JP3682713B2 - Flame-retardant polyolefin-based resin-coated sheet and method for producing the same - Google Patents

Description

【００７６】
【表２】

【００７７】
実施例１〜実施例８の性能評価
実施例１〜実施例８で得られた本発明の難燃性ポリオレフィン系樹脂被覆シートの消防法に基づく防炎試験（ＪＩＳ規格Ｌ−１０９１）において、実施例１〜８のいずれの試験片も、接炎後、シートが溶融し、熱収縮することによって火源から遠ざかり、速やかに延焼を防止すると同時に接炎部に着火した炎はポリオレフィン系樹脂に配合した赤りん粒子の優れた難燃効果によって自己消火し、結果、実施例１〜８の全てのシートは消防法の防炎規定に合格した。
また、これらの難燃性ポリオレフィン系樹脂被覆シートは難燃剤の少量添加で十分な難燃性が得られるため、ポリオレフィン系樹脂強力を大きく損なうことがない。従って本発明の難燃性ポリオレフィン系樹脂被覆シートは、耐摩耗性、接合部の剪断強力、耐熱クリープ性などの耐久性に極めて優れていた。
【００７８】
実施例９
エチレン−酢酸ビニル共重合樹脂（商標：ウルトラセン６３５：東ソー（株）：酢酸ビニル含量２５wt％、メルトフローレート２．４ｇ／１０min ）１００重量部に対し、赤りん粒子（１）（商標：ノーバレッド２８０Ｃ：燐化学工業（株））を１５重量部配合し、さらに添加剤として、滑剤（商標：ＬＴＰ−２：川研ファインケミカル（株））１．０重量部と、紫外線吸収剤（商標：チヌビンＰ：チバ・スペシャルティ・ケミカルズ（株））０．３重量部と、着色剤として酸化チタン（商標：ハイコンクマスターＨＣＭ２０６０ホワイト：酸化チタン含有率６５重量％：大日精化工業（株））５重量部とを配合したコンパウンド（顔料成分だけの添加としては３．２５重量部）を、混合し、この混合物を１３０℃に設定された２本ロールミキサーで５分間混練し、この混練組成物から０．２mm厚のポリオレフィン系樹脂組成物層用フィルムをカレンダー圧延により成形した。この混練組成物のロール混練性及び、カレンダー成形性は良好であり、薄あずき色に着色された外観の良好なフィルムが得られた。このフィルムの酸素指数（ＬＯＩ）は、３５．６であった。
【００７９】
次に、３４０デニールのポリプロピレンマルチフィラメント糸を製織した平織目開き布帛（品番：ＭＳ−３１１２：三菱レイヨン（株）：糸密度経糸２５本／２．５４cm、緯糸２６本／２．５４cm）を、１４０℃の熱風条件に設定したヒートセット機でヒートセットした。この平織目開き布帛の１５０℃、１５分間における乾熱収縮率は、経方向１８．７％、緯方向１４．６％であった。次ぎに、前記ポリオレフィン系樹脂組成物層用フィルムを、前記平織目開き布帛の両面にラミネーターにより熱圧着して貼合わせ、厚さ０．５mm、重量４５０ｇ／ｍ² の難燃性ポリオレフィン系樹脂被覆シートを得た。この時のラミネーターの設定条件において、ポリオレフィン系樹脂組成物層用フィルム通過側の熱ロール温度は１２０℃であり、繊維布帛通過側の熱ロール温度は８０℃であり、圧着圧は１０kg／cm² であり、張合わせ速度は１０ｍ／min であった。
【００８０】
次に、エチレン−酢酸ビニル共重合樹脂（商標：ウルトラセン６３５：東ソー（株）：酢酸ビニル含量２５wt％、メルトフローレート２．４ｇ／１０min ）１００重量部に対し、ポリリン酸アンモニウム（商標：ホスタフラムＡＰ−７４５（ＥＸＯＬＩＴ ＩＦＲ２３）：クラリアント・ジャパン（株）：メラミン樹脂表面被覆タイプ、重合度ｎ＝１０００）３０重量部と、化学発泡剤（商標：ユニホームＡＺ Ｌ−１０：大塚化学（株）：分解温度１９９℃、ガス発生量２４０ml／ｇ）５重量部とを配合し、さらに添加剤として、滑剤（商標：ＬＴＰ−２：川研ファインケミカル（株））１．０重量部、紫外線吸収剤（商標：チヌビンＰ：チバ・スペシャルティ・ケミカルズ（株））０．３重量部、着色剤として酸化チタン（商標：ハイコンクマスターＨＣＭ２０６０ホワイト：酸化チタン含有率６５重量％：大日精化工業（株））及び、シアニングリーン（商標：ハイコンクマスターＨＣＭ１５６０グリーン：シアニングリーン含有率２０重量％：大日精化工業（株））の各々５重量部とを配合し、得られたコンパウンド（顔料成分だけの添加としては４．２５重量部）を５重量部配合したコンパウンド（顔料成分だけの添加としては３．２５重量部）を１３０℃に設定した２本ロールミキサーで５分間混練し、この混練組成物から０．１２mm厚の着色ポリオレフィン系樹脂保護層用フィルムをカレンダー圧延成形した。この混練組成物のロール混練性及び、カレンダー成形性は良好であり、ライトグリーンに着色された外観の良いフィルムが得られた。このフィルムの酸素指数（ＬＯＩ）は、３１．４であった。
【００８１】
次に、この着色ポリオレフィン系樹脂保護層用フィルムを、先に作製した難燃性ポリオレフィン系樹脂被覆シートの片面に、ラミネーターにより熱圧着して貼合わせ、厚さ０．６２mm、重量５６０ｇ／ｍ² の、着色保護層付き難燃性ポリオレフィン系樹脂シートを得た。この時のラミネーターの設定条件において、着色ポリオレフィン系樹脂保護層用フィルム通過側の熱ロール温度は１２０℃であり難燃性ポリオレフィン系樹脂シート通過側の熱ロール温度は８０℃であり、圧着圧は１０kg／cm² であり、張合わせ速度は１０ｍ／min であった。
得られた着色ポリオレフィン系樹脂保護層を片面に有する難燃性ポリオレフィン系樹脂シートの、１５０℃１５分間における乾熱収縮率は、経方向１５．５％、緯方向１２．２％であり、またシートのＬＯＩは２９．４であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表３〜表５に示す。
【００８２】
実施例１０
実施例９と同様にして、着色保護層付き難燃性ポリオレフィン系樹脂被覆シートを作製した。但し、前記ポリオレフィン系樹脂組成物層用フィルムに配合されたエチレン−酢酸ビニル共重合樹脂（商標：ウルトラセン６３５：東ソー（株））１００重量部の代りに、エチレン−アクリル酸共重合樹脂（商標：アクリフトＷＨ−２０６：住友化学工業（株）：メチルメタアクリレート含量２０wt％、メルトフローレート２．０ｇ／１０min ）１００重量部を用いた。また実施例９で使用したものと同じヒートセット処理されたポリプロピレンマルチフィラメント平織目開き布帛を用いて、薄あずき色に着色された厚さ０．５mm、重量４５０ｇ／ｍ² の難燃性ポリオレフィン系樹脂シートを得た。次に、着色ポリオレフィン系樹脂層フィルムとして、実施例９で使用したのと同じ保護層用フィルムを用いた。但し、着色剤としては、酸化チタン（商標：ハイコンクマスターＨＣＭ２０６０ホワイト：大日精化工業（株））５重量部をそのまま用いたが前記シアニングリーン（商標：ハイコンクマスターＨＣＭ１５６０グリーン：大日精化工業（株））５重量部の代りに縮合アゾレッド（商標：ハイコンクマスターＨＣＭ１１７０レッド：縮合アゾレッド含有量２０重量％：大日精化工業（株））５重量部を用いた（顔料成分だけの添加としては４．２５重量部）。実施例９と同様の手順によってピンクに着色されたポリオレフィン系樹脂保護層を片面に有する厚さ０．６２mm、重量５６０ｇ／ｍ² 難燃性ポリオレフィン系樹脂被覆シートを得た。得られた難燃性ポリオレフィン系樹脂シートの１５０℃、１５分間の乾熱収縮率は、経方向１５．３％、緯方向１２．４％であり、またＬＯＩは２８．３であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表３〜表５に示す。
【００８３】
実施例１１
実施例９と同様にして着色保護層付き難燃性ポリオレフィン系樹脂被覆シートを作製した。但し、前記ポリオレフィン系樹脂組成物層用フィルムに配合されたエチレン−酢酸ビニル共重合樹脂（商標：ウルトラセン６３５：東ソー（株））１００重量部のうち、その５０重量部を低密度ポリエチレン樹脂（商標：カーネルＫＦ２８１：日本ポリケム（株）：メルトフローレート２．５ｇ／１０min ）により置き替えた。また実施例９で使用したのと同一の、ヒートセット処理されたポリプロピレンマルチフィラメント平織目開き布帛の両面に前記ポリオレフィン系樹脂組成物層を形成して、薄あずき色に着色された厚さ０．５mm、重量４５０ｇ／ｍ² の難燃性ポリオレフィン系樹脂シートを得た。次に、着色ポリオレフィン系樹脂層用フィルムとして、実施例９で使用したものと同一の保護層用フィルムを用いた。但し、着色剤としては、酸化チタン（商標：ハイコンクマスターＨＣＭ２０６０ホワイト：大日精化工業（株））５重量部をそのまま用いたが、シアニングリーン（商標：ハイコンクマスターＨＣＭ１５６０グリーン：大日精化工業（株））５重量部の代りに、シアニンブルー（商標：ハイコンクマスターＨＣＭ１６１７ブルー：シアニンブルー含有量２０重量％：大日精化工業（株））５重量部を用いた。（顔料成分だけの添加としては４．２５重量部）。実施例９と同様の手順によってライトブルーに着色されたポリオレフィン系樹脂保護層を片面に有し、厚さ０．６２mm、重量５６０ｇ／ｍ² の保護層付き難燃性ポリオレフィン系樹脂シートを得た。得られた難燃性ポリオレフィン系樹脂シートの１５０℃、１５分間における乾熱収縮率は、経方向１５．１％、緯方向１２．６％であり、またＬＯＩは２８．５であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表３〜表５に示す。
【００８４】
実施例１２
実施例１１と同様にして着色保護層付き難燃性ポリオレフィン系樹脂被覆シートを作製した。但し、前記ポリプロピレンマルチフィラメント平織目開き布帛（ヒートセット処理あり）の代りに、７５０デニールのポリエステル（ＰＥＴ）マルチフィラメント糸から製織された平織り目開き布帛（品番：Ｔ−７５４７５：帝人（株）：糸密度経糸１９本／２．５４cm、緯糸２０本／２．５４cm）を、ヒートセット処理なしで使用した。実施例１１と同様の手順によって、ライトブルーに着色されたポリオレフィン系樹脂保護層を片面に有する厚さ０．７２mm、重量６００ｇ／ｍ² の保護層付き難燃性ポリオレフィン系樹脂被覆シートを得た。得られた難燃性ポリオレフィン系樹脂シートの１５０℃、１５分間における乾熱収縮率は、経方向９．４％、緯方向８．２％であり、またＬＯＩは２８．４であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表３〜表５に示す。
【００８５】
実施例１３
実施例１１と同様にして着色保護層付き難燃性ポリオレフィン系樹脂被覆シートを作製した。但し、前記ポリオレフィン系樹脂組成物層用フィルムにされたエチレン−酢酸ビニル共重合樹脂（商標：ウルトラセン６３５：東ソー（株））１００重量部のうち、その７０重量部をエチレン−アクリル酸共重合樹脂（商標：アクリフトＷＨ−２０６：住友化学工業（株）：メチルメタアクリレート含量２０wt％、メルトフローレート２．０ｇ／１０min ）により置き替えた。更に前記ポリプロピレンマルチフィラメント平織目開き布帛（ヒートセット処理あり）の代りに、４２０デニールのポリアミド（ナイロン）マルチフィラメント糸から製織された平織り目開き布帛（品番：ＡＫＮ−４４２５：旭化成（株）：糸密度経糸２４本／２．５４cm、緯糸２４本／２．５４cm）を、ヒートセット処理なしで使用した。実施例１１と同様の手順により、ライトブルーに着色されたポリオレフィン系樹脂保護層を片面に有する、厚さ０．６５mm、重量５７５ｇ／ｍ² の保護層付き難燃性ポリオレフィン系樹脂被覆シートを得た。得られた難燃性ポリオレフィン系樹脂シートの１５０℃、１５分間における乾熱収縮率は、経方向７．６％、緯方向７．２％であり、またＬＯＩは２８．６であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表３〜表５に示す。
【００８６】
実施例１４
実施例９と同様にして、着色保護層付き難燃性ポリオレフィン系樹脂被覆シートを作製した。但し、前記ポリオレフィン系樹脂被覆層用フィルムに配合されたエチレン−酢酸ビニル共重合樹脂（商標：ウルトラセン６３５：東ソー（株））１００重量部の代りに、エチレン−アクリル酸共重合樹脂（商標：アクリフトＷＨ−２０６：住友化学工業（株）メチルメタアクリレート含量２０wt％、メルトフローレート２．０ｇ／１０min ）５０重量部と、低密度ポリエチレン樹脂（商標：カーネルＫＦ２８１：日本ポリケム（株）：メルトフローレート２．５ｇ／１０min ）５０重量部とを用い、更に赤りん粒子（１）（商標：ノーバレッド２８０Ｃ（酸化チタン表面処理品）：燐化学工業（株））１５重量部の代りに、赤りん粒子（２）（商標：ヒシガードＣＰ（水酸化アルミニウム表面処理品）：日本化学工業（株））１５重量部を用いた。実施例９で使用されたものと同一のヒートセット処理されたポリプロピレンマルチフィラメント平織目開き布帛を用いて、あずき色に着色された厚さ０．５mm、重量４５０ｇ／ｍ² の難燃性ポリオレフィン系樹脂シートを得た。次に、着色ポリオレフィン系樹脂層用フィルムとして、実施例１３で使用したものと同一の保護層用フィルムを前記難燃性ポリオレフィン系樹脂被覆シートの両面に積層した。但し、着色剤としては、酸化チタン（商標：ハイコンクマスターＨＣＭ２０６０ホワイト：大日精化工業（株））５重量部をそのまま用いたが、シアニングリーン（商標：ハイコンクマスターＨＣＭ１５６０グリーン：大日精化工業（株））５重量部の使用を省略した。（顔料成分だけの添加としては３．２５重量部）。実施例９と同様の手順により、白色に着色されたポリオレフィン系樹脂保護層を両面に有する厚さ０．７４mm、重量６７０ｇ／ｍ² の保護層付き難燃性ポリオレフィン系樹脂シートを得た。得られた難燃性ポリオレフィン系樹脂シートの１５０℃、１５分間における乾熱収縮率は、経方向１５．３％、緯方向１２．７％であり、またＬＯＩは２８．３であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表３〜表５に示す。
【００８７】
実施例１５
実施例１４と同様にして着色保護層付きポリオレフィン系樹脂被覆シートを作製した。但し、前記ポリプロピレンマルチフィラメント平織目開き布帛（ヒートセット処理あり）の代りに、７５０デニールのポリエステル（ＰＥＴ）マルチフィラメント糸から製織された平織り目開き布帛（品番：Ｔ−７５４７５：帝人（株）：糸密度経糸１９本／２．５４cm、緯糸２０本／２．５４cm）をヒートセット処理なしで使用した。実施例１４と同様の手順により、白色のポリオレフィン系樹脂保護層を両面に有する厚さ０．８４mm、重量７１０ｇ／ｍ² の保護層付き難燃性ポリオレフィン系樹脂シートを得た。得られた難燃性ポリオレフィン系樹脂シートの１５０℃、１５分間における乾熱収縮率は、経方向９．６％、緯方向８．３％であり、またＬＯＩは２８．８であった。ポリオレフィン系樹脂組成物用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表３〜表５に示す。
【００８８】
実施例１６
実施例１４と同様にして着色保護層付きポリオレフィン系樹脂被覆シートを作製した。但し、前記ポリプロピレンマルチフィラメント平織目開き布帛（ヒートセット処理あり）の代りに、７５０デニールのポリアミド（ナイロン）マルチフィラメント糸から製織された平織り目開き布帛（品番：ＡＫＮ−４４２５：旭化成（株）：糸密度経糸２４本／２．５４cm、緯糸２４本／２．５４cm）をヒートセット処理なしで使用した。実施例１４と同様の手順によって白色ポリオレフィン系樹脂保護層を両面に有する厚さ０．７７mm、重量６８５ｇ／ｍ² の保護層付き難燃性ポリオレフィン系樹脂組成物シートを得た。得られた難燃性ポリオレフィン系樹脂シートの１５０℃、１５分間における乾熱収縮率は、経方向７．８％、緯方向６．９％であり、またＬＯＩは２８．４であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表３〜表５に示す。
【００８９】
【表３】

