JP4014477B2 - Flame-retardant leather-like sheet substrate and method for producing the same - Google Patents

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【００６８】
《実施例１》［難燃性皮革様シート基材およびスエード調人工皮革の製造］
（１） 製造例１で得られたリン原子を含まないポリエステルを島成分とする海島型複合紡糸繊維のステープルを用いてクロスラップ法で常法にしたがって目付１３０ｇ／ｍ²のウエブを製造した。
（２） 製造例３で得られたリン共重合ポリエステルを島成分とする海島型複合紡糸繊維のステープルを用いてクロスラップ法で常法にしたがって目付５２０ｇ／ｍ²のウエブを製造した。
（３） 上記（１）で得られたウエブと上記（２）で得られたウエブを積層して、目付６５０ｇ／ｍ²の積層ウエブとした後、両面から交互に合計で約２５００ｐ／ｃｍ²のニードルパンチングを行った。次いで、９０℃の熱水中で収縮処理した後、乾燥巾セットし、加熱された状態でカレンダーロールにてプレスすることで表面の平滑な絡合不織布を製造した。これにより得られた絡合不織布の目付は７６０ｇ／ｍ²および見掛密度は０．４８ｇ／ｃｍ³であった。
【００６９】
（４） ポリカーボネート系ポリウレタン（日本ポリウレタン工業株式会社製「ニッポラン９９０Ｎ」）を主体とするポリウレタンのジメチルホルムアミド（ＤＭＦ）溶液（固形分１４質量％）１００質量部に対して、平均粒径１μｍの水酸化アルミニウムをＤＭＦ中の４０質量％の濃度で分散させた液１７．５質量部を添加して、水酸化アルミニウム含有ポリウレタン液（ポリウレタン：水酸化アルミニウムの質量比＝１００：５０）を調製した。
（５） 上記（４）で調製した水酸化アルミニウム含有ポリウレタン液中に、上記（３）で得られた絡合不織布を含浸させ、次いで絡合不織布を該ポリウレタン液から取り出し、凝固浴［ＤＭＦ／水＝３０／２０（質量比）］中に浸漬して湿式凝固させた後、それを凝固浴から取り出して、熱トルエン（温度９０℃）中に浸漬して、絡合不織布を形成している海島型複合紡糸繊維中の海成分（ポリエチレン）を溶出除去して極細繊維化し、非難燃化ポリエステル極細繊維よりなる絡合不織布層内に水酸化アルミニウムを含有するポリウレタンを有する層［層（Ａ）］と難燃性ポリエステル極細繊維よりなる絡合不織布層に水酸化アルミニウムを含有するポリウレタンを有する層［層（Ｂ）］からなる難燃性皮革様シート基材（厚さ１．３ｍｍ）を製造した。
これにより得られた難燃性皮革様シート基材の層（Ａ）および層（Ｂ）を形成している非難燃化ポリエステル極細繊維および難燃性ポリエステル極細繊維の単繊維繊度はいずれも０．２デシテックスであった。また、難燃性皮革様シート基材中でにポリエステル極細繊維とポリウレタンの質量比は約７９：２１であった。また、得られた難燃性皮革様シート基材の厚さ方向の断面を顕微鏡にて観察したところ、水酸化アルミニウム粒子が多孔質ポリウレタンの内部に多く存在していることが確認された。
【００７０】
（６） 上記（５）で得られた難燃性皮革様シート基材の層（Ａ）側の表面を所望の毛足しとなるようにバッフィングしてスエード調人工皮革とした後、下記の染色条件で染色して、染色したスエード調人工皮革を製造した。
［スエード調人工皮革の染色条件］
染 料 ：「Ｍiketon Ｐolyester Ｂlue ＦＢＬ」 ３％ｏｗｆ
（三井化学株式会社製）
染料温度：１２０℃
染料時間：６０分
浴 比 ： １：２０
染色装置:高圧液流染色機［(株)テクサム技研製「MINI-JET D200」）
【００７１】
（７） 上記（５）で得られた難燃性皮革様シート基材と上記（６）で得られたスエード調人工皮革の難燃性、上記（５）で得られた難燃性皮革様シート基材のリン原子濃度および耐摩耗性、並びに上記（６）で得られたスエード調人工皮革の風合を上記した方法で測定または評価したところ、下記の表２に示すとおりであった。
【００７２】
《実施例２》［難燃性皮革様シート基材およびスエード調人工皮革の製造］
（１） 製造例１で得られたリン原子を含まないポリエステルを島成分とする海島型複合紡糸繊維のステープルを用いて実施例１の（１）と同様にして目付３９０ｇ／ｍ²のウエブを製造した。
（２） 製造例４で得られたリン共重合ポリエステルを島成分とする海島型複合紡糸繊維のステープルを用いて実施例１の（２）と同様にして目付２６０ｇ／ｍ²のウエブを製造した。
（３） 上記（１）で得られたウエブと上記（２）で得られたウエブを積層して、目付６５０ｇ／ｍ²の積層ウエブとした後、実施例１の（３）と同様にしてニードルパンチング、収縮処理、乾燥巾セット、カレンダーロールによるプレス処理を行って、表面の平滑な絡合不織布を製造した（目付１，０５０ｇ／ｍ²、見掛密度０．４５ｇ／ｃｍ³）。
【００７３】
（４） 上記（３）で得られた絡合不織布を用いて、実施例１の（４）および（５）と同様の操作を行って、非難燃化ポリエステル極細繊維よりなる絡合不織布層内に水酸化アルミニウムを含有するポリウレタンを有する層［層（Ａ）］と難燃性ポリエステル極細繊維よりなる絡合不織布層に水酸化アルミニウムを含有するポリウレタンを有する層［層（Ｂ）］からなる難燃性皮革様シート基材（厚さ１．３ｍｍ）を製造した。
これにより得られた難燃性皮革様シート基材の層（Ａ）および層（Ｂ）を形成している非難燃化ポリエステル極細繊維および難燃性ポリエステル極細繊維の単繊維繊度はいずれも０．２デシテックスであった。また、難燃性皮革様シート基材中でにポリエステル極細繊維とポリウレタンの質量比は約７９：２１であった。また、得られた難燃性皮革様シート基材の厚さ方向の断面を顕微鏡にて観察したところ、水酸化アルミニウム粒子が多孔質ポリウレタンの内部に多く存在していることが確認された。
【００７４】
（５） 上記（４）で得られた難燃性皮革様シート基材の層（Ａ）側の表面を実施例１の（６）と同様にしてバッフィングしてスエード調人工皮革とした後、実施例１の（６）と同様にして染色して、染色したスエード調人工皮革を製造した。
（６） 上記（４）で得られた難燃性皮革様シート基材および上記（５）で得られた染色後のスエード調人工皮革の難燃性、上記（４）で得られた難燃性皮革様シート基材のリン原子濃度および耐摩耗性、並びに上記（５）で得られた染色後のスエード調人工皮革の風合を上記した方法で測定または評価したところ、下記の表２に示すとおりであった。
【００７５】
《実施例３》［難燃性皮革様シート基材およびスエード調人工皮革の製造］
（１） 製造例１で得られたリン原子を含まないポリエステルを島成分とする海島型複合紡糸繊維のステープルを用いてクロスラップ法で常法にしたがって目付６５０ｇ／ｍ²のウエブを製造し、両面から交互に合計で約２５００ｐ／ｃｍ²のニードルパンチングを行った。次いで、９０℃の熱水中で収縮処理した後、乾燥巾セットし、加熱された状態でカレンダーロールにてプレスすることで表面の平滑な絡合不織布を製造した。これにより得られた絡合不織布の目付は７７０ｇ／ｍ²および見掛密度は０．４９ｇ／ｃｍ³であった。
（２） ポリカーボネート系ポリウレタン（日本ポリウレタン工業株式会社製「ニッポラン９９０Ｎ」）を主体とするポリウレタンのジメチルホルムアミド（ＤＭＦ）溶液（固形分１４質量％）１００質量部に対して、平均粒径１μｍの水酸化アルミニウムをＤＭＦ中の４０質量％の濃度で分散させた液１７．５質量部を添加して、水酸化アルミニウム含有ポリウレタン液（ポリウレタン：水酸化アルミニウムの質量比＝１００：５０）を調製した。
【００７６】
（３） 上記（２）で調製した水酸化アルミニウム含有ポリウレタン液中に、上記（１）で得られた絡合不織布を含浸させ、次いで絡合不織布を該ポリウレタン液から取り出し、凝固浴［ＤＭＦ／水＝３０／２０（質量比）］中に浸漬して湿式凝固させた後、それを凝固浴から取り出して、熱トルエン（温度９０℃）中に浸漬して、絡合不織布を形成している海島型複合紡糸繊維中の海成分（ポリエチレン）を溶出除去して極細繊維化し、非難燃化ポリエステル極細繊維よりなる絡合不織布の内部に水酸化アルミニウムを含有するポリウレタンを有する厚さ１．３ｍｍのシート基体を製造した。このシート基体を、片面から０．３５ｍｍの厚さでスライスした後、スライス面をバッフィングして厚さ０．２６ｍｍのシート（Ａ）とした。
（４） 製造例３で得られたリン共重合ポリエステルを島成分とする海島型複合紡糸繊維のステープルを用いて、上記（１）と同様にして絡合不織布を製造し、その絡合不織布を用いて上記（２）〜（３）と同様の操作を行って、リン共重合ポリエステル極細繊維よりなる絡合不織布内に水酸化アルミニウムを含有するポリウレタンを有する厚さ１．０ｍｍのシート（Ｂ）（非バッフィングシート）を製造した。
【００７７】
（５） 上記（４）で得られたシート（Ｂ）の片面に、ポリウレタン（大日精化株式会社製「ハイムレンＮＰＵ−５」；ポリエーテル系ポリウレタン）をＤＭＦに溶解して調製した接着剤（固形分濃度２５質量％）を、グラビアロース（１４０メッシュ）を用いて点状に塗布し（塗布量：固形分３ｇ／ｍ²）、その直後に上記（３）で得られたシート（Ａ）のバッフィング面を重ね合わせて接着して、難燃性皮革様シート基材を製造した。
これにより得られた難燃性皮革様シート基材におけるシート（Ａ）［層(Ａ)］およびシート（Ｂ）［層（Ｂ）］を形成している非難燃化ポリエステル極細繊維および難燃性ポリエステル極細繊維の単繊維繊度はいずれも０．２デシテックスであった。また、難燃性皮革様シート基材における層（Ａ）と層（Ｂ）を構成するポリエステル極細繊維の質量比は、目付からの計算値で２０：８０であった。
【００７８】
（６） 上記（５）で得られた難燃性皮革様シート基材の層（Ａ）側の表面を実施例１の（６）と同様にしてバッフィングしてスエード調人工皮革とした後、実施例１の（６）と同様にして染色して、染色したスエード調人工皮革を製造した。
（７） 上記（５）で得られた難燃性皮革様シート基材および上記（６）で得られた染色後のスエード調人工皮革の難燃性、上記（５）で得られた難燃性皮革様シート基材のリン原子濃度および耐摩耗性、並びに上記（６）で得られた染色後のスエード調人工皮革の風合を上記した方法で測定または評価したところ、下記の表２に示すとおりであった。
【００７９】
《比較例１》［難燃性皮革様シート基材およびスエード調人工皮革の製造］
（１） 製造例３で得られたリン共重合ポリエステルを島成分とする海島型複合紡糸繊維のステープルを用いて実施例１の(１)と同様にして目付６５０ｇ／ｍ²のウエブを製造した。
（２） 上記（１）で得られたウエブのみを用いて、実施例１の（３）と同様の操作を行って絡合不織布を製造した後、実施例１の（４）および（５）と同様にして、水酸化アルミニウム含有ポリウレタン液の含浸とポリウレタンの凝固、並びに絡合不織布を形成している海島型複合紡糸繊維中の海成分（ポリエチレン）を溶出除去による極細繊維化を行って、難燃性ポリエステル極細繊維よりなる絡合不織布の内部に水酸化アルミニウムを含有するポリウレタンを有する難燃性皮革様シート基材（厚さ１．３ｍｍ）を製造した。
これにより得られた難燃性皮革様シート基材における絡合不織布を形成している難燃性ポリエステル極細繊維の単繊維繊度は０．２デシテックスであった。また、難燃性皮革様シート基材中でのポリエステル極細繊維とポリウレタンの質量比は約７９：２１であった。また、得られた難燃性皮革様シート基材の厚さ方向の断面を顕微鏡にて観察したところ、水酸化アルミニウム粒子が多孔質ポリウレタンの内部に多く存在していることが確認された。
【００８０】
（３） 上記（２）で得られた難燃性皮革様シート基材の表面を実施例１の(６)と同様にしてバッフィングしてスエード調人工皮革とした後、実施例１の(６)と同様にして染色して、染色したスエード調人工皮革を製造した。
（４） 上記（２）で得られた難燃性皮革様シート基材および上記（３）で得られた染色後のスエード調人工皮革の難燃性、上記（２）で得られた難燃性皮革様シート基材のリン原子濃度および耐摩耗性、並びに上記（３）で得られた染色後のスエード調人工皮革の風合を上記した方法で測定または評価したところ、下記の表２に示すとおりであった。
【００８１】
《比較例２》［皮革様シート基材およびスエード調人工皮革の製造］
（１） 製造例１で得られたリン原子を含まないポリエステルを島成分とする海島型複合紡糸繊維のステープルを用いてクロスラップ法で常法にしたがって目付３９０ｇ／ｍ²のウエブを製造した。
（２） 製造例４で得られたリン共重合ポリエステルを島成分とする海島型複合紡糸繊維のステープルを用いてクロスラップ法で常法にしたがって目付２６０ｇ／ｍ²のウエブを製造した。
（３） 上記（１）で得られたウエブと上記（２）で得られたウエブを積層して、目付６５０ｇ／ｍ²の積層ウエブとした後、実施例１の（３）と同様にしてニードルパンチング、収縮処理、乾燥巾セット、カレンダーロールによるプレス処理して絡合不織布を製造した（目付１，０６０ｇ／ｍ²、見掛密度は０．４５ｇ／ｃｍ³）。
【００８２】
（４） ポリカーボネート系ポリウレタン（日本ポリウレタン工業株式会社製「ニッポラン９９０Ｎ」）を主体とするポリウレタンをＤＭＦに溶解して、水酸化アルミニウムを含有しないポリウレタン溶液（固形分１４質量％）を調製し、このポリウレタン液中に、上記（３）で得られた絡合不織布を含浸させ、以下実施例１の（５）と同様の操作を行って、非難燃化ポリエステル極細繊維よりなる絡合不織布層［層（Ａ）］および難燃性ポリエステル極細繊維よりなる絡合不織布層［層（Ｂ）］の内部に水酸化アルミニウム（難燃性付与成分）を含有しないポリウレタンを含有する皮革様シート基材（厚さ１．３ｍｍ）を製造した。
これにより得られた皮革様シート基材における非難燃化ポリエステル極細繊維および難燃性ポリエステル極細繊維の単繊維繊度はいずれも０．２デシテックスであった。また、皮革様シート基材中でにポリエステル極細繊維とポリウレタンの質量比は約８５：１５であった。また、得られた皮革様シート基材の厚さ方向の断面を顕微鏡にて観察したところ、多孔質ポリウレタンの内部には水酸化アルミニウムが存在しないことが確認された。
【００８３】
（５） 上記（４）で得られた皮革様シート基材の層（Ａ）側の表面を実施例１の（６）と同様にしてバッフィングしてスエード調人工皮革とした後、実施例１の（６）と同様にして染色して、染色したスエード調人工皮革を製造した。
（６） 上記（４）で得られた皮革様シート基材および上記（５）で得られた染色後のスエード調人工皮革の難燃性、上記（４）で得られた皮革様シート基材のリン原子濃度および耐摩耗性、並びに上記（５）で得られた染色後のスエード調人工皮革の風合を上記した方法で測定または評価したところ、下記の表２に示すとおりであった。
【００８４】
【表２】

【００８５】
上記の表２の結果に見るように、非難燃化ポリエステル極細繊維（ａ）からなる絡合不織布の内部に難燃性付与成分（水酸化アルミニウム）を含む弾性重合体（ｃ）（ポリウレタン）を含有させてなる層（Ａ）、および難燃性ポリエステル極細繊維（ｂ）（リン共重合ポリエステル極細繊維）からなる絡合不織布の内部に難燃性付与成分（水酸化アルミニウム）を含む弾性重合体（ｃ）（ポリウレタン）を含有させてなる層（Ｂ）を有する実施例１〜３の難燃性皮革様シート基材およびそれから得られた人工皮革（スエード調人工皮革）は、自己消火性で難燃性に優れ、摩耗量が少なく耐摩耗性に優れ、摩耗試験後も外観に優れていて表面強度が高く、しかも風合にも優れている。
【００８６】
それに対して、比較例１の皮革様シート基材は、非難燃化ポリエステル極細繊維（ａ）からなる絡合不織布層を表面層として有しておらず、難燃性ポリエステル極細繊維よりなる絡合不織布内に難燃性付与成分（水酸化アルミニウム）を含有する弾性重合体（ｃ）（ポリウレタン）を有する単一層からなることにより、難燃性の点では優れているものの、摩耗量が多く、耐摩耗性に劣り、摩耗試験後の外観が不良であり、表面強度が低い。
また、比較例２の皮革様シート基材は、非難燃化ポリエステル極細繊維（ａ）からなる絡合不織布層および難燃性ポリエステル極細繊維（ｂ）（リン共重合ポリエステル極細繊維）からなる絡合不織布層の内部に含有させたポリウレタンが難燃性付与成分（水酸化アルミニウム）を含有していないために、易燃性であり、難燃性に劣っている。
【００８７】
《参考例１》［皮革様シート基材およびスエード調人工皮革の製造］
（１） 製造例１で得られたリン原子を含まないポリエステルを島成分とする海島型複合紡糸繊維のステープルを用いて実施例１の（１）と同様にして目付１３０ｇ／ｍ²のウエブを製造した。
（２） 製造例２で得られたリン共重合ポリエステルを島成分とする海島型複合紡糸繊維のステープルを用いて実施例１の(２)と同様にして目付５２０ｇ／ｍ²のウエブを製造した。
（３） 上記（１）で得られたウエブと上記（２）で得られたウエブを積層して、目付６５０ｇ／ｍ²の積層ウエブとした後、実施例１の（３）と同様にしてニードルパンチング、収縮処理、乾燥巾セット、カレンダーロールによるプレス処理を行って、表面の平滑な絡合不織布を製造した。
【００８８】
（４） 上記（３）で得られた絡合不織布を用いて、実施例１の（４）および（５）と同様の操作を行って、非難燃化ポリエステル極細繊維よりなる絡合不織布層内に水酸化アルミニウムを含有するポリウレタンを有する層［層（Ａ）］と難燃性ポリエステル極細繊維よりなる絡合不織布層に水酸化アルミニウムを含有するポリウレタンを有する層［層（Ｂ）］からなる皮革様シート基材（厚さ１．３ｍｍ）を製造した。
これにより得られた皮革様シート基材の層（Ａ）および層（Ｂ）を形成している非難燃化ポリエステル極細繊維および難燃性ポリエステル極細繊維の単繊維繊度はいずれも０．２デシテックスであった。また、この皮革様シート基材中でのポリエステル極細繊維とポリウレタンの質量比は約７９：２１であった。また、得られた皮革様シート基材の厚さ方向の断面を顕微鏡にて観察したところ、水酸化アルミニウム粒子が多孔質ポリウレタンの内部に多く存在していることが確認された。
【００８９】
（５） 上記（４）で得られた皮革様シート基材の層（Ａ）側の表面を実施例１の（６）と同様にしてバッフィングしてスエード調人工皮革とした後、実施例１の（６）と同様にして染色して、染色したスエード調人工皮革を製造した。
（６） 上記（４）で得られた皮革様シート基材におけるリン原子濃度を上記した方法で測定したところ２４００ｐｐｍであり、実施例１〜３で得られた難燃性皮革様シート基材に比べてリン原子濃度が低かった。
また、上記（４）で得られた皮革様シート基材の耐摩耗性を上記した方法で評価したところ、摩耗量は２４ｍｇと少なく耐摩耗性に優れており、さらに摩耗試験後の外観評点が４点であり表面強度が高かった。さらに、上記（５）で得られた染色後のスエード調人工皮革の風合を上記した方法で評価したところ、良好であった。また、上記（４）で得られた皮革様シート基材および上記（５）で得られた染色後のスエード調人工皮革の難燃性を上記した方法で評価したところ、層（Ａ）の絡合不織布を形成している難燃性ポリエステル極細繊維を構成するポリエステルにおけるリン含有化合物の共重合割合が実施例１〜３に比べて少なく、それに伴って皮革様シート基材におけるリン原子濃度が低いために、実施例１〜３のものに比べて難燃性が低かった。
【００９０】
《実施例４》［銀付調人工皮革の製造］
（１） ポリカーボネート系ポリウレタン（大日本インキ化学工業株式会社製「ＮＹ−２１４」）１００質量部をＤＭＦ３５質量部に溶解し、これに黒色顔料（大日本インキ化学工業株式会社製「ＤＵＴ−４７９０」）３０質量部を添加して、黒色に調色したポリウレタン液を調製し、この液を離型紙上に塗布し乾燥して、厚さ１５μｍの被膜を形成した。
（２） 上記（２）で形成した離型紙上の被膜の上に、２液型ポリウレタン（大日精化工業株式会社製「ＵＤ−８３１０］）１００質量部、ポリイソシアネート硬化剤（武田薬品工業株式会社製「Ｄ−１１０Ｎ」）１０質量部、アミン系触媒（武田薬品工業株式会社製「ＱＳ」）１．５質量部、ＤＭＦ１０質量部および酢酸エチル２０質量部からなる混合液を、固形分で２０ｇ／ｍ²の割合で塗布し、乾燥して、乾燥直後の粘着性を有する状態のものを、実施例１の（６）で得られた染色したスエード調人工皮革の表面（スエード面側）に重ね合わせ、プレスして貼り合わせた。その後、６０℃で４８時間放置してから離型紙を剥がして、銀付調人工皮革を得た。
