JP2004182922A - Flame retardant resin composition - Google Patents
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- JP2004182922A JP2004182922A JP2002353646A JP2002353646A JP2004182922A JP 2004182922 A JP2004182922 A JP 2004182922A JP 2002353646 A JP2002353646 A JP 2002353646A JP 2002353646 A JP2002353646 A JP 2002353646A JP 2004182922 A JP2004182922 A JP 2004182922A
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【０００１】
【発明の属する技術分野】
本発明は、柔軟で、燃焼時に有毒なハロゲン系ガス、ダイオキシン、シアン等を発生せず、高度な難燃性を有し、かつ機械的特性に優れ、耐トラッキング性を有し、成形・加工性に優れた難燃性樹脂組成物及びその成形体に関するものである。
【０００２】
【従来の技術】
従来、様々な分野において、可撓性、柔軟性等に優れた種々の素材が使用されており、それらの中でも、塩化ビニル樹脂は、その特性から幅広く使用されている。しかしながら、近年、環境問題が重要視され、特に塩化ビニル樹脂は、燃焼時にダイオキシン類が発生する問題があった。そこで、塩化ビニル樹脂の代替として、種々の熱可塑性樹脂や熱可塑性エラストマーが検討されている。
【０００３】
一方、火災等に対する安全性から、それら代替素材の難燃化が要求され、ＵＬ９４の垂直試験に適合するような高い難燃性を得るためには、ハロゲン原子を有する有機化合物や三酸化アンチモン等を使用しなくてはならず、これらの燃焼時においても、塩化ビニル樹脂と同様にダイオキシン類の発生が問題化している。
【０００４】
そこで、ハロゲン原子を有する有機化合物を使用しない難燃性樹脂組成物が検討され、これまでに数多くの組成物が提案されている。例えば、ポリエチレン、エチレン−酢酸ビニル共重合体、エチレン−エチルアクリレート共重合体、ポリプロピレン等のオレフィン系樹脂と称される樹脂に、水酸化マグネシウムや窒素系難燃剤あるいはリン系難燃剤等を添加する方法である。しかしながら、ＵＬ９４の垂直試験に適合するような高い難燃性を得るためには、多量の難燃剤を添加する必要があり、その結果、機械的特性の低下が避けられず、実用に耐えうる物とは言えなかった。
【０００５】
機械的特性の低下を改善するために、ポリオレフィン系樹脂、ケン化エチレン−酢酸ビニル共重合体、金属水酸化物からなる難燃性樹脂組成物が提案されている（特許文献１参照）。しかしながら、ケン化エチレン−酢酸ビニル共重合体は、エチレン−酢酸ビニル共重合体と比較して、ケン化エチレン−酢酸ビニル共重合体単独では機械的特性が向上するが、ケン化エチレン−酢酸ビニル共重合体とエチレン−酢酸ビニル共重合体との相溶性に問題があるので、これらの混合物では機械的特性が向上しない。
【０００６】
また、本発明者らは、熱可塑性ポリアミドエラストマーや部分ケン化エチレン−酢酸ビニル共重合体にメラミンシアヌレート等を添加した難燃性樹脂組成物を提案した（特許文献２参照）。当該組成物は、十分な難燃性と機械的強度を有しているものの、樹脂や難燃剤を構成する原子に窒素原子が含まれるので、燃焼時にシアン化合物が発生する危険性があるという問題点があり、より安全性に優れた難燃性樹脂組成物が求められている。
【０００７】
【特許文献１】
特開２００１−１３９７４１号公報
【特許文献２】
特開平１０−１０１９２８号公報
【０００８】
【発明が解決しようとする課題】
本発明が解決しようとする課題は、柔軟で、燃焼時にハロゲン系ガス、ダイオキシン、シアン等の有毒ガスが発生せず、高度な難燃性を有し、耐トラッキング性を有し、機械的特性の低下がなく、成形性及び加工性等に優れた難燃性樹脂組成物及びその成形体を提供することにある。
【０００９】
より具体的には、フィルム、シート、粘着フィルム、クランプカバー、電線防護管への使用を考慮し、難燃性は厚さ１ｍｍでＵＬ９４のＶ−２相当、厚さ０．１ｍｍでＶＴＭ−０相当、ＪＩＳ Ａ １３２２の防炎２級相当以上であり、機械的特性として、引張強度１０ＭＰａ以上、引張伸び１５０％以上、低温脆化温度−２０℃以下、ＪＩＳ Ｃ ３００５の塩水噴霧耐トラッキング性試験１０１回以上に適合する難燃性樹脂組成物及びその成形体を提供することにある。
【００１０】
【課題を解決するための手段】
本発明者らは、上記目的を達成させるために鋭意検討した結果、特定の部分ケン化エチレン−酢酸ビニル共重合体に金属水酸化物を添加することにより上記目的が達成し得ることを見出し、本発明を完成するに至った。
【００１１】
即ち、本発明は上記課題を解決するために、部分ケン化エチレン−酢酸ビニル共重合体及び金属水酸化物を含有する難燃性樹脂組成物であって、（１）前記部分ケン化エチレン−酢酸ビニル共重合体が、エチレン及び酢酸ビニルを含有し、酢酸ビニルの含有割合が２８〜４２質量％の重合性組成物から成るエチレン−酢酸ビニル共重合体のケン化物であって、かつ、ケン化度が１０〜８０質量％の部分ケン化エチレン−酢酸ビニル共重合体であること、（２）前記部分ケン化エチレン−酢酸ビニル共重合体と前記金属水酸化物の割合が質量比で４０：６０〜９０：１０であること
を特徴とする難燃性樹脂組成物を提供する。
【００１２】
【発明の実施の形態】
以下、本発明の難燃性樹脂組成物及びその成形体について詳細に説明する。
【００１３】
本発明で使用する部分ケン化エチレン−酢酸ビニル共重合体は、エチレン及び酢酸ビニルを含有し、酢酸ビニルの含有割合が２８〜４２質量％の重合性組成物から成るエチレン−酢酸ビニル共重合体のケン化物であって、かつ、ケン化度が１０〜８０質量％の部分ケン化エチレン−酢酸ビニル共重合体である。部分ケン化エチレン−酢酸ビニル共重合体の原料となるケン化前のエチレン−酢酸ビニル共重合体として、当該共重合体を構成する全モノマー中の酢酸ビニルの含有割合が２８質量％未満のものを用いた場合、目的とする厚さ１ｍｍでＵＬ９４のＶ−２相当、厚さ０．１ｍｍでＶＴＭ−０相当、ＪＩＳ Ａ １３２２の防炎２級相当以上の難燃性を有する樹脂組成物が得られない。また、ケン化前のエチレン−酢酸ビニル共重合体として、当該共重合体を構成する全モノマー中の酢酸ビニルの含有割合が４２質量％より多いものを用いた場合、機械的特性の低下が著しく、実用に耐えない。
【００１４】
さらに、ケン化度が８０質量％より高い部分ケン化エチレン−酢酸ビニル共重合体を用いた場合、得られる難燃性樹脂組成物から成る成形体の機械的強度の低下及び低温脆化温度の上昇が著しく、目的とする難燃性樹脂組成物が得られない。さらにまた、ケン化度が１０質量％より低い部分ケン化エチレン−酢酸ビニル共重合体を用いた場合、目的とする難燃性及び機械的強度を有する樹脂組成物が得られない。以上のように、良好な機械的特性、低温脆化温度を得るためには、ケン化度は１０から８０質量％であることが必要である。
【００１５】
部分ケン化エチレン−酢酸ビニル共重合体は、エチレン−酢酸ビニル共重合体を公知の方法によりケン化することにより製造することができる。例えば、エチレン−酢酸ビニル共重合体を粒状又は粉末状のまま、低級アルコール等に分散させ、アルカリ触媒を用いてケン化反応させた後、低級アルコールと触媒を濾過除去し、さらに低級アルコールで洗浄し、乾燥させる、いわゆる「不均一ケン化法」等により、製造することができる。また、高ケン化率のエチレン−酢酸ビニル共重合体ケン化物は、特開平７−５３６３１号公報に記載された方法、すなわち、エチレン−酢酸ビニル共重合体を有機溶媒中、金属アルコラートを用いてケン化する際に、アルカリ金属水酸化物の共存下に実施する方法等で製造することができる。
【００１６】
このようにして得られるエチレン及び酢酸ビニルを含有し、酢酸ビニルの含有割合が２８〜４２質量％の重合性組成物から成るエチレン−酢酸ビニル共重合体のケン化物であって、かつ、ケン化度が１０〜８０質量％の部分ケン化エチレン−酢酸ビニル共重合体のメルトマスフローレートは、温度１９０℃、荷重２．１６ｋｇの条件下で１．０〜５０．０ｇ／１０分の範囲が好ましい。
【００１７】
エチレン及び酢酸ビニルを含有し、酢酸ビニルの含有割合が２８〜４２質量％の重合性組成物から成るエチレン−酢酸ビニル共重合体としては、この範囲に入るもので、かつ、部分ケン化後の部分ケン化エチレン−酢酸ビニル共重合体の物性が上記した範囲に入るものであれば、特に制限なく、使用することができる。
【００１８】
そのようなエチレン−酢酸ビニル共重合体の市販品としては、例えば、「エバフレックスＰ２８０５」（三井・デュポンポリケミカル（株）製：共重合体を構成する酢酸ビニルの割合＝２８質量％）、「エバフレックス４０ＬＸ」（三井・デュポンポリケミカル（株）製：共重合体を構成する酢酸ビニルの割合＝４１質量％）、などが挙げられる。
【００１９】
エチレン及び酢酸ビニルを含有し、酢酸ビニルの含有割合が２８〜４２質量％の重合性組成物から成るエチレン−酢酸ビニル共重合体のケン化物であって、かつ、ケン化度が１０〜８０質量％の部分ケン化エチレン−酢酸ビニル共重合体の市販品としては、例えば、「テクノリンクＲ４００」（田岡化学工業（株）製：ケン化度＝６０質量％：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝４２質量％）、「テクノリンクＲ４００−８０」（同社製：ケン化度８０質量％：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝４２質量％）、「テクノリンクＫ４３１−１０」（同社製：ケン化度１０質量％：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝２８質量％）、「テクノリンクＫ４３１−６０」（同社製：ケン化度６０質量％：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝２８質量％）、「テクノリンクＫ４３１−８０」（同社製：ケン化度８０質量％：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝２８質量％）、などが挙げられる。
【００２０】
本発明で使用する金属水酸化物としては、例えば、水酸化マグネシウム、水酸化アルミニウム、水酸化カルシウム、などが挙げられるが、耐水性に優れる水酸化マグネシウム及び水酸化アルミニウムが特に好ましい。金属水酸化物は、その表面をシランカップリング剤の如き表面処理剤で処理して、加工性や耐水性向上させたものを用いることもできる。表面処理剤の種類や量は、得られる難燃性樹脂組成物の特性に影響を与えない。また、水酸化マグネシウムの合成品と天然品での差は見られない。
【００２１】
部分ケン化エチレン−酢酸ビニル共重合体と金属水酸化物の割合は質量比で４０：６０〜９０：１０であることが好ましい。金属水酸化物が１０質量％未満であると、十分な難燃性及び耐トラッキング性が得られず、また、６０質量％より多いと、機械的特性の低下が著しく、実用に耐えない。