【００９０】
【表４】

【００９１】
【表５】

【００９２】
実施例９〜実施例１６の性能評価
実施例９〜実施例１６で得られた本発明の着色保護層付き難燃性ポリオレフィン系樹脂シートの消防法に基づく防炎試験（ＪＩＳ規格Ｌ−１０９１）は、いずれの実施例の試験片も接炎後、シートが溶融し、熱収縮することによって火源から遠ざかり、速やかに延焼を防止すると同時に接炎部に着火した炎はポリオレフィン系樹脂に配合した赤りん粒子の優れた難燃効果によって自己消火し、結果、実施例全てのシートは消防法の防炎規定に合格した。
また、これらの難燃性シートは難燃剤の少量添加で十分な難燃性が得られるため、ポリオレフィン系樹脂強力を大きく損なうことがない。従って本発明の難燃性ポリオレフィン系樹脂シートは耐摩耗性、接合部の剪断強力、耐熱クリープ性などの耐久性に極めて優れていた。また本発明の難燃性ポリオレフィン系樹脂シートは、シートの表面に非ハロゲン系難燃剤を含む着色されたポリオレフィン系樹脂保護層を設けることによって、着色の自在性が得られた。
【００９３】
比較例１
実施例９と同様にして、ポリオレフィン系樹脂被覆シートを作製した。但し、前記ポリオレフィン系樹脂組成物層用フィルムに配合されている赤りん粒子（１）（商標：ノーバレッド２８０Ｃ（酸化チタン表面処理品）：燐化学工業（株））１５重量部を用いずに、その代りに水酸化マグネシウム（商標：キスマ５Ａ：協和化学工業（株））１５０重量部を配合し、また、着色ポリオレフィン系保護層用フィルムの組成成分からポリリン酸アンモニウム３０重量部と化学発泡剤５重量部とを省いた。実施例９と同様の配合及び着色、同様の手順によって厚さ０．６２mm、重量５９０ｇ／ｍ² の着色保護層付きポリオレフィン系樹脂被覆シートを得た。得られたポリオレフィン系樹脂被覆シートの１５０℃、１５分間における乾熱収縮率は、経方向１５．１％、緯方向１１．８％であり、またＬＯＩは２０．２であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表６〜表８に示す。
【００９４】
比較例２
実施例１０と同様にして、ポリオレフィン系樹脂被覆シートを作製した。但し、前記ポリオレフィン系樹脂組成物層用フィルムに配合されている赤りん粒子（１）（商標：ノーバレッド２８０Ｃ（酸化チタン表面処理品）：燐化学工業（株））１５重量部を省き、その替わりに水酸化マグネシウム（商標：キスマ５Ａ：協和化学工業（株））１５０重量部を配合した。実施例１０と同様の配合及び着色、同様の手順によって厚さ０．６２mm、重量５９０ｇ／ｍ² の着色保護層付きポリオレフィン系樹脂被覆シートを得た。得られたポリオレフィン系樹脂シートの１５０℃、１５分間における乾熱収縮率は、経方向１５．７％、緯方向１２．０％であり、またＬＯＩは２６．３であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表６〜表８に示す。
【００９５】
比較例３
実施例３と同様にして、ポリオレフィン系樹脂被覆シートを作製した。但し、前記ポリオレフィン系樹脂組成物層用フィルムに配合された赤りん粒子（１）（商標：ノーバレッド２８０Ｃ（酸化チタン表面処理品）：燐化学工業（株））１５重量部を省き、その替わりに水酸化マグネシウム（商標：キスマ５Ａ：協和化学工業（株））１５０重量部を配合した。実施例３と同様の配合及び着色、同様の手順によって厚さ０．５mm、重量４８０ｇ／ｍ² の保護層なしのポリオレフィン系樹脂シートを得た。得られたポリオレフィン系樹脂被覆シートの１５０℃、１５分間における乾熱収縮率は、経方向１５．４％、緯方向１２．３％であり、またＬＯＩは２４．２であった。ポリオレフィン系樹脂組成物層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表６〜表８に示す。
【００９６】
比較例４
実施例４と同様のポリオレフィン系樹脂被覆シート（保護層なし）を作製した。但し、前記ポリオレフィン系樹脂組成物層用フィルムに配合された赤りん粒子（１）（商標：ノーバレッド２８０Ｃ（酸化チタン表面処理品）：燐化学工業（株））１５重量部を省き、その替わりに水酸化マグネシウム（商標：キスマ５Ａ：協和化学工業（株））１５０重量部を配合した。実施例４と同様の配合及び着色、同様の手順によって、厚さ０．６mm、重量５２０ｇ／ｍ² のポリオレフィン系樹脂シートを得た。得られたポリオレフィン系樹脂シートの１５０℃、１５分間における乾熱収縮率は、経方向９．６％、緯方向９．３％であり、またＬＯＩは２４．２であった。ポリオレフィン系樹脂組成物層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表６〜表８に示す。
【００９７】
比較例５
実施例５と同様のポリオレフィン系樹脂被覆シート（保護層なし）を作製した。但し、前記ポリオレフィン系樹脂組成物層用フィルムに配合されている赤りん粒子（１）（商標：ノーバレッド２８０Ｃ（酸化チタン表面処理品）：燐化学工業（株））１５重量部を省き、その替わりに水酸化マグネシウム（商標：キスマ５Ａ：協和化学工業（株））１５０重量部を配合した。実施例５と同様の配合及び着色、同様の手順によって厚さ０．５３mm、重量５０５ｇ／ｍ² のポリオレフィン系樹脂被覆シートを得た。得られたポリオレフィン系樹脂被覆シートの１５０℃、１５分間における乾熱収縮率は、経方向７．６％、緯方向７．３％であり、またＬＯＩは２４．２であった。ポリオレフィン系樹脂組成物層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表６〜表８に示す。
【００９８】
比較例６
実施例１４と同様にして着色保護層付きポリオレフィン系樹脂被覆シートを作製した。但し、前記ポリオレフィン系樹脂組成物層用フィルムに配合された赤りん粒子（２）（商標：ヒシガードＣＰ（水酸化アルミニウム表面処理品）：日本化学工業（株））１５重量部を省き、その替わりに水酸化マグネシウム（商標：キスマ５Ａ：協和化学工業（株））１５０重量部を配合した。また、前記着色ポリオレフィン系樹脂保護層用フィルムに配合されていたポリリン酸アンモニウム３０重量部と化学発泡剤５重量部とを省き、これらの替わりに水酸化マグネシウム（商標：キスマ５Ａ：協和化学工業（株））１００重量部を配合した。実施例１４と同様の配合及び着色、同様の手順によって厚さ０．７４mm、重量７３０ｇ／ｍ² のポリオレフィン系樹脂被覆シートを得た。得られたポリオレフィン系樹脂被覆シートの１５０℃、１５分間における乾熱収縮率は、経方向１４．４％、緯方向１１．７％であり、またＬＯＩは２２．３であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表６〜表８に示す。
【００９９】
比較例７
実施例１５と同様にして、着色保護層付きポリオレフィン系樹脂被覆シートを作製した。但し、前記ポリオレフィン系樹脂組成物層用フィルムに配合されている赤りん粒子（２）（商標：ヒシガードＣＰ（水酸化アルミニウム表面処理品）：日本化学工業（株））１５重量部を省き、その替わりに水酸化マグネシウム（商標：キスマ５Ａ：協和化学工業（株））１５０重量部を配合した。また、着色ポリオレフィン系樹脂保護層フィルムに配合されているポリリン酸アンモニウム３０重量部と化学発泡剤５重量部とを省き、これらの替わりに水酸化マグネシウム（商標：キスマ５Ａ：協和化学工業（株））１５０重量部を配合した。実施例１５と同様の配合及び着色、同様の手順によって厚さ０．８４mm、重量７７０ｇ／ｍ² のポリオレフィン系樹脂シートを得た。得られたポリオレフィン系樹脂シートの１５０℃、１５分間における乾熱収縮率は、経方向９．７％、緯方向９．２％であり、またＬＯＩは２３．８であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表６〜表８に示す。
【０１００】
比較例８
実施例１６と同様にして、着色保護層付きポリオレフィン系樹脂被覆シートを作製した。但し、前記ポリオレフィン系樹脂組成物層用フィルムに配合されている赤りん粒子（２）（商標：ヒシガードＣＰ（水酸化アルミニウム表面処理品）：日本化学工業（株））１５重量部を省き、その替わりに水酸化マグネシウム（商標：キスマ５Ａ：協和化学工業（株））１５０重量部を配合した。また、着色ポリオレフィン系樹脂保護層用フィルムに配合されているポリリン酸アンモニウム３０重量部を省き、その替わりに水酸化マグネシウム（商標：キスマ５Ａ：協和化学工業（株））１００重量部を配合した。実施例１６と同様の配合及び着色、同様の手順によって厚さ０．７７mm、重量７５５ｇ／ｍ² のポリオレフィン系樹脂被覆シートを得た。
得られたポリオレフィン系樹脂被覆シートの１５０℃、１５分間における乾熱収縮率は、経方向７．５％、緯方向７．１％であり、またＬＯＩは２３．０であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表６〜表８に示す。
【０１０１】
【表６】

【０１０２】
【表７】

【０１０３】
【表８】

【０１０４】
比較例１〜比較例８の性能評価
比較例１〜比較例８ではポリオレフィン系樹脂層フィルムにおいて、難燃剤として、赤りん粒子の代りに多量の水酸化マグネシウムに変更したことによって、消防法に基づく防炎試験（ＪＩＳ規格Ｌ−１０９１）において、いずれの比較例の試験片も接炎後、シートが溶融すると同時に着炎し、着炎した状態で熱収縮することによって延焼を促進した。着火した炎は水酸化マグネシウムの難燃効果により自己消火することができずに全焼し、結果、比較例全てのシートは消防法の防炎規定に不適合であった。また、これらの比較例のシートは難燃剤の多量添加によっても十分な難燃性が得られないばかりか、耐摩耗性、接合部の剪断強力、耐熱クリープ性などの耐久性においても著しく不良であるなどポリオレフィン系樹脂の強力を大きく損なうものであり、実用性がないものであった。（比較例１、比較例２のみ耐摩耗性は良好であった）
【０１０５】
比較例９
実施例９と同様の保護層付きポリオレフィン系樹脂被覆シートを作製した。但し、前記３４０デニールのポリプロピレンマルチフィラメント糸を製織した平織目開き布帛（品番：ＭＳ−３１１２：三菱レイヨン（株））のヒートセット処理を省略した。この平織目開き布帛の１５０℃、１５分間における乾熱収縮率は、経方向３４．６％、緯方向３１．３％であった。また、前記着色ポリオレフィン系樹脂保護層用フィルムに配合されているポリリン酸アンモニウム３０重量部を省き、その代りに水酸化マグネシウム（商標：キスマ５Ａ：協和化学工業（株））１５０重量部を配合した。実施例９と同様の配合及び着色、同様の手順によって厚さ０．６５mm、重量６０５ｇ／ｍ² の着色保護層付きポリオレフィン系樹脂シートを得た。得られたポリオレフィン系樹脂シートの１５０℃、１５分間における乾熱収縮率は、経方向２８．６％、緯方向２６．３％であり、またＬＯＩは２７．４であった。しかし、ポリプロピレン平織目開き布帛のヒートセットを省略したために、難燃性ポリオレフィン系樹脂フィルムの熱ラミネート工程において、ポリプロピレン平織目開き布帛（基布）の熱収縮が大きく、加工性とシート外観が著く悪いものであった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表９〜表１１に示す。
【０１０６】
比較例１０
実施例１０と同様の保護層付きポリオレフィン系樹脂被覆シートを作製した。但し、前記３４０デニールのポリプロピレンマルチフィラメント糸を製織した平織目開き布帛（品番：ＭＳ−３１１２：三菱レイヨン（株））のヒートセット処理温度を１４０℃から１７０℃に変更した。この平織目開き布帛の１５０℃、１５分間における乾熱収縮率は、経方向３．３％、緯方向３．０％であった。実施例１０と同様の配合及び着色、同様の手順によって厚さ０．６２mm、重量５６０ｇ／ｍ² の着色保護層付きポリオレフィン系樹脂シートを得た。得られたポリオレフィン系樹脂シートの１５０℃、１５分間における乾熱収縮率は、経方向３．１％、緯方向２．８％であり、またＬＯＩは２８．０であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表９〜表１１に示す。
【０１０７】
比較例１１
実施例３と同様にして保護層なしポリオレフィン系樹脂被覆シートを作製した。但し、前記３４０デニールのポリプロピレンマルチフィラメント糸を製織した平織目開き布帛（品番：ＭＳ−３１１２：三菱レイヨン（株））のヒートセット処理温度を１４０℃から１７０℃に変更した。この平織目開き布帛の１５０℃、１５分間における乾熱収縮率は、経方向３．３％、緯方向３．０％であった。実施例３と同様の配合及び着色、同様の手順によって厚さ０．５mm、重量４５０ｇ／ｍ² のポリオレフィン系樹脂被覆シートを得た。得られたポリオレフィン系樹脂シートの１５０℃、１５分間における乾熱収縮率は、経方向２．１％、緯方向１．８％であり、またＬＯＩは２８．１であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表９〜表１１に示す。
【０１０８】
比較例１２
実施例４と同様にして、保護層なしポリオレフィン系樹脂被覆シートを作製した。但し、前記７５０デニールのポリエステルマルチフィラメント糸を製織した平織目開き布帛（品番：Ｔ−７５４７５：帝人（株））にヒートセット処理を２００℃の熱条件で施した。この平織目開き布帛の１５０℃、１５分間における乾熱収縮率は、経方向２．６％、緯方向２．２％であった。実施例４と同様の配合及び着色、同様の手順によって厚さ０．６mm、重量４９０ｇ／ｍ² のポリオレフィン系樹脂被覆シートを得た。得られたポリオレフィン系樹脂被覆シートの１５０℃、１５分間における乾熱収縮率は、経方向２．４％、緯方向２．０％であり、またＬＯＩは２９．３であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表９〜表１１に示す。
【０１０９】
比較例１３
実施例５と同様にして、保護層なしポリオレフィン系樹脂被覆シートを作製した。但し、前記４２０デニールのポリアミド（ナイロン）マルチフィラメント糸を製織した平織目開き布帛（品番：ＡＫＮ−４４２５：旭化成（株））にヒートセット処理を２００℃の熱条件で施した。この平織目開き布帛の１５０℃、１５分間における乾熱収縮率は、経方向２．４％、緯方向２．１％であった。実施例５と同様の配合及び着色、同様の手順によって厚さ０．５３mm、重量４６５ｇ／ｍ² のポリオレフィン系樹脂被覆シートを得た。得られたポリオレフィン系樹脂被覆シートの１５０℃、１５分間における乾熱収縮率は、経方向２．２％、緯方向１．９％であり、またＬＯＩは２８．７であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表９〜表１１に示す。
【０１１０】
比較例１４
実施例１４と同様にして両面着色保護層付きポリオレフィン系樹脂被覆シートを作製した。但し、前記３４０デニールのポリプロピレンマルチフィラメント糸を製織した平織目開き布帛（品番：ＭＳ−３１１２：三菱レイヨン（株））のヒートセット処理を省略した。この平織目開き布帛の１５０℃、１５分間における乾熱収縮率は、経方向３４．６％、緯方向３１．３％であった。実施例１４と同様の配合及び着色、同様の手順によって厚さ０．７４mm、重量６７０ｇ／ｍ² のポリオレフィン系樹脂被覆シートを得た。得られたポリオレフィン系樹脂被覆シートの１５０℃、１５分間における乾熱収縮率は、経方向２８．６％、緯方向２６．３％であり、またＬＯＩは２６．８であった。しかし、ポリプロピレン平織目開き布帛のヒートセットを省略したために、難燃性ポリオレフィン系樹脂フィルムの熱ラミネート工程においてポリプロピレン平織目開き布帛の熱収縮が大きく、加工性とシート外観が著く悪いものであった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表９〜表１１に示す。
【０１１１】
比較例１５
実施例１５と同様にして、両面着色保護層付きポリオレフィン系樹脂被覆シートを作製した、但し、前記７５０デニールのポリエステルマルチフィラメント糸を製織した平織目開き布帛（品番：Ｔ−７５４７５：帝人（株））にヒートセット処理を２００℃の熱条件で施した。この平織目開き布帛の１５０℃での乾熱収縮率は、経方向２．６％、緯方向２．２％であった。実施例１５と同様の配合及び着色、同様の手順によって厚さ０．８４mm、重量７１０ｇ／ｍ² のポリオレフィン系樹脂被覆シートを得た。得られたポリオレフィン系樹脂被覆シートの１５０℃、１５分間における乾熱収縮率は、経方向２．４％、緯方向１．９％であり、またＬＯＩは２８．７であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表９〜表１１に示す。
【０１１２】
比較例１６
実施例１６と同様にして、両面着色保護層付きポリオレフィン系樹脂被覆シートを作製した。但し、前記４２０デニールのポリアミド（ナイロン）マルチフィラメント糸を製織した平織目開き布帛（品番：ＡＫＮ−４４２５：旭化成（株））にヒートセット処理を２００℃の熱条件で施した。この平織目開き布帛の１５０℃、１５分間における乾熱収縮率は、経方向２．４％、緯方向２．１％であった。実施例１６と同様の配合及び着色、同様の手順によって厚さ０．７７mm、重量６８０ｇ／ｍ² のポリオレフィン系樹脂被覆シートを得た。得られたポリオレフィン系樹脂被覆シートの１５０℃、１５分間における乾熱収縮率は、経方向２．２％、緯方向１．９％であり、またＬＯＩは２８．１であった。ポリオレフィン系樹脂組成物層用フィルムの配合、着色ポリオレフィン系樹脂保護層用フィルムの配合、基布用布帛の性能及び、上記試験（Ｉ）〜（VI）の結果を表９〜表１１に示す。
【０１１３】
【表９】