これにより得られた銀付調人工皮革は、平滑で高級感のある外観とソフトで良好な風合を有していた。また、この銀付調人工皮革の難燃性をＭＶＳＳ試験機（株式会社大栄科学精機製作所製「ＦＭＶＳＳ−３０２」)を用いて試験したところ、難燃と判定された。
【００９１】
《実施例５》［自動車用座席（カーシート）の製造］
実施例１の（６）で得られた染色したスエード調人工皮革および実施例４で得られた銀付調人工皮革のそれぞれを上張材として用いて、常法にしたがって自動車用座席（カーシート）を作製したところ、強度不足などに起因する加工上のトラブルを全く発生することなく、良好な作業性で円滑に製造することができた。得られた自動車用座席の上張部分は、天然皮革に近似した良好な感触および外観を有し、しかも自動車用座席に要求される優れた難燃性と強度を有していた。
【００９２】
【発明の効果】
本発明の難燃性皮革様シート基材およびそれから得られる人工皮革は、難燃性に極めて優れており、しかもソフトで高級感に優れる風合および外観を有し、さらには高い耐摩耗性や剥離強度などを有し、表面強度などの力学的特性に優れている。
特に、本発明の難燃性皮革様シート基材およびそれから得られる人工皮革において、層（Ｂ）の絡合不織布を構成する難燃性ポリエステル極細繊維が、ハロゲン原子を持たずリン原子を分子中に有するリン含有共重合ポリエステルから形成され、且つ難燃性皮革様シート基材を構成する絡合不織布の内部に含まれる弾性重合体中に含有させる難燃性付与成分が非ハロゲン系難燃剤、特に水酸化アルミニウムである場合は、難燃性皮革様シート基材およびそれからなる人工皮革は環境などに有害なハロゲンを含まないために、上記した種々の優れた特性と併せて、安全性の点でも極めて優れている。
本発明の難燃性皮革様シート基材およびそれからなる人工皮革は、前記した優れた特性を活かして、高い難燃性、安全性、良好な風合、外観、高い表面強度などが要求される鉄道乗物用座席、自動車用座席、航空機用座席、船舶用座席などの乗物用座席の上張材、ソファー、クッション、椅子などのインテリア製品の上張材として特に有用であり、また前記用途以外にも、衣料、靴、鞄、小物入れ、手袋などの広範な用途に有効に用いることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a flame-retardant leather-like sheet base material, a production method thereof, artificial leather using the flame-retardant leather-like sheet base material, and chairs or vehicle seats using the artificial leather as an upholstery material Related to the kind. More specifically, the present invention is a flame-retardant leather-like sheet base material having a good texture that is soft and superior in quality, and also excellent in surface strength such as wear resistance and peel strength, and its production The present invention relates to a method and an artificial leather using the flame-retardant leather-like sheet substrate. The flame-retardant leather-like sheet base material of the present invention and the artificial leather using the same are required to have a high-class feeling and flame-retardant properties by taking advantage of the above-described properties, and also have high wear resistance and peeling. It is particularly suitably used as various materials for which high surface strength such as strength is required, particularly as an upholstery material for interior products such as vehicle seats, cushion sheets, sofas and chairs.
[0002]
[Prior art]
Artificial leather has been used for various purposes such as interiors, clothing, shoes, bags, gloves, and vehicle seat upholstery. Among them, in the field of interior furniture overlays such as railcar seats, automobile seats, aircraft seats, ship seats, cushion seats, sofas, chairs, etc. There is a strong demand for artificial leather imparted with flame retardancy.
[0003]
Artificial leather is roughly classified into two types: artificial leather with a silver surface that has a silver surface formed by a wet or dry method on the surface of a leather-like sheet base material, and suede-like artificial leather with a brushed surface of a leather-like sheet base material. However, the leather-like sheet base material that forms the base of any artificial leather generally has a structure in which an elastic polymer is contained in the entangled space of the entangled nonwoven fabric.
As a method for imparting flame retardancy to such a leather-like sheet base material or artificial leather based thereon, (1) a leather-like sheet base material or a silver-like artificial leather or suede-like texture formed using the same Post-processing method of impregnating a flame retardant to artificial leather, (2) a method of adhering a woven or knitted fabric having flame resistance to the back surface of a leather-like sheet substrate, and (3) a fiber produced by adding flame retardant fine particles A method for producing a leather-like sheet base material by using (4) a method using a flame retardant added as an elastic polymer contained in the entangled space of the entangled nonwoven fabric constituting the leather-like sheet base material is generally used. It has been adopted.
[0004]
However, in the case of the post-processing method (1) described above, when the leather-like sheet base is formed of an ultrafine fiber bundle, even if the flame retardant is in the form of fine particles, it can penetrate into the ultrafine fiber bundle. It is extremely difficult, and most of the flame retardant is present on the outside of the ultrafine fiber bundle and on the outer surface of the elastic polymer. As a result, the appearance of the artificial leather is deteriorated by being stained with the flame retardant, and the flame retardant is easily dropped off, and it is difficult to obtain a durable flame retardant effect. In addition, in order to prevent the flame retardant from falling off, there is a method of adding a flame retardant to the binder resin liquid and impregnating it into a leather-like sheet base material or artificial leather. It is difficult to infiltrate the flame retardant into the inside of the fiber bundle. Rather, the flame retardant effect is greatly reduced because the surface of the flame retardant is covered with the binder resin. In addition, the impregnation with the binder resin tends to cause the disadvantage that the flexibility of the leather-like sheet base material or the artificial leather is impaired and a sufficient napped state cannot be obtained.
[0005]
The method (2) is generally a method in which a flame retardant sheet material obtained by applying a flame retardant such as a phosphorus compound or a halogen compound to a woven or knitted fabric is bonded to a leather-like sheet substrate or the back surface of artificial leather. However, by attaching a flame retardant sheet material, the soft and high-quality texture unique to artificial leather tends to be impaired.
[0006]
Further, the fiber used in the method (3) is generally produced by adding flame retardant fine particles to a fiber-forming polymer such as polyamide or polyester and melt spinning, but it is difficult to perform the spinning at the time of melt spinning. From the viewpoint of the stability of the flame retardant and the polymer, there are limitations on the setting of the spinning temperature, the selection of the polymer and the flame retardant, etc. Moreover, yarn breakage is likely to occur, and there is a problem in terms of productivity. In addition, the fiber produced by adding the flame retardant fine particles has a large decrease in fiber properties, and when such a fiber is used as a leather-like sheet base material of a suede-like artificial leather, the wear resistance is greatly decreased. . In addition, when it is used as a leather-like sheet base material for a silver-tone artificial leather, the peel strength of the silver surface is lowered, and an artificial leather with practical value cannot be obtained.
[0007]
In addition, in the case of the method (4) above, without adding a flame retardant into the fiber forming the entangled nonwoven fabric in the leather-like sheet base material, adding only the flame retardant contained in the nonwoven fabric, In general, a sufficient flame retardant effect cannot be obtained. In this method, if the amount of the flame retardant added to the elastic polymer is increased in order to increase the flame retardant effect, the texture of the artificial leather becomes hard and the high-class feeling is lost.
[0008]
For the purpose of solving the problems of the prior art as described above, a fiber substrate is formed using a fiber comprising a flame retardant polyester copolymerized with a phosphorus compound or a halogen compound, and a bromine-containing modified urethane compound is formed on the fiber substrate. A microporous fiber substrate is formed by impregnating with a flame retardant polyurethane solution containing water and coagulating wet, and a polycarbonate polyurethane adhesive layer containing antimony trioxide and a bromine-containing modified urethane compound is formed on the microporous fiber substrate. Synthetic leather in which a specific polycarbonate polyurethane film layer is laminated has been proposed (see Patent Document 1). However, since this synthetic leather uses a bromine-containing modified urethane compound containing halogen as a flame retardant polyurethane impregnated into a fiber base and a polyurethane as an adhesive, it is easy to generate harmful gases during incineration. Undesirable from the viewpoint of environmental pollution. In addition, this synthetic leather is formed by using a flame retardant polyester fiber copolymerized with a phosphorus compound or a halogen compound or a fiber added with a halogen flame retardant for the entire fiber substrate constituting the base microporous fiber substrate. However, since these flame retardant fibers are not strong enough, there is a drawback that the surface strength such as wear resistance and peel strength is inferior.
