JP2013018896A - 剥離性と耐熱性を有する難燃性組成物、難燃性樹脂の製造方法及び絶縁電線 - Google Patents
剥離性と耐熱性を有する難燃性組成物、難燃性樹脂の製造方法及び絶縁電線 Download PDFInfo
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- JP2013018896A JP2013018896A JP2011154405A JP2011154405A JP2013018896A JP 2013018896 A JP2013018896 A JP 2013018896A JP 2011154405 A JP2011154405 A JP 2011154405A JP 2011154405 A JP2011154405 A JP 2011154405A JP 2013018896 A JP2013018896 A JP 2013018896A
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- silane
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 76
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- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
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- 230000008961 swelling Effects 0.000 description 1
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
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- 239000011135 tin Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
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- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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Abstract
【解決手段】ポリエチレン系樹脂にシランカップリング剤をグラフト重合させたシラン変性ポリエチレン系樹脂を含有するA成分と、ポリエチレン系樹脂に水酸化マグネシウムと、融点150℃以上のトリアジン系化合物と、ベンズイミダゾール系化合物と、酸化亜鉛と、銅害防止剤を配合してなるB成分と、ポリエチレン系樹脂にシラン架橋触媒を配合してなるC成分を混練し、導体の外周を被覆するように成形した後、水架橋を行い架橋された難燃性樹脂からなる絶縁体を形成して絶縁電線を得た。
【選択図】なし
Description
シラン変性ポリエチレン系樹脂40〜80質量部と、ポリエチレン系樹脂20〜60質量部を含有するポリマー成分100質量部に対し、
水酸化マグネシウム又は/及び水酸化アルミニウム30〜200質量部、融点150℃以上のトリアジン系化合物0.5〜5質量部、ベンズイミダゾール系化合物1〜10質量部、酸化亜鉛1〜10質量部、銅害防止剤0.1〜5質量部含有することを要旨とするものである。
ポリエチレン系樹脂にシランカップリング剤をグラフト重合させたシラン変性ポリエチレン系樹脂を含有するA成分と、
ポリエチレン系樹脂に、水酸化マグネシウム又は/及び水酸化アルミニウムと、融点150℃以上のトリアジン系化合物と、ベンズイミダゾール系化合物と、酸化亜鉛と、銅害防止剤を配合してなるB成分と、
ポリエチレン系樹脂に、シラン架橋触媒を配合してなるC成分と、
を混練し成形した後、水架橋を行うことを要旨とするものである。
〔供試材料及び調製方法〕
本実施例及び比較例において使用した各成分の供試材料及び調製方法を示す。
・ポリエチレン[デュポン ダウ エラストマージャパン社製、商品名「エンゲージ 8003」、密度0.885g/cm3]
・シランカップリング剤(ビニル系)[東レダウコーニング社製、商品名「SZ6300」]
・ジクミルパーオキサイド(DCP)[日本油脂社製、商品名「パークミルD」]
ポリエチレン65質量部と、シランカップリング剤0.33質量部と、DCP0.07質量部とを2軸押出混練機に加え200℃で0.1〜2分間加熱混練した後、ペレット化して、シラン変性したポリエチレンを調製した。
・ポリエチレン[デュポン ダウ エラストマージャパン社製、商品名「エンゲージ 8003」、密度0.885g/cm3]
・水酸化マグネシウム[協和化学社製、商品名「キスマ5」]