【０１１４】
【表１０】

【０１１５】
【表１１】

【０１１６】
比較例９〜比較例１６の性能評価
比較例１０〜比較例１３、比較例１５、比較例１６のシートでは、ポリオレフィン系樹脂組成物層用フィルムの難燃剤として実施例と同じ赤りん粒子を使用しても、用いる繊維布帛基布の熱収縮率が小さいため、接炎後、着炎部が火源から遠ざかる挙動に劣り、更に接炎端部が火源に向かって巻き爪状に収縮して、部分的な垂直状態を形成するために自己消火できず全焼し、その結果、これらの比較例のシートは消防法の防炎試験（ＪＩＳ規格Ｌ−１０９１）に不適合となった。また、比較例９、比較例１４のシートは、消防法の防炎試験に適合はするものの、繊維布帛基布の熱収縮率が大き過ぎて、シートの製造が困難であると同時にシートの外観も悪く、更に高周波ウエルダー融着時に接合部が激しく収縮するなど、実用性がないものであった。また更に、比較例１０、比較例１１のシートにおいては、ポリプロピレンマルチフィラメント糸から製織された繊維布帛基布の熱収縮率がヒートセット処理によって極めて少なく抑えられた結果として、ポリプロピレンマルチフィラメント糸微細構造の結晶化度の低下を引き起こすために、接合部剪断強力、接合部の耐熱クリープ性など、シート自体の強力的物性を損ない、全く実用性がないものであった。
【０１１７】
【発明の効果】
本発明の難燃性ポリオレフィン系樹脂被覆シートは、消防法の防炎試験に適合する優れた難燃性を有するとともに、その加工性及び、着色性にも優れたものであった。
また、本発明の難燃性ポリオレフィン系樹脂被覆シートは、従来問題であった機械的物性低下の課題も十分に解決された極めて耐久性に優れたシートである。よって本発明の難燃性ポリオレフィン系樹脂被覆シートは、従来使用されている軟質ポリ塩化ビニル加工品シートの代用品として、特に防炎性を必要とするテント用膜材、シート倉庫用膜材、建築現場用養生シート、建築現場用遮音シートなどの産業資材向けに適したシートである。[0001]
BACKGROUND OF THE INVENTION
INDUSTRIAL APPLICABILITY The present invention is particularly suitable for buildings, structures, etc., is excellent in flexibility, mechanical properties, wear resistance, outdoor durability, etc., does not generate combustion, particularly toxic gas, and is a fabric base fabric. The present invention relates to a flame retardant polyolefin resin-coated sheet containing More specifically, the present invention does not generate a halogen gas during combustion, and is suitable for a flameproof test stipulated in the Fire Service Act, a film material for a sheet warehouse, a curing sheet for a construction site, a building The present invention relates to a flame-retardant polyolefin-based resin-coated sheet that is useful as a sound insulation sheet for on-site use.
[0002]
[Prior art]
In recent years, since halogen contained in vinyl chloride resin products is released as a toxic gas at the time of combustion, a problem has been raised in terms of safety in waste treatment or flame. Due to such a social background, various measures for reducing the halogen content as much as possible have been studied. For example, a non-halogen-containing flame retardant resin composition in which a polyolefin resin is used as an alternative to a vinyl chloride resin and a metal hydroxide, a metal oxide, a phosphorus compound, etc. is added as a flame retardant has been proposed. (Japanese Patent Laid-Open Nos. 63-20348, 63-61055, 63-128038, 63-154760, and 3-20342).
[0003]
However, the resin compositions according to these proposals are certainly non-halogen-containing compositions, but metal hydroxides (for example, magnesium hydroxide, aluminum hydroxide, etc.) in order to impart sufficient flame retardancy to the polyolefin resin. Alternatively, a metal oxide (for example, antimony trioxide, zinc borate, titanium dioxide, etc.) needs to be added in a large amount of 100 to 300 parts by weight. As a result, the processability of the polyolefin resin composition is reduced, Problems such as a significant decrease in mechanical strength have occurred. Especially when applied to sheet-like processed products, not only the texture becomes hard, but also there are problems such as fatigue deterioration due to bending and surface scratches easily, balance between practicality and flame retardancy, Is in a state where the balance with cost cannot be established well.
[0004]
Therefore, in order to reduce the amount of non-halogen flame retardant added, it has been proposed to use red phosphorus particles or heat-expandable graphite in combination with the above non-halogen flame retardant as a flame retardant aid (Japanese Patent Laid-Open No. 1). No. -4632, JP-A-6-184330, JP-A-6-73251, JP-A-6-25476, JP-A-8-302202). Although these methods can certainly reduce the amount of non-halogen flame retardant added to some extent to obtain a flame retardant composition, the amount of non-halogen flame retardant added is still 50 parts by weight or more. Is still not at a level that can avoid the deterioration of the mechanical properties of the polyolefin resin composition. In addition, since the molded product is colored reddish brown by adding red phosphorus particles, and the molded product is colored black by adding heat-expandable graphite, the colorability of the molded product is impaired, and coloring and toning properties are also reduced. However, there is a drawback that it cannot be used for applications that require.
[0005]
Conventionally, synthetic fiber knitted fabric is used as a core material, and the use of fiber reinforced products obtained by forming a conventional polyvinyl chloride resin layer on the surface, such as tents, sheet warehouses, building site curing sheets, sound insulation for building sites For applications for buildings and structures such as sheets, canvases and tarpaulins formed by coating or laminating a fiber chloride resin composition layer on a fiber fabric are used. Since polyvinyl chloride resin itself has a high degree of flame retardancy, these canvas and tarpaulins for construction use 5 to 20 weight percent of a flame retardant such as antimony trioxide or aluminum hydroxide in polyvinyl chloride resin. By using it with a small amount of addition, it is possible to meet the flameproof standard defined in the Fire Service Act (Article 4 of the Fire Service Construction Rules: JIS Standard L-1091). However, when these constituent resins of canvas and tarpaulin are replaced with polyolefin resins, the polyolefin resins themselves are flammable, and further include non-halogen flame retardants by including flammable synthetic fiber fabrics. However, there is a problem that it is difficult to obtain more sufficient flame retardancy.
[0006]
For this reason, for the purpose of imparting flame retardancy to the synthetic fiber fabric, a flame retardant treatment in which a flame retardant is dispersed or dissolved in water or an organic solvent is impregnated or applied to the synthetic fiber fabric, dried and heat-treated. Thus, a method of making a synthetic fiber fabric flame-retardant is adopted. For example, for non-halogen flame retardant of polyester fiber fabrics, flame retardancy with an oxygen index (LOI: JIS standard K7201) of about 27 to 28 can be imparted using an aliphatic phosphate flame retardant (Dyeing Industry Vol. 32). No. 2).
This level of LOI: 27-28 falls under the category of flame retardancy according to “Polymer Flame Retardancy (page 105): Taiseisha”. When designing canvas or tarpaulin coated with polyolefin resin using this flame retardant polyester fiber fabric, the flame retardant level of the polyolefin resin layer is also raised to the same level of LOI as flame retardant polyester fiber fabric. There is a need to. The LOI of polyolefin resins (polyethylene resin, polypropylene resin) is 17.5 (polymer flame retarding (page 122): Taiseisha). For this purpose, non-halogen such as magnesium hydroxide or aluminum hydroxide is used. It is necessary to add as much as 100 to 200 parts by weight of the flame retardant, and as a result, the workability, mechanical properties, durability, wear resistance, etc. of the flame retardant resin layer obtained as described above are significantly deteriorated. Therefore, it becomes impractical ("Polymer Digest" 1988. Vol. 10).
[0007]
Therefore, in the flameproof sheet product obtained by making the polyolefin resin non-halogen flame retardant, it is excellent in mechanical strength, flexibility, wear resistance, outdoor durability, and also excellent in workability, colorability, and cost. Polyolefin canvas or tarpaulins have not yet been developed.
[0008]
[Problems to be solved by the invention]
The present invention solves the problem of mechanical property deterioration in the above conventional non-halogen flame retardant polyolefin resin-coated sheet, and exhibits excellent flame retardancy suitable for the flame proof test prescribed in the Fire Service Act. Another object of the present invention is to provide a flame-retardant polyolefin resin-coated sheet that is excellent in processability, colorability, and low cost, includes a fabric base fabric, and is suitable for a sheet for industrial materials.
[0009]
[Means for Solving the Problems]
The present invention is to provide a non-halogen composition polyolefin resin sheet having mechanical properties and durability similar to those of an industrial material sheet having a conventional soft polyvinyl chloride resin coating layer and excellent in flame retardancy. As a result of the study, in the flame-retardant polyolefin resin-coated sheet, a melt flow rate (MFR) of 0.2 to 5.0 g / f, comprising 5 to 35 parts by weight of red phosphorus particles with respect to 100 parts by weight of the polyolefin resin. A polyolefin resin composition film of 10 min is produced by adhering to both surfaces of a fiber fabric woven from a multifilament yarn having a dry heat shrinkage in a specific range obtained by spinning a specific thermoplastic resin at a specific temperature condition. A polyolefin resin-coated sheet having a dry heat shrinkage rate in the range of 5 to 25% within the warp direction and the warp direction by heating at 150 ° C. for 15 minutes, At the time of ignition in the flameproof test, the polyolefin resin composition film and the fabric base fabric are quickly melted away from the fire source, and at the same time, the residual flame in the melted part self-extinguishes, and the mechanical properties of this sheet In addition, the inventors have found that the wear resistance is excellent and have completed the present invention.
[0010]
The flame-retardant polyolefin-based resin-coated sheet of the present invention includes a base fabric including a fabric knitted from thermoplastic resin filament yarns, and front and back double-sided resin layers formed from a polyolefin-based resin composition on both sides of the base fabric. A composite sheet having
The polyolefin resin composition comprises 100 parts by weight of a polyolefin resin and 5 to 35 parts by weight of red phosphorus particles mixed therewith and has a melt flow rate of 0.2 to 5.0 g / 10 min ( MFR) (according to the test method of JIS K 6760, where temperature: 190 ° C., load: 21.18 N (2.16 kgf))
as well as,
The composite sheet has a dry heat shrinkage of 5-25% in the warp and weft directions by heating at 150 ° C. for 15 minutes,
It is characterized by.
In the flame-retardant polyolefin resin-coated sheet of the present invention, the thermoplastic resin forming the thermoplastic resin filament yarn for base fabric is preferably selected from polyolefin resins, polyester resins, and polyamide resins.
In the flame-retardant polyolefin resin-coated sheet of the present invention, the filament yarn for base fabric is preferably selected from multifilament yarn, monofilament yarn, tape yarn, split yarn, and split yarn.
In the flame-retardant polyolefin resin-coated sheet of the present invention, the polyolefin resin composition is at least one selected from 1 to 20 parts by weight of an inorganic pigment and an organic pigment with respect to 100 parts by weight of the polyolefin resin. A colorant composed of seeds may be further included.
In the flame-retardant polyolefin resin-coated sheet of the present invention, the thermoplastic resin filament yarn is selected from polyethylene filament yarn, polypropylene filament yarn, and mixed filament yarn of polyethylene resin and polypropylene resin. It is preferable to consist of 1 or more types.
In the flame-retardant polyolefin-based resin-coated sheet of the present invention, the base fabric is a woven fabric, and is heat-set, and 5 to 25% in the warp and weft directions by heating at 150 ° C. for 15 minutes. It shows a dry heat shrinkage ratio of 5 to 25% in the warp and weft directions when heated at 150 ° C. for 15 minutes. Preferably there is.
In the flame-retardant polyolefin resin-coated sheet of the present invention, the red phosphorus particles have aluminum hydroxide, magnesium hydroxide, titanium oxide, zinc oxide, formalin resin, phenol resin, melamine resin, urea resin, and epoxy on the surface. It is preferable that the surface-coated red phosphorus particles are coated with one or more selected from resins, and that the average particle diameter of the surface-coated red phosphorus particles is 5 to 25 μm.
In the flame-retardant polyolefin resin-coated sheet of the present invention, a polyolefin resin protective layer colored without containing the red phosphorus particles is formed on at least one of the front and back double-sided polyolefin resin composition layers. May be.
In the flame-retardant polyolefin resin-coated sheet of the present invention, the colored polyolefin resin protective layer is composed of 5 to 50 parts by weight of a phosphoric acid compound component and 1 to 20 parts by weight of a chemical foaming agent component based on 100 parts by weight of the polyolefin resin. And a melt flow rate (MFR) of 0.2 to 5.0 g / 10 minutes, and 1 to 20 parts by weight of a colorant component composed of at least one selected from inorganic pigments and organic pigments It is preferable that it is formed with the colored polyolefin resin composition which has.
In the flame-retardant polyolefin-based resin-coated sheet of the present invention, the phosphoric acid compound component includes at least one selected from a phosphoric ester, a phosphate, a phosphoric ester salt, and a condensed phosphate. preferable.
In the flame-retardant polyolefin resin-coated sheet of the present invention, the condensed phosphate preferably contains at least one selected from ammonium polyphosphate, thermosetting resin-coated ammonium polyphosphate, and melamine polyphosphate.
In the flame-retardant polyolefin resin-coated sheet of the present invention, the chemical foaming agent component preferably contains at least one selected from an azo compound, a sulfohydrazide compound, and a nitroso compound.
In the flame retardant polyolefin resin-coated sheet of the present invention, the colored polyolefin resin protective layer preferably has a thickness of 10 to 50% of the total thickness of the flame retardant polyolefin resin-coated sheet.
The method for producing a flame-retardant polyolefin resin-coated sheet of the present invention comprises a polyolefin-based resin composition using a heating laminator on both front and back surfaces of a base fabric including a fabric woven from thermoplastic resin filament yarns. Including a step of attaching a film to form a composite sheet,
The polyolefin resin composition comprises 100 parts by weight of polyolefin resin and 5 to 25 parts by weight of red phosphorus particles mixed therewith, and has a melt flow rate (MFR) of 0.2 to 50 g / 10 min ( According to the test method of JIS K 6760, with a temperature of 190 ° C. and a load of 21.18 N (2.16 kgf))
In the sticking step using the heating laminator, the heat roll surface on the sticking side of the polyolefin resin composition film is heated to a temperature of 70 to 180 ° C., and the temperature of the base fabric is adjusted to 120 ° C. or less. Continuously heat-pressing the film to the base fabric, and
At this time, controlling the dry heat shrinkage rate of the obtained composite sheet by heating at 150 ° C. for 15 minutes to 5 to 25%,
It is characterized by.
In the method for producing a flame-retardant polyolefin resin-coated sheet of the present invention, a polyolefin resin protective layer colored without containing the red phosphorus particles is formed on at least one surface of the front and back double-sided polyolefin resin composition layer. The process of carrying out may be further included.
In the method for producing a flame-retardant polyolefin resin-coated sheet according to the present invention, the forming step of the polyolefin-based resin protective layer attaches the polyolefin-based resin film, or contains the polyolefin-based resin. May be carried out by coating and drying.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The flame-retardant polyolefin-based resin-coated sheet of the present invention includes a base fabric including a fabric knitted from thermoplastic resin filament yarns, and front and back double-sided resin layers formed from a polyolefin-based resin composition on both sides of the base fabric. It is comprised by the composite sheet which has these. The polyolefin resin composition includes 100 parts by weight of polyolefin resin and 5 to 35 parts by weight of red phosphorus particles mixed therewith, and has a melt flow rate (MFR) of 0.2 to 5.0 g / 10 minutes. ) (According to the test method of JIS K 6760, however, temperature: 190 ° C., load: 21.18 N (2.16 kgf)). Moreover, the dry heat shrinkage rate in the warp and weft directions of the composite sheet by heating at 150 ° C. for 15 minutes is in the range of 5 to 25%.
[0012]
The types of polyolefin resins used in the flame-retardant polyolefin resin-coated sheet according to the present invention include ethylene-α-olefin copolymers, low density polyethylene, medium density polyethylene, high density polyethylene, and ethylene-vinyl acetate copolymers. , Ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-methyl methacrylic acid copolymer, ethylene-methyl Examples thereof include a methacrylic acid ester copolymer, an ethylene-ethyl acrylic acid copolymer, an ethylene-ethyl acrylic acid ester copolymer, and a mixture of two or more of these. As the polyolefin resin used in the present invention, those produced by radical polymerization or ionic polymerization can be used.
[0013]
The polyethylene-based resin obtained by the radical polymerization method includes an ethylene homopolymer or a copolymer obtained by copolymerizing ethylene and a monomer capable of radical polymerization therewith. Examples of the monomer capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, esterified products and acid anhydrides thereof, and vinyl esters such as vinyl acetate. Examples of the esterified product of unsaturated carboxylic acid include ethyl acrylate, methyl methacrylate, glycidyl methacrylate and the like. These monomers can be used alone or in combination of two or more.
[0014]
The polyethylene resin obtained by the ionic polymerization method is obtained by copolymerizing a polymer of ethylene alone or ethylene and an α-olefin having 3 to 18 carbon atoms using a transition metal solid catalyst or a metallocene homogeneous catalyst. Examples of the α-olefin include propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, octadecene-1, etc. It is preferable to use an α-olefin having 4 to 10 atoms. These α-olefins may be used alone or in combination of two or more.
[0015]
The polyolefin resin used in the flame retardant polyolefin resin coated sheet of the present invention is not limited to the above polyolefin resin, but an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, Ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-methyl methacrylic acid copolymer, ethylene-methyl methacrylic acid ester copolymer, ethylene -Ethylene copolymers such as ethylacrylic acid copolymer and ethylene-ethyl acrylate copolymer can be preferably used because they have the advantage of high-frequency welder properties. Furthermore, these ethylene-based copolymers have a melt flow rate of 0.5 to 10 g / 10 min, particularly 0.5 to 5.0 g / 10 min, when used alone or in a blend composition of two or more. Those having a comonomer content of 5 to 35% by weight, particularly 15 to 25% by weight, can be suitably used in the present invention. If the melt flow rate is less than 0.5 g / 10 min, molding of the resulting flame-retardant polyolefin resin-coated sheet may be difficult, and if it is higher than 10 g / 10 min, the resulting resin coating The strength and heat resistance of the sheet may be insufficient, and the adhesiveness may be increased to cause inconveniences such as blocking. If the copolymer monomer content is less than 5% by weight, the resulting copolymer may have insufficient high-frequency welder properties. If the copolymer monomer content is more than 35% by weight, The resulting polyolefin resin film has insufficient mechanical strength, increases the adhesiveness during processing, and causes disadvantages such as extremely difficult molding.
[0016]
Furthermore, the polyolefin resin used in the flame-retardant polyolefin resin-coated sheet of the present invention has a melt flow rate of 0.5 to 10 g for the purpose of enhancing durability such as mechanical resin strength and abrasion resistance. / 10 min, a crystalline polyolefin-based resin composed of one or more of metallocene-catalyzed polyethylene, ethylene-α-olefin, low-density polyethylene, medium-density polyethylene, polypropylene, etc., the ethylene-vinyl acetate copolymer resin and the ethylene- It is preferably a blend with one or more copolymer resins selected from acrylic copolymer resins. The blend ratio of the crystalline polyolefin resin and the copolymer resin is not particularly limited, but the monomer copolymerized with ethylene in the copolymer resin with respect to 100% by weight of the polyolefin resin blend, that is, The total amount of vinyl acetate and acrylic monomer is preferably 5 to 35% by weight from the viewpoint of high frequency welder properties. Furthermore, it is preferable that the melt flow rate of the polyolefin resin blend used for the flame retardant polyolefin resin coating sheet of the present invention is 0.5 to 10 g / 10 min. If the melt flow rate is less than 0.5 g / 10 min, it may be difficult to mold the flame retardant polyolefin resin-coated sheet obtained. On the other hand, if it is higher than 10 g / 10 min, not only the mechanical strength and heat-resistant creep resistance of the resulting resin-coated sheet will be insufficient, but also problems such as increased tackiness and blocking may occur. . Further, when the content of the copolymerization monomer contained in the polyolefin resin blend is less than 5% by weight, the high-frequency welder property of the resulting polyolefin resin composition layer may be insufficient, When the amount is more than 35% by weight, mechanical strength of the resulting polyolefin-based resin film becomes insufficient, adhesiveness during processing increases, and molding processing may be difficult.
[0017]
Moreover, as polyolefin resin used for the flame retardant polyolefin resin coating sheet of the present invention, in addition to the above polyolefin resins, polypropylene resins having a melt flow rate of 0.5 to 10 g / 10 min, such as polypropylene, Reactor polymerization resin of polypropylene and ethylene-propylene rubber (EPR rubber), or PP-EPR resin which is a polymer alloy thereof, reactor polymerization resin of polypropylene and ethylene-propylene-conjugated diene rubber (EPDM rubber), or These polymer alloy bodies such as PP-EPDM resin can be blended and used.
[0018]
The red phosphorus particles contained in the polyolefin resin composition of the flame-retardant polyolefin resin-coated sheet of the present invention are those obtained by converting yellow phosphorus by heating at 250 to 350 ° C. in an inert gas atmosphere. Used as a powdery body having an average particle size of 5 to 25 μm. The red phosphorus particles that can be used in the present invention include inorganic compounds of aluminum hydroxide, magnesium hydroxide, titanium oxide, and zinc oxide, or thermosetting of formalin resin, phenol resin, melamine resin, urea resin, and epoxy resin. It is preferable to use red phosphorus particles which are surface-coated with one or more selected from a functional resin and have an average particle diameter of 5 to 25 μm. In particular, white-treated red phosphorus particles whose surface is coated with titanium oxide can be preferably used because they have a high degree of coloration with respect to the flame-retardant polyolefin resin-coated sheet of the present invention.
[0019]
The red phosphorus particles used in the polyolefin resin composition layer of the flame retardant polyolefin resin coating sheet of the present invention are blended in an amount of 5 to 35 parts by weight with respect to 100 parts by weight of the polyolefin resin. When the amount of red phosphorus particles is less than 5 parts by weight, the resulting flame-retardant property of the polyolefin-based resin composition layer becomes insufficient, and the flameproof test standard of the Fire Service Act cannot be met.
On the other hand, if the amount of red phosphorus particles exceeds 35 parts by weight, the flame retardancy level is saturated and does not improve, but rather the processability of the polyolefin resin composition layer (film) deteriorates, and the polyolefin system obtained at the same time. The mechanical strength of the resin composition layer (film) is significantly deteriorated. The melt flow rate of the flame retardant polyolefin resin composition obtained by blending 5 to 35 parts by weight of red phosphorus particles, particularly 10 to 20 parts by weight with respect to 100 parts by weight of the polyolefin resin is 0.2. It is -5.0g / 10min, It is preferable that it is 0.5-3.0g / 10min. When the melt flow rate is less than 0.2 g / 10 min, the processing fluidity of the resulting polyolefin resin composition is deteriorated, not only the productivity is lowered, but also the film surface appearance is deteriorated. On the other hand, when the melt flow rate exceeds 5.0 g / 10 min, not only the mechanical strength and heat-resistant creep resistance of the resulting resin-coated sheet are insufficient, but also the tackiness is increased and blocking occurs.
[0020]
The polyolefin-based resin composition layer of the flame-retardant polyolefin-based resin-coated sheet of the present invention may be colored with an organic pigment, an inorganic pigment, or the like, if necessary. Insoluble monoazo pigments, insoluble disazo pigments, azo lake pigments, condensed azo pigments, metal complex azo pigments, phthalocyanine pigments, acid dye lake pigments, basic dye lake pigments, etc. Polycyclic pigments such as anthraquinone pigments, thioindigo pigments, perinone pigments, perylene pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, isoindoline pigments, and other nitroso pigments, Alizarin lake pigment, metal complex azomethine pigment, aniline Such as pigments, and the like.
[0021]
Inorganic pigments include zinc oxide (zinc flower), titanium oxide (rutile type, anatase type), antimony trioxide, iron oxide, ferrocyanide (bitumen), lead oxide, chromium oxide, zirconium oxide, cobalt oxide and oxide. Metal oxide such as composite of aluminum (cobalt blue), composite of cobalt oxide, zinc oxide and magnesium oxide (cobalt green), composite of zinc sulfide and barium sulfate (lithopone), calcium sulfide, strontium sulfide, sulfide Metal sulfides such as zinc, zinc cadmium sulfide, cadmium sulfide, cadmium sulfide and selenium-cadmium composite (cadmium red, cadmium orange, cadmium yellow) antimony sulfide and antimony trioxide (antimony vermilion), barium sulfate , Calcium sulfate, lead sulfate, basic Metal sulfides such as lead acid, barium carbonate, calcium carbonate, magnesium carbonate, metal carbonates such as composites of lead carbonate and lead hydroxide (lead white), magnesium hydroxide, aluminum hydroxide (alumina white), hydroxide Metal hydroxides such as composites of aluminum and calcium sulfate (satin white), composites of aluminum hydroxide and barium sulfate (gross white), lead chromate (yellow lead), barium chromate, lead chromate and molybdate Chromic acid metal salt such as composite of lead and lead sulfate (chromium vermillion), composite of lead molybdate and lead sulfate (molybdenum red), spinel type (XY₂O_Four) Structural oxide, rutile type [Ti (XY) O₂] Structural oxides, carbon black, titanium black, acetylene black, graphite, silica, white carbon, diatomaceous earth, talc, clay, aluminum powder pigment, bronze powder, nickel powder, stainless steel powder, pearl pigment, etc. .
[0022]
In addition, these organic pigments and inorganic pigments are compounded and filled into thermosetting resins such as melamine resin, benzoguanamine resin, urea resin, phenol resin, epoxy resin, etc. May be used. In addition, these organic pigments and inorganic pigment products are treated with a dispersant to improve dispersibility when used in coloring applications such as synthetic resin molded products, films, synthetic fibers, and synthetic resin paints. It is preferable to use processed pigments. As the dispersant, aqueous lignin sulfonate, sodium alkyl sulfate ester, sodium alkyl aryl sulfonate, sodium naphthalene sulfonate formalin condensate, marcel soap, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, Styrene-maleic acid resin, polyacrylic acid derivatives, etc. are mentioned, and oil dispersants include lecithin, sorbitan fatty acid ester, partial fatty acid ester of polyacrylic acid, alkylamine fatty acid salt, alkyldiamine, alkyltriamine, naphthenic acid metal soap, etc. Can be mentioned.