【００２２】
本発明の難燃性樹脂組成物は、高度な難燃性、機械的特性、加工性を有し、Ｔダイ、インフレーション等の押出成形、射出成形、異型押出成形等種々の加工が可能であり、種々の成形体を得ることができる。
【００２３】
本発明の難燃性樹脂組成物は、特にその優れた特性から、フィルム、シート、粘着フィルムの基材フィルム又はシート、クランプカバー、電線防護管、電線被膜に有用である。
【００２４】
本発明の難燃性樹脂組成物に使用する部分ケン化エチレン−酢酸ビニル共重合体に電子線の如き活性エネルギー線を照射すると、そのエネルギーにより共重合体中に残存するポリエチレン等に残っている二重結合や主鎖等が切断されラジカル（架橋点）が発生し、これらのラジカルの結合により架橋され網目構造となり、耐熱性や強度が向上することが知られている。この架橋反応を促進するために、被照射物に架橋助剤等を添加することもできる。架橋助剤としては、一般に、分子中に二重結合を有する化合物が挙げられる。本発明の難燃性樹脂組成物は、必要に応じて、上記架橋助剤を添加し、シートおよびフィルム等に成形した後、電子線等を使用して、適度に架橋させることによって、他の特性を低下させることなく、機械的特性と耐熱性を向上することもできる。
【００２５】
粘着フィルムは、本発明の難燃性樹脂組成物を用いて作成したフィルムあるいはシートに、公知の粘着剤、例えば、アクリル系粘着剤、ゴム系粘着剤等を用いて、公知慣用の方法で粘着剤層を形成することによって製造することができる。
【００２６】
本発明の難燃性樹脂組成物には、必要に応じて、シリカ、炭酸カルシウム、タルク等の無機化合物、フェノール系、チオエーテル系、ホスファイト系、ラクトン系、ビタミン類等の酸化防止剤、ベンゾトリアゾール系、ベンゾフェノン系、ベンゾエート系、トリアジン系等の紫外線吸収剤、ヒンダードアミン系等の耐光安定剤、金属不活性化剤、シリコーン系、フッソ系、アマイド系等の離型及びメヤニ防止及び滑剤、金属石鹸、アマイド系等の分散剤、染料や有機系及び無機系顔料等の着色剤、結晶核剤、帯電防止剤等を添加することができる。
【００２７】
また、本発明の難燃性樹脂組成物は、特にポリアミドエラストマーとの相溶性に優れているので、本発明の難燃性樹脂組成物にポリアミドエラストマーを添加し、種々の機械的特性を低下させずに、耐熱性を向上させることができる。ただし、ポリアミドエラストマーを添加した場合、燃焼時のシアン発生は懸念される。また、本発明の難燃性樹脂組成物に、エチレン−酢酸ビニル共重合体、エチレン−エチルアクリレート共重合体、エチレン−メチルメタアクリレート共重合体を添加することもできる。これらの共重合体を添加した場合には、やや相溶性に問題があり、機械的強度は低下するものの、難燃性を維持することができる。
【００２８】
本発明の難燃性樹脂組成物は、構成する材料が、炭素原子、水素原子、酸素原子及び金属から成るので、燃焼させても、有毒なハロゲン系ガス、ダイオキシン、シアン等を発生しないことが明らかである。
【００２９】
また、本発明の難燃性樹脂組成物は、加工性に優れ、種々の成形体を容易に得ることができるので、本発明の難燃性樹脂組成物は、その優れた特性から、シート、フィルム、粘着テープの基材フィルム又はシート、電線被膜、クランプカバー、電線防護管又は筐体の成形材料に用いることができる。
【００３０】
【実施例】
以下、実施例及び比較例を挙げて本発明を具体的に説明する。なお、実施例及び比較例に用いた各成分の詳細及び試験方法、評価を例示するが、本発明の趣旨を逸脱しない限り、本発明はこれらの実施例の範囲に限定されるものではない。なお、実施例及び比較例における「％」は、特に断りがない限り、質量基準である。
【００３１】
＜実施例１＞
「エバフレックス４０ＬＸ」（三井デュポンポリケミカル（株）製のエチレン−酢酸ビニル共重合体：共重合体を構成する酢酸ビニルの割合＝４１％）を公知のケン化法によりケン化し、ケン化度が１０％の部分ケン化エチレン−酢酸ビニル共重合体（以下、「ＥＶＯＨ１」と略す）を得た。
【００３２】
「ＥＶＯＨ１」９０％及び「キスマ５Ｐ」（協和化学工業（株）製のシラン処理合成水酸化マグネシウム：以下、「Ｍｇ１」と略す）１０％をミキサーにて混合し、２軸押出機にて１６０℃で溶融混練した後、ペレット化した。得られたペレットを用いて、１８０℃の熱プレス、水冷の冷却プレスにて１ｍｍ厚、２ｍｍ厚シートを作成した。また、Ｔダイにて１６０℃で０．１ｍｍ厚シートを作成した。
【００３３】
＜実施例２＞
実施例１において、配合割合を「ＥＶＯＨ１」４０％及び「Ｍｇ１」６０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００３４】
＜実施例３＞
実施例１において、配合割合を「テクノリンクＲ４００」（田岡化学工業（株）製のケン化度６０％の部分ケン化エチレン−酢酸ビニル共重合体：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝４２％）（以下、「ＥＶＯＨ２」と略す）９０％及び「Ｍｇ１」１０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００３５】
＜実施例４＞
実施例１において、配合割合を「ＥＶＯＨ２」４０％及び「Ｍｇ１」６０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００３６】
＜実施例５＞
実施例１において、配合割合を「テクノリンクＲ４００−８０」（田岡化学工業（株）製のケン化度８０％の部分ケン化エチレン−酢酸ビニル共重合体：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝４２％）（以下、「ＥＶＯＨ３」と略す）９０％及び「Ｍｇ１」１０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００３７】
＜実施例６＞
実施例１において、配合割合を「ＥＶＯＨ３」４０％及び「Ｍｇ１」６０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００３８】
＜実施例７＞
実施例１において、配合割合を「テクノリンクＫ４３１−１０」（田岡化学工業（株）製のケン化度１０％の部分ケン化エチレン−酢酸ビニル共重合体：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝２８％）（以下、「ＥＶＯＨ４」と略す）９０％及び「Ｍｇ１」１０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００３９】
＜実施例８＞
実施例１において、配合割合を「ＥＶＯＨ４」４０％及び「Ｍｇ１」６０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００４０】
＜実施例９＞
実施例１において、配合割合を「テクノリンクＫ４３１−６０」（田岡化学工業（株）製のケン化度６０％の部分ケン化エチレン−酢酸ビニル共重合体：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝２８％）（以下、「ＥＶＯＨ５」と略す）９０％及び「Ｍｇ１」１０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００４１】
＜実施例１０＞
実施例１において、配合割合を「ＥＶＯＨ５」４０％及び「Ｍｇ１」６０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００４２】
＜実施例１１＞
実施例１において、配合割合を「テクノリンクＫ４３１−８０」（田岡化学工業（株）製のケン化度８０％の部分ケン化エチレン−酢酸ビニル共重合体：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝２８％）（以下、「ＥＶＯＨ６」と略す）９０％及び「Ｍｇ１」１０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００４３】
＜実施例１２＞
実施例１において、配合割合を「ＥＶＯＨ６」４０％及び「Ｍｇ１」６０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００４４】
＜実施例１３＞
実施例１において、配合割合を「ＥＶＯＨ２」７０％及び「Ｍｇ１」３０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００４５】
＜実施例１４＞
実施例１において、配合割合を「ＥＶＯＨ２」７０％及び「キスマ５Ａ」（協和化学工業（株）製の脂肪酸処理合成水酸化マグネシウム：以下、「Ｍｇ２」と略す）３０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００４６】
＜実施例１５＞
実施例１において、配合割合を「ＥＶＯＨ２」７０％及び「マグシーズＮ−１」（神島化学工業（株）製の天然水酸化マグネシウム：以下、「Ｍｇ３」と略す）３０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００４７】
＜実施例１６＞
実施例１において、配合割合を「ＥＶＯＨ２」７０％及び「ハイジライトＨ−３２ＳＴ」（昭和電工（株）製のシラン処理水酸化アルミニウム：以下、「ＡＬ」と略す）３０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００４８】
＜実施例１７＞
実施例１において、配合割合を「ＥＶＯＨ２」７０％、「Ｍｇ１」２０％及び「ＡＦＦ９５」（ファイマテック（株）製の炭酸カルシウム）１０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００４９】
＜実施例１８＞
実施例１において、配合割合を「ＥＶＯＨ２」７０％、「Ｍｇ１」２７％及び「ＤＣ４−７０８１」（東レ・ダウコーニング（株）製のシリコーン）３％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００５０】
＜比較例１＞
実施例１において、配合割合を「エバフレックス４０ＬＸ」（三井・デュポンポリケミカル（株）製のエチレン−酢酸ビニル共重合体：共重合体を構成する酢酸ビニルの割合＝４１％）（以下、「ＥＶＡ１」と略す）９０％及び「Ｍｇ１」１０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００５１】
＜比較例２＞
実施例１において、配合割合を「ＥＶＡ１」４０％及び「Ｍｇ１」６０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００５２】
＜比較例３＞
実施例１において、配合割合を「エバフレックスＰ２８０５」（三井・デュポンポリケミカル（株）製のエチレン−酢酸ビニル共重合体：共重合体を構成する酢酸ビニルの割合＝２８％）（以下ＥＶＡ２と略す）９０％及び「Ｍｇ１」１０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００５３】
＜比較例４＞
実施例１において、配合割合を「ＥＶＡ２」４０％及び「Ｍｇ１」６０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００５４】