・融点が150℃以上のトリアジン系化合物:1,3,5−トリス(3,5−ジ−tert−ブチル−4ヒドロキシベンジル)−1,3,5−トリアジン−2,4,6(1H,3H,5H)トリオン[BASF社製、商品名「イルガノックス3114」、融点226℃]
・フェノール系酸化防止剤(1)[BASF社製、商品名「イルガノックス1010」]
・フェノール系酸化防止剤(2)[アデカ社製、商品名「AO80」]
・フェノール系酸化防止剤(3)[BASF社製、商品名「イルガノックス1330」]
・ベンズイミダゾール系化合物[大内新興化学社製、商品名「ノクラックMB」]
・酸化亜鉛[ハクスイテック社製、商品名「酸化亜鉛1種」]
・銅害防止剤[アデカ社製、商品名「CD−1」]
表1〜2に示す配合質量比で、B成分の各成分を2軸押出混練機に加え、200℃で0.1〜2分間加熱混練した後、ペレット化して、難燃剤バッチを調製した。
・ポリエチレン[デュポン ダウ エラストマージャパン社製、商品名「エンゲージ 8003」、密度0.885g/cm3]
・シラン架橋触媒(ジブチル錫ジラウレート)[和光純薬社製、試薬]
表1〜2に示す配合質量比でポリエチレンとシラン架橋触媒を2軸押出混練機に加え、200℃で0.1〜2分間加熱混練した後、ペレット化して、触媒バッチを調製した。
上記シラングラフトバッチと、上記難燃剤バッチと、上記触媒バッチとを押出機のホッパーで混合して押出機の温度を約180〜200℃に設定して、押出加工を行った。外径2.4mmの導体上に厚さ0.7mmの絶縁体として押出被覆した(被覆外径3.8mm)。その後、60℃、90%湿度の高湿高温槽で24時間水架橋処理を施して絶縁電線を作製した。
JASO D608−92に従い、300mmの試料を用意し、水平燃焼試験を実施した。口径10mmのブンゼンバーナーを用いて還元炎の先端を試料中央部の下側から10秒間当て、炎を静かに取り去った後の残炎時間を測定した。炎がすぐに消えるものを良好「◎」、この残炎時間が30秒以内のものを合格「○」、残炎時間が30秒を超えるものを不合格「×」とした。
150mm以上の試料を用意し、180℃の恒温槽に504時間投入し、その後、室温で電線径の1.5倍の直径のマンドレルに巻付けて絶縁体のヒビ割れ有無を観察した。なお180℃の恒温槽に504時間投入することは、アレニウスプロットの外挿にてISO6722の150℃3000時間の長期耐熱評価に相当することが判っている。試験の結果、変色が少なくヒビ割れのないものを良好「◎」、ヒビ割れが無かったものを合格「○」、ヒビ割れが有ったものを不合格「×」とした。
JIS C 3005の引張試験に準拠して、引張試験及び引張伸びを測定した。すなわち絶縁電線を150mmの長さに切り出し、導体を取り除いて絶縁被覆材のみの管状試験片とした後、23℃±5℃の室温下にて、試験片の両端を引張試験機チャックに取り付けた後、引張速度200mm/分で引っ張り、試験片の破断時の荷重及び伸びを測定した。引張強度11MPa以上かつ伸び200%以上のものを良好「◎」、引張強度10MPa以上かつ伸び150%以上のものを合格「○」、引張強度10MPa未満あるいは伸び150%未満のものを不合格「×」とした。
100mmの電線2本をテープで巻付けたものを、150℃×24時間の条件下に放置した後、テープを取り去り2本の電線を剥がした。すぐに剥がれ接着跡がほとんどついていないものを良好「◎」、剥がれるが接着跡がまばらについているものを合格「○」、剥がれにくく接着跡が全面的についているものを不合格「×」とした。
Claims (5)
- シラン変性ポリエチレン系樹脂40〜80質量部と、ポリエチレン系樹脂20〜60質量部を含有するポリマー成分100質量部に対し、
水酸化マグネシウムまたは/および水酸化アルミニウム30〜200質量部、融点150℃以上のトリアジン系化合物0.5〜5質量部、ベンズイミダゾール系化合物1〜10質量部、酸化亜鉛1〜10質量部、銅害防止剤0.1〜5質量部含有することを特徴とする難燃性組成物。 - 上記ポリマー成分100質量部に対し、更にフェノール系酸化防止剤1〜10質量部含有することを特徴とする請求項1記載の難燃性組成物。
- ポリエチレン系樹脂にシランカップリング剤をグラフト重合させたシラン変性ポリエチレン系樹脂を含有するA成分と、
ポリエチレン系樹脂に、水酸化マグネシウムまたは/および水酸化アルミニウムと、融点150℃以上のトリアジン系化合物と、ベンズイミダゾール系化合物と、酸化亜鉛と、銅害防止剤を配合してなるB成分と、
ポリエチレン系樹脂に、シラン架橋触媒を配合してなるC成分と、
を混練し成形した後、水架橋を行うことを特徴とする難燃性樹脂の製造方法。 - 上記B成分が、更にフェノール系酸化防止剤を配合してなるものであることを特徴とする請求項3記載の難燃性樹脂の製造方法。
- 請求項1又は2に記載の難燃性組成物から形成された絶縁体により、導体の外周が被覆されていることを特徴とする絶縁電線。
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