[0023]
These dispersant-treated organic pigments and inorganic pigments are added with other vehicles, press cakes, resins, waxes, plasticizers, water, etc., in order to improve processing handling properties in various applications. It is desirable to use processed pigments adjusted to forms such as flushed color, aqueous liquid color, oily liquid color, paste color (vinyl toner color), dry color, moisture color, masterbatch, and colored pellets, respectively.
[0024]
In the production of the polyolefin resin composition layer film of the present invention, when carrying out melt kneading of a thermoplastic resin such as calendering, T-die extrusion, inflation, etc., dry color, master batch, colored pellets are used. It is suitable to use. Especially for molding processing of olefinic resin compositions, it is more preferable to use colored pellets in which organic and inorganic pigments are filled with a dispersant, wax, and polyolefin resin such as polyethylene and polypropylene together with a high concentration. it can. In addition, when the polyolefin resin is based on an aqueous emulsion, an aqueous liquid color can be used. In the case of a solvent-based polyolefin resin coating agent, a flashed color, paste color, dry color, oily liquid color, etc. Can be used.
[0025]
As a colorant for the polyolefin resin composition layer of the flame retardant polyolefin resin coating sheet of the present invention, an inorganic pigment and an organic pigment can be used in combination. The combination of these colorants is not particularly limited because it is a combination according to the target hue adjustment, but these inorganic pigments and / or organic pigments are used with respect to 100 parts by weight of the polyolefin resin. Is preferably 1 to 20 parts by weight, particularly 3 to 10 parts by weight. When the added amount of the pigment is 1 part by weight or less, the colorability of the polyolefin resin containing red phosphorus particles may be insufficient, and the concealability of the red phosphorus particles may not be obtained. Moreover, when it exceeds 20 weight part, not only the moldability of a polyolefin-type resin composition layer film will be deteriorated but a flame retardance may be reduced. The melt flow rate of the colored flame retardant polyolefin resin composition is 0.2 to 5.0 g / 10 min, and preferably 0.5 to 3.0 g / 10 min. When the melt flow rate is less than 0.2 g / 10 min, the processing fluidity of the resulting resin composition is deteriorated and not only the productivity is lowered but also the film surface appearance may be deteriorated. Moreover, when the melt flow rate exceeds 5.0 g / 10 min, not only the mechanical strength and heat-resistant creep resistance of the resulting resin-coated sheet become insufficient, but also the adhesiveness may be increased to cause blocking. .
[0026]
For the polyolefin resin composition layer of the flame retardant polyolefin resin coating sheet of the present invention, a weather resistance stabilizer such as an antistatic agent, an antioxidant, a hindered amine compound, an ultraviolet absorber, a lubricant, etc. Can be added. In addition, an inorganic filler can be added and used in combination for the purpose of reducing the production cost as long as various properties of the obtained flame-retardant polyolefin resin-coated sheet are not impaired. Examples of the inorganic filler include calcium carbonate, talc, clay, silica, and glass powder. In addition to the commonly used additives such as plasticizers, softeners, stabilizers, foaming agents, surfactants, crosslinking agents, curing agents, conductive fillers, antifungal agents, antibacterial agents, etc. You may mix | blend in the range which does not deviate.
[0027]
There is no particular limitation on the method for producing the polyolefin resin composition layer film used in the present invention, and red phosphorus particles, organic pigments, inorganic pigments, etc. are uniformly dispersed in the polyolefin resin used in the present invention. Any method can be used as long as it can be mixed and formed into a film. As a mixing method, each component such as red phosphorus particles, organic pigment, inorganic pigment and polyolefin resin are granulated after being melt-kneaded by a known method using, for example, a Banbury mixer, a kneader, a biaxial kneader or the like. Prepare a master batch of polyolefin resin composition containing red phosphorus particles, organic pigments, inorganic pigments and other components at high concentrations using a method or a Banbury mixer, and add polyolefin resin to the tumbler blender and tumble. A method of dry blending using a mixer such as a mixer or a Henschel mixer, or a method of melt kneading and granulating with a single screw extruder, twin screw extruder or the like after mixing can be employed.
[0028]
The polyolefin-based resin composition layer film used in the present invention can be produced by a known film processing technique such as a T-die method, an inflation method, a calender method, etc. In order to reliably and stably carry out uniform dispersion in the resin composition, there is a calendar method capable of significantly lowering the molding processing temperature compared to the T-die method and the inflation method. Are suitable. In the production of the flame retardant polyolefin-based resin composition layer film of the present invention, it is desirable to perform a molding process by a calendar method in a temperature range of 80 to 200 ° C.
[0029]
The film for the polyolefin resin composition layer of the flame retardant polyolefin resin coating sheet of the present invention preferably has a thickness of 80 to 800 μm, particularly 130 to 450 μm. If the thickness is less than this range, molding is difficult, and when laminated on a fabric base fabric, the film will be cut off due to thermocompression bonding with the uneven surface of the base fabric surface, impairing the waterproof property. May not be used for tents and sheets. On the other hand, when the thickness is greater than 800 μm, not only calendering becomes difficult, but also it is heavy and lacks flexibility, resulting in poor handling.
[0030]
In addition, in order to form the flame-retardant polyolefin resin composition layer of the present invention on a base fabric, an aqueous composition in which red phosphorus particles are dispersed and blended in a polyolefin resin emulsion is coated on the base fabric and dried. You may go by doing. As a method for forming a polyolefin-based resin composition layer using this polyolefin-based resin emulsion, the emulsion composition for forming a polyolefin-based resin composition layer directly on a base fabric may be applied by coating and drying, Alternatively, an emulsion for forming a polyolefin-based resin composition layer on a release paper or a release film may be applied by coating and drying the composition, and this may be laminated on a base fabric.
Examples of polyolefin resin emulsions include ethylene-vinyl acetate copolymer resins, vinyl acetate-ethylene copolymer resins, ethylene-acrylic acid copolymer resins, ethylene-acrylic acid copolymer ionomer resins, and ethylene-propylene copolymer resins. Can be used.
[0031]
For forming the polyolefin resin composition layer of the present invention, the polyolefin resin is dissolved in an organic solvent, and a solvent composition in which red phosphorus particles are dispersed and blended in this solution is coated and dried.
[0032]
The thermoplastic resin forming the thermoplastic resin filament yarn used in the fabric for the base fabric of the flame-retardant polyolefin resin-coated sheet of the present invention is selected from, for example, polyethylene resin, polypropylene resin, polyester resin, and polyamide resin It is preferable that
The filament yarn for base fabric is preferably selected from multifilament yarns, monofilament yarns, tape yarns, split yarns and split yarns, more preferably multifilament yarns. These yarns can be produced by a normal thermoplastic filament yarn production method.
For example, as a spinning method of the multifilament yarn, for example, the thermoplastic resin is heated to a temperature equal to or higher than the melting temperature (melting point) to obtain a fluid viscous melt, which is a specific diameter (0.2 to A conventionally known melt spinning method that passes through a spinneret having pores of about 0.6 mmφ) and extrudes into an inert cooling medium such as air, nitrogen, water, etc., and rapidly solidifies by cooling to form a continuous filament spinning yarn. And a method of manufacturing using equipment.
[0033]
The unstretched long fiber spinning yarn is stretched 3.0 to 5.0 times by, for example, heat stretching at 80 to 100 ° C. or cold stretching near room temperature to arrange and crystallize the fiber microstructure. The fiber can be given strength. This drawing process may be incorporated in the spinning process, and it is preferable that the drawing process and the multifilament twisting process are performed simultaneously. Furthermore, heat treatment two-stage stretching may be performed as necessary. These melt spinning speeds are not particularly specified because the spinning speeds differ depending on the thermoplastic resin to be used and the equipment. For example, the spinning speed in the case of melt spinning from a polyester resin is 1,000 to 10,000 m / min. In particular, those spun at a speed of 2,000 to 6,000 m / min can be preferably used.
[0034]
As a standard of the multifilament yarn used for the fiber fabric of the flame-retardant polyolefin-based resin-coated sheet of the present invention, for example, 100 to 2200 denier spun from the thermoplastic resin and added with any number of twists, Preferably, a multifilament yarn of 200 to 1600 denier, more preferably 250 to 1100 denier can be used. If the multifilament yarn is less than 100 denier, the tear strength of the resulting sheet may be insufficient, and if it exceeds 2200 denier, the breaking strength and tear strength will surely improve, but the diameter of the yarn becomes thicker. In some cases, the thickness of the sheet increases, and the handleability of the sheet becomes insufficient.
[0035]
The filament yarn used in the fabric for base fabric of the flame-retardant polyolefin resin-coated sheet of the present invention is preferably a filament yarn spun from polyethylene resin or polypropylene resin, and a mixture of polyethylene resin and polypropylene resin. Examples thereof include filament yarns, multifilament yarns spun from polyethylene resin, and multifilament yarns spun from polypropylene resin. The polyethylene resin used as the raw material for the polyethylene resin filament yarn (especially multifilament yarn) is, for example, a density of 0.94 to 0.97 g / cm obtained by a medium-low pressure polymerization method of ethylene monomer.^ThreeHigh-density polyethylene having a crystallinity of 70 to 95% and a melt flow rate of 0.4 to 1.2 can be preferably used from the viewpoint of fiber strength and melt spinnability. In addition, as a polypropylene resin used as a raw material for polypropylene resin filament yarn (particularly multifilament yarn), for example, an isotactic structure obtained by polymerizing propylene monomer using a stereoregular catalyst such as a Ziegler-Natta catalyst. Polypropylene can be preferably used from the viewpoint of fiber strength and spinnability. Polypropylene resin filament yarn and mixed filament yarn of polyethylene resin and polypropylene resin are, for example, slit into a tape shape of a polypropylene resin film or a mixed film of polyethylene resin and polypropylene resin, and stretched 5 to 15 times. Further, after the molecular orientation, the fiber may be made into a split fiber and twisted by a mechanical operation.
[0036]
The dry heat shrinkage (JIS standard L-1073) of the polyethylene filament yarn, polypropylene filament yarn, and polyethylene-polypropylene mixed filament yarn is 5 to 25%, particularly within 5 to 15% when heated at 120 ° C. for 15 minutes. It is preferable that When the dry heat shrinkage rate is less than 5%, when the flame retardant polyolefin resin sheet obtained is flared in a flameproof test, the fiber fabric quickly melts and is inferior in physical shrinkage behavior away from the fire source. As a result, it may not conform to the item of the carbonized area of the flameproof standard stipulated in the Fire Service Law. On the other hand, when the dry heat shrinkage rate exceeds 25%, the fiber fabric melts rapidly at the time of flaming, and the physical shrinkage behavior away from the fire source is excellent, but the processability and heat resistance of the flame retardant sheet of the present invention are excellent. Creepability may be insufficient.
[0037]
A multifilament yarn spun from a polyester resin is preferably used as the filament yarn used for the fabric for the base fabric of the flame-retardant polyolefin resin-coated sheet of the present invention. Polyester resins used as raw materials for polyester multifilament yarn include polyethylene terephthalate (PET) obtained by polycondensation of terephthalic acid and ethylene glycol, and polybutylene terephthalate (PBT) obtained by polycondensation of terephthalic acid and butylene glycol. Can be mentioned. Of these, polyester fibers melt-spun from polyethylene terephthalate resin are preferably used from the viewpoints of fiber strength and melt-spinnability. In addition to the above monomers, polyethylene terephthalate may contain about 5% by weight of a copolymer monomer such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid and diethylene glycol. A polyester multifilament yarn having a dry heat shrinkage (JIS standard L-1073) of 5 to 25%, particularly 5 to 15% when heated at 150 ° C. for 15 minutes is preferably used. When the dry heat shrinkage rate is less than 5%, when the flame retardant test of the obtained flame-retardant polyolefin-based resin-coated sheet is applied to the flame, the fiber fabric quickly melts and is inferior in physical shrinkage behavior away from the fire source, Residual flames are likely to occur at the melted end of the sheet, and as a result, it may not conform to the item of carbonization area of the flameproof standard stipulated in the Fire Service Law. Moreover, when the dry heat shrinkage rate exceeds 25%, the base fabric melts quickly at the time of flaming, and the physical shrinkage behavior away from the fire source is excellent, but the processability of the flame retardant sheet of the present invention is excellent. And heat-resistant creep resistance may be insufficient.
[0038]
A multifilament yarn spun from a polyamide resin can be used as the filament yarn used in the fabric for the base fabric of the flame-retardant polyolefin resin-coated sheet of the present invention.
Examples of the polyamide resin used as a raw material for the polyamide multifilament yarn include nylon 6 obtained by ring-opening polymerization of ε-caprolactam, nylon 66 obtained by polycondensation of adipic acid and hexamethylenediamine, and the like. The dry heat shrinkage (JIS standard L-1073) of the polyamide multifilament yarns obtained from these nylon 6 and nylon 66 is preferably 5 to 25% when heated at 150 ° C. for 15 minutes, particularly 5 to 15%. More preferably. When the dry heat shrinkage rate is less than 5%, the fiber fabric melts rapidly when flame-retardant in the flame-retardant polyolefin resin-coated sheet obtained, and the physical shrinkage behavior away from the fire source is inferior. As a result, it may not conform to the item of the carbonized area of the flameproof standard stipulated in the Fire Service Law. Further, when the dry heat shrinkage rate exceeds 25%, the fiber fabric melts quickly at the time of flaming and is excellent in physical shrinkage behavior away from the fire source, but the processability of the flame retardant sheet of the present invention is excellent. In addition, the thermal creep resistance may be insufficient.
[0039]
The filament yarn used in the fabric for the base fabric of the flame-retardant polyolefin resin-coated sheet of the present invention is a colored yarn spun from a thermoplastic resin containing a colorant such as an organic pigment, an inorganic pigment, or a dye. It may be a filament yarn.
[0040]
As the fabric for the base fabric that can be used for the flame-retardant polyolefin resin-coated sheet of the present invention, any of woven fabric, knitted fabric, and nonwoven fabric can be used. This is preferable because of excellent balance of physical properties in the warp direction and the weft direction. Examples of the woven fabric include a plain weave fabric that uses two warps and wefts each as a minimum unit structure of a woven structure, a twill weave fabric that uses three warps and wefts as a minimum unit structure, and warps As a woven fabric for the base fabric of the flame-retardant polyolefin-based resin-coated sheet of the present invention, a woven fabric with openings is used. When used, the bridge fusion effect at the time of thermal lamination of the polyolefin resin film can be obtained. As such a mesh woven fabric, a plain woven fabric that can easily design the mesh density of the mesh is particularly preferable.
Moreover, it is most preferable to use a plain woven fabric from the viewpoint of balance of physical properties in the warp direction and the weft direction of the flame-retardant polyolefin resin sheet of the present invention. These woven fabrics can be woven using conventionally known looms such as a shuttle loom and a shuttleless loom (rapier method, gripper method, water jet method, air jet method).
[0041]
There is no particular limitation on the warp and weft yarn density of the fabric for base fabric that can be used in the flame-retardant polyolefin resin-coated sheet of the present invention. For example, the yarn density is 100 to 2200 denier obtained by melt spinning from the thermoplastic resin. 10 to 50 multifilament yarns per inch, for example 20 to 30 multifilament yarns of 250 denier, or 15 to 25 denier multifilament yarns of 500 to 1000 denier, or 1500 denier A stitched plain woven fabric in which multifilament yarns are woven at a weaving density of about 10 to 20 per inch is suitable. Further, the basis weight of these stitched plain woven fabrics is 50 to 500 g / m.²Is suitable.
[0042]
Examples of the fabric for the base fabric that can be used for the flame-retardant polyolefin resin-coated sheet of the present invention include any of the polyethylene multifilament yarn, the polypropylene multifilament yarn, the polyethylene-polypropylene mixed multifilament yarn, or The fabric woven by mixing is subjected to a known heat setting treatment, and the dry heat shrinkage (JIS A-6008) at 150 ° C. for 15 minutes is controlled to 5% to 25%, preferably 5 to 15%. Although not heat-set, a woven fabric having a dry heat shrinkage of 5 to 25%, preferably 5 to 15% when heated at 150 ° C. for 15 minutes is used. If the dry heat shrinkage of the woven fabric is less than 5%, the physical shrinkage behavior that the fiber fabric melts rapidly and moves away from the fire source when the obtained flame-retardant polyolefin resin-coated sheet is applied in a flameproof test. Inferior to this, it tends to cause a residual flame at the melted end of the sheet, and as a result, it may not conform to the item of the carbonized area of the flameproof standard stipulated in the Fire Service Law. Further, when the dry heat shrinkage rate exceeds 25%, the fiber fabric melts quickly at the time of flaming and is excellent in physical shrinkage behavior away from the fire source, but the processability of the flame retardant sheet of the present invention is excellent. And heat resistance creep resistance is insufficient.
[0043]
As the fabric for base fabric that can be used for the flame-retardant polyolefin resin-coated sheet of the present invention, for example, a fiber fabric woven with the above-mentioned polyester multifilament yarn is subjected to dry heat shrinkage when heated at 150 ° C. for 15 minutes by heating ( JIS standard A-6008) is 5% to 25%, especially woven fabric controlled within 5 to 15%, or dry heat shrinkage when heated at 150 ° C. for 15 minutes without heat setting is 5 to 25 %, Especially 5 to 15% or less of woven fabric is preferred. If the dry heat shrinkage of the woven fabric is less than 5%, the physical shrinkage behavior that the fiber fabric melts rapidly and moves away from the fire source when the obtained flame-retardant polyolefin resin-coated sheet is applied in a flameproof test. Inferior to this, it tends to cause a residual flame at the melted end of the sheet, and as a result, it may not conform to the item of the carbonized area of the flameproof standard stipulated in the Fire Service Law. Moreover, when the dry heat shrinkage rate exceeds 25%, the fiber fabric melts quickly at the time of flame, and although the physical shrinkage behavior away from the fire source is excellent, the workability of the flame-retardant sheet of the present invention, Heat resistance creep resistance may be insufficient.
[0044]
The fabric for base fabric used in the flame-retardant polyolefin resin-coated sheet of the present invention may be subjected to a flame-retardant treatment if necessary, or is woven with flame-retarded fibers. It may be a fabric. As the fabric subjected to flame retardant treatment, phosphoric acid ester compound flame retardant, ammonium polyphosphate compound flame retardant, (iso) cyanuric acid derivative compound flame retardant, cyanamide compound flame retardant, urea, depending on the type of fiber Flame retardant containing one or more selected from a flame retardant compound and a sulfur compound flame retardant as a dispersion medium using water or an organic solvent, or emulsion and latex as a dispersion medium Examples thereof include those obtained by impregnating the above-mentioned fiber fabric with a chemical treatment agent, followed by drying and heat treatment. In addition, as the fiber that has been flame-retarded in advance, at least one selected from the above flame retardants is blended and melt-spun at the stage where the yarn is spun from a thermoplastic resin such as polyethylene resin, polypropylene resin, polyester resin, or polyamide resin. In the stage of synthesizing the flame retardant fiber or thermoplastic resin, it is melt-spun from a polyester resin or polyamide resin obtained by synthesizing a part of the raw material monomer with a phosphate ester-containing monomer or a halogen-containing monomer. In order to impart excessive flame retardancy to the fabric for the base fabric used in the flame retardant polyolefin-based resin-coated sheet of the present invention, The flameproof balance may deteriorate in the area to be carbonized. In order to impart flame retardancy to these fiber fabrics, it is preferable that an appropriate flame retardant treatment is performed in accordance with the melting level and self-extinguishing level of the polyolefin resin layer film of the present invention.
[0045]
Lamination of the base fabric and the polyolefin-based resin composition layer film may be performed by laminating the film only on one side of the base fabric or on both sides thereof, but considering durability for outdoor use. It is preferable to laminate a film for a polyolefin resin composition layer on both sides of the base fabric. Moreover, as a lamination method, an adhesive layer may be provided between the polyolefin resin composition layer film and the base fabric, or lamination and fusion may be performed without an adhesive. The method of laminating the base fabric used for the production of the flame-retardant polyolefin-based resin-coated sheet of the present invention and the polyolefin-based resin composition layer film is a calender topping in which the film is heat-laminated and laminated on the base fabric simultaneously with the molding process. Or a T-die laminating method, or a film is once molded by a calendar method, a T-die method, an inflation method, etc., and then laminated on a base fabric by thermocompression bonding with a laminator. A method may be used. For the production of the flame-retardant polyolefin resin-coated sheet according to the present invention, a method by thermocompression bonding between a polyolefin resin composition layer film molded by a calender method and a polyester fiber plain woven base fabric is efficient and economical. Is. At this time, the woven structure of the plain weave base fabric is more preferably a hollow plain weave. Also, when the method for forming a film for a polyolefin resin composition layer used in the flame retardant polyolefin resin coating sheet of the present invention is performed by coating application-drying of a blended composition using a polyolefin resin emulsion May be a high-thread-density non-open plain weave as the fibrous plain weave base fabric.
[0046]
The surface of the colored polyolefin resin composition layer of the flame retardant polyolefin resin coating sheet of the present invention may be provided with a protective layer made of a colored polyolefin resin not containing the red phosphorus particles. The colored polyolefin resin protective layer containing no red phosphorus particles preferably contains a non-halogen flame retardant and is flame retardant. The phosphoric acid compound flame retardant 5 with respect to 100 parts by weight of the polyolefin resin. ~ 50 parts by weight, chemical foaming agent 1-20 parts by weight, inorganic pigment and / or organic pigment 1-20 parts by weight, melt flow rate (MFR) 0.2-5.0 g A colored protective layer formed from a composition of / 10 min is preferable.
[0047]
The polyolefin resin that can be used in the colored polyolefin resin protective layer of the flame retardant polyolefin resin coating sheet of the present invention is selected from the polyolefin resins that can be used in the flame retardant polyolefin resin composition layer of the present invention, The flow rate (MFR: JIS K6760) is 0.5 to 10 g / 10 min, preferably 0.5 to 5.0 g / 10 min, and the comonomer content is 5 to 35 wt%, preferably 15 to 25 wt%. Are preferably selected from those described above. If the melt flow rate is less than 0.5 g / 10 min, molding of the resulting colored polyolefin-based resin protective layer may be extremely difficult, and if it is higher than 10 g / 10 min, the protective layer obtained Not only is the abrasion resistance and heat resistance inferior, it may increase the tackiness and cause blocking. When the copolymerization monomer content is less than 5% by weight, the protective layer obtained may have insufficient high-frequency welder properties, and when the copolymerization monomer content is more than 35% by weight, it is obtained. The mechanical strength of the protective layer becomes insufficient, the tackiness during processing increases, and the molding process may be extremely difficult.
[0048]
Furthermore, the polyolefin resin that can be used for the colored polyolefin resin protective layer has a melt flow rate of 0.5 to 10 g / 10 min for the purpose of imparting sufficient durability such as mechanical resin strength and abrasion resistance. At least one selected from the group consisting of crystalline polyolefin resins such as polyethylene, ethylene-α-olefin, low density polyethylene, medium density polyethylene, and polypropylene, and the ethylene-vinyl acetate copolymer resin, ethylene-acrylic. A blend with at least one selected from a copolymer resin is preferable. Although there is no restriction | limiting in particular in these blend ratios, it is high frequency welder property that the total amount of a vinyl acetate component and an acrylic acid-type component is 5-35 weight% with respect to 100 weight% of polyolefin-type resin blend bodies. It is preferable from the viewpoint. Further, blends having a melt flow rate of 0.5 to 10 g / 10 min can be suitably used for the colored polyolefin resin protective layer of the flame retardant polyolefin resin coated sheet of the present invention. If the melt flow rate is less than 0.5 g / 10 min, it may be very difficult to mold the resulting colored polyolefin resin protective layer. On the other hand, if it is higher than 10 g / 10 min, not only the wear resistance and heat creep resistance of the sheet become insufficient, but also the tackiness may be increased and blocking may occur. If the copolymerization monomer content is less than 5% by weight, the resulting protective layer has insufficient high-frequency welder properties. If the copolymerization monomer content is more than 35% by weight, the resulting protective layer machine The mechanical strength becomes insufficient, the tackiness during processing increases, and the molding process may be extremely difficult.
