2009-11-27 | 2011-06-09 | Tosoh Corp | Ethylene-vinyl acetate copolymer resin composition, film comprising the same and laminate containing the same |
| EP3731243A1 (en) | 2019-04-25 | 2020-10-28 | Prysmian S.p.A. | Flame- retardant electrical cable |
| US11031152B2 (en) | 2019-04-25 | 2021-06-08 | Prysmian S.P.A. | Flame- retardant electrical cable |
| EP4002395A1 (en) | 2020-11-11 | 2022-05-25 | Prysmian S.p.A. | Flame-retardant cable with self-extinguishing coating layer |
| EP4207218A1 (en) | 2021-12-30 | 2023-07-05 | Prysmian S.p.A. | Flame-retardant cable with self-extinguishing coating layer |
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