[0009]
Under such circumstances, the present inventors have no disadvantages as in the prior arts (1) to (4) described above, and are halogen-free and environmentally friendly while maintaining a soft and high-quality feeling. Research has been conducted for the purpose of developing a flame-retardant leather-like sheet substrate having less pollution problems, excellent safety, and good flame retardancy. Then, an entangled nonwoven fabric is formed from flame retardant ultrafine fibers having a single fiber fineness of 0.5 dtex or less made of a flame retardant copolyester obtained by copolymerizing an organic phosphorus compound, and aluminum hydroxide is contained inside the entangled nonwoven fabric. Invented a flame-retardant leather-like sheet substrate containing an elastic polymer to be applied (see Patent Document 2). This flame-retardant leather-like sheet substrate invented by the present inventors has a soft and high-quality texture and good flame retardancy, and does not contain harmful halogens. It is also excellent in terms of preventing environmental pollution. Therefore, artificial leather such as silver-added artificial leather and suede-like artificial leather formed using this flame-retardant leather-like sheet substrate is particularly suitable as a veneer for vehicle seats and interior products.
The present inventors have made further studies based on the present invention. However, in applications such as the above-mentioned vehicle seats and interior product upholstery materials that require high surface strength, patent documents by the present inventors are available. It has been found that it is desirable to further improve the surface strength by further improving the flame-retardant leather-like sheet substrate of the second invention.
[0010]
In addition to the above, it is conventionally known to form fibers using a flame-retardant polyester copolymerized with a phosphorus-containing compound (see, for example, Patent Documents 3 to 6), and derived from a phosphorus compound in a polyurethane molecule. A flame retardant polyurethane having a structural unit introduced therein is also known (see, for example, Patent Document 7). However, these patent documents do not disclose the use of the flame-retardant polyester fiber or the flame-retardant polyurethane for the production of the flame-retardant leather-like sheet base material, and therefore, the wind and the high-quality feeling are excellent. In these patent documents, there is any description or suggestion about providing a flame retardant leather-like sheet base material having excellent flame retardancy and excellent surface strength such as abrasion resistance and peel strength. It has not been.
[0011]
[Patent Document 1]
JP-A-63-85185
[Patent Document 2]
JP 2002-115183 A
[Patent Document 3]
JP 51-82392 A
[Patent Document 4]
JP-A-55-7888
[Patent Document 5]
Japanese Patent Publication No. 55-41610
[Patent Document 6]
JP 2001-164423 A
[Patent Document 7]
Japanese Patent Laid-Open No. 9-194559
[0012]
[Problems to be solved by the invention]
The object of the present invention is excellent in flame retardancy, soft and superior in texture and appearance, and has high wear resistance, peel strength, etc. and excellent mechanical properties such as surface strength, It is to provide a durable flame retardant leather-like sheet substrate.
And the objective of this invention is providing the manufacturing method of such a flame-retardant leather-like sheet base material, and the artificial leather which uses this flame-retardant leather-like sheet base material. In particular, the present invention has flame retardancy, such as railway seats, automobile seats, aircraft seats, marine seats and other vehicle seats, as well as interior products such as sofas, cushion seats, chairs, etc. A flame-retardant leather-like sheet base material and artificial leather that can be used effectively in applications that require high surface strength such as softness, good texture and texture, and excellent wear resistance and peel strength. It is an important purpose to provide.
[0013]
[Means for Solving the Problems]
As described above, the present inventors have further studied based on the invention of Patent Document 2 by the present inventors. As a result, the flame retardancy described or disclosed in Patent Documents 1 and 2 above, in which an elastic polymer containing a flame retardant is contained in an entangled nonwoven fabric made of flame retardant polyester ultrafine fibers. In the leather-like sheet substrate, instead of forming the entangled nonwoven fabric constituting the leather-like sheet substrate by using a flame-retardant polyester microfiber alone, it is difficult to form a nonwoven fabric layer made of polyester microfiber containing no flame-retardant component. When a laminated structure composed of non-woven layers made of flammable polyester microfibers and an elastic polymer containing a flame-retardant component is contained in these non-woven layers, a soft and high-quality texture and appearance, as well as excellent difficulty While maintaining the flammability, the surface strength such as abrasion resistance and peel strength is greatly improved, so the artificial leather formed from the flame-retardant leather-like sheet base material has good wind And appearance, it is required to have a high surface strength with excellent flame retardancy, we have found that it is extremely suitable as such as overlayer materials seats and interior furniture for various vehicles.
[0014]
Furthermore, the inventors of the present invention, when making the entangled nonwoven fabric constituting the flame-retardant leather-like sheet base material into the above-mentioned specific laminated structure, the polyester extra-fine fiber layer constituting the polyester extra-fine fiber layer not containing the flame retardant imparting component It has been found that when the tensile strength of the fiber is 1.6 g / dtex or more, the mechanical properties such as the surface strength of the flame-retardant leather-like sheet base material and the artificial leather formed therefrom are further improved.
Moreover, the present inventors do not use a halogen-based flame retardant component that generates a harmful substance during combustion as the flame retardant polyester ultra fine fiber constituting the flame retardant polyester ultra fine fiber layer. In addition, aluminum hydroxide is used as a flame retardant component to be contained in an elastic polymer made of a phosphorus-containing polyester copolymer obtained by copolymerizing a phosphorus-containing compound and present inside an entangled nonwoven fabric made of ultrafine fibers. It has been found that the use of can maintain high flame retardancy while eliminating the use of harmful halogen flame retardants, and is extremely preferable.
Furthermore, the present inventors have found a method suitable for producing a flame-retardant leather-like sheet base material having the above-mentioned specific laminated structure, and have completed the present invention based on these various findings.
[0015]
That is, the present invention
(1) (A) Elastic polymer (c) containing a flame retardancy-imparting component inside an entangled non-woven fabric made of polyester microfiber (a) having a single fiber fineness of 0.5 dtex or less and not containing a flame retardancy imparting component A layer comprising: and
(B) An elastic polymer (c) containing a flame retardant imparting component is contained inside an entangled nonwoven fabric comprising flame retardant polyester ultrafine fibers (b) having a single fiber fineness of 0.5 dtex or less containing the flame retardant imparting component. A layer to be contained;
A flame-retardant leather-like sheet base material having a lamination mass ratio of polyester ultrafine fiber (a): flame-retardant polyester ultrafine fiber (b) in the flame-retardant leather-like sheet base material of 10:90 to 90: 10 is a flame-retardant leather-like sheet base material.
[0016]
And this invention,
(2) The tensile strength of the polyester ultrafine fiber (a) that does not contain the flame retardant imparting component forming the entangled nonwoven fabric constituting the layer (A) is 1.6 g / dtex or more. Flame retardant leather-like sheet substrate;
(3) The flame retardant polyester ultrafine fiber (b) forming the entangled nonwoven fabric constituting the layer (B) is an ultrafine fiber made of a copolyester obtained by copolymerizing a phosphorus-containing compound (1) or (2) flame retardant leather-like sheet substrate;
(4) The flame-retardant leather-like sheet base material according to (3), wherein the phosphorus atom concentration in the copolyester forming the flame-retardant polyester ultrafine fiber (b) is 6,000 to 50,000 ppm;
(5) The flame retardant which forms the entangled nonwoven fabric which comprises the polyester extra fine fiber (a) which does not contain the flame retardance provision component which forms the entangled nonwoven fabric which comprises a layer (A), and a layer (B) The flame-retardant leather-like sheet base material according to (3) or (4), wherein the phosphorus atom concentration with respect to the total mass of the conductive polyester microfiber (b) is 3,000 ppm or more;
(6) The above-mentioned (1), wherein the flame retardancy-imparting component contained in the elastic polymer (c) contained in the entangled nonwoven fabric constituting the layers (A) and (B) is aluminum hydroxide. A flame retardant leather-like sheet substrate of any one of to (5); and
(7) The total content of aluminum hydroxide is 10 to 10 parts by mass with respect to a total of 100 parts by mass of the elastic polymer (c) formed in the entangled nonwoven fabric constituting the layer (A) and the layer (B). The flame-retardant leather-like sheet base material according to (6), which is 200 parts by mass;
It is.
[0017]
Furthermore, the present invention provides
(8) (I) Ultrafine fiber generating fiber (a) capable of forming a polyester ultrafine fiber having a single fiber fineness of 0.5 dtex or less and not containing a flame retardant component (a₀) And an ultrafine fiber generating type fiber (b) capable of forming a flame retardant polyester ultrafine fiber having a single fiber fineness of 0.5 dtex or less containing a flame retardant imparting component (b)₀) To produce an entangled nonwoven fabric by entangled and integrated with each other;
(II) Then
-(II) -1: After providing the entangled nonwoven fabric obtained in the step (I) with the elastic polymer (c) containing the flame retardant imparting component, the ultrafine fiber generating fiber (a₀) And extra fine fiber generating fiber (b)₀) Are made into ultrafine fibers, and each of them contains a polyester ultrafine fiber (a) having a single fiber fineness of 0.5 dtex or less and containing a flame retardancy imparting component and a flame retardancy having a single fiber fineness of 0.5 dtex or less. A polyester microfiber (b); or
-(II) -2: Ultra-fine fiber generating fiber (a) that forms an entangled nonwoven fabric by converting the entangled nonwoven fabric obtained in step (I) to ultrafine fibers₀) And extra fine fiber generating fiber (b)₀) Each of polyester fine fibers (a) having a single fiber fineness of 0.5 dtex or less and containing no flame retardancy imparting component, and flame retardant polyester ultrafine fibers having a single fiber fineness of 0.5 dtex or less containing a flame retardancy imparting component (b) To give an elastic polymer (c) containing a flame retardancy-imparting component;
It is the manufacturing method of the flame-retardant leather-like sheet base material characterized by the above-mentioned.
[0018]
  And this invention,
(9) (i) The following steps;
(I) -1: Ultrafine fiber generating fiber (a) capable of forming a polyester ultrafine fiber having a single fiber fineness of 0.5 dtex or less and not containing a flame retardant component (a₀) Entangled nonwoven fabric (NWa)₀) And an ultrafine fiber generating fiber (b) capable of forming a flame retardant polyester ultrafine fiber having a single fiber fineness of 0.5 dtex or less containing a flame retardancy-imparting component (b)₀) Entangled nonwoven fabric (NWb)₀), An elastic polymer (c) containing a flame retardancy-imparting component is imparted to each of the entangled nonwoven fabric (NWa).₀) Forming ultrafine fiber generating fiber (a₀) And entangled nonwoven fabric (NWb)₀) Forming ultrafine fiber generating fiber (b)₀) Are made into ultrafine fibers, and an elastic body containing a flame retardancy-imparting component inside an entangled nonwoven fabric composed of polyester ultrafine fibers (a) having a single fiber fineness of 0.5 dtex or less and not containing a flame retardancy imparting component Entangled nonwoven fabric (A) containing (c)₀) And an elastic polymer (c) containing a flame retardancy-imparting component inside an entangled nonwoven fabric composed of flame-retardant polyester ultrafine fiber (b) having a single fiber fineness of 0.5 dtex or less containing the flame retardancy-imparting component Entangled nonwoven fabric (B₀) Each of; or
Step (i) -2: Ultrafine fiber generating fiber (a) capable of forming a polyester ultrafine fiber having a single fiber fineness of 0.5 dtex or less that does not contain a flame retardant component (a₀) Entangled nonwoven fabric (NWa)₀) And an ultrafine fiber-generating fiber (b₀) Entangled nonwoven fabric (NWb)₀) Are made into ultrafine fibers, and entangled nonwoven fabrics (NW) composed of polyester ultrafine fibers (a) having a single fiber fineness of 0.5 dtex or less that do not contain a flame retardant component.a ₁) And an intertwined nonwoven fabric (NWb) composed of flame retardant polyester extra fine fiber (b) having a single fiber fineness of 0.5 dtex or less containing a flame retardant component₁), And the entangled nonwoven fabric (NWa)₁) And entangled nonwoven fabric (NWb)₁) Is provided with an elastic polymer (c) containing a flame retardancy-imparting component, and entangled with polyester microfibers (a) having a single fiber fineness of 0.5 dtex or less and not including the flame retardancy imparting component. An entangled nonwoven fabric (A) containing an elastic body (c) containing a flame retardant component inside the nonwoven fabric₀) And an elastic polymer (c) containing a flame retardancy-imparting component inside an entangled nonwoven fabric composed of flame-retardant polyester ultrafine fiber (b) having a single fiber fineness of 0.5 dtex or less containing the flame retardancy-imparting component Entangled nonwoven fabric (B₀) Each of;
(Ii) Entangled nonwoven fabric (A) obtained in the above step (i)₀) And entangled nonwoven fabric (B₀);
It is the manufacturing method of the flame-retardant leather-like sheet base material characterized by the above-mentioned.
[0019]
Furthermore, the present invention provides
(10) Suede artificial leather using the flame-retardant leather-like sheet base material according to any one of (1) to (7);
(11) Silver-finished artificial leather using the flame-retardant leather-like sheet base material according to any one of (1) to (7);
(12) Chairs or vehicle seats using the suede-like artificial leather of (10) or the silver-tone artificial leather of (11) as an upholstery material;
It is.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
The flame-retardant leather-like sheet base material of the present invention contains an elastic polymer (c) containing a flame retardancy-imparting component inside an entangled nonwoven fabric composed of polyester ultrafine fibers (a) that does not contain a flame retardancy-imparting component. An elastic polymer (c) containing a flame retardant imparting component is contained inside the entangled nonwoven fabric composed of the layer (A) and the flame retardant polyester extra fine fiber (b) containing the flame retardant imparting component. It is necessary to have a layer (B).
Here, the “flame retardancy-imparting component” as used herein refers to a flame retardant (flame retardancy imparting additive) added to the polyester ultrafine fiber in order to impart flame retardancy to the polyester ultrafine fiber. Further, it means at least one kind of a flame retardancy-imparting copolymer component that is copolymerized in the polyester to impart flame retardancy to the polyester that forms the ultrafine fibers.
Therefore, the “polyester ultrafine fiber (a) that does not contain a flame retardancy-imparting component” forming the entangled nonwoven fabric constituting the layer (A) is an additive for imparting flame retardancy and flame retardancy. It means an ultrafine fiber made of polyester that does not contain any copolymerization component. Moreover, the "flame retardant polyester extra fine fiber (b) containing a flame retardant imparting component" forming the entangled nonwoven fabric constituting the layer (B) means a flame retardant imparting additive and a flame retardancy imparting agent. This means an ultrafine fiber made of polyester containing at least one kind of copolymerization component.
[0021]
Addition of flame retardants to polyester or copolymerization of flame retardant copolymer components improves flame retardancy, while fibers made of such polyesters have mechanical strength such as tensile strength and elongation. It tends to decrease. In the flame-retardant leather-like sheet base material of the present invention, the polyester extra-fine fiber forming the entangled nonwoven fabric constituting the layer (A) is a polyester extra-fine fiber (a) that does not contain a flame-retardant imparting component (hereinafter referred to as this) It may be referred to as “non-flame retardant polyester extra fine fiber (a)”) and does not contain any of the flame retardant additive and the flame retardant copolymer component. Compared to polyester microfibers containing imparting components, it has excellent mechanical strength such as tensile strength, abrasion resistance, and elongation, thereby improving surface strength of the flame-retardant leather-like sheet substrate of the present invention. Improves mechanical properties.