[0049]
The polyolefin resin used for the colored polyolefin resin protective layer may be a polypropylene resin having a melt flow rate of 0.5 to 10 g / 10 min, such as polypropylene, polypropylene and ethylene-propylene, in addition to the above polyolefin resin. Reactor polymerized resin with rubber (EPR rubber), or PP-EPR resin which is a polymer alloy of these, reactor polymerized resin of polypropylene and ethylene-propylene-conjugated diene rubber (EPDM rubber), or a polymer alloy of these It is also possible to blend and use PP-EPDM resin or the like.
[0050]
As the non-halogen flame retardant used in the colored polyolefin-based resin protective layer, the phosphoric acid compound is one or more selected from phosphoric acid ester, phosphoric acid salt, phosphoric acid ester salt, and condensed phosphoric acid salt. Can be used in an amount of 5 to 50 parts by weight based on 100 parts by weight of the polyolefin resin. Among these phosphoric acid compounds, it is particularly preferable to use a condensed phosphate. As the condensed phosphate, it is preferable to use one or more selected from ammonium polyphosphate, thermosetting resin-coated ammonium polyphosphate, and melamine polyphosphate. Ammonium polyphosphate having a degree of polymerization of 200 or more is preferably used. Further, the surface of ammonium polyphosphate is coated with a thermosetting resin such as melamine resin, urea resin, phenol resin, etc., and is hardly soluble in water. Are preferably used. Moreover, when the polymerization degree of ammonium polyphosphate is less than 200, ammonium polyphosphate becomes water-soluble, the water resistance of the colored polyolefin-based resin protective layer is lowered, or the sustainability of the flame retarding effect becomes poor. May be inappropriate for outdoor use. As the condensed phosphorus compound used for the colored polyolefin-based resin protective layer, ammonium polyphosphate having a polymerization degree of 600 to 1200 surface-treated with a melamine resin can be preferably used. The flame retardant polyolefin resin sheet obtained when the added amount of these phosphoric flame retardants is less than 5 weights is insufficient in flame retardancy and cannot meet the flameproofing test stipulated in the Fire Service Act. There is. Moreover, when the addition amount exceeds 50 weight part, not only the workability of the resin composition obtained will worsen, but the abrasion resistance of a colored polyolefin resin protective layer may become inadequate.
[0051]
Chemical foaming agents used in the colored polyolefin resin protective layer include azo compounds such as azodicarbonamide and azobisisobutyronitrile, N, N′-dinitrosopentamethylenetetramine, N, N′-dimethyl-N. Polyolefin resin 100 using one or more of nitroso compounds such as N, N'-dinitrosotephthalamide and sulfonyl hydrazide compounds such as p, p'oxybis (benzenesulfonyl hydrazide), benzenesulfonyl hydrazide and toluenesulfonyl hydrazide. 1 to 20 parts by weight can be used with respect to parts by weight. In particular, azodicarbonamide is preferably used alone or in an amount of 50% by weight or more of the amount of chemical blowing agent added. Azodicarbonamide is a pyrolysis product gas (N₂, CO, CO₂, NH_Three), Nitrogen-containing decomposed solids and sublimates such as urazole, biurea, isocyanuric acid, and shea merit are by-produced, and these nitrogen-containing decomposed solids and sublimated products are highly advanced by synergistic effects with the phosphoric acid compounds. The flame retardancy is obtained. If the amount of these chemical foaming agents added is less than 1% by weight, the flame-retardant polyolefin resin sheet obtained will have insufficient flame retardancy and may not be able to meet the flame-proof test stipulated in the Fire Service Act. is there. Moreover, when the addition amount exceeds 20 weight part, not only the workability of the resin composition obtained will worsen, but the abrasion resistance of a colored polyolefin resin protective layer may become inadequate.
[0052]
These chemical foaming agents are preferably uniformly dispersed without being thermally decomposed during molding of the colored polyolefin resin layer of the flame-retardant polyolefin resin-coated sheet of the present invention. If the chemical foaming agent is thermally decomposed during molding, it is not preferable because not only the flame resistance of the resulting sheet is remarkably deteriorated, but also the appearance of the sheet is impaired. In addition, as a thermal decomposition aid for chemical foaming agents, inorganic salts such as zinc oxide, lead oxide, tribasic lead sulfate, dibasic lead phosphite, lead stearate, stearic acid, etc. The decomposition rate can be controlled by using appropriate amounts of metal soaps such as barium and calcium stearate, and urea.
[0053]
As the inorganic pigment and the organic pigment used in the colored polyolefin resin protective layer, the inorganic pigment and the organic pigment can be used alone or in combination. Combinations of these colorants are combined according to the target hue, and the composition thereof is not particularly limited, but these inorganic pigments and / or organic pigments are used with respect to 100 parts by weight of the polyolefin resin. The addition amount is preferably 1 to 20 parts by weight, more preferably 3 to 10 parts by weight.
[0054]
Melt flow of a resin composition obtained by blending the phosphoric acid compound, the chemical foaming agent, and the inorganic pigment and / or organic pigment into the polyolefin resin that can be used for the colored polyolefin resin protective layer The rate (MFR: JIS K6760) is preferably 0.5 to 10 g / 10 min, and more preferably 0.5 to 5.0 g / 10 min. If the melt flow rate is less than 0.5 g / 10 min, molding of the resulting colored polyolefin resin protective layer may be extremely difficult, and if it is higher than 10 g / 10 min, the resulting colored polyolefin resin is obtained. The protective layer may have insufficient wear resistance and heat resistance, and may further increase the tackiness and cause blocking.
[0055]
The colored polyolefin-based resin protective layer film can be produced by a known film processing technique such as a T-die method, an inflation method, or a calender method, but a calender method that can be processed at a temperature lower than the thermal decomposition temperature of the chemical foaming agent is suitable. In the production of the colored polyolefin-based resin protective layer of the present invention, it is most desirable to perform calender molding in a temperature range of 80 to 200 ° C.
The colored polyolefin resin film may be adhered on at least one of the front and back double-sided polyolefin resin composition layers to form a protective layer, or a coating solution containing the colored polyolefin resin May be applied and dried to form a protective layer.
[0056]
The thickness of the colored polyolefin-based resin protective layer is preferably 10 to 50% of the thickness of the flame-retardant polyolefin-based resin-coated sheet (the total of the thickness of the base fabric and the thickness of the front and back double-sided resin layers). . When the thickness is less than 10%, the molding process becomes difficult, and the hue concentration that masks the hue of the flame-retardant polyolefin resin-coated sheet when laminated on the surface of the flame-retardant polyolefin resin composition layer May be insufficient. Moreover, when the thickness exceeds 50%, the flameproof balance of the resulting laminated sheet may be deteriorated, and it may be difficult to meet the flameproof test prescribed in the Fire Service Law. The sheet becomes heavy, lacks flexibility, and handling may be poor.
[0057]
As a method for laminating the colored polyolefin resin protective layer film, an adhesive layer may be provided between the colored polyolefin resin protective layer film and the flame retardant polyolefin resin composition layer, or without an adhesive. You may laminate. The method for laminating the colored polyolefin resin protective layer film and the flame retardant polyolefin resin composition layer is the same as that for forming the colored polyolefin resin protective layer film on the flame retardant polyolefin resin composition layer. A calender topping method or a T-die laminating method for heat laminating can be used, or a colored polyolefin resin protective layer film is once molded and processed by a calendering method, a T-die method, an inflation method, etc. Is laminated on the flame retardant polyolefin resin composition layer by thermocompression bonding with a laminator, etc., but the flame retardant polyolefin resin coated sheet according to the present invention is colored by a calendering method. Polyolefin resin protective layer film with flame retardant polyolefin How to thermocompression bonding system resin composition layer is, efficient and economically desirable.
[0058]
Further, for the formation of the colored polyolefin-based resin protective layer, a water-based composition in which the phosphorus-based compound, the chemical foaming agent, and the inorganic pigment and / or organic pigment are dispersed and blended in a polyolefin-based resin emulsion, A method of applying a coating on the resin composition layer and drying it may be used. As a method for forming a colored polyolefin resin protective layer using this polyolefin resin emulsion, the emulsion composition for forming the colored polyolefin resin protective layer is directly coated on the flame retardant polyolefin resin composition layer. -A method of forming by drying may be used. Or you may apply | coat and dry the emulsion which forms the said colored polyolefin resin protective layer on a release paper or a release film, and may laminate this on the said flame-retardant polyolefin resin composition layer. As the polyolefin resin emulsion, ethylene-vinyl acetate copolymer resin, vinyl acetate-ethylene copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-acrylic acid copolymer ionomer resin, ethylene-propylene copolymer resin, etc. can be used. . In addition, the colored polyolefin-based resin protective layer is formed in a solution obtained by dissolving the polyolefin-based resin in an organic solvent, the phosphorus compound, the chemical foaming agent, the inorganic pigment, and / or A method in which an organic pigment is dispersed and blended, and the resulting composition is coated and dried may be used.
[0059]
The method for producing a flame-retardant polyolefin-based resin-coated sheet according to the present invention includes a step of unwinding, drying, and drying the flame-retardant polyolefin-based resin composition layer film on the both sides of the fabric for base fabric. It is preferable to use a thermal laminator having a laminating part (constructed from a chrome-plated steel drive heating roll and a rubber-coated steel pressing roll) and a winding part. In the heat laminator, the temperature of the heat roll on the film passing side for the flame retardant polyolefin resin composition layer is adjusted to 70 ° C. or higher and 180 ° C. or lower by using an auxiliary heating device such as an infrared heater. The temperature of the heat roll heated at either the medium method or the steam method and the fabric passing side or the fabric passing side for the base fabric on which the flame retardant polyolefin-based resin composition layer is formed by heat bonding is 120 ° C. The production method in which the film for a surface flame retardant polyolefin resin composition layer and the film for a back flame retardant polyolefin resin composition layer are continuously heat-bonded one side at a time in a single step is adjusted as follows. It is preferable.
It is preferable that the dry heat shrinkage rate in the warp direction and the weft direction of the flame retardant polyolefin resin sheet obtained by this production method is within 5 to 25% when heated at 150 ° C. for 15 minutes. If the dry heat shrinkage rate is less than 5%, it may not meet the flameproof test specified in the Fire Service Law. If the dry heat shrinkage rate exceeds 25%, the sheets are joined together by high frequency welder fusion. Alternatively, when performing by hot hot air fusion, the joint may shrink and the sheet may be distorted.
[0060]
【Example】
Next, the present invention will be described more specifically with reference to the following examples. However, the flame-retardant polyolefin resin-coated sheet of the present invention is not limited to the scope of these examples.
[0061]
In the following examples and comparative examples, the flame retardancy evaluation of the flame-retardant polyolefin resin-coated sheet of the present invention, the evaluation of oxygen index (LOI), the evaluation of wear resistance, the shear strength retention of the high-frequency welder joint piece, and Test methods such as heat resistance creep resistance are as follows.
(I) Flame resistance of sheet
Tested in accordance with Article 4 of the Fire Service Act Construction Rules (JIS Standard L-1091: A-2 Method Category 3: Heating for 2 minutes), and evaluated according to the following criteria.
○: Carbonization area 40cm²Hereinafter, the afterflame time is 5 seconds or less, the residual dust time is 20 seconds or less, and the carbonization distance is 20 cm or less.
X: One or more items of the carbonization area, the after flame time, the residual time, and the carbonization distance exceed the standard numerical values.
[0062]
(II) Flame retardancy of films and sheets
The evaluation was made based on the limiting oxygen index defined in JIS standard K-7231.
(III) Sheet wear resistance
JIS standard L-1096: wear strength test C method (Taber method: wear wheel CS-18: load 1 kg) was used to determine the weight loss and evaluated according to the following criteria.
○: Wear loss 30 mg or less
Δ: Loss on wear of 31 to 99 mg
×: Wear loss of 100 mg or more
[0063]
(IV) Shear strength retention of high frequency welder joints
Two sheets are aligned with their front sides facing each other, and the end of each sheet is 3cm wide, and a 3cm x 30cm weld bar (tooth shape: convex parts are 3cm wide linearly spaced at 9cm) /25.4mm, convex part height 0.5mm: concave parts are 3cm wide and linearly shaped, 9 linear shaped molds / 25.4mm, concave part depth 0.5mm) (High frequency welder fusion machine (Yamamoto Vinita Co., Ltd.) ) YF-7000 type: output 7KW). A test piece having a test piece width of 3 cm and a test piece length of 30 cm including the joint portion was collected from the obtained joining sheet and used as a sample for measuring shear strength. (Measurement of shear strength was in accordance with JIS standard L-1096: Tensile strength A method.)
Welder fusion conditions: Fusion time 4 to 10 seconds, cooling time 4 to 10 seconds
Anode current 0.4-2.0A, weld bar temperature 40-60 ° C
The shear strength retention was determined by setting the shear strength value of a high-frequency welder bonded test piece obtained from a composition containing no flame retardant in the polyolefin resin as 100%.
Shear strength retention rate (%) = (shear strength value of bonded sheet obtained from composition containing flame retardant) × (shear strength value of bonded sheet obtained from composition not containing flame retardant) × 100
[0064]
(V) Heat-resistant creep resistance of high-frequency welder welded joints
The same sample as the sample for measuring shear strength used in the shear strength retention rate (IV) of the high-frequency welder joined piece was prepared and used as a test piece.
Thermal creep resistance test: A test piece having a test piece width of 3 cm and a test piece length of 30 cm including a joint portion is collected from the welder bonding sheet, and this is used as a heat-resistant creep test piece, and a creep tester (manufactured by Toyo Seiki Seisakusho: 100 LDR type) The heat resistance creep resistance test at 50 ° C. × 25 kgf load × 24 hours was evaluated.
○: After 24 hours, the joint was not broken and withstands a load of 25 kgf.
X: The joint was peeled and broken within 24 hours.
[0065]
(VI) Dry heat shrinkage
40 cm long and 40 cm long test specimens are taken from the fabric for the base fabric or the test sheet, and in accordance with JIS standard A-6008, a standard line with a 30 cm longitudinal direction and a standard line with a 30 cm longitudinal direction are each 10 cm apart. Three points were marked, and after standing for 15 minutes in a gear oven at 150 ° C., the test piece was returned to room temperature, and the marked lengths in the warp direction and the weft direction were measured to determine the shrinkage ratio of the fabric or sheet.
Dry heat shrinkage rate = (30 cm−measured value of marked line length cm) / (30 cm) × 100 (%)
[0066]
Example 1
Red phosphorus particles (1) (trademark: Nova) with respect to 100 parts by weight of ethylene-vinyl acetate copolymer resin (trademark: Ultrasen 635: Tosoh Corporation: vinyl acetate content 25 wt%, melt flow rate 2.4 g / 10 min) 15 parts by weight of Red 280C (titanium oxide surface-treated product): Phosphorus Chemical Industry Co., Ltd. and, as an additive, 1.0 part by weight of a lubricant (trademark: LTP-2: Kawaken Fine Chemicals Co., Ltd.) UV absorber (Trademark: Tinuvin P: Ciba Specialty Chemicals Co., Ltd.) 0.3 parts by weight and titanium oxide as a colorant (Trademark: High Conk Master HCM2060 White: Titanium oxide content 65% by weight: Dainichi Seika Kogyo Co., Ltd.) 5 parts by weight and cyanine green (trademark: High Conk Master HCM1560 Green: cyanine green content 20% by weight: large Seika Kogyo Co., Ltd.) was mixed with 5 parts by weight of a compound (4.25 parts by weight for the addition of the pigment component), and this mixture was kneaded for 5 minutes with a two-roll mixer set at 130 ° C. From this kneaded composition, a 0.2 mm thick flame-retardant polyolefin-based resin composition film was calender-rolled. The kneaded composition had good roll kneadability and calendar moldability, and a film having a good appearance colored light green was obtained. The oxygen index (LOI) of this film was 34.3.
[0067]
Plain weave fabric obtained by weaving 340 denier polypropylene (PP) multifilament yarn (product number: MS-3112: Mitsubishi Rayon Co., Ltd .: yarn density warp 25 / 2.54 cm, weft 26/2. 54 cm) was heat-set with a heat-setting machine set to hot air conditions of 140 ° C. The dry heat shrinkage of the plain weave fabric at 150 ° C. for 15 minutes was 18.7% in the warp direction and 14.6% in the weft direction. Next, the polyolefin resin composition film is bonded by thermocompression bonding with a laminator on both sides of the plain weave fabric, thickness 0.5 mm, weight 450 g / m.²The flame-retardant polyolefin resin-coated sheet of the present invention was prepared. Under the setting conditions of the laminator at this time, the heat roll temperature on the polyolefin resin composition layer film passing side is 120 ° C., the heat roll temperature on the fiber fabric passing side is 80 ° C., and the pressure bonding pressure is 10 kg / cm.²The laminating speed was 10 m / min. The obtained flame-retardant polyolefin resin-coated sheet had a dry heat shrinkage rate at 150 ° C. for 15 minutes of 16.5% in the warp direction and 12.4% in the weft direction, and LOI was 30.4. . Tables 1 to 2 show the composition of the polyolefin resin composition layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0068]
Example 2
In the same manner as in Example 1, a flame-retardant polyolefin resin-coated sheet was produced. However, instead of 100 parts by weight of the ethylene-vinyl acetate copolymer resin (trademark: Ultrasen 635: Tosoh Corporation) blended in the polyolefin resin composition layer film, an ethylene-acrylic acid copolymer resin (trademark: Aclift WH-206: Sumitomo Chemical Co., Ltd .: methyl methacrylate content 20 wt%, melt flow rate 2.0 g / 10 min) 100 parts by weight were used. As a colorant, 5 parts by weight of titanium oxide (trademark: High Conc Master HCM2060 White: Dainichi Seika Kogyo Co., Ltd.) was used as it was, but cyanine green (trademark: High Conc Master HCM 1560 Green: Dainichi Seika Kogyo). Instead of 5 parts by weight, 5 parts by weight of condensed azo red (trademark: High Conc Master HCM1170 Red: 20% by weight of condensed azo red: Dainichi Seika Kogyo Co., Ltd.) was used. The addition amount of only the pigment component was 4.25 parts by weight. According to the same procedure as in Example 1, the film was laminated on both sides of the same heat-set polypropylene multifilament plain weave mesh fabric as in Example 1 and colored pink, thickness 0.5 mm, weight 450 g / m²The flame-retardant polyolefin resin-coated sheet of the present invention was obtained. The dry heat shrinkage of the obtained flame-retardant polyolefin resin sheet at 150 ° C. for 15 minutes was 16.6% in the warp direction, 12.7% in the weft direction, and LOI was 28.5. Tables 1 and 2 show the composition of the polyolefin-based resin composition layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0069]
Example 3
In the same manner as in Example 1, a flame-retardant polyolefin resin-coated sheet was produced. However, 50 parts by weight of 100 parts by weight of ethylene-vinyl acetate copolymer resin (trademark: Ultrasen 635: Tosoh Corp.) blended in the polyolefin resin composition layer film is low-density polyethylene resin (trademark) : Kernel KF281: Nippon Polychem Co., Ltd .: Melt flow rate 2.5 g / 10 min) was replaced with 50 parts by weight. As a colorant, 5 parts by weight of titanium oxide (trademark: High Conc Master HCM2060 White: Dainichi Seika Kogyo Co., Ltd.) was used as it was, but cyanine green (trademark: High Conc Master HCM 1560 Green: Dainichi Seika Kogyo). In place of 5 parts by weight, 5 parts by weight of cyanine blue (trademark: High Conk Master HCM1617 Blue: 20% by weight of cyanine blue: Dainichi Seika Kogyo Co., Ltd.) was used. The addition amount of only the pigment component was 4.25 parts by weight. Using the same heatset-treated polypropylene multifilament plain weave fabric as in Example 1, using the same procedure as in Example 1, a thickness of 0.5 mm and a weight of 450 g colored in a light blue color / M²The flame-retardant polyolefin resin-coated sheet of the present invention was prepared. The dry heat shrinkage ratio of the obtained flame-retardant polyolefin resin sheet at 150 ° C. for 15 minutes was 16.9% in the warp direction, 12.8% in the weft direction, and LOI was 28.7. Tables 1 and 2 show the composition of the polyolefin-based resin composition layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0070]
Example 4
In the same manner as in Example 3, a flame-retardant polyolefin resin-coated sheet was produced. However, instead of the polypropylene multifilament plain weave mesh (with heat set treatment), a plain weave mesh fabric woven from 750 denier polyester (PET) multifilament yarn (Product No .: T-75475: Teijin Ltd .: yarn) Density warp yarns 19 / 2.54 cm, weft yarns 20 / 2.54 cm) were used without heat setting. The same composition and the same coloring thickness as Example 3 0.6mm, weight 490g / m²The flame-retardant polyolefin resin-coated sheet of the present invention was obtained. However, the dry heat shrinkage rate of the obtained flame-retardant polyolefin resin-coated sheet at 150 ° C. for 15 minutes was 9.4% in the warp direction and 8.2% in the weft direction, and the LOI was 28.7. It was. Tables 1 and 2 show the composition of the polyolefin-based resin composition layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0071]
Example 5
In the same manner as in Example 3, a flame retardant polyolefin resin-coated sheet was produced. However, instead of the polypropylene multifilament plain weave fabric (with heat set treatment), plain weave fabric woven from 420 denier polyamide (nylon) multifilament yarn (product number: AKN-4425: Asahi Kasei Co., Ltd.): Yarn density warp yarns 24 / 2.54 cm, weft yarns 24 / 2.54 cm) were used without heat setting. Same composition as Example 3 and same color thickness 0.53 mm, weight 465 g / m²The flame-retardant polyolefin resin-coated sheet of the present invention was obtained. The dry heat shrinkage rate of the obtained flame-retardant polyolefin resin-coated sheet at 150 ° C. for 15 minutes was 7.4% in the warp direction and 7.1% in the weft direction, and the LOI was 28.7. Tables 1 and 2 show the composition of the polyolefin-based resin composition layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0072]
Example 6
In the same manner as in Example 1, a flame-retardant polyolefin resin-coated sheet was produced. However, instead of 100 parts by weight of the ethylene-vinyl acetate copolymer resin (trademark: Ultrasen 635: Tosoh Corporation) blended in the polyolefin resin composition layer film, an ethylene-acrylic acid copolymer resin (trademark) : Aclift WH-206: 50 parts by weight of Sumitomo Chemical Co., Ltd. methyl methacrylate content 20 wt%, melt flow rate 2.0 g / 10 min) and low density polyethylene resin (trademark: Kernel KF281: Nippon Polychem Co., Ltd .: Melt Red phosphorus particles (1) (trademark: Nova Red 280C (titanium oxide surface-treated product): Phosphorous Chemical Industry Co., Ltd.) instead of 15 parts by weight. Phosphor particles (2) (trademark: Hishiguard CP (aluminum hydroxide surface-treated product): Nippon Chemical Industry Co., Ltd.) 15 parts by weight were used. . As a colorant, 5 parts by weight of titanium oxide (trademark: High Conc Master HCM2060 White: Dainichi Seika Kogyo Co., Ltd.) is used as it is, and Cyanine Green (trademark: High Conc Master HCM 1560 Green: Dainichi Seika Kogyo Co., Ltd.) )) Instead of 5 parts by weight, 2 parts by weight of carbon black (trademark: High Conk Master HCM1717 Black: 10% by weight of carbon black: Dainichi Seika Kogyo Co., Ltd.) was used. The addition amount of only the pigment component was 3.45 parts by weight. Using the same procedure as in Example 1, the same heat-set polypropylene multifilament plain weave fabric as used in Example 1 was used, and the thickness was 0.5 mm and the weight was 450 g. / M²The flame-retardant polyolefin resin sheet of the present invention was obtained. The dry heat shrinkage of the obtained flame-retardant polyolefin resin sheet at 150 ° C. for 15 minutes was 16.7% in the warp direction, 12.5% in the weft direction, and LOI was 28.5. Tables 1 and 2 show the composition of the polyolefin-based resin composition layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0073]
Example 7
A flame-retardant polyolefin resin-coated sheet was produced in the same manner as in Example 6. However, instead of the polypropylene multifilament plain weave fabric (with heat set treatment), a plain weave mesh fabric woven from 750 denier polyester (PET) multifilament yarn (product number: T-75475: Teijin Limited): Yarn density warp 19 yarns / 2.54 cm, weft yarn 20 yarns / 2.54 cm) were used without heat setting. Thickness 0.6 mm, weight 490 g / m having the same composition and color as in Example 6.²The flame-retardant polyolefin resin-coated sheet of the present invention was obtained. The obtained flame-retardant polyolefin resin-coated sheet had a dry heat shrinkage of 9.8% in the warp direction and 8.4% in the weft direction at 150 ° C. for 15 minutes, and LOI was 28.5. Tables 1 and 2 show the composition of the polyolefin-based resin composition layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0074]
Example 8
A flame-retardant polyolefin resin-coated sheet was produced in the same manner as in Example 6. However, instead of the polypropylene multifilament plain weave fabric (with heat set treatment), plain weave fabric woven from 420 denier polyamide (nylon) multifilament yarn (product number: AKN-4425: Asahi Kasei Co., Ltd.): Yarn density warp yarns 24 / 2.54 cm, weft yarns 24 / 2.54 cm) were used without heat setting. A thickness of 0.53 mm and a weight of 465 g / m having the same composition and the same color as in Example 6.²The flame-retardant polyolefin resin-coated sheet of the present invention was obtained. The obtained flame-retardant polyolefin resin-coated sheet had a dry heat shrinkage of 150% at 15 ° C. for 15 minutes with a warp direction of 7.7% and a weft direction of 7.3%, and a LOI of 28.5. Tables 1 and 2 show the composition of the polyolefin-based resin composition layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0075]
[Table 1]

