JPWO2014010500A1 - ノンハロゲン難燃性樹脂組成物及び当該樹脂組成物を有する絶縁電線・ケーブル - Google Patents
ノンハロゲン難燃性樹脂組成物及び当該樹脂組成物を有する絶縁電線・ケーブル Download PDFInfo
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- JPWO2014010500A1 JPWO2014010500A1 JP2014524767A JP2014524767A JPWO2014010500A1 JP WO2014010500 A1 JPWO2014010500 A1 JP WO2014010500A1 JP 2014524767 A JP2014524767 A JP 2014524767A JP 2014524767 A JP2014524767 A JP 2014524767A JP WO2014010500 A1 JPWO2014010500 A1 JP WO2014010500A1
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- flame retardant
- resin
- ethylene
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- 239000011342 resin composition Substances 0.000 title claims abstract description 85
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 32
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- 239000011347 resin Substances 0.000 claims abstract description 92
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 36
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 36
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 36
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- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 2
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
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Abstract
Description
(a1)エチレン−酢酸ビニル共重合体:
本発明の難燃性樹脂組成物に(a1)エチレン−酢酸ビニル共重合体(EVA)を含有させることにより、難燃性を向上することができる。
本発明の難燃性樹脂組成物に(a2)ポリエチレンやエチレン−αオレフィン共重合体を含有させることにより、機械的強度、伸び特性を向上することができる。
本発明の難燃性樹脂組成物に(a3)不飽和カルボン酸変性ポリオレフィン樹脂(不飽和カルボン酸で変性したポリオレフィン樹脂のこと。以下同じ。)を含有させることにより、機械的特性、耐磨耗性等を向上させることができる。不飽和カルボン酸変性ポリオレフィン樹脂における不飽和カルボン酸による変性量は、ポリオレフィン樹脂に対し、0.5〜15質量%のものを好ましく使用することができる。
本発明の難燃性樹脂組成物に(a4)プロピレン系樹脂を含有させることにより、耐熱性を向上させることができ、UL1581で規定されている、121℃で1時間後の加熱変形特性を満足することができることになる。
(b1)水酸化マグネシウム及び(b2)水酸化アルミニウム:
本発明では、使用できる金属水和物を(b1)水酸化マグネシウム及び(b2)水酸化アルミニウムを併用するようにする。水酸化マグネシウムと水酸化アルミニウムを併用することにより、それぞれを単独で使用する場合と比較して難燃性が向上する。
本発明の難燃性樹脂組成物では、難燃剤である(b1)水酸化マグネシウム及び(b2)水酸化アルミニウムに加えて、難燃助剤として、(b3)1,3,5−トリアジン誘導体化合物を併用する。本発明において1,3,5−トリアジン誘導体化合物は難燃助剤として作用し、金属水和物の水酸化マグネシウム及び水酸化アルミニウムと併用することにより、これらとの相乗効果を得られるため、(a1)エチレン−酢酸ビニル共重合体における酢酸ビニル含有量を比較的少なくすることができる。そして、エチレン−酢酸ビニル共重合体における酢酸ビニル含有量を比較的少なくすることにより、機械的特性、耐寒性及び絶縁特性の低下を抑え、優れた機械的特性、耐寒性、絶縁特性を維持することが可能となる。
本発明の難燃性樹脂組成物には、電線、ケーブル、コード、チューブ、電線部品、シート等の被覆材料において、一般的に使用されている各種の添加剤、例えば、酸化防止剤、金属不活性剤、難燃(助)剤((B)で挙げているものを除く。)、充填剤、滑剤等を任意成分として、本発明の目的を損なわない範囲で適宜配合することができる。なお、下記の任意成分は、1種を単独で使用してもよく、2種以上を組み合わせて使用するようにしてもよい。また、ここに挙げた以外の添加物や樹脂等を、本発明の目的を損なわない範囲で、添加するようにしてもよい。