In the flame-retardant leather-like sheet base material of the present invention, the entangled nonwoven fabric of the layer (A) is constituted in order to further improve the mechanical properties such as surface strength and to impart high wear resistance and peel strength. The non-flame retardant polyester ultrafine fiber (a) preferably has a tensile strength of 1.6 g / dtex or more, and more preferably 2.0 g / dtex or more. Such a non-flame retardant polyester extra fine fiber (a) is composed of one or more polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and the like (flame retardant). ) Or a polyester not containing a copolymer component. In particular, the non-flame retardant polyester ultrafine fiber (a) is particularly preferably formed from polyethylene terephthalate that does not contain a flame retardant for imparting flame retardancy or a copolymer component.
[0022]
The flame-retardant polyester extra fine fiber (b) forming the entangled nonwoven fabric constituting the layer (B) is conventionally used as a flame-retardant imparting component for flame-retarding polyester resins and polyester fibers. Various flame retardant additives (for example, organic phosphorus-containing compounds, inorganic phosphorus-containing compounds, organic halogen-containing compounds, inorganic halogen-containing compounds, organic phosphorus / halogen-containing compounds, inorganic phosphorus / halogen-containing compounds, antimony oxide, 1 type or 2 types or more of titanium oxide and metal hydroxide) and / or the polyester forming the ultrafine fiber may have a flame retardant imparting copolymer component Good.
Among them, the flame retardant polyester extra fine fiber (b) is formed from a copolymer polyester having a flame retardant imparting copolymer component, which produces a flame retardant leather-like sheet base material and artificial leather at the time of spinning. In the various steps for achieving this, the flame retardancy-imparting component does not fall off, which is preferable. In particular, the flame-retardant polyester extra fine fiber (b) is preferably formed from a copolymer polyester having a copolymer unit derived from a halogen-containing phosphorus-containing compound in the molecule, thereby imparting flame retardancy. In addition to the above-described effect of preventing the falling off of the glass, it is possible to prevent the problem of environmental pollution caused by halogen.
[0023]
When the flame retardant polyester microfiber (b) is made of a copolymerized polyester having a copolymerized unit derived from a halogen-containing phosphorus-containing compound in the molecule, the copolymerized unit is described in Patent Documents 2 to 7 described above. For example, oxaphospholane, phosphinic acid derivatives, phosphaphenanthrene derivatives, phosphoric triesters, of which the phosphorus component is A structural unit derived from a phosphorus-containing compound contained in the side chain is preferable from the viewpoints of good handleability during polymerization and prevention of strength reduction due to hydrolysis. Preferable examples include structural units having a skeleton derived from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
As the polyester as the base of the copolymer polyester having a structural unit derived from a phosphorus-containing compound, known polyesters such as polyethylene terephthalate and polybutylene terephthalate, modified polymers thereof, mixed polymers, and copolymer polymers may be used. it can.
The production method of the copolyester having a structural unit derived from a phosphorus-containing compound is not particularly limited. For example, when a base polyester is produced by transesterification, it is produced by adding a phosphorus-containing compound during the transesterification reaction. can do. Moreover, when manufacturing the above-mentioned base polyester by direct esterification reaction, it can manufacture by adding a phosphorus containing compound before the polycondensation reaction or the initial stage of reaction.
[0024]
When the flame-retardant polyester ultrafine fiber (b) is an ultrafine fiber made of a copolymerized polyester having a copolymer unit derived from a halogen-containing phosphorus-containing compound in the molecule, phosphorus in the flame-retardant polyester ultrafine fiber is used. The atomic concentration is preferably 6,000 to 50,000 ppm, and more preferably 9,000 to 20,000 ppm. When the phosphorus atom concentration in the flame retardant polyester extra fine fiber (b) is less than 6,000 ppm, the flame retardancy of the flame retardant leather-like sheet base material tends to be insufficient, and when it exceeds 50,000 ppm, It becomes easy to cause embrittlement of the polyester constituting the fiber, a decrease in melt spinnability, and a decrease in strength and elongation of the flame-retardant polyester ultrafine fiber.
[0025]
In addition, when the flame-retardant polyester extra fine fiber (b) is an extra fine fiber made of a copolyester having in its molecule a copolymer unit derived from a phosphorus-containing compound containing no halogen, the layer (A) is added. Phosphorus atoms relative to the total mass of the non-flammable polyester ultrafine fiber (a) forming the entangled nonwoven fabric (a) and the flame retardant polyester ultrafine fiber (b) forming the layer (B) The concentration is preferably 3,000 ppm or more, and more preferably 4,500 ppm or more. When the phosphorus atom concentration is less than 3,000 ppm with respect to the total mass of the non-flame retardant polyester extra fine fiber (a) and the flame retardant polyester extra fine fiber (b), the entanglement constituting the layer (A) and the layer (B) Even when the elastic polymer (c) containing a flame retardancy-imparting component is contained in the synthetic nonwoven fabric, the flame retardancy of the flame retardant leather-like sheet base material tends to be insufficient.
[0026]
In the flame-retardant leather-like sheet base material of the present invention, it is difficult to form the entangled nonwoven fabric of the non-flame retardant polyester ultrafine fiber (a) and the layer (B) forming the entangled nonwoven fabric of the layer (A). From the viewpoint of the appearance and texture of the flame-retardant leather-like sheet base material and the artificial leather made of the flame-retardant polyester extra fine fiber (b), it is necessary that the single fiber fineness is 0.5 dtex or less. Yes, it is preferably 0.0001 to 0.3 dtex, and more preferably 0.001 to 0.2 dtex.
When the single fiber fineness of the non-flame retardant polyester extra fine fiber (a) and the flame retardant polyester extra fine fiber (b) exceeds 0.5 dtex, the texture of the flame retardant leather-like sheet base material becomes poor, and a sense of fulfillment In particular, when a suede-like artificial leather is produced from a flame-retardant leather-like sheet base material, the feather feeling and the lighting effect tend to be inferior. Moreover, when the single fiber fineness of the non-flame-retardant polyester ultrafine fiber (a) and the flame-retardant polyester ultrafine fiber (b) is less than 0.0001 dtex, the dyeing property is lowered and color tone is liable to occur.
[0027]
In the flame-retardant leather-like sheet base material of the present invention, it is difficult to form the entangled nonwoven fabric of the non-flame retardant polyester ultrafine fiber (a) and the layer (B) forming the entangled nonwoven fabric of the layer (A). The flame-retardant polyester extra-fine fiber (b) may be one or two kinds of colorants such as carbon black and dyes and pigments, various stabilizers such as light stabilizers, matting agents, antibacterial agents and antistatic agents, as required. It may contain seeds or more. For example, when carbon black is contained and deposited in black, the addition amount of carbon black is preferably about 0.5 to 8% by mass from the viewpoint of spinnability and flame retardancy.
Since carbon black is easily flammable, for example, when carbon black is contained at a ratio of 1 part by mass with respect to 100 parts by mass in total of non-flame retardant polyester extra fine fiber (a) and flame retardant polyester extra fine fiber (b) Preferably has a phosphorus atom concentration in the flame-retardant polyester microfiber (b) of 6,000 ppm or more. When carbon black is contained in a proportion of 2 parts by mass, for example, the flame-retardant polyester microfiber (b) ) Is preferably set to 8,000 ppm or more.
[0028]
Furthermore, the flame-retardant leather-like sheet base material of the present invention has a lamination mass ratio of 10: non-flame-resistant polyester ultrafine fiber (a): flame-retardant polyester ultrafine fiber (b) in the flame-retardant leather-like sheet base material: It is necessary that it is 90-90: 10, it is preferable that it is 15: 85-85: 15, and it is more preferable that it is 20: 80-80: 20.
When the lamination mass ratio of the non-flame retardant polyester extra fine fiber (a) is less than 10 mass% [the lamination mass percentage of the flame retardant polyester extra fine fiber (b) exceeds 90 mass%], the flame retardant leather-like sheet base The high elongation property of the material is lowered, and the surface strength such as surface wear resistance is lowered. On the other hand, the non-flammable polyester ultrafine fiber (a) has a lamination mass ratio exceeding 90 mass% [the flame retardant polyester ultrafine fiber (b) lamination mass ratio is less than 10 mass%], and flame retardant leather-like. The flame retardancy of the sheet substrate is reduced.
Here, “non-flame retardant polyester extra fine fiber (a): stacking mass ratio of flame retardant polyester extra fine fiber (b)” in the present specification means a flame retardant leather having a layer (A) and a layer (B). Of the flame retardant polyester extra fine fiber (a) contained in the layer (A) and the flame retardant polyester extra fine fiber (b) contained in the layer (B) per unit area of the sheet base material Mean mass ratio.
[0029]
The elastic polymer (c) contained in the entangled nonwoven fabric constituting the layer (A) and the entangled nonwoven fabric constituting the layer (B) in the flame-retardant leather-like sheet base material is flexible and elastic recoverable. And any elastic polymer having properties such as durability and wear resistance. For example, polyurethane elastomer, polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, styrene-isoprene block copolymer Examples include elastic hydrogenated products, acrylic rubber, natural rubber, SBR, NBR, polychloroprene, polyisoprene, and isobutylene isoprene rubber. These elastic polymers may be used alone or in combination of two or more. May be.
Among them, the elastic polymer (c) is excellent in flexibility and elastic recovery, excellent in durability such as abrasion resistance, excellent in mechanical properties such as tensile strength and dyeing properties, and porous. A polyurethane elastomer is preferably used because it is easy to form a structure.
[0030]
As the polyurethane elastomer, any polyurethane resin having elasticity can be used. In particular, a high molecular diol having a number average molecular weight of 500 to 5000 is used as a soft segment component, an organic diisocyanate is used as a hard segment component, and a low molecular weight together with these components. A polyurethane obtained by reacting a chain extender is preferably used.
When the number average molecular weight of the polymer diol used for the production of polyurethane is less than 500, the soft segment is too short and the polyurethane lacks flexibility, and it may be difficult to obtain a leather-like sheet substrate. On the other hand, when the number average molecular weight of the polymer diol exceeds 5,000, the proportion of urethane bonds in the polyurethane is relatively reduced, resulting in a decrease in durability, heat resistance, hydrolysis resistance, and the like. It becomes difficult to obtain a flame-retardant leather-like sheet base material and artificial leather having
[0031]
Examples of the polymer diol used in the production of polyurethane include polyester diol, polylactone diol, polycarbonate diol, polyester polycarbonate diol, polyether diol and the like obtained by reaction of a dicarboxylic acid component and a diol component. One or more of these polymer diols can be used.
[0032]
As the organic diisocyanate used in the production of polyurethane, any of the organic diisocyanates conventionally used in the production of polyurethane can be used. For example, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, xylylene Aromatic diisocyanates such as diisocyanate, isophorone diisocyanate, 1,5-naphthylene diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; alicyclic diisocyanates such as 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, etc. Can be mentioned. One or more of the above-mentioned organic diisocyanates can be used.
[0033]
As the low molecular chain extender used in the production of polyurethane, any of low molecular chain extenders conventionally used in the production of polyurethane, particularly low molecular chain extenders having a molecular weight of 400 or less, can be used. For example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, N-methyldiethanolamine, 1,4-cyclohexanediol, bis Diols such as-(β-hydroxyethyl) terephthalate, xylylene glycol, 1,4-bis (β-hydroxyethoxy) benzene; hydrazine, ethylenediamine, propylenediamine, isophoronediamine, piperazine and derivatives thereof, phenylenediamine, tolylenediamine Diamines such as ethylene, xylylenediamine, adipic acid dihydrazide, isophthalic acid dihydrazide, hexamethylenediamine, 4,4'-diaminophenylmethane, 4,4'-dicyclohexylmethanediamine; amino such as aminoethyl alcohol and aminopropyl alcohol Alcohols etc. can be mentioned, These 1 type (s) or 2 or more types can be used.
[0034]
In the production of polyurethane, the above-mentioned equivalent ratio of [total isocyanate groups] / [total functional groups that react with isocyanate groups such as hydroxyl groups and amino groups] is in the range of 0.9 to 1.1. It is preferable to react a high molecular diol, an organic diisocyanate, and a low molecular chain extender from the viewpoint of obtaining a flame-retardant leather-like sheet base material and artificial leather having high tear strength.
In addition, for the purpose of improving the solvent resistance, heat resistance, hot water resistance, etc. of polyurethane, it is crosslinked in the polyurethane by reacting with trifunctional or higher polyols such as trimethylolpropane or trifunctional amines as necessary. You may give a structure.
[0035]
As the flame retardancy imparting component to be contained in the elastic polymer (c), flame retardants conventionally used for flame retarding organic polymer materials can be used, for example, organic phosphorus flame retardants, organic halogen-based flame retardants. Examples thereof include organic flame retardants such as flame retardants and organic nitrogen flame retardants, inorganic flame retardants such as metal hydroxides, red phosphorus and silicon, among which aluminum hydroxide is preferably used. Aluminum hydroxide does not cause deterioration of the elastic polymer (c), the non-flame retardant polyester ultrafine fiber (a) and the flame retardant polyester ultrafine fiber (b), and is also an elastic polymer (c ) Is solidified in the elastic polymer (c) because it is not dissolved, decomposed or altered by the coagulation bath for coagulating) or the treatment liquid for converting the ultrafine fiber-generating fiber to ultrafine fibers. It can be contained and held in a state, thereby imparting good flame retardancy to the leather-like sheet substrate.
The particle size of aluminum hydroxide is not particularly limited, but the average particle size is preferably 2 μm or less and more preferably 1 μm or less from the viewpoints of dispersion stability in the impregnating solution, flame retardancy and the like. The aluminum hydroxide may be subjected to various treatments for improving performance such as moisture resistance, heat resistance, water resistance, acid resistance and the like as necessary.
[0036]
When aluminum hydroxide is used as the flame retardant component, the content of aluminum hydroxide in the elastic polymer (c) is that of the elastic polymer (c) constituting the layer (A) and the layer (B). It is preferable that it is 10-200 mass parts with respect to a total of 100 mass parts, and it is more preferable that it is 30-100 mass parts. If the content of aluminum hydroxide is less than 10 parts by mass, it will be difficult to impart sufficient flame retardancy to the flame retardant leather-like sheet substrate, while if it exceeds 200 parts by mass, the elastic weight will be increased. It becomes difficult to contain aluminum hydroxide in a stable state in the coalescence (c), the elastic polymer (c) containing aluminum hydroxide is likely to be embrittled and deteriorated in physical properties, and is also flame retardant. The texture of the leather-like sheet base material tends to become hard.
[0037]
In the flame-retardant leather-like sheet base material of the present invention, as described above, the flame-retardant polyester microfiber (b) constituting the entangled nonwoven fabric of the layer (B) has no halogen atom and phosphorus atoms in the molecule. By using aluminum hydroxide as a flame retardant component that is formed from the phosphorus-containing copolymer polyester and contained in the elastic polymer (c), it is sufficient without causing environmental problems associated with the use of halogenated compounds. Flame retardant levels can be achieved.