[0076]
[Table 2]

[0077]
Performance evaluation of Examples 1 to 8
In the flameproof test (JIS standard L-1091) based on the fire fighting method of the flame-retardant polyolefin-based resin-coated sheet of the present invention obtained in Examples 1 to 8, any of the test pieces of Examples 1 to 8 After flame contact, the sheet melts and heat shrinks away from the fire source, quickly preventing the spread of fire, and at the same time, the flame igniting the flame contact part is excellent flame retardant effect of red phosphorus particles blended in polyolefin resin As a result, all the sheets of Examples 1 to 8 passed the fire prevention regulations of the Fire Service Act.
In addition, these flame retardant polyolefin resin-coated sheets do not significantly impair the polyolefin resin strength because sufficient flame retardancy can be obtained by adding a small amount of flame retardant. Therefore, the flame-retardant polyolefin resin-coated sheet of the present invention was extremely excellent in durability such as wear resistance, shear strength at the joint, and heat-resistant creep resistance.
[0078]
Example 9
Red phosphorus particles (1) (trademark: Nova) with respect to 100 parts by weight of ethylene-vinyl acetate copolymer resin (trademark: Ultrasen 635: Tosoh Corporation: vinyl acetate content 25 wt%, melt flow rate 2.4 g / 10 min) 15 parts by weight of Red 280C: Phosphor Chemical Co., Ltd. is blended, and as additives, 1.0 part by weight of a lubricant (trademark: LTP-2: Kawaken Fine Chemical Co., Ltd.) and an ultraviolet absorber (trademark: Tinuvin P: 0.3 parts by weight of Ciba Specialty Chemicals Co., Ltd. and titanium oxide as a colorant (trademark: High Conk Master HCM2060 White: titanium oxide content 65% by weight: Dainichi Seika Kogyo Co., Ltd.) 5 2 parts by weight of the compound (3.25 parts by weight as the addition of the pigment component) was mixed and the mixture was mixed at 130 ° C. It was kneaded for 5 minutes at over and molded by calendering a polyolefin resin composition layer film of 0.2mm thickness from the kneaded composition. The kneaded composition had good roll kneading properties and calendar moldability, and a film having a good appearance colored in a light brown color was obtained. The oxygen index (LOI) of this film was 35.6.
[0079]
Next, a plain weave fabric (product number: MS-3112: Mitsubishi Rayon Co., Ltd .: yarn density warp 25 / 2.54 cm, weft 26 / 2.54 cm) woven from 340 denier polypropylene multifilament yarn, It heat-set with the heat set machine set to the 140 degreeC hot-air conditions. The dry heat shrinkage of the plain weave fabric at 150 ° C. for 15 minutes was 18.7% in the warp direction and 14.6% in the weft direction. Next, the polyolefin resin composition layer film is bonded by thermocompression bonding with a laminator on both sides of the plain weave fabric, thickness 0.5 mm, weight 450 g / m.²The flame retardant polyolefin resin-coated sheet was obtained. Under the setting conditions of the laminator at this time, the heat roll temperature on the polyolefin resin composition layer film passing side is 120 ° C., the heat roll temperature on the fiber fabric passing side is 80 ° C., and the pressure bonding pressure is 10 kg / cm.²The laminating speed was 10 m / min.
[0080]
Next, with respect to 100 parts by weight of ethylene-vinyl acetate copolymer resin (trademark: Ultrasen 635: Tosoh Corporation: vinyl acetate content 25 wt%, melt flow rate 2.4 g / 10 min), ammonium polyphosphate (trademark: Hostafram) AP-745 (EXOLIT IFR23): Clariant Japan Co., Ltd .: Melamine resin surface coating type, polymerization degree n = 1000) and chemical foaming agent (trademark: Uniform AZ L-10: Otsuka Chemical Co., Ltd.): 5 parts by weight of a decomposition temperature of 199 ° C. and a gas generation amount of 240 ml / g) were added, and as additives, 1.0 part by weight of a lubricant (trademark: LTP-2: Kawaken Fine Chemical Co., Ltd.), an ultraviolet absorber ( Trademark: Tinuvin P: Ciba Specialty Chemicals Co., Ltd. 0.3 parts by weight, titanium oxide as a colorant (trademark: High Conch Star HCM2060 white: titanium oxide content 65% by weight: Dainichi Seika Kogyo Co., Ltd.) and cyanine green (trademark: High Conk Master HCM1560 Green: cyanine green content 20% by weight: Dainichi Seika Kogyo Co., Ltd.) 130 parts of a compound (3.25 parts by weight for the addition of only the pigment component) containing 5 parts by weight of each compound and 5 parts by weight of the resulting compound (4.25 parts for the addition of the pigment component). The mixture was kneaded for 5 minutes with a two-roll mixer set at 0 ° C., and a 0.12 mm thick colored polyolefin resin protective layer film was calender-rolled from this kneaded composition. The kneaded composition had good roll kneadability and calendar moldability, and a film having a good appearance colored light green was obtained. The oxygen index (LOI) of this film was 31.4.
[0081]
Next, this colored polyolefin-based resin protective layer film was bonded to one side of the previously prepared flame-retardant polyolefin-based resin-coated sheet by thermocompression bonding with a laminator, thickness 0.62 mm, weight 560 g / m.²The flame-retardant polyolefin resin sheet with a colored protective layer was obtained. In the setting conditions of the laminator at this time, the heat roll temperature on the colored polyolefin resin protective layer film passing side is 120 ° C., the heat roll temperature on the flame retardant polyolefin resin sheet passing side is 80 ° C., and the pressure bonding pressure is 10kg / cm²The laminating speed was 10 m / min.
The resulting flame-retardant polyolefin resin sheet having a colored polyolefin resin protective layer on one side has a dry heat shrinkage at 150 ° C. for 15 minutes of 15.5% in the warp direction and 12.2% in the weft direction. The LOI of the sheet was 29.4. Tables 3 to 5 show the blending of the polyolefin resin composition layer film, the blending of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0082]
Example 10
In the same manner as in Example 9, a flame-retardant polyolefin resin-coated sheet with a colored protective layer was produced. However, instead of 100 parts by weight of ethylene-vinyl acetate copolymer resin (trademark: Ultrasen 635: Tosoh Corporation) blended in the polyolefin-based resin composition layer film, ethylene-acrylic acid copolymer resin (trademark) : Acrylift WH-206: Sumitomo Chemical Co., Ltd .: Methyl methacrylate content 20 wt%, melt flow rate 2.0 g / 10 min) 100 parts by weight were used. The same heat-set polypropylene multifilament plain weave fabric as used in Example 9 was used, and the thickness was 0.5 mm and the weight was 450 g / m.²The flame retardant polyolefin resin sheet was obtained. Next, the same protective layer film as used in Example 9 was used as the colored polyolefin-based resin layer film. However, as the colorant, 5 parts by weight of titanium oxide (trademark: High Conc Master HCM 2060 White: Dainichi Seika Kogyo Co., Ltd.) was used as it was, but the cyanine green (trademark: High Conc Master HCM 1560 Green: Dainichi Seika Kogyo) was used. (Inc.) Instead of 5 parts by weight, 5 parts by weight of condensed azo red (trademark: High Conc Master HCM1170 Red: 20% by weight of condensed azo red: Dainichi Seika Kogyo Co., Ltd.) was used (as addition of pigment component only) Is 4.25 parts by weight). Thickness 0.62 mm, weight 560 g / m having a polyolefin-based resin protective layer colored in pink by the same procedure as in Example 9.²A flame retardant polyolefin resin-coated sheet was obtained. The obtained flame-retardant polyolefin-based resin sheet had a dry heat shrinkage of 150% at 15 ° C. for 15 minutes with a warp direction of 15.3% and a weft direction of 12.4%, and a LOI of 28.3. Tables 3 to 5 show the blending of the polyolefin resin composition layer film, the blending of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0083]
Example 11
In the same manner as in Example 9, a flame-retardant polyolefin resin-coated sheet with a colored protective layer was produced. However, 50 parts by weight of 100 parts by weight of ethylene-vinyl acetate copolymer resin (trademark: Ultrasen 635: Tosoh Corporation) blended in the polyolefin resin composition layer film was used as a low-density polyethylene resin ( Trademark: Kernel KF281: Nippon Polychem Co., Ltd .: Melt flow rate 2.5 g / 10 min). In addition, the same polyolefin resin composition layer as that used in Example 9 was formed on both sides of a heat-set polypropylene multifilament plain weave fabric, and the thickness 0. 5mm, weight 450g / m²The flame retardant polyolefin resin sheet was obtained. Next, the same protective layer film as that used in Example 9 was used as the colored polyolefin resin layer film. However, as a colorant, 5 parts by weight of titanium oxide (trademark: High Conk Master HCM2060 White: Dainichi Seika Kogyo Co., Ltd.) was used as it was, but cyanine green (trademark: High Conk Master HCM1560 Green: Dainichi Seika Kogyo). In place of 5 parts by weight, 5 parts by weight of cyanine blue (trademark: High Conk Master HCM1617 Blue: 20% by weight of cyanine blue: Dainichi Seika Kogyo Co., Ltd.) was used. (The addition of only the pigment component is 4.25 parts by weight). It has a polyolefin resin protective layer colored light blue by the same procedure as in Example 9 on one side, a thickness of 0.62 mm, and a weight of 560 g / m.²A flame retardant polyolefin resin sheet with a protective layer was obtained. The obtained flame-retardant polyolefin-based resin sheet had a dry heat shrinkage rate at 150 ° C. for 15 minutes of 15.1% in the warp direction and 12.6% in the weft direction, and LOI was 28.5. Tables 3 to 5 show the blending of the polyolefin resin composition layer film, the blending of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0084]
Example 12
In the same manner as in Example 11, a flame-retardant polyolefin resin-coated sheet with a colored protective layer was produced. However, instead of the polypropylene multifilament plain weave fabric (with heat set treatment), a plain weave mesh fabric woven from 750 denier polyester (PET) multifilament yarn (product number: T-75475: Teijin Limited): Yarn density warps 19 / 2.54 cm, 20 wefts / 2.54 cm) were used without heat setting. According to the same procedure as in Example 11, a thickness of 0.72 mm having a polyolefin resin protective layer colored light blue on one side and a weight of 600 g / m.²A flame retardant polyolefin resin-coated sheet with a protective layer was obtained. The obtained flame-retardant polyolefin resin sheet had a dry heat shrinkage of 9.4% in the warp direction and 8.2% in the weft direction at 150 ° C. for 15 minutes, and LOI was 28.4. Tables 3 to 5 show the blending of the polyolefin resin composition layer film, the blending of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0085]
Example 13
In the same manner as in Example 11, a flame-retardant polyolefin resin-coated sheet with a colored protective layer was produced. However, 70 parts by weight of 100 parts by weight of ethylene-vinyl acetate copolymer resin (trademark: Ultrasen 635: Tosoh Corporation) made into the polyolefin resin composition layer film was ethylene-acrylic acid copolymer. The resin was replaced by a resin (trade name: ACRIFTH WH-206: Sumitomo Chemical Co., Ltd .: methyl methacrylate content 20 wt%, melt flow rate 2.0 g / 10 min). Further, instead of the polypropylene multifilament plain weave mesh (with heat set treatment), a plain weave mesh fabric woven from 420 denier polyamide (nylon) multifilament yarn (product number: AKN-4425: Asahi Kasei Co., Ltd .: yarn) Density warps 24 / 2.54 cm, 24 wefts / 2.54 cm) were used without heat setting. According to the same procedure as in Example 11, a polyolefin-based resin protective layer colored in light blue is provided on one side, a thickness of 0.65 mm, and a weight of 575 g / m.²A flame retardant polyolefin resin-coated sheet with a protective layer was obtained. The obtained flame-retardant polyolefin resin sheet had a dry heat shrinkage of 150% at 15 ° C. for 15 minutes with a warp direction of 7.6% and a weft direction of 7.2%, and a LOI of 28.6. Tables 3 to 5 show the blending of the polyolefin resin composition layer film, the blending of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0086]
Example 14
In the same manner as in Example 9, a flame-retardant polyolefin resin-coated sheet with a colored protective layer was produced. However, instead of 100 parts by weight of ethylene-vinyl acetate copolymer resin (trademark: Ultrasen 635: Tosoh Corporation) blended in the polyolefin resin coating layer film, ethylene-acrylic acid copolymer resin (trademark: ACLIFT WH-206: Sumitomo Chemical Co., Ltd. methyl methacrylate content 20 wt%, melt flow rate 2.0 g / 10 min 50 parts by weight, low density polyethylene resin (trademark: Kernel KF281: Nippon Polychem Co., Ltd .: Melt Flow In addition to red phosphorus particles (1) (trademark: Nova Red 280C (titanium oxide surface-treated product): Phosphorous Chemical Industry Co., Ltd.) Phosphor particles (2) (trademark: Hishiguard CP (aluminum hydroxide surface-treated product): Nippon Chemical Industry Co., Ltd.) 15 parts by weight were used. . Using the same heat-set treated polypropylene multifilament plain weave fabric as used in Example 9, the thickness is 0.5 mm and the weight is 450 g / m.²The flame retardant polyolefin resin sheet was obtained. Next, as the colored polyolefin resin layer film, the same protective layer film as used in Example 13 was laminated on both sides of the flame retardant polyolefin resin coated sheet. However, as a colorant, 5 parts by weight of titanium oxide (trademark: High Conk Master HCM2060 White: Dainichi Seika Kogyo Co., Ltd.) was used as it was, but cyanine green (trademark: High Conk Master HCM1560 Green: Dainichi Seika Kogyo). The use of 5 parts by weight was omitted. (The addition of only the pigment component is 3.25 parts by weight). Thickness 0.74 mm, weight 670 g / m having a polyolefin resin protective layer colored in white on both sides in the same procedure as in Example 9.²A flame retardant polyolefin resin sheet with a protective layer was obtained. The obtained flame-retardant polyolefin-based resin sheet had a dry heat shrinkage rate at 150 ° C. for 15 minutes of 15.3% in the warp direction and 12.7% in the weft direction, and LOI was 28.3. Tables 3 to 5 show the blending of the polyolefin resin composition layer film, the blending of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0087]
Example 15
A polyolefin resin-coated sheet with a colored protective layer was produced in the same manner as in Example 14. However, instead of the polypropylene multifilament plain weave fabric (with heat set treatment), a plain weave mesh fabric woven from 750 denier polyester (PET) multifilament yarn (product number: T-75475: Teijin Limited): Yarn density warp 19 yarns / 2.54 cm, weft yarn 20 yarns / 2.54 cm) were used without heat setting. According to the same procedure as in Example 14, a thickness of 0.84 mm having a white polyolefin resin protective layer on both sides and a weight of 710 g / m.²A flame retardant polyolefin resin sheet with a protective layer was obtained. The dry heat shrinkage ratio of the obtained flame-retardant polyolefin resin sheet at 150 ° C. for 15 minutes was 9.6% in the warp direction and 8.3% in the weft direction, and the LOI was 28.8. Tables 3 to 5 show the composition of the polyolefin resin composition film, the composition of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0088]
Example 16
A polyolefin resin-coated sheet with a colored protective layer was produced in the same manner as in Example 14. However, instead of the polypropylene multifilament plain weave fabric (with heat set treatment), a plain weave fabric woven from 750 denier polyamide (nylon) multifilament yarn (product number: AKN-4425: Asahi Kasei Corporation): Yarn density warp yarns 24 / 2.54 cm, weft yarns 24 / 2.54 cm) were used without heat setting. A thickness of 0.77 mm and a weight of 685 g / m having a white polyolefin-based resin protective layer on both sides by the same procedure as in Example 14.²A flame retardant polyolefin resin composition sheet with a protective layer was obtained. The resulting flame-retardant polyolefin resin sheet had a dry heat shrinkage of 150% at 15 ° C. for 15 minutes with a warp direction of 7.8% and a weft direction of 6.9%, and a LOI of 28.4. Tables 3 to 5 show the blending of the polyolefin resin composition layer film, the blending of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0089]
[Table 3]