＜比較例５＞
実施例１において、配合割合を「テクノリンクＲ１００」（田岡化学工業（株）製のケン化度９５％の部分ケン化エチレン−酢酸ビニル共重合体：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝４２％）（以下、「ＥＶＯＨ７」と略す）９０％及び「Ｍｇ１」１０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００５５】
＜比較例６＞
実施例１において、配合割合を「ＥＶＯＨ７」４０％及び「Ｍｇ１」６０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００５６】
＜比較例７＞
実施例１において、配合割合を「テクノリンクＫ４００」（田岡化学工業（株）製のケン化度５０％の部分ケン化エチレン−酢酸ビニル共重合体：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝２５％）（以下、「ＥＶＯＨ８」と略す）９０％及び「Ｍｇ１」１０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００５７】
＜比較例８＞
実施例１において、配合割合を「ＥＶＯＨ８」４０％及び「Ｍｇ１」６０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００５８】
＜比較例９＞
実施例１において、配合割合を「テクノリンクＫ１３１」（田岡化学工業（株）製のケン化度９５％の部分ケン化エチレン−酢酸ビニル共重合体：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝２８％）（以下、「ＥＶＯＨ９」と略す）９０％及び「Ｍｇ１」１０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００５９】
＜比較例１０＞
実施例１において、配合割合を「ＥＶＯＨ９」４０％及び「Ｍｇ１」６０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００６０】
＜比較例１１＞
実施例１において、配合割合を「ＥＶＯＨ２」３５％、「ＥＶＡ１」３５％及び「Ｍｇ１」３０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００６１】
＜比較例１２＞
実施例１において、配合割合を「ＥＶＯＨ２」３５％、「アクリフトＷＨ２０６」（住友化学工業（株）製のエチレン−メチルメタアクリレート共重合体：共重合体を構成するメチルメタアクリレートの割合＝２０％）３５％及び「Ｍｇ１」３０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００６２】
＜比較例１３＞
実施例１において、配合割合を「ＥＶＯＨ２」３５％、「ＴＰＡＥ−８」（富士化成工業（株）製のポリエーテルエステルアミドエラストマー）３５％及び「Ｍｇ１」３０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００６３】
＜比較例１４＞
実施例１において、配合割合を「ＥＶＯＨ２」７０％及び「ＭＣ６４０」（日産化学工業（株）製のメラミンシアヌレート）（以下、「ＭＣＡ」と略す）３０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００６４】
＜比較例１５＞
実施例１において、配合割合を「ＥＶＯＨ２」７０％、「Ｍｇ１」２０％及び「ＭＣＡ」１０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００６５】
＜比較例１６＞
実施例１において、配合割合を「ＥＶＯＨ２」７０％、「Ｍｇ１」２０％及び「ＦＰ６００」（旭電化工業（株）製の縮合リン酸エステル）１０％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００６６】
＜比較例１７＞
「ＥＶＯＨ２」を単独で用いて、１８０℃の熱プレス、水冷の冷却プレスにて１ｍｍ厚、２ｍｍ厚シートを、またＴダイにて１６０℃で０．１ｍｍ厚シートを作成した。
【００６７】
＜比較例１８＞
「ＥＶＯＨ５」を単独で用いて、１８０℃の熱プレス、水冷の冷却プレスにて１ｍｍ厚、２ｍｍ厚シートを、またＴダイにて１６０℃で０．１ｍｍ厚シートを作成した。
【００６８】
＜比較例１９＞
実施例１において、配合割合を「ＥＶＯＨ２」３５％及び「Ｍｇ１」６５％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００６９】
＜比較例２０＞
実施例１において、配合割合を「ＥＶＯＨ５」３５％及び「Ｍｇ１」６５％に変更した以外は、実施例１と同様にして、０．１ｍｍ厚、１ｍｍ厚、２ｍｍ厚シートを作成した。
【００７０】
＜評価＞
実施例１〜１８及び比較例１〜２０で得た各シートについて、以下に記載した方法に従って評価を行い、その結果を表１〜１０にまとめて示した。
【００７１】
（１）燃焼性１
ＵＬ９４の垂直燃焼試験を厚さ１ｍｍのシートを用いて実施した。Ｖ−０、Ｖ−２相当に適合するか判定した。適合する場合には「Ｖ−０」あるいは「Ｖ−２」と表記し、適合しない場合は「不適合」と表記した。
【００７２】
（２）燃焼性２
ＵＬ９４の薄物燃焼試験を厚さ０．１ｍｍのシートを用いて実施した。ＶＴＭ−０、ＶＴＭ−２相当に適合するか判定した。適合する場合には「ＶＴＭ−０」あるいは「ＶＴＭ−２」と表記し、適合しない場合は「不適合」と表記した。
【００７３】
（３）燃焼性３
ＪＩＳ Ａ １３２２に準拠して、厚さ０．１ｍｍのシートを用いて評価した。防炎１級、防炎２級に適合するか判定した。適合する場合には「防炎１級」あるいは「防炎２級」と表記し、適合しない場合は「不適合」と表記した。
【００７４】
（４）引張強度（単位＝ＭＰａ）
ＪＩＳ Ｋ ７１１３ に準拠して実施した。厚さ１ｍｍのシートを使用し、ＪＩＳ Ｋ ６２５１の３号試験片にて、引張速度２００ｍｍ／分で測定した。
【００７５】
（５）引張伸び（単位＝％）
ＪＩＳ Ｋ ７１１３ に準拠して実施した。厚さ１ｍｍのシートを使用し、ＪＩＳ Ｋ ６２５１の３号試験片にて、引張速度２００ｍｍ／分で測定した。
【００７６】
（６）低温脆化温度（単位＝℃）
ＪＩＳ Ｋ ７２１６ に準拠して厚さ２ｍｍのシートを用いて実施した。測定は１０℃間隔とした。表中では「脆化温度」と表記した。
【００７７】
（７）耐トラッキング性
ＪＩＳ Ｃ ３００５ の塩水噴霧耐トラッキング性試験に準拠し、厚さ２ｍｍのシートを用いて評価した。なお、表中では「耐トラ」と記した。噴霧回数１０１回以上を適合、１０１回未満を不適合で表示した。
【００７８】
【表１】
【表２】
【表３】
【表４】
【表５】
【表６】
【表７】
【表８】
【表９】
【表１０】
表１から表１０に記載した略号は以下の通りである。
ＥＶＯＨ１：「エバフレックス４０ＬＸ」（三井デュポンポリケミカル（株）製のエチレン−酢酸ビニル共重合体：共重合体を構成する酢酸ビニルの割合＝４１％）を公知のケン化法によりケン化し、ケン化度が１０％の部分ケン化エチレン−酢酸ビニル共重合体
ＥＶＯＨ２：「テクノリンクＲ４００」（田岡化学工業（株）製のケン化度６０％の部分ケン化エチレン−酢酸ビニル共重合体：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝４２％）
ＥＶＯＨ３：「テクノリンクＲ４００−８０」（田岡化学工業（株）製のケン化度８０％の部分ケン化エチレン−酢酸ビニル共重合体：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝４２％）
ＥＶＯＨ４：「テクノリンクＫ４３１−１０」（田岡化学工業（株）製のケン化度１０％の部分ケン化エチレン−酢酸ビニル共重合体：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝２８％）
ＥＶＯＨ５：「テクノリンクＫ４３１−６０」（田岡化学工業（株）製のケン化度６０％の部分ケン化エチレン−酢酸ビニル共重合体：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝２８％）
ＥＶＯＨ６：「テクノリンクＫ４３１−８０」（田岡化学工業（株）製のケン化度８０％の部分ケン化エチレン−酢酸ビニル共重合体：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝２８％）
【００８９】
ＥＶＯＨ７：「テクノリンクＲ１００」（田岡化学工業（株）製のケン化度９５％の部分ケン化エチレン−酢酸ビニル共重合体：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝４２％）
ＥＶＯＨ８：「テクノリンクＫ４００」（田岡化学工業（株）製のケン化度５０％の部分ケン化エチレン−酢酸ビニル共重合体：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝２５％）
ＥＶＯＨ９：「テクノリンクＫ１３１」（田岡化学工業（株）製のケン化度９５％の部分ケン化エチレン−酢酸ビニル共重合体：ケン化前のエチレン−酢酸ビニル共重合体を構成する酢酸ビニルの割合＝２８％）
【００９０】
ＥＶＡ１：「エバフレックス４０ＬＸ」（三井・デュポンポリケミカル（株）製のエチレン−酢酸ビニル共重合体：共重合体を構成する酢酸ビニルの割合＝４１％）
ＥＶＡ２：「エバフレックスＰ２８０５」（三井・デュポンポリケミカル（株）製のエチレン−酢酸ビニル共重合体：共重合体を構成する酢酸ビニルの割合＝２８％）
【００９１】
ＴＰＡＥ：「ＴＰＡＥ−８」（富士化成工業（株）製のポリエーテルエステルアミドエラストマー）
ＥＭＭＡ：「アクリフトＷＨ２０６」（住友化学工業（株）製のエチレン−メチルメタアクリレート共重合体：共重合体を構成するメチルメタクリレートの割合＝２０％）
【００９２】
Ｍｇ１：「キスマ５Ｐ」（協和化学工業（株）製のシラン処理合成水酸化マグネシウム）
Ｍｇ２：「キスマ５Ａ」（協和化学工業（株）製の脂肪酸処理合成水酸化マグネシウム）
Ｍｇ３：「マグシーズＮ−１」（神島化学工業（株）製の天然水酸化マグネシウム
【００９３】
ＡＬ：「ハイジライトＨ−３２ＳＴ」（昭和電工（株）製のシラン処理水酸化アルミニウム）
Ｐ：「ＦＰ６００」（旭電化工業（株）製の縮合リン酸エステル）
ＣＣＡ：「ＡＦＦ９５」（ファイマテック（株）製の炭酸カルシウム）
ＭＣＡ：「ＭＣ６４０」（日産化学工業（株）製のメラミンシアヌレート）
ＳＩ：「ＤＣ４−７０８１」（東レ・ダウコーニング（株）製のシリコーン）
【００９４】
表１〜１０に示した結果から、実施例１〜１２の難燃性樹脂組成物は、エチレン及び酢酸ビニルを含有し、酢酸ビニルの含有割合が２８〜４２質量％の重合性組成物から成るエチレン−酢酸ビニル共重合体のケン化物であって、かつ、ケン化度が１０〜８０質量％の部分ケン化エチレン−酢酸ビニル共重合体を使用し、部分ケン化エチレン−酢酸ビニル共重合体と水酸化マグネシウムの割合が質量比で４０：６０〜９０：１０の範囲に限定しているので、難燃性、機械的特性、低温脆化温度、耐トラッキング性に優れることが理解できる。また、実施例１３〜１６の結果から、難燃性樹脂組成物に使用する金属水酸化物の種類には影響されず、水酸化アルミニウムも水酸化マグネシウムと同様の特性が得られることが理解できる。さらに、実施例１７及び実施例１８の結果から、有毒ガス発生の危険性が無い特定の無機化合物や有機化合物を添加しても、その特性が低下しないことが理解できる。