Although it is difficult to theoretically prove the detailed reason, the combustion suppression mechanism and water by the carbonization film formation by the phosphorus component contained in the phosphorus-containing copolymer polyester which forms a flame-retardant polyester extra fine fiber (b) and water It is presumed that the combustion suppression machine due to the endothermic heat of aluminum oxide exhibits a synergistic effect by suppressing combustion at a plurality of locations in the combustion process.
[0038]
The elastic polymer (c) may contain carbon black as necessary for the purpose of improving the dark color of the flame retardant leather-like sheet base material, and is processed into a high density color such as black. Preferably contains carbon black. When carbon black is contained in the elastic polymer (c), the amount is preferably 7 parts by mass or less, more preferably 5 parts by mass or less with respect to 100 parts by mass of the elastic polymer (c). . In this case, the content of aluminum hydroxide is preferably adjusted to be a large amount within the range of 100 to 200 parts by mass. For example, when 3 parts by mass of carbon black is contained with respect to 100 parts by mass of the elastic polymer (c), the content of aluminum hydroxide is preferably 25 parts by mass or more, and 40 parts by mass or more. Is more preferable.
[0039]
In the flame-retardant leather-like sheet base material of the present invention, from the viewpoint of obtaining a soft texture like natural leather, wear resistance, and ensuring flame resistance, The total mass of the non-flame retardant polyester extra fine fibers (a) and the flame retardant polyester extra fine fibers (b)]: [the mass of the elastic polymer (c) (the elastic polymer that does not include the flame retardant component ( The mass ratio of only c) is preferably 30:70 to 95: 5, and more preferably 40:60 to 85:15. When the total ratio of the non-flame retardant polyester extra fine fiber (a) and the flame retardant polyester extra fine fiber (b) is less than 30% by mass with respect to the total mass of these extra fine fibers and the elastic polymer (c). The rubber-like texture tends to be obtained, and the flame retardancy tends to become unstable. On the other hand, when it exceeds 95% by mass, it becomes easy to cause dropping of ultrafine fibers, a decrease in pilling resistance, and the like.
[0040]
In the flame-retardant leather-like sheet base material of the present invention, the flame-retardant polyester extra-fine fiber (a) and the flame-retardant polyester extra-fine fiber (b) are contained inside the entangled nonwoven fabric formed from these extra-fine fibers. It is preferable that the elastic polymer (c) is not substantially bonded and the ultrafine fibers and the elastic polymer (c) are separated. Since the ultrafine fibers and the elastic polymer (c) are not bonded, the ultrafine fibers are not restrained by the elastic polymer, and the freedom of movement is increased, so that a soft texture like natural leather can be imparted. .
[0041]
The thickness of the flame retardant leather-like sheet base material can be arbitrarily selected according to the use, etc., but generally, about 0.5 to 2.0 mm in terms of texture, strength, ease of handling, etc. It is preferable that the thickness is about 0.6 to 1.5 mm. In addition, the basis weight of the flame-retardant leather-like sheet base material is 250 to 1,000 g / m in order to obtain a soft texture, an appropriate waist feeling and resilience.²Preferably, 300 to 600 g / m²It is more preferable that
Furthermore, in the flame-retardant leather-like sheet base material, the ratio of the thickness of the layer (A) and the layer (B) is 50:50 to 20:80, so that flame retardancy, strength, abrasion resistance, etc. From the point of view, it is preferable.
[0042]
The method for producing the flame-retardant leather-like sheet substrate of the present invention is not particularly limited, and may be produced by any method capable of producing the flame-retardant leather-like sheet substrate of the present invention having the structure and characteristics described above. . As the polyester ultrafine fiber constituting the flame-retardant leather-like sheet base material, an ultrafine fiber directly produced by a melt blown method or the like can be used. However, the following production method (1) or production method using an ultrafine fiber-generating fiber ( 2), it can be manufactured smoothly.
[0043]
○Production method of flame retardant leather-like sheet base material (1):
(I): Ultrafine fiber generating fiber (a) capable of forming a polyester ultrafine fiber having a single fiber fineness of 0.5 dtex or less and containing no flame retardancy imparting component (a)₀) And an ultrafine fiber generating type fiber (b) capable of forming a flame retardant polyester ultrafine fiber having a single fiber fineness of 0.5 dtex or less containing a flame retardant imparting component (b)₀) To produce an entangled nonwoven fabric by entanglement and integration;
(II)-After providing the entangled nonwoven fabric obtained in the step (I) with an elastic polymer (c) containing a flame retardancy-imparting component, an ultrafine fiber generating fiber (a₀) And extra fine fiber generating fiber (b)₀) To be made into non-flame retardant polyester extra fine fibers (a) having a single fiber fineness of 0.5 dtex or less and flame retardant polyester extra fine fibers (b) having a single fiber fineness of 0.5 dtex or less [as described above Step (II) -1]; or
-Ultra-fine fiber generating fiber (a) that forms an entangled nonwoven fabric by converting the entangled nonwoven fabric obtained in the step (I) into ultrafine fibers₀) And extra fine fiber generating fiber (b)₀) Are made into a non-flame retardant polyester ultrafine fiber (a) having a single fiber fineness of 0.5 dtex or less and a flame retardant polyester ultrafine fiber (b) having a single fiber fineness of 0.5 dtex or less, and then a flame retardancy imparting component is included. A method for producing a flame-retardant leather-like sheet substrate by applying an elastic polymer (c) [described above step (II) -2].
[0044]
○Production method of flame retardant leather-like sheet base material (2):
(I)-Ultrafine fiber generating fiber (a) capable of forming a polyester ultrafine fiber having a single fiber fineness of 0.5 dtex or less and containing no flame retardant component (a)₀) Entangled nonwoven fabric (NWa)₀) And an ultrafine fiber generating fiber (b) capable of forming a flame retardant polyester ultrafine fiber having a single fiber fineness of 0.5 dtex or less containing a flame retardancy-imparting component (b)₀) Entangled nonwoven fabric (NWb)₀), An elastic polymer (c) containing a flame retardancy-imparting component is imparted to each of the entangled nonwoven fabric (NWa).₀) Forming ultrafine fiber generating fiber (a₀) And entangled nonwoven fabric (NWb)₀) Forming ultrafine fiber generating fiber (b)₀) Each of which is made into ultrafine fibers and contains an elastic body (c) containing a flame retardancy-imparting component inside an entangled nonwoven fabric composed of non-flame retardant polyester ultrafine fibers (a) having a single fiber fineness of 0.5 dtex or less Entangled nonwoven fabric (A₀) And an entangled nonwoven fabric containing an flame retardant polyester ultrafine fiber (b) having a single fiber fineness of 0.5 dtex or less and containing an elastic polymer (c) containing a flame retardant component. (B₀) Respectively [the above-mentioned step (i) -1]; or
-Ultrafine fiber generating fiber that can form a polyester ultrafine fiber having a single fiber fineness of 0.5 dtex or less that does not contain a flame retardant component (a₀) Entangled nonwoven fabric (NWa)₀) And an ultrafine fiber generating fiber (b) capable of forming a flame retardant polyester ultrafine fiber having a single fiber fineness of 0.5 dtex or less containing a flame retardancy-imparting component (b)₀) Entangled nonwoven fabric (NWb)₀) Are made into ultrafine fibers and entangled nonwoven fabric (NWa) composed of non-flame retardant polyester ultrafine fibers (a) having a single fiber fineness of 0.5 dtex or less₁) And an intertwined non-woven fabric (NWb) composed of flame retardant polyester extra fine fiber (b) having a single fiber fineness of 0.5 dtex or less₁), And the entangled nonwoven fabric (NWa)₁) And entangled nonwoven fabric (NWb)₁) Is provided with an elastic polymer (c) containing a flame retardancy-imparting component, and the inside of the entangled nonwoven fabric composed of non-flame retardant polyester ultrafine fibers (a) having a single fiber fineness of 0.5 dtex or less is difficult. Intertwined nonwoven fabric (A) containing an elastic body (c) containing a combustible component₀) And an entangled nonwoven fabric containing an flame retardant polyester ultrafine fiber (b) having a single fiber fineness of 0.5 dtex or less and containing an elastic polymer (c) containing a flame retardant component. (B₀) [The above step (i) -2];
(Ii) Entangled nonwoven fabric (A) obtained in step (i) above₀) And entangled nonwoven fabric (B₀) To produce a flame retardant leather-like sheet base material.
[0045]
In the above production method (1) and production method (2), an ultrafine fiber generating fiber (a₀) As an island component of a polyester that does not contain a flame retardancy-imparting component, and a sea-island type mixed spun fiber or composite spun fiber comprising another polymer that is different in solubility or degradability from the polyester as a sea component; Multi-layer bonded mixed-spun fibers and composite-spun fibers comprising a polyester that does not contain an imparting component and another polymer that is different in solubility or degradability from the polyester; a polyester that does not contain a flame-retardant imparting component and the polyester Mixed spinning fiber, composite spinning fiber, etc. having island components bonded to other polymers having different solubility or decomposability, and sea components of other polyesters having different solubility or degradability from the polyester Preferably used.
Moreover, in said manufacturing method (1) and manufacturing method (2), the ultrafine fiber generation type | mold fiber (b which forms a web or an intertwined nonwoven fabric (b)₀) As an island component of a polyester containing a flame retardancy-imparting component, and a sea-island mixed spun fiber or composite spun fiber comprising another polymer that is different in solubility or degradability from the polyester as a sea component; A multi-layer bonded mixed spun fiber or composite spun fiber comprising a polyester containing a component and another polymer having different solubility or decomposability from the polyester; a polyester containing a flame retardant imparting component and the polyester A mixed spinning fiber, composite spinning fiber, or the like having an island component bonded in a multilayer with another polymer having different degradability and using another polymer having different solubility or degradability from the polyester as a sea component is preferably used. It is done.
Ultra-fine fiber generation type fiber (a₀) And extra fine fiber generating fiber (b)₀) Can be produced by a conventionally known melt mixing spinning method, melt compound spinning method, or the like.
[0046]
Extra fine fiber generation type fiber (a₀) Or ultrafine fiber generating fiber (b₀), The other polymer used in combination with the polyester not containing the flame retardant imparting component or the polyester containing the flame retardant imparting component (other polymers having solubility or degradability different from polyester) include, for example, polyethylene, Examples thereof include polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polystyrene, and styrene-ethylene copolymer. These other polymers are readily soluble in solvents such as toluene and trichlene, while polyesters are not soluble in these solvents, so ultrafine fiber-generating fibers (a₀) Or ultrafine fiber generating fiber (b₀), Or other entangled nonwoven fabric is treated with a solvent such as toluene or trichlene before or after impregnation of the elastic polymer (c), so that other polymers can be easily dissolved and removed, and the non-flammable polyester extra fine It becomes a fiber (a) or a flame-retardant polyester extra fine fiber (b). At that time, the non-flame retardant polyester extra fine fiber (a) or the flame retardant polyester extra fine fiber (b) is ultra fine in the layer (A) and the layer (B) constituting the flame retardant leather-like sheet base material, respectively. A non-woven fabric is formed by forming a fiber bundle and intertwining each other.
[0047]
More specifically, the production method (1) and the production method (2) can be performed as follows.
<< Description of Manufacturing Method (1) >>
(1) -1a: Whether to perform sea-island type mixed spinning or composite spinning using polyester that does not contain flame retardancy as an island component and other polymer as a sea component by melt blend spinning, melt composite spinning, or the like Or a multi-layer bonded type mixed spinning or composite spinning made of polyester and other polymer that does not contain a flame retardancy-imparting component, and a sea-island type or multi-layer bonded type ultrafine fiber generating fiber (a₀), And then through a drawing, crimping and cutting process, a staple is produced.
The staple preferably has a single fiber fineness of about 1.0 to 10.0 dtex, particularly about 3.0 to 6.0 dtex from the viewpoint of good card passing properties. Next, the staple is defibrated with a card, a web is formed through a web bar, the web is overlapped with a desired weight and thickness, and an ultrafine fiber generating fiber (a₀) Made of web (Wa₀).
(1) -1b: Using a polyester containing a flame retardancy imparting component instead of a polyester not containing a flame retardancy imparting component, the same operation as in the above (1) -1 is performed, and an ultrafine fiber generating fiber (B₀) Made of web (Wb₀).
[0048]
(1) -2: Next, the webs (Wa) obtained in the above (1) -1a and (1) -1b₀) And web (Wb₀). How to superimpose the web (Wa₀) As the upper layer (Wb₀) Is preferably laminated in two layers so that it is a lower layer, but is not limited thereto, and in some cases (Wa₀) / (Wb₀) / (Wa₀) Or a (Wb)₀) / (Wa₀) / (Wb₀), And after entanglement treatment, after impregnation with an elastic polymer or after ultrafine fiber formation, slice the web (Wa₀) You may take 2 sheets so that a layer may become the surface (upper surface). Web (Wa₀) And web (Wb₀In the flame-retardant leather-like sheet base material obtained after the formation of ultrafine fibers, the non-flammable polyester ultrafine fibers (a) forming the entangled nonwoven fabric of layer (A): layer (B) It is necessary to carry out so that the lamination | stacking mass ratio of the flame-retardant polyester extra fine fiber (b) which forms the entangled nonwoven fabric may be 10: 90-90: 10, and it is 15: 85-50: 50. It is preferable to do so.
[0049]
(1) -3: Next, the web overlap obtained in the above (1) -2 is entangled by a known method such as a needle punch method or a high-pressure hydroentanglement method. A entangled nonwoven fabric is produced by performing an entanglement treatment using a water stream or the like in a state in which a woven or knitted fabric is further laminated on a web overlapped product. The entangled nonwoven fabric obtained in this step has a basis weight of 200 to 1500 g / m.²The thickness is preferably about 1 to 10 mm from the viewpoint of handling properties in the process.
Moreover, the process which attaches the polyvinyl alcohol-type paste to the entangled nonwoven fabric obtained at this process, melt | dissolves the surface of a constituent fiber, adhere | attaches the fibers which comprise a nonwoven fabric, and temporarily fixes a nonwoven fabric is carried out. You may go. By performing such a treatment, it is possible to prevent structural breakage of the nonwoven fabric from being caused by tension or the like during the subsequent impregnation step of the elastic polymer. In particular, when the surface of the fiber constituting the nonwoven fabric is melted and surfaced, the surface smoothness of the obtained flame-retardant leather-like sheet base material can be improved.
[0050]
(1) -4: Next, after providing the entangled nonwoven fabric obtained in the above (1) -3 with an elastic polymer (c) containing a flame retardant imparting component, generation of ultrafine fibers constituting the entangled nonwoven fabric Type fiber (a₀) And extra fine fiber generating fiber (b)₀) Or ultrafine fiber generating fiber (a) constituting the entangled nonwoven fabric obtained in the above (1) -3₀) And extra fine fiber generating fiber (b)₀) Is made into an ultrafine fiber, and then an elastic polymer (c) containing a flame retardant imparting component is imparted to form a flame retardant leather-like sheet base material.