[0090]
[Table 4]

[0091]
[Table 5]

[0092]
Performance evaluation of Examples 9 to 16
The flameproof test (JIS standard L-1091) based on the fire fighting method of the flame-retardant polyolefin resin sheet with a colored protective layer of the present invention obtained in Examples 9 to 16 is the test piece of any example. After flame contact, the sheet melts and heat shrinks away from the fire source, quickly preventing fire spread and simultaneously igniting the flame contact area due to the excellent flame retardant effect of red phosphorus particles blended in polyolefin resin. Self-extinguishing, and as a result, all the sheets in the examples passed the fire prevention regulations of the Fire Service Act.
Moreover, since these flame retardant sheets can obtain sufficient flame retardancy by adding a small amount of flame retardant, the strength of the polyolefin resin is not greatly impaired. Therefore, the flame retardant polyolefin resin sheet of the present invention was extremely excellent in durability such as wear resistance, shear strength at the joint, and heat creep resistance. In addition, the flame retardant polyolefin resin sheet of the present invention was provided with a colorability by providing a colored polyolefin resin protective layer containing a non-halogen flame retardant on the surface of the sheet.
[0093]
Comparative Example 1
In the same manner as in Example 9, a polyolefin resin-coated sheet was produced. However, without using 15 parts by weight of red phosphorus particles (1) (trademark: Nova Red 280C (titanium oxide surface-treated product): Phosphorous Chemical Co., Ltd.) blended in the polyolefin resin composition layer film. Instead, 150 parts by weight of magnesium hydroxide (trademark: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) is blended, and 30 parts by weight of ammonium polyphosphate and a chemical foaming agent are added from the composition components of the colored polyolefin protective layer 5 parts by weight were omitted. The same composition and coloring as in Example 9, with a similar procedure, a thickness of 0.62 mm, and a weight of 590 g / m²A polyolefin-based resin-coated sheet with a colored protective layer was obtained. The resulting polyolefin resin-coated sheet had a dry heat shrinkage rate at 150 ° C. for 15 minutes of 15.1% in the warp direction and 11.8% in the weft direction, and LOI was 20.2. Tables 6 to 8 show the composition of the polyolefin resin composition layer film, the composition of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0094]
Comparative Example 2
In the same manner as in Example 10, a polyolefin resin-coated sheet was produced. However, 15 parts by weight of red phosphorus particles (1) (trademark: Nova Red 280C (titanium oxide surface-treated product): Phosphorous Chemical Industry Co., Ltd.) blended in the polyolefin-based resin composition layer film is omitted. Instead, 150 parts by weight of magnesium hydroxide (trademark: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) was blended. The same composition and coloring as in Example 10, and a thickness of 0.62 mm and a weight of 590 g / m by the same procedure.²A polyolefin-based resin-coated sheet with a colored protective layer was obtained. The resulting polyolefin resin sheet had a dry heat shrinkage at 150 ° C. for 15 minutes of 15.7% in the warp direction and 12.0% in the weft direction, and LOI was 26.3. Tables 6 to 8 show the composition of the polyolefin resin composition layer film, the composition of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0095]
Comparative Example 3
In the same manner as in Example 3, a polyolefin resin-coated sheet was produced. However, 15 parts by weight of red phosphorus particles (1) (trademark: Nova Red 280C (titanium oxide surface-treated product): Phosphorous Chemical Industry Co., Ltd.) blended in the polyolefin resin composition layer film is omitted and replaced. 150 parts by weight of magnesium hydroxide (trademark: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) was added. The same composition and coloring as in Example 3, with a similar procedure, a thickness of 0.5 mm and a weight of 480 g / m²A polyolefin resin sheet without a protective layer was obtained. The resulting polyolefin resin-coated sheet had a dry heat shrinkage of 150.degree. C. for 15 minutes with a warp direction of 15.4%, a weft direction of 12.3%, and a LOI of 24.2. Tables 6 to 8 show the composition of the polyolefin resin composition layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0096]
Comparative Example 4
A polyolefin resin-coated sheet similar to Example 4 (without a protective layer) was produced. However, 15 parts by weight of red phosphorus particles (1) (trademark: Nova Red 280C (titanium oxide surface-treated product): Phosphorous Chemical Industry Co., Ltd.) blended in the polyolefin resin composition layer film is omitted and replaced. 150 parts by weight of magnesium hydroxide (trademark: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) was added. According to the same composition and coloring as in Example 4 and the same procedure, a thickness of 0.6 mm and a weight of 520 g / m.²A polyolefin resin sheet was obtained. The resulting polyolefin resin sheet had a dry heat shrinkage of 9.6% in the warp direction and 9.3% in the weft direction at 15O 0 C for 15 minutes, and an LOI of 24.2. Tables 6 to 8 show the composition of the polyolefin resin composition layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0097]
Comparative Example 5
A polyolefin resin-coated sheet similar to Example 5 (without a protective layer) was produced. However, 15 parts by weight of red phosphorus particles (1) (trademark: Nova Red 280C (titanium oxide surface-treated product): Phosphorous Chemical Industry Co., Ltd.) blended in the polyolefin-based resin composition layer film is omitted. Instead, 150 parts by weight of magnesium hydroxide (trademark: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) was blended. The same composition and coloring as in Example 5 and a thickness of 0.53 mm and a weight of 505 g / m by the same procedure.²A polyolefin-based resin-coated sheet was obtained. The resulting polyolefin resin-coated sheet had a dry heat shrinkage of 150% at 15 ° C. for 15 minutes with a warp direction of 7.6%, a weft direction of 7.3%, and a LOI of 24.2. Tables 6 to 8 show the composition of the polyolefin resin composition layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0098]
Comparative Example 6
A polyolefin resin-coated sheet with a colored protective layer was produced in the same manner as in Example 14. However, 15 parts by weight of red phosphorus particles (2) (trademark: Hishigard CP (aluminum hydroxide surface-treated product): Nippon Chemical Industry Co., Ltd.) blended in the polyolefin resin composition layer film is omitted and replaced. 150 parts by weight of magnesium hydroxide (trademark: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) was added. Further, 30 parts by weight of ammonium polyphosphate and 5 parts by weight of the chemical foaming agent blended in the colored polyolefin resin protective layer film were omitted, and instead of these, magnesium hydroxide (trademark: Kisuma 5A: Kyowa Chemical Industry ( Ltd.) 100 parts by weight were blended. Mixing and coloring similar to Example 14, thickness 0.74 mm, weight 730 g / m by similar procedure²A polyolefin-based resin-coated sheet was obtained. The resulting polyolefin-based resin-coated sheet had a dry heat shrinkage rate at 150 ° C. for 15 minutes of 14.4% in the warp direction, 11.7% in the weft direction, and LOI of 22.3. Tables 6 to 8 show the composition of the polyolefin resin composition layer film, the composition of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0099]
Comparative Example 7
In the same manner as in Example 15, a polyolefin resin-coated sheet with a colored protective layer was produced. However, 15 parts by weight of red phosphorus particles (2) (trademark: Hishigard CP (aluminum hydroxide surface-treated product): Nippon Chemical Industry Co., Ltd.) blended in the polyolefin resin composition layer film is omitted. Instead, 150 parts by weight of magnesium hydroxide (trademark: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) was blended. Further, 30 parts by weight of ammonium polyphosphate and 5 parts by weight of chemical foaming agent blended in the colored polyolefin-based resin protective layer film are omitted, and instead of these, magnesium hydroxide (trademark: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) ) 150 parts by weight were blended. The same formulation and coloring as in Example 15 and a thickness of 0.84 mm and a weight of 770 g / m by the same procedure.²A polyolefin resin sheet was obtained. The resulting polyolefin resin sheet had a dry heat shrinkage at 150 ° C. for 15 minutes of 9.7% in the warp direction and 9.2% in the weft direction, and LOI of 23.8. Tables 6 to 8 show the composition of the polyolefin resin composition layer film, the composition of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0100]
Comparative Example 8
In the same manner as in Example 16, a polyolefin resin-coated sheet with a colored protective layer was produced. However, 15 parts by weight of red phosphorus particles (2) (trademark: Hishigard CP (aluminum hydroxide surface-treated product): Nippon Chemical Industry Co., Ltd.) blended in the polyolefin resin composition layer film is omitted. Instead, 150 parts by weight of magnesium hydroxide (trademark: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) was blended. Further, 30 parts by weight of ammonium polyphosphate blended in the colored polyolefin resin protective layer film was omitted, and 100 parts by weight of magnesium hydroxide (trade name: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) was blended instead. Mixing and coloring similar to Example 16, thickness 0.77 mm, weight 755 g / m by similar procedure²A polyolefin-based resin-coated sheet was obtained.
The resulting polyolefin resin-coated sheet had a dry heat shrinkage of 150% at 15 ° C. for 15 minutes with a warp direction of 7.5%, a weft direction of 7.1%, and a LOI of 23.0. Tables 6 to 8 show the composition of the polyolefin resin composition layer film, the composition of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0101]
[Table 6]