【００９５】
一方、比較例１〜４の難燃性樹脂組成物は、ケン化をしていないエチレン−酢酸ビニル共重合体を使用しているので、十分な難燃性が得られないことが理解できる。また、比較例５〜１０の難燃性樹脂組成物は、部分ケン化エチレン−酢酸ビニル共重合体として、酢酸ビニルの含有割合が２８質量％未満の重合性組成物から成るエチレン−酢酸ビニル共重合体のケン化物、あるいは、酢酸ビニルの含有割合が２８〜４２質量％の重合性組成物から成るエチレン−酢酸ビニル共重合体のケン化物であって、かつ、ケン化度が１０質量％未満又は８０質量％よりも高い部分ケン化エチレン−酢酸ビニル共重合体を使用しているので、十分な難燃性や低温脆化温度が得られないことが理解できる。さらに、比較例１１及び１２の難燃性樹脂組成物は、エチレン−酢酸ビニル共重合体を使用している、あるいはエチレン−メチルメタアクリレート共重合体と部分ケン化エチレン−酢酸ビニル共重合体とを併用しているので、十分な難燃性は得られるものの、機械的特性の低下が著しいことが理解できる。
【００９６】
また、比較例１３の難燃性樹脂組成物は、ポリアミドエラストマーと部分ケン化エチレン−酢酸ビニル共重合体を併用しているので、部分ケン化エチレン−酢酸ビニル共重合体単独より良好な諸特性が得られる。しかしながら、ポリアミドエラストマーは窒素原子を有しているので、燃焼時にシアンを発生する可能性があることが理解できる。また、比較例１４の難燃性樹脂組成物は、難燃剤としてメラミンシアヌレートを使用することによって、十分な難燃性と機械的特性等が得られるものの、耐トラッキング性が得られないばかりでなく、難燃剤分子に窒素原子を有しているので、燃焼時にシアンを発生する可能性があることが理解できる。さらに、比較例１５及び比較例１６の難燃性樹脂組成物は、難燃剤として水酸化マグネシウムとメラミンシアヌレートあるいは縮合リン酸エステルを併用することによって、十分な難燃性が得られるものの、特段に優れた併用効果は見出せない。また、難燃剤分子に窒素原子あるいはリン原子を有しているので、燃焼時にシアンあるいはホスフィンを発生する可能性があることが理解できる。
【００９７】
また、比較例１７及び比較例１８の樹脂組成物は、本願発明で規定した特定の部分ケン化エチレン−酢酸ビニル共重合体を単独で使用したものであり、金属水酸化物を含まないので、耐トラッキング性が得られないことが理解できる。また、金属水酸化物を併用しない場合、部分ケン化エチレン−酢酸ビニル共重合体の原料として、エチレン−酢酸ビニル共重合体を構成するモノマー中の酢酸ビニル含有量が高いエチレン−酢酸ビニル共重合体を用いることによって、得られた樹脂組成物は、不十分ながらも、難燃性が改善される傾向にあることが理解できる。
【００９８】
さらに、比較例１９及び比較例２０の難燃性樹脂組成物は、本願発明で規定した特定の部分ケン化エチレン−酢酸ビニル共重合体に、本願発明で規定した割合を上回る金属水酸化物を混合したものであるので、十分な機械的特性や低温脆化温度が得られないだけではなく、十分な難燃性が得られないことがあることが理解できる。
【００９９】
【発明の効果】
本発明の難燃性樹脂組成物は、柔軟で、機械的特性の低下がなく、高度な難燃性を有し、燃焼時に有毒なガスを発生せず、しかも、成形・加工性に優れているので、シート、フィルム、電線被覆、筐体への加工が容易である。従って、本発明の難燃性樹脂組成物は、クランプカバー及び電線防護管等の電設材料、建築材料及び工事用シート等の工業用フィルム、シート、粘着テープ及び一般家庭用の壁紙、電線被覆材料、電子部品成形材料等に応用することができ、さらに他の素材と組み合わせて使用することができるので、工業的価値が高いものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention is flexible, does not generate toxic halogen-based gas, dioxin, cyanide, etc. during combustion, has high flame retardancy, has excellent mechanical properties, has tracking resistance, and is molded and processed. The present invention relates to a flame-retardant resin composition having excellent heat resistance and a molded article thereof.
[0002]
[Prior art]
Conventionally, in various fields, various materials excellent in flexibility, flexibility and the like have been used, and among them, vinyl chloride resin is widely used due to its properties. However, in recent years, environmental issues have been emphasized, and in particular, vinyl chloride resin has a problem that dioxins are generated during combustion. Therefore, various thermoplastic resins and thermoplastic elastomers have been studied as alternatives to vinyl chloride resins.
[0003]
On the other hand, fire safety and the like require flame-retardant alternative materials, and in order to obtain high flame retardancy suitable for the UL94 vertical test, organic compounds having halogen atoms, antimony trioxide, etc. Must be used, and the generation of dioxins has become a problem during the combustion as in the case of the vinyl chloride resin.
[0004]
Therefore, a flame-retardant resin composition not using an organic compound having a halogen atom has been studied, and many compositions have been proposed so far. For example, magnesium hydroxide, a nitrogen-based flame retardant, or a phosphorus-based flame retardant is added to a resin called an olefin-based resin such as polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and polypropylene. Is the way. However, it is necessary to add a large amount of a flame retardant in order to obtain a high flame retardancy suitable for the vertical test of UL94. I couldn't say.
[0005]
In order to improve the mechanical properties, a flame-retardant resin composition comprising a polyolefin resin, a saponified ethylene-vinyl acetate copolymer, and a metal hydroxide has been proposed (see Patent Document 1). However, the saponified ethylene-vinyl acetate copolymer has improved mechanical properties by using the saponified ethylene-vinyl acetate copolymer alone as compared with the ethylene-vinyl acetate copolymer, but the saponified ethylene-vinyl acetate copolymer has Since there is a problem in the compatibility between the copolymer and the ethylene-vinyl acetate copolymer, the mechanical properties of these mixtures are not improved.
[0006]
Further, the present inventors have proposed a flame-retardant resin composition in which melamine cyanurate or the like is added to a thermoplastic polyamide elastomer or a partially saponified ethylene-vinyl acetate copolymer (see Patent Document 2). Although the composition has sufficient flame retardancy and mechanical strength, there is a risk that a cyanide compound may be generated during combustion because nitrogen atoms are included in atoms constituting the resin and the flame retardant. Therefore, there is a demand for a flame-retardant resin composition having better safety.