In this step, the entangled non-woven fabric before or after ultrafine fiber formation is immersed in a solution or dispersion of an elastic polymer (c) containing a flame retardancy imparting component to impart the elastic polymer and flame retardancy. After impregnating the components into the entangled nonwoven fabric, immersing it in a coagulation bath to solidify the elastic polymer (c) into a porous state, or entangled nonwoven fabric before or after ultrafine fiber formation A method in which the emulsion is heated and gelled after the elastic polymer and the flame retardancy imparting component are impregnated into the entangled nonwoven fabric by immersion in the emulsion of the elastic polymer (c) containing the flame retardancy imparting component is preferably employed. .
When an insoluble material such as aluminum hydroxide is used as the flame retardancy-imparting component, it is necessary to disperse the insoluble flame retardancy-imparting component in advance in the liquid containing the elastic polymer (c). For the purpose of improving the properties, additives such as a coagulation regulator and a dispersant may be blended as necessary. Moreover, you may add the deterioration preventing agent, coloring agent, etc. of an elastic polymer (c) in the liquid containing an elastic polymer (c) in the range which does not impair the objective of this invention.
[0051]
Also, the ultrafine fiber generating fiber (a₀) And extra fine fiber generating fiber (b)₀) Is made into ultrafine fiber generating fiber (a₀) And extra fine fiber generating fiber (b)₀) Is not dissolved or decomposed, but a solvent that dissolves another polymer or an agent that decomposes is used. In that case, when the entangled nonwoven fabric contains the elastic polymer (c) in advance, it is necessary to use a solvent that does not dissolve the elastic polymer (c) or a chemical that does not decompose. When the flame retardancy-imparting component contained in the elastic polymer (c) is aluminum hydroxide, aluminum hydroxide is not dissolved or decomposed by a solvent or other agent that dissolves other polymers. Most of these are retained stably in the elastic polymer (c) as they are.
In the flame-retardant leather-like sheet base material after ultrafine fiber obtained in this way, the content of the elastic polymer (c) is 10% by mass as a solid content with respect to the mass of the flame-retardant leather-like sheet base material. It is preferable that it is the above, and it is more preferable that it is 30-50 mass%. When the content of the elastic polymer (c) is less than 10% by mass, it becomes difficult to form a dense porous elastic polymer in the entangled nonwoven fabric, and the flame retardancy-imparting component of aluminum hydroxide tends to fall off. In addition, the mechanical properties of the obtained flame-retardant leather-like sheet base material tend to be lowered.
[0052]
<< Description of Manufacturing Method (2) >>
(2) -1: The same operation as (1) -1a and (1) -1b in the production method (1)₀) And ultrafine fiber generating fiber (b)₀), And the same operation as in production method (1) -3 is performed on each web to produce ultrafine fiber-generating fibers (a₀) Entangled nonwoven fabric (NWa)₀) And ultrafine fiber generating fiber (b₀) Entangled nonwoven fabric (NWb)₀) Respectively.
(2) -2: Next, entangled nonwoven fabric (NWa₀) And entangled nonwoven fabric (NWb)₀), An elastic polymer (c) containing a flame retardant imparting component is imparted to each of the entangled nonwoven fabric (NWa)₀) Forming ultrafine fiber generating fiber (a₀) And entangled nonwoven fabric (NWb)₀) Forming ultrafine fiber generating fiber (b)₀), Or entangled nonwoven fabric (NWa)₀) Forming ultrafine fiber generating fiber (a₀) And entangled nonwoven fabric (NWb)₀) Forming ultrafine fiber generating fiber (b)₀Non-flame retardant which added the elastic polymer (c) containing a flame retardance provision component to each, and contained the elastic polymer (c) containing a flame retardance provision component Entangled nonwoven fabric (A) made of polyester microfiber (a)₀) And a flame-retardant polyester extra fine fiber (b)₀) Each. At this time, the elastic polymer (c) containing the flame retardant imparting component and the imparting of the flame retardant imparting component to each entangled nonwoven fabric before or after the ultrafine fiber is formed Entangled nonwoven fabric before or after imparting (NWa₀) And entangled nonwoven fabric (NWb)₀) Is made in the same manner as (1) -4 above.
[0053]
(2) -3: Next, an elastic polymer (c) containing a flame retardancy-imparting component inside the entangled nonwoven fabric made of the non-flame retardant polyester ultrafine fiber (a) obtained in (2) above. Including non-woven fabric (A₀) And an entangled nonwoven fabric (B) containing an elastic polymer (c) containing a flame retardant imparting component inside an entangled nonwoven fabric made of flame retardant polyester extra fine fiber (b)₀) Are laminated using an adhesive to produce a flame retardant leather-like sheet substrate having layers (A) and (B). Although there is no restriction | limiting in particular about the kind of adhesive agent used for adhesion | attachment of a layer (A) and a layer (B), The adhesive agent based on the polymer of the same kind as the polymer which comprises an elastic polymer (c) is used preferably. It is done. For example, when the elastic polymer (c) is a polyurethane elastomer, a urethane-based adhesive is preferably used.
Entangled nonwoven fabric (A₀) And / or entangled nonwoven fabric (B₀The method for applying the adhesive to () is not particularly limited, and examples thereof include a method in which an adhesive resin is dissolved in a solvent and a hot melt method. As the application form of the adhesive, from the viewpoint of the texture, flexibility, etc. of the flame retardant leather-like sheet base material obtained, it is not applied to the entire surface, for example, it is discontinuous, such as dotted, linear It is preferable to apply, and a coating method using a gravure roll is more preferably employed. In this case, it is preferable to apply in a dot shape at an application interval of 50 to 200 mesh. Moreover, the application amount of the adhesive is 1 to 30 g / m in solid content.²It should be a degree. However, even when the adhesive is applied to the entire surface, it is possible to prevent the texture and flexibility from being lowered by reducing the amount of application.
[0054]
Entangled nonwoven fabric (A₀) And intertwined nonwoven fabric (B₀) With an adhesive to produce a flame-retardant leather-like sheet base material (2) requires an adhesion process, making the process more complex and costly than method (1) Entangled nonwoven fabric (A₀) And intertwined nonwoven fabric (B₀) And the content of the flame retardancy imparting component of the elastic polymer (c) imparted to the both entangled nonwoven fabrics.₀) And intertwined nonwoven fabric (B₀), Whereby a flame-retardant leather-like sheet base material suitable for each purpose and application can be produced.
For example, an entangled nonwoven fabric (A₀The non-flame retardant polyester extra fine fiber (a) constituting the fine fiber (a) is made finer and the entangled nonwoven fabric (B₀By increasing the single fiber fineness of the flame-retardant polyester ultrafine fiber (b) constituting the above, it is possible to maintain high strength properties while further improving the appearance.
Also, for example, entangled nonwoven fabric (A₀) In the elastic polymer (c) contained in the inside of the entangled nonwoven fabric (A₀The surface strength of the flame retardant leather-like sheet base material can be improved by increasing the content of flame retardant imparting components such as aluminum hydroxide in the elastic polymer (c) contained in On the other hand, imparting flame retardancy to the flame retardant leather-like sheet substrate is more reliably performed by reversing the content of the flame retardancy imparting component in the elastic polymer (c).
[0055]
The flame retardant leather-like sheet base material of the present invention is fluffed using a known method on the surface on the layer (A) side formed from an entangled nonwoven fabric made of non-flame retardant polyester ultrafine fibers (a). It can be made into suede-like artificial leather. Further, the layer (A) side surface of the flame retardant leather-like sheet base material is fluffed after being melted or melted with a solvent or heat, or the layer (A) side surface is fluffed and then the solvent or heat is used. By melting or dissolving, it is possible to obtain artificial leather having a short fluffy, nubuck-like appearance or an intermediate appearance with suede and silver.
[0056]
Furthermore, the flame-retardant leather-like sheet base material of the present invention forms a resin film on the surface on the layer (A) side formed from the entangled nonwoven fabric made of non-flame-retardant polyester ultrafine fibers (a) ( (Hereinafter sometimes referred to as “skin-making”). The surface forming method is not particularly limited, and may be performed by a known wet method, dry method, or a method in which the surface of the substrate is dissolved or melted by a solvent or heat, and then the surface is smoothed by embossing or the like, or unevenness is imparted to the surface. Can do.
The resin used for the surface forming is preferably the same type of resin as the elastic polymer (c) constituting the flame-retardant leather-like sheet base material. For example, when the elastic polymer (c) is a polyurethane elastomer, polyurethane is preferably used as the surface-forming resin. The thickness of the resin to be formed is not particularly limited, but is usually preferably about 10 to 300 μm. When the thickness of the surface-forming resin layer exceeds 50 μm, for example, 50 μm, it is preferable to add a flame retardant also to the surface-forming resin layer. As the flame retardant in that case, one or more of phosphorus-based organic or inorganic compounds, aluminum hydroxide or other metal hydroxides are preferably used. The amount of the flame retardant added to the surface-forming resin layer is not particularly limited, but is 100 parts by mass or less with respect to 100 parts by mass of the surface-forming resin from the viewpoint of process stability during surface formation, strength of the surface-forming film, and the like. It is preferable to use in proportion.
[0057]
The suede-like artificial leather and the silver-like artificial leather of the present invention obtained as described above are used for vehicle seats, particularly automobile seats, railcar seats, and airplane seats that require high surface strength as well as flame retardancy. It is suitably used as an upholstery material for interior products such as marine seats, cushions, seats and chairs. When the artificial leather of the present invention is used as a covering material for the above-described seats and interior products, a reinforcing material such as a woven or knitted fabric may be laminated on the back surface as necessary. In that case, it is desirable to make the reinforcing material flame-retardant. At that time, it is desirable to make the reinforcing material flame-retardant using a non-halogen flame retardant.
The artificial leather of the present invention is not limited to the above-mentioned use, and can be widely used for clothing, shoes, bags, accessory cases, gloves, and other miscellaneous goods.
[0058]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In the following examples, the single fiber fineness of the fiber, the average particle size of aluminum hydroxide, the leather-like sheet base material and the flame retardancy of the dyed suede-like artificial leather obtained by buffing and dyeing it, the leather-like sheet base material The phosphorus atom concentration, the abrasion resistance of the leather-like sheet base material, and the texture of the suede-like artificial leather obtained by buffing the surface of the leather-like sheet base material were measured or evaluated as follows.
[0059]
(I) Single fiber fineness of the fiber:
The fiber diameter was measured by observing with an electron microscope at a magnification of about 500 to 2000 times, and the single fiber fineness (dtex) was determined from the measured value.
[0060]
(Ii) Average particle size of aluminum hydroxide:
The diameter of a large number (about 100) of aluminum hydroxide particles was measured by observing with an electron microscope, and the average value was obtained.
[0061]
(Iii) Flame retardancy of leather-like sheet substrate and dyed artificial leather:
In accordance with JIS D1201, "Combustion test method for organic materials for automobile interiors", a combustion test was performed on a leather-like sheet base material, and evaluation was performed based on the following criteria. In addition, the artificial leather obtained by dyeing after the buffing of the leather-like sheet base material by the method described in the section of [6) Suede-like artificial leather is burnt in the same manner. A test was conducted to evaluate flame retardancy.
[Evaluation criteria for flame retardancy]
・ Flammability: Burning speed exceeding 100 mm / min.
・ Slow flammability: Combustion rate of 100 mm / min or less.
-Self-extinguishing: Fire extinguished within 50 mm and within 60 seconds from the marked line.
[0062]
(Iv) Phosphorus atom concentration in polyester and leather-like sheet substrate:
(Iv) -1: Phosphorus atom concentration in polyester:
After the material was decomposed and dissolved with a strong acid, the concentration of phosphorus atoms in the polyester was measured using an ICP emission analyzer “IRIS AP” manufactured by Charlerh Ash.
(Iv) -2: Phosphorus atom concentration in the leather-like sheet substrate:
With the measured value of the phosphorus atom concentration in the polyester measured in (iv) -1, the non-flammable polyester ultrafine fiber forming the entangled nonwoven fabric of the layer (A) or the entangled nonwoven fabric of the layer (B) is formed. It is assumed that the phosphorus atom concentration of the flame-retardant polyester extra-fine fiber is the same, and from the lamination mass ratio of the non-flame-resistant polyester extra-fine fiber and the flame-retardant polyester extra-fine fiber in the leather-like sheet base material, The phosphorus atom concentration with respect to the total mass of the fiber was determined.
[0063]
(V) Abrasion resistance of leather-like sheet substrate:
In accordance with JIS L1096 “Abrasion Strength E Method (Martindale Method)”, a standard wear cloth was used, and a mass reduction (mg) was measured when tested at a pressure load of 12 kPa and a rotation speed of 50 rpm for 1,000 minutes. In addition, the appearance of the leather-like sheet base material after the wear test was visually observed and scored based on the following criteria.
[Evaluation criteria for wear resistance]
5 points: No wear at all and no change.
4 points: There is almost no wear and almost no change.
3 points: Some wear is observed.
2 points: There is considerable wear.
1 point: Abrasion is severe.
[0064]
(Vi) Suede-like artificial leather texture:
Touching the buffing surface of the dyed suede-like artificial leather obtained in the following examples or comparative examples with a hand to make a smooth touch of natural leather suede-like (○), smoothness of natural leather suede-like The case where there was no was evaluated as bad (x).
[0065]
<< Production Examples 1 to 4 >> [Production of polyester, spinning and production of staples]
(1) To terephthalic acid and ethylene glycol, titanium dioxide was added at a rate of 0.04% by mass based on the mass of terephthalic acid, and antimony trioxide was added at a rate of 500 ppm based on the mass of terephthalic acid. A low polymer was produced by heating under a condition of 0.0 Pa and carrying out an esterification reaction until the esterification rate reached 95% or more. This low polymer and reactive phosphorus-based flame retardant (“M-Ester” manufactured by Sanko Co., Ltd., molecular weight 434, phosphorus atom content 7 mass%) was added in the proportions shown in Table 1 below and mixed thoroughly. Thereafter, melt polymerization was performed at a temperature of 280 ° C. under a reduced pressure of 40.0 Pa to produce a prepolymer having an intrinsic viscosity of 0.65 dl / g, which was extruded from a nozzle into a strand shape and cut into a cylindrical chip. This chip was pre-dried at 120 ° C. for 2 hours, and then subjected to solid state polymerization at 210 ° C. for 20 hours under a reduced pressure of 13.3 Pa or less, and the polyester having a phosphorus atom concentration of 0 ppm shown in Table 1 below, and Phosphorus copolyesters having a phosphorus atom concentration of 3,000 ppm, 8,000 ppm or 12,000 ppm were produced, respectively.
[0066]
(2) High fluidity low density polyethylene ("Mirason FL-60" manufactured by Mitsui Chemicals, MFR = 70 g / 10 min) using the polyester or phosphorus atom copolymerized polyester obtained in (1) above as an island component Was used as a sea component, and a melt composite spinning was performed at 300 ° C. with a mass ratio of polyester: polyethylene = 65: 35 and 50 islands to produce a sea-island composite spun fiber, and then in warm water at 75 ° C. After stretching 2.5 times, applying a fiber oil agent, drying by applying mechanical crimping, it was cut to a length of 51 mm to produce a staple having a single fiber fineness of 5.0 dtex.
[0067]
[Table 1]

[0068]
<< Example 1 >> [Production of flame-retardant leather-like sheet base material and suede-like artificial leather]
(1) A basis weight of 130 g / m in accordance with a conventional method by a cross wrap method using staples of sea-island type composite spun fibers having the island component of the polyester containing no phosphorus atom obtained in Production Example 1.²The web was manufactured.