表1及び表2に組成を示す各成分((A)樹脂成分、(B)難燃剤及び難燃助剤、(C)任意成分)を、バンバリーミキサーを用いて混合し、溶融混練した後、ペレット化して難燃性樹脂組成物(コンパウンド)を得た。
(a1)エチレン−酢酸ビニル共重合体:
(1)エチレン−酢酸ビニル共重合体(酢酸ビニル(VA)含有量 33質量%)(商品名:エバフレックスEV180、三井・デュポンポリケミカル(株)製)
(4)エチレン−1へキセン共重合体(商品名:カーネルKS240T、日本ポリエチレン(株)製)(密度 0.880g/cm3)
(5)マレイン酸変性ポリエチレン(商品名:アドテックスL6100M、日本ポリエチレン(株)製)
(6)エチレン−プロピレンブロック共重合体(商品名:ノバテックBC8A、日本ポリプロ(株)製)(エチレン含有量 15質量%)
(b1)水酸化マグネシウム:
(7)シランカップリング剤で表面処理された水酸化マグネシウム(商品名:キスマ5L、協和化学工業(株)製)
(8)無処理水酸化アルミニウム(商品名:ハイジライトH42M、昭和電工(株)製)
(9)メラミンシアヌレート(商品名:MC6000、日産化学工業(株)製)
(10)ヒンダードフェノール系酸化防止剤(商品名:イルガノックス1076、BASF社製)
得られた実施例1〜実施例17、比較例1〜比較例11の絶縁電線について、下記に示したUL1581に準拠した試験方法を用いて、「(1)引張試験」、「(2)垂直燃焼試験(VW−1)」、「(3)加熱変形試験」、「(4)低温巻き付け試験」、「(5)絶縁抵抗試験」及び「(6)電線融着性」の各試験を実施して、比較・評価した。結果を表1(実施例)及び表2(比較例)に示した。
絶縁電線から導体を抜き取った管状サンプルを準備し、標点距離25mm、引張速度500mm/分で、破断伸び(%)、破断強度(MPa)を測定した。破断強度が10.3MPa以上、破断伸びが150%以上を「○(合格)」とし、10.3MPa未満のものを「×」とした。なお、「○(合格)」のうち、特に、破断強度が12.0MPa以上、破断伸びが180%以上のものを「◎」とした。
絶縁電線サンプルを、たるみのない状態で垂直に張った状態のサンプル上部に指示旗、サンプル下部に綿を設置し、フードを外した状態で15秒の着火と60秒の離火を5回繰り返した。60秒以上のサンプルの燃焼、指示旗の燃焼及び綿の燃焼の全てが観察されなかったサンプルを「○(合格)」とし、それ以外を「×」とした。なお、「○(合格)」のうち、特に、着火1〜5回目のうち、全ての回が30秒以下の燃焼の場合を「◎」とした。
UL1581に基づき、絶縁電線サンプルの絶縁材料の加熱変形特性を測定した。250gfの負荷荷重を、50%以下を「○(合格)」とし、50%を超えるものを「×」とした。なお、「○(合格)」のうち、特に、25%以下のものは「◎」とした。
UL1581に基づき、絶縁電線サンプルを−10℃の環境下で4時間以上放置した後、同様に−10℃の環境下で冷却した、絶縁電線サンプル外径の2倍径を有する金属マンドレルに巻き付けた。巻き付け後に、絶縁材料にクラックが観察されなかったものを「○(合格)」とし、クラックが観察されたものを「×」とした。
50mの絶縁電線サンプルを20℃の水槽に24時間浸漬させ、絶縁抵抗値を測定した。測定電圧、荷電時間、測定時間はそれぞれ500V、10秒、50秒で行った。絶縁抵抗値が10MΩ・km以上であるものを「○(合格)」とし、10MΩ・km未満のものを「×」とした。なお、「○(合格)」のうち、特に、50MΩ・km以上のものを「◎」とした。
絶縁電線サンプルをボビンに巻き付け、60℃の環境下で24時間以上放置した。放置後、絶縁電線サンプル同士が融着せずにスムースに繰り出すことができたものを「○(合格)」とし、繰り出しが困難だったものを「×」とした。
Claims (4)
- 下記(a1)〜(a4)を(A)樹脂成分とし、
(a1)エチレン−酢酸ビニル共重合体:(A)樹脂成分全体に対して20〜80質量%、
(a2)ポリエチレン及びエチレン−αオレフィン共重合体のうち少なくとも1種:(A)樹脂成分全体に対して5〜50質量%、
(a3)不飽和カルボン酸変性ポリオレフィン樹脂:(A)樹脂成分全体に対して0〜20質量%、
(a4)プロピレン系樹脂:(A)樹脂成分全体に対して5〜20質量%、
前記(A)樹脂成分の酢酸ビニル含有量を、前記(A)樹脂成分全体に対して10〜30質量%とし、
さらに、前記(A)樹脂成分100質量部に対して、
(b1)水酸化マグネシウム:120〜220質量部、
(b2)水酸化アルミニウム:20〜120質量部、
(b3)1,3,5−トリアジン誘導体化合物:30〜75質量部、
を含有することを特徴とするノンハロゲン難燃性樹脂組成物。 - 前記(b1)水酸化マグネシウム及び(b2)水酸化アルミニウムの総和が、(A)樹脂成分100質量部に対して150〜280質量部であることを特徴とする請求項1に記載のノンハロゲン難燃性樹脂組成物。
- 前記(b3)1,3,5−トリアジン誘導体化合物が、メラミンシアヌレートであることを特徴とする請求項1または請求項2に記載のノンハロゲン難燃性樹脂組成物。
- 前記請求項1ないし請求項3のいずれかに記載のノンハロゲン難燃性樹脂組成物が絶縁被覆材料として被覆されていることを特徴とする絶縁電線・ケーブル。
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