[0102]
[Table 7]

[0103]
[Table 8]

[0104]
Performance evaluation of Comparative Examples 1 to 8
In Comparative Example 1 to Comparative Example 8, in the polyolefin-based resin layer film, a flameproof test based on the Fire Service Law (JIS standard L-1091) by changing to a large amount of magnesium hydroxide instead of red phosphorus particles as a flame retardant In each of the test pieces of Comparative Examples, after flame contact, the sheet was melted and fired at the same time, and the flame spread was promoted by heat shrinking in the fired state. The ignited flame could not be extinguished due to the flame retardant effect of magnesium hydroxide and burned out completely. As a result, all the sheets of the comparative examples were incompatible with the fire prevention regulations of the Fire Service Act. In addition, the sheets of these comparative examples are not only poor in flame resistance, but also in durability such as abrasion resistance, joint shear strength, and heat-resistant creep resistance. For example, the strength of polyolefin resin is greatly impaired, and it is not practical. (Only Comparative Example 1 and Comparative Example 2 had good wear resistance.)
[0105]
Comparative Example 9
A polyolefin resin-coated sheet with a protective layer similar to that in Example 9 was produced. However, the heat-set treatment of the plain weave fabric (product number: MS-3112: Mitsubishi Rayon Co., Ltd.) in which the 340 denier polypropylene multifilament yarn was woven was omitted. The dry heat shrinkage of the plain weave fabric at 150 ° C. for 15 minutes was 34.6% in the warp direction and 31.3% in the weft direction. Further, 30 parts by weight of ammonium polyphosphate blended in the colored polyolefin-based resin protective layer film was omitted, and 150 parts by weight of magnesium hydroxide (trademark: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) was blended instead. . The same composition and coloring as in Example 9, and a thickness of 0.65 mm and a weight of 605 g / m by the same procedure.²A colored resin layer-coated polyolefin resin sheet was obtained. The resulting polyolefin resin sheet had a dry heat shrinkage of 150.degree. C. for 15 minutes with a warp direction of 28.6%, a weft direction of 26.3%, and a LOI of 27.4. However, because heat setting of the polypropylene plain weave fabric is omitted, the heat shrinkage of the polypropylene plain weave fabric (base fabric) is large in the heat laminating process of the flame retardant polyolefin resin film, and the workability and sheet appearance are remarkable. It was bad. Tables 9 to 11 show the composition of the polyolefin resin composition layer film, the composition of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0106]
Comparative Example 10
A polyolefin resin-coated sheet with a protective layer similar to that in Example 10 was produced. However, the heat setting temperature of the plain weave fabric (product number: MS-3112: Mitsubishi Rayon Co., Ltd.) in which the 340 denier polypropylene multifilament yarn was woven was changed from 140 ° C to 170 ° C. The dry heat shrinkage of the plain weave fabric at 150 ° C. for 15 minutes was 3.3% in the warp direction and 3.0% in the weft direction. The same composition and coloring as in Example 10, and a thickness of 0.62 mm and a weight of 560 g / m by the same procedure.²A colored resin layer-coated polyolefin resin sheet was obtained. The resulting polyolefin resin sheet had a dry heat shrinkage of 150% at 15 ° C. in a warp direction of 3.1%, a weft direction of 2.8%, and a LOI of 28.0. Tables 9 to 11 show the composition of the polyolefin resin composition layer film, the composition of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0107]
Comparative Example 11
In the same manner as in Example 3, a polyolefin resin-coated sheet without a protective layer was produced. However, the heat setting temperature of the plain weave fabric (product number: MS-3112: Mitsubishi Rayon Co., Ltd.) in which the 340 denier polypropylene multifilament yarn was woven was changed from 140 ° C to 170 ° C. The dry heat shrinkage of the plain weave fabric at 150 ° C. for 15 minutes was 3.3% in the warp direction and 3.0% in the weft direction. The same composition and coloring as in Example 3, with a similar procedure, thickness 0.5 mm, weight 450 g / m²A polyolefin-based resin-coated sheet was obtained. The obtained polyolefin resin sheet had a dry heat shrinkage of 150% at 15 ° C. for 15 minutes with a warp direction of 2.1% and a weft direction of 1.8%, and a LOI of 28.1. Tables 9 to 11 show the composition of the polyolefin resin composition layer film, the composition of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0108]
Comparative Example 12
In the same manner as in Example 4, a polyolefin resin-coated sheet without a protective layer was produced. However, a heat-set treatment was applied to the plain weave fabric (product number: T-75475: Teijin Ltd.) woven from the 750 denier polyester multifilament yarn under a heat condition of 200 ° C. The dry heat shrinkage of the plain weave fabric at 150 ° C. for 15 minutes was 2.6% in the warp direction and 2.2% in the weft direction. The same composition and coloring as in Example 4, and a thickness of 0.6 mm and a weight of 490 g / m by the same procedure.²A polyolefin-based resin-coated sheet was obtained. The obtained polyolefin resin-coated sheet had a dry heat shrinkage of 150% at 15 ° C. for 15 minutes, a warp direction of 2.4%, a weft direction of 2.0%, and a LOI of 29.3. Tables 9 to 11 show the composition of the polyolefin resin composition layer film, the composition of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0109]
Comparative Example 13
In the same manner as in Example 5, a polyolefin resin-coated sheet without a protective layer was produced. However, a heat-set treatment was performed at 200 ° C. on a plain weave fabric (product number: AKN-4425: Asahi Kasei Co., Ltd.) in which the 420 denier polyamide (nylon) multifilament yarn was woven. The dry heat shrinkage of the plain weave fabric at 150 ° C. for 15 minutes was 2.4% in the warp direction and 2.1% in the weft direction. The same composition and coloring as in Example 5, and a thickness of 0.53 mm and a weight of 465 g / m by the same procedure.²A polyolefin-based resin-coated sheet was obtained. The resulting polyolefin resin-coated sheet had a dry heat shrinkage of 150% at 15 ° C. for 15 minutes with a warp direction of 2.2%, a weft direction of 1.9%, and a LOI of 28.7. Tables 9 to 11 show the composition of the polyolefin resin composition layer film, the composition of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0110]
Comparative Example 14
A polyolefin resin-coated sheet with a double-sided colored protective layer was produced in the same manner as in Example 14. However, the heat-set treatment of the plain weave fabric (product number: MS-3112: Mitsubishi Rayon Co., Ltd.) in which the 340 denier polypropylene multifilament yarn was woven was omitted. The dry heat shrinkage of the plain weave fabric at 150 ° C. for 15 minutes was 34.6% in the warp direction and 31.3% in the weft direction. Mixing and coloring similar to Example 14, thickness 0.74 mm, weight 670 g / m by similar procedure²A polyolefin-based resin-coated sheet was obtained. The resulting polyolefin resin-coated sheet had a dry heat shrinkage of 150.degree. C. for 15 minutes with a warp direction of 28.6%, a weft direction of 26.3%, and a LOI of 26.8. However, because the heat setting of the polypropylene plain weave fabric was omitted, the thermal shrinkage of the polypropylene plain weave fabric was large in the heat laminating process of the flame retardant polyolefin resin film, and the workability and the sheet appearance were significantly poor. It was. Tables 9 to 11 show the composition of the polyolefin resin composition layer film, the composition of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0111]
Comparative Example 15
A polyolefin-based resin-coated sheet with a double-sided colored protective layer was produced in the same manner as in Example 15, except that the plain weave fabric (product number: T-75475: Teijin Ltd.) woven with the 750-denier polyester multifilament yarn. ) Was subjected to a heat setting treatment at 200 ° C. The dry heat shrinkage of this plain weave fabric at 150 ° C. was 2.6% in the warp direction and 2.2% in the weft direction. The same formulation and coloring as in Example 15 and a thickness of 0.84 mm and a weight of 710 g / m by the same procedure.²A polyolefin-based resin-coated sheet was obtained. The resulting polyolefin resin-coated sheet had a dry heat shrinkage of 150% at 15 ° C. for 15 minutes with a warp direction of 2.4% and a weft direction of 1.9%, and an LOI of 28.7. Tables 9 to 11 show the composition of the polyolefin resin composition layer film, the composition of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0112]
Comparative Example 16
In the same manner as in Example 16, a polyolefin resin-coated sheet with a double-sided colored protective layer was produced. However, a heat-set treatment was performed at 200 ° C. on a plain weave fabric (product number: AKN-4425: Asahi Kasei Co., Ltd.) in which the 420 denier polyamide (nylon) multifilament yarn was woven. The dry heat shrinkage of the plain weave fabric at 150 ° C. for 15 minutes was 2.4% in the warp direction and 2.1% in the weft direction. Mixing and coloring similar to Example 16, thickness 0.77 mm, weight 680 g / m by similar procedure²A polyolefin-based resin-coated sheet was obtained. The resulting polyolefin resin-coated sheet had a dry heat shrinkage of 150% at 15 ° C. for 15 minutes with a warp direction of 2.2%, a weft direction of 1.9%, and a LOI of 28.1. Tables 9 to 11 show the composition of the polyolefin resin composition layer film, the composition of the colored polyolefin resin protective layer film, the performance of the fabric for the base fabric, and the results of the tests (I) to (VI).
[0113]
[Table 9]

[0114]
[Table 10]

[0115]
[Table 11]

[0116]
Performance evaluation of Comparative Examples 9 to 16
In the sheets of Comparative Examples 10 to 13, Comparative Example 15, and Comparative Example 16, even if the same red phosphorus particles as in Examples were used as the flame retardant for the polyolefin resin composition layer film, Because the heat shrinkage rate is small, after flame contact, the flame flaming part is inferior in the behavior of moving away from the fire source, and the flame contact end shrinks in a claw shape toward the fire source, forming a partial vertical state Therefore, the self-extinguishing could not be performed, and as a result, the sheets of the comparative examples were not compliant with the fire prevention test (JIS standard L-1091) of the Fire Service Act. Further, although the sheets of Comparative Examples 9 and 14 conform to the fireproofing test of the Fire Service Law, the thermal shrinkage rate of the fiber fabric base fabric is too large, and the sheet is difficult to manufacture, and at the same time, the appearance of the sheet In addition, the joint was severely shrunk when the high-frequency welder was fused, and it was not practical. Furthermore, in the sheets of Comparative Example 10 and Comparative Example 11, as a result of the heat shrinkage rate of the fiber fabric base fabric woven from the polypropylene multifilament yarn being extremely reduced by the heat setting treatment, the polypropylene multifilament yarn microstructure In order to cause a decrease in the crystallinity of the sheet, the strong physical properties of the sheet itself, such as the shear strength at the joint and the heat-resistant creep resistance at the joint, were impaired, and there was no practicality at all.
[0117]
【The invention's effect】
The flame-retardant polyolefin-based resin-coated sheet of the present invention has excellent flame retardancy that complies with the flameproof test of the Fire Service Act, and also has excellent processability and colorability.
Moreover, the flame-retardant polyolefin resin-coated sheet of the present invention is an extremely durable sheet in which the problem of lowering mechanical properties, which has been a problem in the past, has been sufficiently solved. Therefore, the flame-retardant polyolefin-based resin-coated sheet of the present invention is a substitute for a conventionally used soft polyvinyl chloride processed product sheet, especially a membrane material for a tent that requires flame resistance, a membrane material for a sheet warehouse, This sheet is suitable for industrial materials such as building site curing sheets and building site sound insulation sheets.

Claims (16)

A composite sheet comprising a base fabric including a fabric knitted from thermoplastic resin filament yarns, and front and back double-sided resin layers formed from a polyolefin-based resin composition on both sides of the base fabric,
The polyolefin resin composition comprises 100 parts by weight of a polyolefin resin and 5 to 35 parts by weight of red phosphorus particles mixed therewith and has a melt flow rate of 0.2 to 5.0 g / 10 min ( MFR) (according to the test method of JIS K 6760, where temperature: 190 ° C., load: 21.18 N (2.16 kgf))
as well as,
The composite sheet has a dry heat shrinkage of 5 to 25% in the warp and weft directions by heating at 150 ° C. for 15 minutes,
A flame-retardant polyolefin resin-coated sheet characterized by The flame retardant polyolefin resin-coated sheet according to claim 1, wherein the thermoplastic resin forming the thermoplastic resin filament yarn for base fabric is selected from polyolefin resins, polyester resins, and polyamide resins. The flame-retardant polyolefin resin-coated sheet according to claim 1 or 2, wherein the filament yarn for base fabric is selected from multifilament yarn, monofilament yarn, tape yarn, split yarn, and split yarn. The polyolefin resin composition further includes 1 to 20 parts by weight of a colorant composed of at least one selected from an inorganic pigment and an organic pigment with respect to 100 parts by weight of the polyolefin resin. The flame-retardant polyolefin resin-coated sheet according to 1. 2. The difficulty according to claim 1, wherein the thermoplastic resin filament yarn is made of at least one selected from polyethylene filament yarn, polypropylene filament yarn, and mixed filament yarn of polyethylene resin and polypropylene resin. Flammable polyolefin resin-coated sheet. The base fabric is a woven fabric and is heat-set, and exhibits a dry heat shrinkage of 5 to 25% in the warp and weft directions by heating at 150 ° C. for 15 minutes, or The flame-retardant polyolefin system according to claim 1, which is not heat-set and exhibits a dry heat shrinkage of 5 to 25% in the warp and weft directions by heating at 150 ° C for 15 minutes. Resin coated sheet. The red phosphorus particles have their surfaces coated with one or more selected from aluminum hydroxide, magnesium hydroxide, titanium oxide, zinc oxide, formalin resin, phenol resin, melamine resin, urea resin, and epoxy resin. The flame-retardant polyolefin resin-coated sheet according to claim 1, wherein the surface-coated red phosphorus particles have an average particle diameter of 5 to 25 μm. The polyolefin resin protective layer colored without including the red phosphorus particles is formed on at least one of the front and back double-sided polyolefin resin composition layers. The flame-retardant polyolefin resin-coated sheet as described. The colored polyolefin resin protective layer was selected from 5 to 50 parts by weight of a phosphoric acid compound component, 1 to 20 parts by weight of a chemical foaming agent component, an inorganic pigment, and an organic pigment with respect to 100 parts by weight of the polyolefin resin. The colored polyolefin resin composition comprising 1 to 20 parts by weight of at least one colorant component and having a melt flow rate (MFR) of 0.2 to 5.0 g / 10 minutes. The flame-retardant polyolefin resin-coated sheet according to 8, The flame-retardant polyolefin-based resin-coated sheet according to claim 9, wherein the phosphoric acid-based compound component includes at least one selected from a phosphoric acid ester, a phosphoric acid salt, a phosphoric acid ester salt, and a condensed phosphoric acid salt. . The flame-retardant polyolefin-based resin-coated sheet according to claim 10, wherein the condensed phosphate contains at least one selected from ammonium polyphosphate, thermosetting resin-coated ammonium polyphosphate, and melamine polyphosphate. The flame retardant polyolefin resin-coated sheet according to claim 9, wherein the chemical foaming agent component contains at least one selected from an azo compound, a sulfohydrazide compound, and a nitroso compound. The flame retardant polyolefin resin-coated sheet according to claim 8, wherein the thickness of the colored polyolefin resin protective layer is 10 to 50% of the total thickness of the flame retardant polyolefin resin coated sheet. Including a step of forming a composite sheet by attaching a film made of a polyolefin-based resin composition on both the front and back surfaces of a base fabric including a fabric woven from thermoplastic resin filament yarns, using a heating laminator;
The polyolefin resin composition comprises 100 parts by weight of a polyolefin resin and 5 to 25 parts by weight of red phosphorus particles mixed therewith and has a melt flow rate (MFR) of 0.2 to 50 g / 10 min. (According to the test method of JIS K 6760, however, temperature: 190 ° C., load: 21.18 N (2.16 kgf)),
In the sticking step using the heating laminator, the surface of the hot roll on the sticking side of the polyolefin resin composition film is heated to a temperature of 70 to 180 ° C., and the temperature of the base fabric is adjusted to 120 ° C. or less. The film is continuously heat-bonded to the base fabric, and at this time, the dry heat shrinkage rate of the resulting composite sheet by heating at 150 ° C. for 15 minutes is controlled to 5 to 25%.
A process for producing a flame-retardant polyolefin resin-coated sheet characterized by the following. The flame-retardant polyolefin according to claim 14, further comprising a step of forming a polyolefin-based resin protective layer colored without containing the red phosphorus particles on at least one surface of the front and back double-sided polyolefin-based resin composition layer. Of manufacturing a resin-coated sheet. The step of forming the polyolefin resin protective layer is carried out by sticking a film of the polyolefin resin or by applying and drying a coating liquid containing the polyolefin resin. The manufacturing method of the flame-retardant polyolefin resin coating sheet of description.