(2) Weight per unit area of 520 g / m in accordance with a conventional method using a cross-wrap method using staples of sea-island type composite spun fibers using the phosphorus copolymerized polyester obtained in Production Example 3 as an island component²The web was manufactured.
(3) The web obtained in the above (1) and the web obtained in the above (2) are laminated to have a basis weight of 650 g / m.²About 2500 p / cm alternately from both sides²Needle punching was performed. Subsequently, after shrinking in hot water at 90 ° C., a dry width was set, and a entangled nonwoven fabric having a smooth surface was produced by pressing with a calender roll in a heated state. The basis weight of the entangled nonwoven fabric thus obtained is 760 g / m.²And the apparent density is 0.48 g / cm^ThreeMet.
[0069]
(4) Water having an average particle diameter of 1 μm with respect to 100 parts by mass of a dimethylformamide (DMF) solution (solid content: 14% by mass) of polyurethane mainly composed of polycarbonate-based polyurethane (“Nipporan 990N” manufactured by Nippon Polyurethane Industry Co., Ltd.) 17.5 parts by mass of a liquid in which aluminum oxide was dispersed at a concentration of 40% by mass in DMF was added to prepare an aluminum hydroxide-containing polyurethane liquid (mass ratio of polyurethane: aluminum hydroxide = 100: 50).
(5) The entangled nonwoven fabric obtained in (3) above is impregnated into the aluminum hydroxide-containing polyurethane liquid prepared in (4) above, and then the entangled nonwoven fabric is taken out of the polyurethane liquid and coagulated bath [DMF / After being immersed in water = 30/20 (mass ratio)] and wet coagulated, it is removed from the coagulation bath and immersed in hot toluene (temperature 90 ° C) to form an entangled nonwoven fabric. A layer having polyurethane containing aluminum hydroxide in an entangled nonwoven fabric layer made of non-flame retardant polyester ultrafine fibers by eluting and removing sea components (polyethylene) in sea-island type composite spun fibers [layer (A) And a flame-retardant leather-like sheet base material (thickness 1.3 mm) comprising a layer [layer (B)] having polyurethane containing aluminum hydroxide in an entangled nonwoven fabric layer made of flame-retardant polyester ultrafine fibers It was prepared.
The single fiber fineness of the non-flame retardant polyester ultrafine fiber and the flame retardant polyester ultrafine fiber forming the layer (A) and the layer (B) of the flame retardant leather-like sheet base material obtained in this way is 0. 2 decitex. Moreover, the mass ratio of the polyester microfiber to the polyurethane in the flame-retardant leather-like sheet base material was about 79:21. Moreover, when the cross section of the thickness direction of the obtained flame-retardant leather-like sheet base material was observed with the microscope, it was confirmed that many aluminum hydroxide particles exist in the inside of porous polyurethane.
[0070]
(6) After buffing the surface on the layer (A) side of the flame-retardant leather-like sheet base material obtained in the above (5) so as to obtain a desired hair addition, to obtain a suede-like artificial leather, the following dyeing A dyed suede-like artificial leather was produced by dyeing under conditions.
[Dyeing conditions for suede artificial leather]
Dyeing: “Miketon Polyester Blue FBL” 3% owf
(Mitsui Chemicals)
Dye temperature: 120 ° C
Dye time: 60 minutes
Bath ratio: 1:20
Dyeing machine: High-pressure liquid flow dyeing machine ["Tecsum Giken" MINI-JET D200 "]
[0071]
(7) Flame retardancy of flame retardant leather-like sheet base material obtained in (5) above and suede artificial leather obtained in (6) above, flame retardant leather like obtained in (5) above The phosphorus atom concentration and abrasion resistance of the sheet base material and the texture of the suede-like artificial leather obtained in the above (6) were measured or evaluated by the method described above, and as shown in Table 2 below.
[0072]
Example 2 [Production of flame retardant leather-like sheet base material and suede-like artificial leather]
(1) A weight per unit area of 390 g / m was obtained in the same manner as in (1) of Example 1 by using the sea-island type composite spun fiber staple having the island component of the polyester containing no phosphorus atom obtained in Production Example 1.²The web was manufactured.
(2) A weight per unit area of 260 g / m in the same manner as in (2) of Example 1 using staples of sea-island type composite spun fibers using the phosphorus copolymerized polyester obtained in Production Example 4 as an island component.²The web was manufactured.
(3) The web obtained in the above (1) and the web obtained in the above (2) are laminated to have a basis weight of 650 g / m.²After the laminated web, needle punching, shrinkage treatment, drying width setting, and press treatment with a calender roll were performed in the same manner as in (1) of Example 1 to produce an entangled nonwoven fabric having a smooth surface (weight per unit 1). , 050 g / m²Apparent density 0.45 g / cm^Three).
[0073]
(4) Using the entangled nonwoven fabric obtained in (3) above, the same operation as in (4) and (5) of Example 1 is performed, and the inside of the entangled nonwoven fabric layer made of non-flame-retardant polyester ultrafine fibers A layer [layer (A)] having a polyurethane containing aluminum hydroxide and a layer [layer (B)] having a polyurethane containing aluminum hydroxide in an entangled nonwoven fabric layer made of flame-retardant polyester ultrafine fibers A flammable leather-like sheet substrate (thickness 1.3 mm) was produced.
The single fiber fineness of the non-flame retardant polyester ultrafine fiber and the flame retardant polyester ultrafine fiber forming the layer (A) and the layer (B) of the flame retardant leather-like sheet base material obtained in this way is 0. 2 decitex. Moreover, the mass ratio of the polyester microfiber to the polyurethane in the flame-retardant leather-like sheet base material was about 79:21. Moreover, when the cross section of the thickness direction of the obtained flame-retardant leather-like sheet base material was observed with the microscope, it was confirmed that many aluminum hydroxide particles exist in the inside of porous polyurethane.
[0074]
(5) After buffing the surface on the layer (A) side of the flame-retardant leather-like sheet base material obtained in (4) above in the same manner as in (6) of Example 1 to obtain a suede-like artificial leather, A dyed suede-like artificial leather was produced in the same manner as in Example 1 (6).
(6) Flame retardancy of flame retardant leather-like sheet base material obtained in (4) above and dyed suede-like artificial leather obtained in (5) above, flame retardant obtained in (4) above The phosphorus atom concentration and abrasion resistance of the synthetic leather-like sheet base material, and the texture of the suede-like artificial leather after dyeing obtained in the above (5) were measured or evaluated by the method described above. It was as shown.
[0075]
Example 3 [Production of flame-retardant leather-like sheet base material and suede-like artificial leather]
(1) Weight per unit area of 650 g / m in accordance with a conventional method using a cross-wrap method using staples of sea-island type composite spun fibers having the island component of the polyester containing no phosphorus atom obtained in Production Example 1²A total of about 2500 p / cm alternately from both sides²Needle punching was performed. Subsequently, after shrinking in hot water at 90 ° C., a dry width was set, and a entangled nonwoven fabric having a smooth surface was produced by pressing with a calender roll in a heated state. The basis weight of the entangled nonwoven fabric thus obtained is 770 g / m.²And the apparent density is 0.49 g / cm^ThreeMet.
(2) Water having an average particle diameter of 1 μm with respect to 100 parts by mass of a dimethylformamide (DMF) solution (solid content: 14% by mass) of polyurethane mainly composed of polycarbonate-based polyurethane (“Nipporan 990N” manufactured by Nippon Polyurethane Industry Co., Ltd.) 17.5 parts by mass of a liquid in which aluminum oxide was dispersed at a concentration of 40% by mass in DMF was added to prepare an aluminum hydroxide-containing polyurethane liquid (mass ratio of polyurethane: aluminum hydroxide = 100: 50).
[0076]
(3) The entangled nonwoven fabric obtained in (1) above is impregnated in the aluminum hydroxide-containing polyurethane liquid prepared in (2) above, and then the entangled nonwoven fabric is taken out from the polyurethane liquid, and a coagulation bath [DMF / After being immersed in water = 30/20 (mass ratio)] and wet coagulated, it is removed from the coagulation bath and immersed in hot toluene (temperature 90 ° C) to form an entangled nonwoven fabric. The sea component (polyethylene) in the sea-island type composite spun fiber is eluted and removed to make ultrafine fiber, and the thickness of 1.3 mm having polyurethane containing aluminum hydroxide inside the entangled nonwoven fabric made of non-flame retardant polyester ultrafine fiber A sheet substrate was produced. After slicing the sheet substrate to a thickness of 0.35 mm from one side, the slice surface was buffed to obtain a sheet (A) having a thickness of 0.26 mm.
(4) An entangled nonwoven fabric is produced in the same manner as in (1) above using staples of sea-island type composite spun fibers using the phosphorus copolymerized polyester obtained in Production Example 3 as an island component. Using the same operation as (2) to (3) above, a 1.0 mm-thick sheet (B) having polyurethane containing aluminum hydroxide in an entangled nonwoven fabric made of phosphorus-copolymerized polyester ultrafine fibers (Non-buffing sheet) was produced.
[0077]
(5) On one side of the sheet (B) obtained in (4) above, an adhesive prepared by dissolving polyurethane ("Haimuren NPU-5" manufactured by Dainichi Seika Co., Ltd .; polyether polyurethane) in DMF ( A solid content concentration of 25% by mass was applied in the form of dots using gravureose (140 mesh) (coating amount: solid content 3 g / m).²Immediately thereafter, the buffing surfaces of the sheet (A) obtained in the above (3) were superposed and bonded to produce a flame-retardant leather-like sheet base material.
Non-flammable polyester ultrafine fibers forming the sheet (A) [layer (A)] and the sheet (B) [layer (B)] in the flame-retardant leather-like sheet base material thus obtained, and flame retardancy The single fiber fineness of the polyester ultrafine fibers was 0.2 dtex. Moreover, the mass ratio of the polyester extra fine fiber which comprises the layer (A) and layer (B) in a flame-retardant leather-like sheet base material was 20:80 by the calculated value from a fabric weight.
[0078]
(6) After buffing the surface on the layer (A) side of the flame-retardant leather-like sheet base material obtained in (5) above in the same manner as in (6) of Example 1 to obtain a suede-like artificial leather, A dyed suede-like artificial leather was produced in the same manner as in Example 1 (6).
(7) Flame retardancy of flame retardant leather-like sheet base material obtained in the above (5) and dyed suede artificial leather obtained in the above (6), flame retardant obtained in the above (5) The phosphorus atom concentration and abrasion resistance of the synthetic leather-like sheet base material, and the texture of the dyed suede-like artificial leather obtained in the above (6) were measured or evaluated by the method described above. It was as shown.
[0079]
<< Comparative Example 1 >> [Production of flame-retardant leather-like sheet base material and suede-like artificial leather]
(1) A weight per unit area of 650 g / m in the same manner as in (1) of Example 1 using staples of sea-island type composite spun fibers using the phosphorus copolymerized polyester obtained in Production Example 3 as an island component.²The web was manufactured.
(2) Using only the web obtained in (1) above, the same operation as (3) in Example 1 was performed to produce an entangled nonwoven fabric, and then (4) and (5) in Example 1 In the same manner as above, impregnation with an aluminum hydroxide-containing polyurethane liquid and coagulation of polyurethane, as well as making ultrafine fiber by elution removal of sea component (polyethylene) in sea-island type composite spinning fiber forming entangled nonwoven fabric, A flame-retardant leather-like sheet substrate (thickness: 1.3 mm) having polyurethane containing aluminum hydroxide inside an entangled nonwoven fabric made of flame-retardant polyester ultrafine fibers was produced.
The single fiber fineness of the flame-retardant polyester ultrafine fiber forming the entangled nonwoven fabric in the flame-retardant leather-like sheet base material thus obtained was 0.2 dtex. Moreover, the mass ratio of the polyester microfiber and polyurethane in the flame-retardant leather-like sheet base material was about 79:21. Moreover, when the cross section of the thickness direction of the obtained flame-retardant leather-like sheet base material was observed with the microscope, it was confirmed that many aluminum hydroxide particles exist in the inside of porous polyurethane.
[0080]
(3) After buffing the surface of the flame-retardant leather-like sheet base material obtained in (2) in the same manner as in (6) of Example 1 to obtain a suede-like artificial leather, ) To produce a dyed suede-like artificial leather.
(4) Flame retardancy of flame retardant leather-like sheet substrate obtained in (2) above and dyed suede artificial leather obtained in (3) above, flame retardant obtained in (2) above The phosphorus atom concentration and abrasion resistance of the synthetic leather-like sheet base material and the texture of the suede-like artificial leather after dyeing obtained in the above (3) were measured or evaluated by the method described above. It was as shown.
[0081]
<< Comparative Example 2 >> [Production of leather-like sheet base material and suede-like artificial leather]
(1) A basis weight of 390 g / m in accordance with a conventional method using a cross-wrap method using staples of sea-island type composite spun fibers using the polyester containing no phosphorus atom obtained in Production Example 1 as an island component²The web was manufactured.
(2) A basis weight of 260 g / m in accordance with a conventional method using a cross wrap method using staples of sea-island type composite spun fibers containing the phosphorus copolymerized polyester obtained in Production Example 4 as an island component.²The web was manufactured.
(3) The web obtained in the above (1) and the web obtained in the above (2) are laminated to have a basis weight of 650 g / m.²Then, in the same manner as in (3) of Example 1, needle punching, shrinkage treatment, drying width set, and press treatment with a calender roll were performed to produce an entangled nonwoven fabric (mesh weight: 1,060 g / m²The apparent density is 0.45 g / cm^Three).
[0082]
(4) A polyurethane solution (solid content: 14% by mass) containing no aluminum hydroxide is prepared by dissolving polyurethane mainly composed of polycarbonate-based polyurethane (“Nipporan 990N” manufactured by Nippon Polyurethane Industry Co., Ltd.) in DMF. The entangled nonwoven fabric obtained in the above (3) is impregnated into the polyurethane liquid, and the same operation as in (5) of Example 1 is performed below, and the entangled nonwoven fabric layer composed of non-flame-retardant polyester ultrafine fibers [layer (A)] and an entangled nonwoven fabric layer [layer (B)] made of flame retardant polyester ultrafine fiber, a leather-like sheet substrate (thickness) containing polyurethane that does not contain aluminum hydroxide (a flame retardant component) 1.3 mm) was manufactured.
The single fiber fineness of the non-flame retardant polyester ultrafine fiber and the flame retardant polyester ultrafine fiber in the leather-like sheet base material thus obtained was 0.2 decitex. Moreover, the mass ratio of the polyester microfiber to the polyurethane in the leather-like sheet substrate was about 85:15. Moreover, when the cross section of the thickness direction of the obtained leather-like sheet base material was observed with the microscope, it was confirmed that aluminum hydroxide does not exist in the inside of porous polyurethane.
[0083]
(5) After buffing the surface on the layer (A) side of the leather-like sheet base material obtained in (4) above in the same manner as in (6) of Example 1 to obtain a suede-like artificial leather, Example 1 A dyed suede-like artificial leather was produced in the same manner as in (6).