[0007]
[Patent Document 1]
JP 2001-139741 A
[Patent Document 2]
JP-A-10-10128
[0008]
[Problems to be solved by the invention]
The problem to be solved by the present invention is that it is flexible, does not generate toxic gases such as halogen-based gas, dioxin, and cyan when burning, has high flame retardancy, has tracking resistance, and has mechanical properties. An object of the present invention is to provide a flame-retardant resin composition and a molded article thereof, which are not deteriorated and are excellent in moldability and processability.
[0009]
More specifically, in consideration of use for a film, a sheet, an adhesive film, a clamp cover, and an electric wire protection tube, the flame retardancy is equivalent to UL94 V-2 at a thickness of 1 mm, and VTM-0 at a thickness of 0.1 mm. Equivalent, equivalent to JIS A 1322 flameproof grade 2 or higher, mechanical properties such as tensile strength 10 MPa or more, tensile elongation 150% or more, low temperature embrittlement temperature -20 ° C or less, JIS C 3005 salt spray tracking resistance test An object of the present invention is to provide a flame-retardant resin composition and a molded article thereof that are suitable for 101 times or more.
[0010]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object, and as a result, found that the above object can be achieved by adding a metal hydroxide to a specific partially saponified ethylene-vinyl acetate copolymer. The present invention has been completed.
[0011]
That is, the present invention provides a flame-retardant resin composition containing a partially saponified ethylene-vinyl acetate copolymer and a metal hydroxide, wherein (1) the partially saponified ethylene- The vinyl acetate copolymer is a saponified ethylene-vinyl acetate copolymer comprising a polymerizable composition containing ethylene and vinyl acetate and having a vinyl acetate content of 28 to 42% by mass, and A partially saponified ethylene-vinyl acetate copolymer having a degree of hydrolysis of 10 to 80% by mass, and (2) the ratio of the partially saponified ethylene-vinyl acetate copolymer to the metal hydroxide is 40 by mass. : 60 to 90:10
The present invention provides a flame-retardant resin composition characterized by the following.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the flame-retardant resin composition of the present invention and a molded article thereof will be described in detail.
[0013]
The partially saponified ethylene-vinyl acetate copolymer used in the present invention is an ethylene-vinyl acetate copolymer comprising a polymerizable composition containing ethylene and vinyl acetate and having a vinyl acetate content of 28 to 42% by mass. And a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 10 to 80% by mass. An ethylene-vinyl acetate copolymer before saponification, which is a raw material of a partially saponified ethylene-vinyl acetate copolymer, having a vinyl acetate content of less than 28% by mass in all monomers constituting the copolymer When used, a resin composition having an intended thickness of 1 mm and UL94 equivalent to V-2, a thickness of 0.1 mm equivalent to VTM-0, and a JIS A1322 flame-retardant class 2 equivalent or higher flame-retardant resin composition I can't get it. In addition, when the ethylene-vinyl acetate copolymer before the saponification has a vinyl acetate content of more than 42% by mass in all the monomers constituting the copolymer, mechanical properties are significantly reduced. Not practical.
[0014]
Further, when a partially saponified ethylene-vinyl acetate copolymer having a degree of saponification of higher than 80% by mass is used, the mechanical strength of the molded article composed of the obtained flame-retardant resin composition decreases and the low-temperature embrittlement temperature decreases. The increase is remarkable, and the intended flame-retardant resin composition cannot be obtained. Furthermore, when a partially saponified ethylene-vinyl acetate copolymer having a degree of saponification lower than 10% by mass is used, a resin composition having desired flame retardancy and mechanical strength cannot be obtained. As described above, in order to obtain good mechanical properties and low-temperature embrittlement temperature, the saponification degree needs to be 10 to 80% by mass.
[0015]
The partially saponified ethylene-vinyl acetate copolymer can be produced by saponifying the ethylene-vinyl acetate copolymer by a known method. For example, after dispersing the ethylene-vinyl acetate copolymer in a granular or powdery state in a lower alcohol or the like, and performing a saponification reaction using an alkali catalyst, the lower alcohol and the catalyst are removed by filtration, and further washed with a lower alcohol. Then, it can be manufactured by a so-called “heterogeneous saponification method” or the like. Further, a saponified ethylene-vinyl acetate copolymer having a high saponification rate can be obtained by a method described in JP-A-7-53631, that is, using an ethylene-vinyl acetate copolymer in an organic solvent by using a metal alcoholate. When saponifying, it can be produced by a method carried out in the presence of an alkali metal hydroxide.
[0016]
A saponified ethylene-vinyl acetate copolymer comprising a polymerizable composition containing the thus obtained ethylene and vinyl acetate and having a vinyl acetate content of 28 to 42% by mass. The melt mass flow rate of the partially saponified ethylene-vinyl acetate copolymer having a degree of 10 to 80% by mass is preferably in the range of 1.0 to 50.0 g / 10 minutes at a temperature of 190 ° C. and a load of 2.16 kg. .
[0017]
As an ethylene-vinyl acetate copolymer comprising a polymerizable composition containing ethylene and vinyl acetate and having a vinyl acetate content of 28 to 42% by mass, the ethylene-vinyl acetate copolymer falls within this range, and after the partial saponification. The partially saponified ethylene-vinyl acetate copolymer can be used without any particular limitation as long as the physical properties fall within the above ranges.
[0018]
As commercially available products of such an ethylene-vinyl acetate copolymer, for example, “Evaflex P2805” (manufactured by DuPont-Mitsui Polychemicals: ratio of vinyl acetate constituting the copolymer = 28% by mass), "Evaflex 40LX" (manufactured by Mitsui / Dupont Polychemical Co., Ltd .: ratio of vinyl acetate constituting the copolymer = 41% by mass), and the like.
[0019]
A saponified ethylene-vinyl acetate copolymer comprising a polymerizable composition containing ethylene and vinyl acetate and having a vinyl acetate content of 28 to 42% by mass, and a saponification degree of 10 to 80% by mass. As a commercially available product of a partially saponified ethylene-vinyl acetate copolymer, for example, "Technolink R400" (manufactured by Taoka Chemical Industry Co., Ltd .: saponification degree = 60% by mass: ethylene-vinyl acetate before saponification) Ratio of vinyl acetate constituting the copolymer = 42% by mass), "Technolink R400-80" (manufactured by the company: degree of saponification: 80% by mass: vinyl acetate constituting the ethylene-vinyl acetate copolymer before saponification) % = 42% by mass), "Technolink K431-10" (manufactured by the company: saponification degree: 10% by mass: ratio of vinyl acetate constituting the ethylene-vinyl acetate copolymer before saponification = 28% by mass) "Technolink K431-60" (manufactured by the company: saponification degree 60% by mass: ratio of vinyl acetate constituting the ethylene-vinyl acetate copolymer before saponification = 28% by mass), "Technolink K431-80" ( (Saponification degree: 80% by mass: ratio of vinyl acetate constituting the ethylene-vinyl acetate copolymer before saponification = 28% by mass).
[0020]
Examples of the metal hydroxide used in the present invention include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, and the like, and magnesium hydroxide and aluminum hydroxide, which have excellent water resistance, are particularly preferable. A metal hydroxide whose surface is treated with a surface treatment agent such as a silane coupling agent to improve processability and water resistance can also be used. The type and amount of the surface treatment agent do not affect the properties of the obtained flame retardant resin composition. In addition, there is no difference between synthetic and natural products of magnesium hydroxide.
[0021]
The ratio between the partially saponified ethylene-vinyl acetate copolymer and the metal hydroxide is preferably from 40:60 to 90:10 by mass. If the content of the metal hydroxide is less than 10% by mass, sufficient flame retardancy and tracking resistance cannot be obtained. If the content is more than 60% by mass, the mechanical properties are remarkably deteriorated, and the composition is not practical.
[0022]
The flame-retardant resin composition of the present invention has high flame retardancy, mechanical properties, and processability, and can be subjected to various processes such as extrusion molding such as T-die and inflation, injection molding, and profile extrusion molding. And various molded articles can be obtained.
[0023]
The flame-retardant resin composition of the present invention is useful for a film, a sheet, a base film or sheet of an adhesive film, a clamp cover, an electric wire protective tube, and an electric wire coating because of its particularly excellent properties.
[0024]
When the partially saponified ethylene-vinyl acetate copolymer used in the flame-retardant resin composition of the present invention is irradiated with an active energy ray such as an electron beam, the energy remains in the polyethylene and the like remaining in the copolymer. It is known that a double bond, a main chain or the like is cut to generate radicals (crosslinking points), and the radicals are crosslinked to form a network structure, thereby improving heat resistance and strength. In order to accelerate the crosslinking reaction, a crosslinking aid or the like may be added to the irradiated object. As the crosslinking aid, a compound having a double bond in the molecule is generally mentioned. The flame-retardant resin composition of the present invention, if necessary, is added with the above-mentioned crosslinking aid, formed into sheets, films, and the like, and then appropriately crosslinked by using an electron beam or the like, thereby obtaining another resin. The mechanical properties and heat resistance can be improved without lowering the properties.
[0025]
The pressure-sensitive adhesive film is adhered to a film or sheet prepared using the flame-retardant resin composition of the present invention, using a known pressure-sensitive adhesive, for example, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, or the like, by a known and common method. It can be manufactured by forming an agent layer.
[0026]
The flame-retardant resin composition of the present invention may contain, if necessary, an inorganic compound such as silica, calcium carbonate, and talc; a phenolic compound, a thioether compound; a phosphite compound; a lactone compound; an antioxidant such as a vitamin; UV absorbers such as triazoles, benzophenones, benzoates, and triazines; light stabilizers such as hindered amines; metal deactivators; mold release and lubricant prevention for silicones, fluorine, amides, etc. and lubricants, metals Soaps, dispersants such as amides, coloring agents such as dyes and organic and inorganic pigments, nucleating agents, antistatic agents and the like can be added.
[0027]
Further, since the flame-retardant resin composition of the present invention is particularly excellent in compatibility with the polyamide elastomer, a polyamide elastomer is added to the flame-retardant resin composition of the present invention to reduce various mechanical properties. Without increasing the heat resistance. However, when a polyamide elastomer is added, generation of cyan during combustion is a concern. Further, an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-methyl methacrylate copolymer can be added to the flame-retardant resin composition of the present invention. When these copolymers are added, there is a problem in compatibility a little, and although the mechanical strength is reduced, flame retardancy can be maintained.
[0028]
Since the constituent materials of the flame-retardant resin composition of the present invention are composed of carbon atoms, hydrogen atoms, oxygen atoms, and metals, they do not generate toxic halogen-based gas, dioxin, cyanide, etc. even when burned. it is obvious.
[0029]
Further, the flame-retardant resin composition of the present invention is excellent in processability and various molded articles can be easily obtained.Therefore, the flame-retardant resin composition of the present invention has a sheet, It can be used as a film, a base film or sheet of an adhesive tape, an electric wire coating, a clamp cover, an electric wire protective tube, or a molding material of a housing.
[0030]
【Example】
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The details, test methods, and evaluations of each component used in the examples and comparative examples are illustrated, but the present invention is not limited to the scope of the examples unless departing from the gist of the present invention. In the Examples and Comparative Examples, “%” is based on mass unless otherwise specified.
[0031]
<Example 1>
"Evaflex 40LX" (ethylene-vinyl acetate copolymer manufactured by DuPont-Mitsui Polychemicals Co., Ltd .: ratio of vinyl acetate constituting the copolymer = 41%) was saponified by a known saponification method, and the degree of saponification was determined. To obtain a partially saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as "EVOH1").
[0032]
90% of "EVOH1" and 10% of "Kisuma 5P" (a silane-treated synthetic magnesium hydroxide manufactured by Kyowa Chemical Industry Co., Ltd .; hereinafter abbreviated as "Mg1") are mixed by a mixer, and mixed with a twin-screw extruder. After melt-kneading at ℃, it was pelletized. Using the obtained pellets, a sheet having a thickness of 1 mm and a thickness of 2 mm was formed by a hot press at 180 ° C. and a water-cooled cooling press. Further, a 0.1 mm thick sheet was prepared at 160 ° C. using a T-die.
[0033]
<Example 2>
In Example 1, sheets having a thickness of 0.1 mm, 1 mm and 2 mm were prepared in the same manner as in Example 1 except that the mixing ratio was changed to "EVOH1" 40% and "Mg1" 60%.
[0034]
<Example 3>
In Example 1, the mixing ratio was "Technolink R400" (a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 60% manufactured by Taoka Chemical Industry Co., Ltd .: an ethylene-vinyl acetate copolymer before saponification). The ratio of vinyl acetate constituting: = 42%) (hereinafter abbreviated as "EVOH2"), except that it was changed to 90% and "Mg1" to 10%. A 2 mm thick sheet was made.
[0035]
<Example 4>
In Example 1, sheets having a thickness of 0.1 mm, 1 mm and 2 mm were prepared in the same manner as in Example 1 except that the mixing ratio was changed to “EVOH2” 40% and “Mg1” 60%.
[0036]
<Example 5>
In Example 1, the mixing ratio was "Technolink R400-80" (a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 80% manufactured by Taoka Chemical Industry Co., Ltd .: ethylene-vinyl acetate copolymer before saponification). The ratio of vinyl acetate constituting the polymer = 42%) (hereinafter abbreviated as “EVOH3”), except that it was changed to 90% and “Mg1” to 10%. A 2 mm thick sheet was prepared.
[0037]
<Example 6>
In Example 1, sheets having a thickness of 0.1 mm, 1 mm and 2 mm were prepared in the same manner as in Example 1 except that the mixing ratio was changed to "EVOH3" 40% and "Mg1" 60%.
[0038]
<Example 7>
In Example 1, the mixing ratio was changed to "Technolink K431-10" (a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 10% manufactured by Taoka Chemical Industry Co., Ltd .: ethylene-vinyl acetate copolymer before saponification). The ratio of vinyl acetate constituting the polymer = 28%) (hereinafter abbreviated as “EVOH4”), except that it was changed to 90% and “Mg1” to 10%. A 2 mm thick sheet was prepared.
[0039]
Example 8
In Example 1, sheets having a thickness of 0.1 mm, 1 mm and 2 mm were prepared in the same manner as in Example 1 except that the mixing ratio was changed to "EVOH4" 40% and "Mg1" 60%.
[0040]
<Example 9>
In Example 1, the mixing ratio was "Technolink K431-60" (a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 60% manufactured by Taoka Chemical Industry Co., Ltd .: ethylene-vinyl acetate copolymer before saponification). The ratio of vinyl acetate constituting the polymer = 28%) (hereinafter abbreviated as “EVOH5”), except that it was changed to 90% and “Mg1” to 10%. A 2 mm thick sheet was prepared.
[0041]
<Example 10>
In Example 1, sheets having a thickness of 0.1 mm, 1 mm and 2 mm were prepared in the same manner as in Example 1 except that the mixing ratio was changed to "EVOH5" 40% and "Mg1" 60%.
[0042]
<Example 11>
In Example 1, the mixing ratio was "Technolink K431-80" (a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 80% manufactured by Taoka Chemical Industry Co., Ltd .: ethylene-vinyl acetate copolymer before saponification). The ratio of vinyl acetate constituting the polymer = 28%) (hereinafter abbreviated as “EVOH6”), except that it was changed to 90% and “Mg1” to 10%. A 2 mm thick sheet was prepared.
[0043]
<Example 12>
In Example 1, sheets having a thickness of 0.1 mm, 1 mm and 2 mm were prepared in the same manner as in Example 1 except that the mixing ratio was changed to "EVOH6" 40% and "Mg1" 60%.
[0044]
<Example 13>
In Example 1, a sheet having a thickness of 0.1 mm, 1 mm and 2 mm was prepared in the same manner as in Example 1 except that the mixing ratio was changed to “EVOH2” 70% and “Mg1” 30%.
[0045]
<Example 14>
In Example 1, except that the mixing ratio was changed to 70% "EVOH2" and 30% "Kisuma 5A" (fatty acid-treated synthetic magnesium hydroxide manufactured by Kyowa Chemical Industry Co., Ltd .; hereinafter abbreviated as "Mg2"). In the same manner as in Example 1, a sheet having a thickness of 0.1 mm, 1 mm, and 2 mm was prepared.
[0046]
<Example 15>
In Example 1, except that the mixing ratio was changed to “EVOH2” 70% and “Magsee's N-1” (natural magnesium hydroxide manufactured by Kamishima Chemical Industry Co., Ltd .; hereinafter, abbreviated as “Mg3”) 30%. In the same manner as in Example 1, a sheet having a thickness of 0.1 mm, 1 mm, and 2 mm was prepared.
[0047]
<Example 16>
In Example 1, except that the mixing ratio was changed to 70% of "EVOH2" and 30% of "Heidilite H-32ST" (silane-treated aluminum hydroxide manufactured by Showa Denko KK; hereinafter, abbreviated as "AL"). In the same manner as in Example 1, a sheet having a thickness of 0.1 mm, 1 mm, and 2 mm was prepared.
[0048]
<Example 17>
In the same manner as in Example 1 except that the mixing ratio was changed to “EVOH2” 70%, “Mg1” 20%, and “AFF95” (calcium carbonate manufactured by Fimatec Co., Ltd.) 10% in Example 1, A sheet having a thickness of 0.1 mm, 1 mm and 2 mm was prepared.
[0049]
<Example 18>
Same as Example 1 except that the mixing ratio was changed to 70% "EVOH2", 27% "Mg1", and 3% "DC4-7081" (silicone manufactured by Dow Corning Toray) in Example 1. Then, a sheet having a thickness of 0.1 mm, 1 mm and 2 mm was prepared.
[0050]
<Comparative Example 1>
In Example 1, the compounding ratio was changed to “Evaflex 40LX” (ethylene-vinyl acetate copolymer manufactured by DuPont-Mitsui Polychemicals Co., Ltd .: the ratio of vinyl acetate constituting the copolymer = 41%) (hereinafter, “ A sheet having a thickness of 0.1 mm, 1 mm, and 2 mm was prepared in the same manner as in Example 1 except that 90% of EVA1) and 10% of Mg1 were used.
[0051]
<Comparative Example 2>
In Example 1, sheets having a thickness of 0.1 mm, 1 mm and 2 mm were prepared in the same manner as in Example 1 except that the mixing ratio was changed to "EVA1" 40% and "Mg1" 60%.
[0052]
<Comparative Example 3>
In Example 1, the blending ratio was changed to "Evaflex P2805" (ethylene-vinyl acetate copolymer manufactured by DuPont-Mitsui Polychemicals Co., Ltd .: the ratio of vinyl acetate constituting the copolymer = 28%) (hereinafter referred to as EVA2 (Abbreviated) A sheet having a thickness of 0.1 mm, 1 mm, and 2 mm was prepared in the same manner as in Example 1 except that 90% and “Mg1” were changed to 10%.
[0053]
<Comparative Example 4>
In Example 1, sheets having a thickness of 0.1 mm, 1 mm, and 2 mm were prepared in the same manner as in Example 1 except that the mixing ratio was changed to “EVA2” 40% and “Mg1” 60%.
[0054]
<Comparative Example 5>
In Example 1, the mixing ratio was changed to "Technolink R100" (a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 95% manufactured by Taoka Chemical Industry Co., Ltd .: an ethylene-vinyl acetate copolymer before saponification). The ratio of vinyl acetate constituting: = 42%) (hereinafter abbreviated as "EVOH7") 90% and "Mg1" Except for changing to 10%, a thickness of 0.1 mm, 1 mm, A 2 mm thick sheet was made.
[0055]
<Comparative Example 6>
In Example 1, a sheet having a thickness of 0.1 mm, 1 mm and 2 mm was prepared in the same manner as in Example 1 except that the mixing ratio was changed to “EVOH7” 40% and “Mg1” 60%.
[0056]
<Comparative Example 7>
In Example 1, the mixing ratio was "Technolink K400" (a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 50% manufactured by Taoka Chemical Industry Co., Ltd .: an ethylene-vinyl acetate copolymer before saponification). % Of vinyl acetate constituting 25%) (hereinafter abbreviated as “EVOH8”), except that it was changed to 90% and “Mg1” to 10%. A 2 mm thick sheet was made.
[0057]
<Comparative Example 8>
In Example 1, sheets having a thickness of 0.1 mm, 1 mm and 2 mm were prepared in the same manner as in Example 1 except that the mixing ratio was changed to “EVOH8” 40% and “Mg1” 60%.
[0058]
<Comparative Example 9>
In Example 1, the mixing ratio was "Technolink K131" (a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 95% manufactured by Taoka Chemical Industry Co., Ltd .: an ethylene-vinyl acetate copolymer before saponification). % Of vinyl acetate constituting 28%) (hereinafter abbreviated as “EVOH9”), except that it was changed to 90% and “Mg1” to 10%. A 2 mm thick sheet was made.
[0059]
<Comparative Example 10>
In Example 1, sheets having a thickness of 0.1 mm, 1 mm and 2 mm were prepared in the same manner as in Example 1 except that the mixing ratio was changed to “EVOH9” 40% and “Mg1” 60%.
[0060]
<Comparative Example 11>
0.1 mm thick, 1 mm thick, 2 mm thick sheet in the same manner as in Example 1 except that the mixing ratio was changed to “EVOH2” 35%, “EVA1” 35%, and “Mg1” 30%. It was created.
[0061]
<Comparative Example 12>
In Example 1, the mixing ratio was 35% for "EVOH2" and 35% for "Aclift WH206" (ethylene-methyl methacrylate copolymer manufactured by Sumitomo Chemical Co., Ltd .: ratio of methyl methacrylate constituting the copolymer = 20%) ) A 0.1 mm thick, 1 mm thick, and 2 mm thick sheet was prepared in the same manner as in Example 1 except that 35% and “Mg1” were changed to 30%.
[0062]
<Comparative Example 13>
Example 1 was repeated except that the mixing ratio was changed to 35% "EVOH2", 35% "TPAE-8" (polyetheresteramide elastomer manufactured by Fuji Kasei Kogyo Co., Ltd.) and 30% "Mg1" in Example 1. In the same manner as in 1, a sheet having a thickness of 0.1 mm, 1 mm and 2 mm was prepared.
[0063]
<Comparative Example 14>
Example 1 Example 1 was repeated except that the mixing ratio was changed to 70% “EVOH2” and 30% “MC640” (melamine cyanurate manufactured by Nissan Chemical Industries, Ltd.) (hereinafter abbreviated as “MCA”) in Example 1. A sheet having a thickness of 0.1 mm, 1 mm, and 2 mm was prepared in the same manner as described above.
[0064]
<Comparative Example 15>
0.1 mm thick, 1 mm thick, 2 mm thick sheet in the same manner as in Example 1 except that the mixing ratio was changed to “EVOH2” 70%, “Mg1” 20%, and “MCA” 10%. It was created.
[0065]
<Comparative Example 16>
Same as Example 1 except that the mixing ratio was changed to 70% "EVOH2", 20% "Mg1" and 10% "FP600" (condensed phosphate ester manufactured by Asahi Denka Kogyo KK) in Example 1. Then, a sheet having a thickness of 0.1 mm, 1 mm and 2 mm was prepared.
[0066]
<Comparative Example 17>
Using “EVOH2” alone, a 1 mm-thick and 2 mm-thick sheet was formed by a 180 ° C. hot press and a water-cooled cooling press, and a 0.1 mm thick sheet was formed by a T-die at 160 ° C.
[0067]
<Comparative Example 18>
Using “EVOH5” alone, a 1 mm-thick and 2 mm-thick sheet was prepared by a hot press at 180 ° C. and a water-cooled cooling press, and a 0.1 mm-thick sheet at 160 ° C. by a T-die.
[0068]
<Comparative Example 19>
In Example 1, a sheet having a thickness of 0.1 mm, 1 mm and 2 mm was prepared in the same manner as in Example 1 except that the mixing ratio was changed to "EVOH2" 35% and "Mg1" 65%.
[0069]
<Comparative Example 20>
In Example 1, sheets having a thickness of 0.1 mm, 1 mm and 2 mm were prepared in the same manner as in Example 1, except that the mixing ratio was changed to "EVOH5" 35% and "Mg1" 65%.
[0070]
<Evaluation>
Each sheet obtained in Examples 1 to 18 and Comparative Examples 1 to 20 was evaluated according to the method described below, and the results are summarized in Tables 1 to 10.
[0071]
(1) Combustibility 1
The UL94 vertical burn test was performed using a 1 mm thick sheet. It was determined whether or not V-0 and V-2 were suitable. If they match, they are described as "V-0" or "V-2", and if they do not match, they are described as "incompatible".
[0072]
(2) Combustibility 2
The UL94 thin material burning test was performed using a sheet having a thickness of 0.1 mm. It was determined whether or not VTM-0 and VTM-2 were met. If they match, they are described as "VTM-0" or "VTM-2", and if they do not match, they are described as "incompatible".
[0073]
(3) Combustibility 3
Evaluation was performed using a sheet having a thickness of 0.1 mm in accordance with JIS A 1322. Judgment was made as to whether it complies with Flameproof Class 1 and Flameproof Class 2. If they match, they are described as "Flame Protection Class 1" or "Flame Protection Class 2", and if they do not match, they are described as "Incompatible".
[0074]
(4) Tensile strength (unit = MPa)
The measurement was performed in accordance with JIS K7113. Using a sheet having a thickness of 1 mm, measurement was performed on a No. 3 test piece of JIS K6251 at a tensile speed of 200 mm / min.
[0075]
(5) Tensile elongation (unit =%)
The measurement was performed in accordance with JIS K7113. Using a sheet having a thickness of 1 mm, measurement was performed on a No. 3 test piece of JIS K6251 at a tensile speed of 200 mm / min.
[0076]
(6) Low temperature embrittlement temperature (unit = ° C)
The measurement was performed using a sheet having a thickness of 2 mm in accordance with JIS K 7216. The measurement was performed at 10 ° C. intervals. In the table, it is described as "brittle temperature".
[0077]
(7) Tracking resistance
The evaluation was performed using a sheet having a thickness of 2 mm in accordance with the salt spray tracking resistance test of JIS C 3005. In the table, "Tiger resistance" is described. The number of spraying times of 101 or more is indicated as conforming, and the number of spraying less than 101 times is indicated as nonconforming.
[0078]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
[Table 6]
[Table 7]
[Table 8]
[Table 9]
[Table 10]
The abbreviations described in Tables 1 to 10 are as follows.
EVOH1: "Evaflex 40LX" (ethylene-vinyl acetate copolymer manufactured by Du Pont-Mitsui Polychemicals Co., Ltd .: ratio of vinyl acetate constituting the copolymer = 41%) was saponified by a known saponification method, and saponified. Partially saponified ethylene-vinyl acetate copolymer having a degree of hydrolysis of 10%
EVOH2: "Technolink R400" (a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 60% manufactured by Taoka Chemical Industry Co., Ltd.): A vinyl acetate constituting the ethylene-vinyl acetate copolymer before saponification. (Ratio = 42%)
EVOH3: "Technolink R400-80" (a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 80% manufactured by Taoka Chemical Industry Co., Ltd .: acetic acid constituting the ethylene-vinyl acetate copolymer before saponification) (Ratio of vinyl = 42%)
EVOH4: "Technolink K431-10" (a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 10% manufactured by Taoka Chemical Industry Co., Ltd .: acetic acid constituting the ethylene-vinyl acetate copolymer before saponification) (Ratio of vinyl = 28%)
EVOH5: "Technolink K431-60" (a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 60% manufactured by Taoka Chemical Industry Co., Ltd .: acetic acid constituting the ethylene-vinyl acetate copolymer before saponification) (Ratio of vinyl = 28%)
EVOH6: "Technolink K431-80" (a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 80% manufactured by Taoka Chemical Industry Co., Ltd .: acetic acid constituting the ethylene-vinyl acetate copolymer before saponification) (Ratio of vinyl = 28%)
[0089]
EVOH7: "Technolink R100" (a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 95% manufactured by Taoka Chemical Industry Co., Ltd .: a vinyl acetate constituting the ethylene-vinyl acetate copolymer before saponification) (Ratio = 42%)
EVOH8: "Technolink K400" (a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 50% manufactured by Taoka Chemical Industry Co., Ltd .: a vinyl acetate constituting the ethylene-vinyl acetate copolymer before saponification) (Ratio = 25%)
EVOH9: "Technolink K131" (a partially saponified ethylene-vinyl acetate copolymer having a saponification degree of 95%, manufactured by Taoka Chemical Industry Co., Ltd.): a vinyl acetate constituting the ethylene-vinyl acetate copolymer before saponification. (Ratio = 28%)
[0090]
EVA1: "Evaflex 40LX" (Ethylene-vinyl acetate copolymer manufactured by Du Pont-Mitsui Polychemicals Co., Ltd .: ratio of vinyl acetate constituting the copolymer = 41%)
EVA2: “Evaflex P2805” (Ethylene-vinyl acetate copolymer manufactured by DuPont-Mitsui Polychemicals Co., Ltd .: ratio of vinyl acetate constituting the copolymer = 28%)
[0091]
TPAE: "TPAE-8" (a polyetheresteramide elastomer manufactured by Fuji Chemical Industry Co., Ltd.)
EMMA: “Acriflift WH206” (ethylene-methyl methacrylate copolymer manufactured by Sumitomo Chemical Co., Ltd .: ratio of methyl methacrylate constituting the copolymer = 20%)
[0092]
Mg1: "Kisuma 5P" (silane-treated synthetic magnesium hydroxide manufactured by Kyowa Chemical Industry Co., Ltd.)
Mg2: "Kisuma 5A" (a fatty acid-treated synthetic magnesium hydroxide manufactured by Kyowa Chemical Industry Co., Ltd.)
Mg3: “Magsee's N-1” (natural magnesium hydroxide manufactured by Kamishima Chemical Co., Ltd.)
[0093]
AL: "Heidilite H-32ST" (silane-treated aluminum hydroxide manufactured by Showa Denko KK)
P: "FP600" (condensed phosphate ester manufactured by Asahi Denka Kogyo Co., Ltd.)
CCA: "AFF95" (Calcium carbonate manufactured by Fimatec Corporation)
MCA: "MC640" (melamine cyanurate manufactured by Nissan Chemical Industries, Ltd.)
SI: "DC4-7081" (Silicone manufactured by Dow Corning Toray Co., Ltd.)
[0094]
From the results shown in Tables 1 to 10, the flame-retardant resin compositions of Examples 1 to 12 contain ethylene and vinyl acetate, and the content ratio of vinyl acetate is 28 to 42% by mass. A partially saponified ethylene-vinyl acetate copolymer which is a saponified ethylene-vinyl acetate copolymer having a saponification degree of 10 to 80% by mass. It is understood that the mass ratio of magnesium hydroxide to magnesium hydroxide is limited to the range of 40:60 to 90:10, so that it has excellent flame retardancy, mechanical properties, low temperature embrittlement temperature, and tracking resistance. Further, from the results of Examples 13 to 16, it can be understood that aluminum hydroxide can obtain the same characteristics as magnesium hydroxide without being affected by the type of metal hydroxide used in the flame-retardant resin composition. . Furthermore, from the results of Example 17 and Example 18, it can be understood that even if a specific inorganic compound or organic compound having no danger of generating toxic gas is added, its characteristics do not deteriorate.
[0095]
On the other hand, since the flame-retardant resin compositions of Comparative Examples 1 to 4 use an unsaponified ethylene-vinyl acetate copolymer, it can be understood that sufficient flame retardancy cannot be obtained. The flame-retardant resin compositions of Comparative Examples 5 to 10 were partially saponified ethylene-vinyl acetate copolymers containing ethylene-vinyl acetate having a vinyl acetate content of less than 28% by mass. A saponified polymer, or a saponified ethylene-vinyl acetate copolymer comprising a polymerizable composition having a vinyl acetate content of 28 to 42% by mass, and a saponification degree of less than 10% by mass Alternatively, since a partially saponified ethylene-vinyl acetate copolymer higher than 80% by mass is used, it can be understood that sufficient flame retardancy and low temperature embrittlement temperature cannot be obtained. Furthermore, the flame-retardant resin compositions of Comparative Examples 11 and 12 use an ethylene-vinyl acetate copolymer or an ethylene-methyl methacrylate copolymer and a partially saponified ethylene-vinyl acetate copolymer. It can be understood that, although the use of a combination of the above, sufficient flame retardancy is obtained, but the mechanical properties are significantly reduced.
[0096]
Further, since the flame retardant resin composition of Comparative Example 13 uses a polyamide elastomer and a partially saponified ethylene-vinyl acetate copolymer in combination, it has better properties than the partially saponified ethylene-vinyl acetate copolymer alone. Is obtained. However, it can be understood that since the polyamide elastomer has a nitrogen atom, cyanide may be generated during combustion. Further, the flame-retardant resin composition of Comparative Example 14, by using melamine cyanurate as a flame retardant, although sufficient flame retardancy and mechanical properties can be obtained, but not only tracking resistance is not obtained. In addition, it can be understood that since the flame retardant molecule has a nitrogen atom, cyanide may be generated during combustion. Furthermore, although the flame-retardant resin compositions of Comparative Examples 15 and 16 can obtain sufficient flame retardancy by using magnesium hydroxide and melamine cyanurate or condensed phosphoric acid ester in combination as flame retardants, No excellent combination effect can be found. Further, since the flame retardant molecule has a nitrogen atom or a phosphorus atom, it can be understood that cyanide or phosphine may be generated during combustion.
[0097]
In addition, the resin compositions of Comparative Examples 17 and 18 use the specific partially saponified ethylene-vinyl acetate copolymer alone specified in the present invention and contain no metal hydroxide, It can be understood that tracking resistance cannot be obtained. When a metal hydroxide is not used in combination, as a raw material of the partially saponified ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer having a high vinyl acetate content in the monomers constituting the ethylene-vinyl acetate copolymer is used. It can be understood that the use of the coalescing tends to improve the flame retardancy of the obtained resin composition although it is insufficient.
[0098]
Further, the flame-retardant resin compositions of Comparative Examples 19 and 20 were prepared by adding a metal hydroxide in a specific partially saponified ethylene-vinyl acetate copolymer specified in the present invention to a metal hydroxide in an amount exceeding the ratio specified in the present invention. It can be understood that not only sufficient mechanical properties and low-temperature embrittlement temperature are not obtained, but also sufficient flame retardancy may not be obtained because of the mixture.
[0099]
【The invention's effect】
The flame-retardant resin composition of the present invention is flexible, has no deterioration in mechanical properties, has a high degree of flame retardancy, does not generate toxic gas upon combustion, and has excellent moldability and processability. Therefore, it can be easily processed into sheets, films, electric wires, and housings. Accordingly, the flame-retardant resin composition of the present invention can be used as an electrical installation material such as a clamp cover and an electric wire protection tube, an industrial film such as a construction material and a construction sheet, an adhesive tape, a general household wallpaper, and an electric wire coating material. Since it can be applied to molding materials for electronic parts and the like and can be used in combination with other materials, it has high industrial value.
Claims (4)
を特徴とする難燃性樹脂組成物。A flame-retardant resin composition containing a partially saponified ethylene-vinyl acetate copolymer and a metal hydroxide, wherein (1) the partially saponified ethylene-vinyl acetate copolymer contains ethylene and vinyl acetate A partially saponified ethylene-vinyl acetate copolymer comprising a polymerizable composition having a vinyl acetate content of 28 to 42% by mass and a saponification degree of 10 to 80% by mass. (2) The ratio of the partially saponified ethylene-vinyl acetate copolymer and the metal hydroxide is 40:60 to 90:10 by mass ratio. Flame-retardant resin composition.
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| JP2002353646A JP4107075B2 (en) | 2002-12-05 | 2002-12-05 | Flame retardant resin composition |
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| JP2002353646A JP4107075B2 (en) | 2002-12-05 | 2002-12-05 | Flame retardant resin composition |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009185231A (en) * | 2008-02-08 | 2009-08-20 | Fuji Electric Fa Components & Systems Co Ltd | Arc-extinguishing resin processed article and circuit breaker using the same |
| US8115134B2 (en) | 2008-05-16 | 2012-02-14 | Fuji Electric Fa Components & Systems Co., Ltd. | Arc extinguishing resin processed article and circuit breaker using the same |
| JP2013249361A (en) * | 2012-05-31 | 2013-12-12 | Tosoh Corp | Tracking resistance-improving agent |
| JP2013253174A (en) * | 2012-06-07 | 2013-12-19 | Tosoh Corp | Polyamide resin composition |
-
2002
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009185231A (en) * | 2008-02-08 | 2009-08-20 | Fuji Electric Fa Components & Systems Co Ltd | Arc-extinguishing resin processed article and circuit breaker using the same |
| JP4655094B2 (en) * | 2008-02-08 | 2011-03-23 | 富士電機機器制御株式会社 | Arc extinguishing resin processed product and circuit breaker using the same |
| US8089023B2 (en) | 2008-02-08 | 2012-01-03 | Fuji Electric Fa Components & Systems Co., Ltd. | Arc-extinguishing processed resin article and circuit breaker that uses same |
| KR101414164B1 (en) | 2008-02-08 | 2014-07-01 | 후지 덴키 기기세이교 가부시끼가이샤 | Arc extinguisher-resin products and circuit breaker using the same |
| US8115134B2 (en) | 2008-05-16 | 2012-02-14 | Fuji Electric Fa Components & Systems Co., Ltd. | Arc extinguishing resin processed article and circuit breaker using the same |
| JP2013249361A (en) * | 2012-05-31 | 2013-12-12 | Tosoh Corp | Tracking resistance-improving agent |
| JP2013253174A (en) * | 2012-06-07 | 2013-12-19 | Tosoh Corp | Polyamide resin composition |
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