(6) The flame-retardant property of the leather-like sheet base material obtained in (4) and the dyed suede artificial leather obtained in (5) above, the leather-like sheet base material obtained in (4) above The phosphorus atom concentration and the wear resistance of the dye, and the texture of the dyed suede-like artificial leather obtained in the above (5) were measured or evaluated by the method described above, and as shown in Table 2 below.
[0084]
[Table 2]

[0085]
As seen in the results of Table 2 above, an elastic polymer (c) (polyurethane) containing a flame retardancy-imparting component (aluminum hydroxide) inside the entangled nonwoven fabric composed of the non-flame retardant polyester extra fine fiber (a) Elastic polymer containing flame retardant component (aluminum hydroxide) inside entangled nonwoven fabric consisting of layer (A) and flame retardant polyester extra fine fiber (b) (phosphorus copolymer polyester extra fine fiber) (C) The flame-retardant leather-like sheet base material of Examples 1 to 3 having a layer (B) containing (polyurethane) and the artificial leather (suede-like artificial leather) obtained therefrom are self-extinguishing. Excellent flame resistance, low wear, excellent wear resistance, excellent appearance after wear test, high surface strength, and excellent texture.
[0086]
On the other hand, the leather-like sheet substrate of Comparative Example 1 does not have an entangled nonwoven fabric layer made of non-flame-retardant polyester ultrafine fibers (a) as a surface layer, and is entangled made of flame-retardant polyester ultrafine fibers. By comprising a single layer having an elastic polymer (c) (polyurethane) containing a flame retardancy-imparting component (aluminum hydroxide) in the nonwoven fabric, although it is excellent in terms of flame retardancy, the amount of wear is large, Inferior to wear resistance, poor appearance after wear test, and low surface strength.
Moreover, the leather-like sheet base material of Comparative Example 2 is an entangled nonwoven fabric layer made of non-flame retardant polyester ultrafine fiber (a) and an entangled fiber made of flame retardant polyester ultrafine fiber (b) (phosphorus copolymer polyester ultrafine fiber). Since the polyurethane contained in the nonwoven fabric layer does not contain a flame retardant component (aluminum hydroxide), it is flammable and inferior in flame retardancy.
[0087]
<< Reference Example 1 >> [Production of leather-like sheet base material and suede-like artificial leather]
(1) A weight per unit area of 130 g / m in the same manner as in Example 1 (1) using staples of sea-island type composite spun fibers having the island component of the polyester containing no phosphorus atom obtained in Production Example 1.²The web was manufactured.
(2) A weight per unit area of 520 g / m in the same manner as in (2) of Example 1 using staples of sea-island type composite spun fibers using the phosphorus copolymerized polyester obtained in Production Example 2 as an island component.²The web was manufactured.
(3) The web obtained in the above (1) and the web obtained in the above (2) are laminated to have a basis weight of 650 g / m.²Then, needle punching, shrinkage treatment, drying width set, and press treatment with a calender roll were performed in the same manner as (3) in Example 1 to produce an entangled nonwoven fabric having a smooth surface.
[0088]
(4) Using the entangled nonwoven fabric obtained in (3) above, the same operation as in (4) and (5) of Example 1 is performed, and the inside of the entangled nonwoven fabric layer made of non-flame-retardant polyester ultrafine fibers A leather comprising a layer [layer (A)] containing polyurethane containing aluminum hydroxide and a layer [layer (B)] containing polyurethane containing aluminum hydroxide in an entangled nonwoven fabric layer made of flame-retardant polyester ultrafine fibers A sheet substrate (thickness 1.3 mm) was produced.
The single fiber fineness of the non-flame retardant polyester ultrafine fiber and the flame retardant polyester ultrafine fiber forming the layers (A) and (B) of the leather-like sheet base material thus obtained is 0.2 decitex. there were. Moreover, the mass ratio of the polyester microfibers and polyurethane in the leather-like sheet substrate was about 79:21. Moreover, when the cross section of the thickness direction of the obtained leather-like sheet base material was observed with the microscope, it was confirmed that many aluminum hydroxide particles exist in the inside of porous polyurethane.
[0089]
(5) After buffing the surface on the layer (A) side of the leather-like sheet base material obtained in (4) above in the same manner as in (6) of Example 1 to obtain a suede-like artificial leather, Example 1 A dyed suede-like artificial leather was produced in the same manner as in (6).
(6) The phosphorus atom concentration in the leather-like sheet base material obtained in the above (4) was measured by the method described above and found to be 2400 ppm, and the flame-retardant leather-like sheet base material obtained in Examples 1 to 3 In comparison, the phosphorus atom concentration was low.
Moreover, when the abrasion resistance of the leather-like sheet base material obtained in the above (4) was evaluated by the above-described method, the abrasion amount was as small as 24 mg, and the abrasion resistance was excellent. The surface strength was high with 4 points. Furthermore, when the texture of the dyed suede-like artificial leather obtained in the above (5) was evaluated by the method described above, it was good. Moreover, when the flame retardancy of the leather-like sheet base material obtained in the above (4) and the dyed suede-like artificial leather obtained in the above (5) was evaluated by the method described above, the entanglement of the layer (A) The copolymerization ratio of the phosphorus-containing compound in the polyester constituting the flame-retardant polyester ultrafine fiber forming the synthetic nonwoven fabric is smaller than in Examples 1 to 3, and accordingly, the phosphorus atom concentration in the leather-like sheet substrate is low. Therefore, the flame retardance was low compared with the thing of Examples 1-3.
[0090]
<< Example 4 >> [Production of silver-finished artificial leather]
(1) 100 parts by mass of polycarbonate-based polyurethane (“NY-214” manufactured by Dainippon Ink & Chemicals, Inc.) is dissolved in 35 parts by mass of DMF, and black pigment (“DUT-4790” manufactured by Dainippon Ink & Chemicals, Inc.) is dissolved therein. 30 parts by mass were added to prepare a black-colored polyurethane liquid, and this liquid was applied onto a release paper and dried to form a film having a thickness of 15 μm.
(2) On the coating on the release paper formed in (2) above, 100 parts by mass of a two-component polyurethane (“UD-8310” manufactured by Dainichi Seika Kogyo Co., Ltd.), a polyisocyanate curing agent (Takeda Pharmaceutical Co., Ltd.) A mixed liquid consisting of 10 parts by mass of “D-110N” manufactured by the company, 1.5 parts by mass of an amine catalyst (“QS” manufactured by Takeda Pharmaceutical Co., Ltd.), 10 parts by mass of DMF and 20 parts by mass of ethyl acetate, 20 g / m²Are applied at a ratio of, and dried, and the one having an adhesive property immediately after drying is superimposed on the surface of the dyed suede-like artificial leather obtained in (6) of Example 1 (suede side), Pressed and bonded together. Then, after leaving it at 60 ° C. for 48 hours, the release paper was peeled off to obtain an artificial leather with silver.
The silver-tone artificial leather thus obtained had a smooth and high-grade appearance and a soft and good texture. Moreover, when the flame retardance of this silver-finished artificial leather was tested using an MVSS tester (“FMVSS-302” manufactured by Daiei Kagaku Seisakusho Co., Ltd.), it was determined to be flame retardant.
[0091]
<< Example 5 >> [Manufacture of a car seat]
Using each of the dyed suede-like artificial leather obtained in (6) of Example 1 and the silver-like artificial leather obtained in Example 4 as an upholstery material, an automobile seat (car seat) according to a conventional method As a result, it was possible to produce smoothly with good workability without causing any trouble in processing due to insufficient strength. The obtained upper part of the automobile seat had a good feel and appearance similar to natural leather, and had excellent flame retardancy and strength required for an automobile seat.
[0092]
【The invention's effect】
The flame-retardant leather-like sheet base material of the present invention and the artificial leather obtained therefrom are extremely excellent in flame retardancy, have a soft and high-quality texture and appearance, and have high abrasion resistance. It has peel strength and is excellent in mechanical properties such as surface strength.
In particular, in the flame-retardant leather-like sheet base material of the present invention and the artificial leather obtained therefrom, the flame-retardant polyester ultrafine fiber constituting the entangled nonwoven fabric of the layer (B) has no halogen atom and a phosphorus atom in the molecule. A non-halogen flame retardant containing a flame retardant component to be contained in the elastic polymer contained in the entangled non-woven fabric that is formed from the phosphorus-containing copolymer polyester and comprises the flame retardant leather-like sheet base material, Particularly in the case of aluminum hydroxide, the flame retardant leather-like sheet base material and the artificial leather comprising the same do not contain halogens harmful to the environment. But it is very good.
The flame-retardant leather-like sheet base material of the present invention and the artificial leather comprising the same are required to have high flame retardancy, safety, good texture, appearance, high surface strength, etc., taking advantage of the above-described excellent characteristics. It is particularly useful as an upholstery material for vehicle seats such as railway vehicle seats, automobile seats, aircraft seats, and ship seats, and interior products such as sofas, cushions, and chairs. Can be effectively used in a wide range of applications such as clothing, shoes, bags, accessory cases and gloves.

Claims (12)

(A) An elastic polymer (c) containing a flame retardancy-imparting component is contained inside an entangled nonwoven fabric made of a polyester ultrafine fiber (a) having a single fiber fineness of 0.5 dtex or less and not containing a flame retardancy imparting component. A layer comprising; and
(B) An elastic polymer (c) containing a flame retardant imparting component is contained inside an entangled nonwoven fabric comprising flame retardant polyester ultrafine fibers (b) having a single fiber fineness of 0.5 dtex or less containing the flame retardant imparting component. A layer to be contained;
A flame retardant leather-like sheet base material having a lamination mass ratio of polyester fine fiber (a): flame retardant polyester fine fiber (b) in the flame retardant leather-like sheet base material of 10:90 to 90: A flame-retardant leather-like sheet base material characterized by being 10. The flame retardancy according to claim 1, wherein the tensile strength of the polyester ultrafine fiber (a) not containing the flame retardancy-imparting component forming the entangled nonwoven fabric constituting the layer (A) is 1.6 g / dtex or more. Leather-like sheet base material. The flame retardant polyester ultrafine fiber (b) forming the entangled nonwoven fabric constituting the layer (B) is an ultrafine fiber made of a copolyester obtained by copolymerizing a phosphorus-containing compound. Flame retardant leather-like sheet base material. The flame-retardant leather-like sheet base material according to claim 3, wherein the phosphorus atom concentration in the copolymerized polyester forming the flame-retardant polyester ultrafine fiber (b) is 6,000 to 50,000 ppm. Non-flammable polyester ultrafine fiber (a) that does not contain the flame-retardant imparting component forming the entangled nonwoven fabric constituting the layer (A) and flame-retardant polyester ultrafine that forms the entangled nonwoven fabric constituting the layer (B) The flame-retardant leather-like sheet base material according to claim 3 or 4, wherein the phosphorus atom concentration with respect to the total mass of the fiber (b) is 3,000 ppm or more. The flame retardant component contained in the elastic polymer (c) contained in the entangled nonwoven fabric constituting the layer (A) and the layer (B) is aluminum hydroxide. The flame-retardant leather-like sheet base material according to claim 1. The total content of aluminum hydroxide is 10 to 200 parts by mass with respect to a total of 100 parts by mass of the elastic polymer (c) contained in the entangled nonwoven fabric constituting the layer (A) and the layer (B). The flame-retardant leather-like sheet base material according to claim 6. (I) A single fiber fineness containing a web composed of an ultrafine fiber-generating fiber (a ₀ ) capable of forming a polyester ultrafine fiber having a single fiber fineness of 0.5 dtex or less and containing no flame retardancy imparting component; A web of ultrafine fiber-generating fibers (b ₀ ) capable of forming flame retardant polyester ultrafine fibers of 0.5 dtex or less is laminated and entangled to produce an entangled nonwoven fabric;
(II) Then
-(II) -1: After providing the entangled nonwoven fabric obtained in the step (I) with the elastic polymer (c) containing the flame retardant imparting component, the ultrafine fiber generating fiber (a ₀₎ and microfine fiber-forming fiber (b ₀₎ and microfine fibers of a single fiber fineness 0.5dtex following polyester superfine fiber each containing no flame-retardant component (a) and a fire resistant component A flame-retardant polyester extra fine fiber (b) having a single fiber fineness of 0.5 dtex or less; or
(II) -2: The entangled nonwoven fabric obtained in the step (I) is made into ultrafine fibers, and the ultrafine fiber generating fiber (a ₀ ) and the ultrafine fiber generating fiber (b ₀ ) constituting the entangled nonwoven fabric. Polyester ultrafine fiber (a) having a single fiber fineness of 0.5 dtex or less and flame retardant polyester ultrafine fiber (b) having a single fiber fineness of 0.5 dtex or less containing a flame retardancy imparting component. And then applying an elastic polymer (c) containing a flame retardant component;
A method for producing a flame-retardant leather-like sheet base material. (I) the following steps;
-(I) -1: An entangled nonwoven fabric (NWa ₀ ) formed using an ultra-fine fiber-generating fiber (a ₀ ) that can form a polyester ultra-fine fiber having a single fiber fineness of 0.5 dtex or less and does not contain a flame retardant component ) And an entangled nonwoven fabric (NWb ₀ ) formed by using an ultrafine fiber generating fiber (b ₀ ) capable of forming a flame retardant polyester ultrafine fiber having a single fiber fineness of 0.5 dtex or less containing a flame retardant imparting component respectively, configuration after applying the elastic polymer containing a flame retardant component (c), microfine fiber-forming fibers constituting the entangled nonwoven fabric (NWa ₀₎ (a ₀₎ and the entangled nonwoven fabric (NWb ₀₎ Each of the ultra fine fiber generating fibers (b ₀ ) to be made into ultra fine fibers is entangled in an entangled nonwoven fabric composed of polyester ultra fine fibers (a) having a single fiber fineness of 0.5 dtex or less and containing no flame retardant component. Contains flame retardant components An entangled nonwoven fabric (A ₀ ) containing an elastic body (c) and a flame retardant polyester ultrafine fiber (b) having a single fiber fineness of 0.5 dtex or less containing a flame retardant component, Producing each of the entangled nonwoven fabrics (B ₀ ) containing the elastic polymer (c) containing a flame retardant component therein; or
- step (i) -2: entangled nonwoven fabric formed by using the microfine fiber-forming fibers capable of forming a single fiber fineness 0.5dtex following polyester superfine fiber containing no flame-retardant component (a ₀₎ (NWa ₀ ) and an entangled nonwoven fabric (NWb ₀ ) formed using ultrafine fiber-generating fibers (b ₀ ) capable of forming flame retardant polyester ultrafine fibers having a single fiber fineness of 0.5 dtex or less containing a flame retardant imparting component Each of the entangled nonwoven fabric (NW a ₁ ) composed of polyester ultrafine fibers (a) having a single fiber fineness of 0.5 dtex or less and containing no flame retardancy imparting component, and a flame retardancy imparting component after producing each composed entangled nonwoven fabric (NWb ₁₎ a single fiber fineness 0.5dtex following flame retardant polyester superfine fiber (b) containing the entangled nonwoven fabric (NWa ₁₎ and the entangled nonwoven fabric (NWb ₁ )of Entanglement composed of polyester microfibers (a) having a single fiber fineness of 0.5 dtex or less, each containing an elastic polymer (c) containing a flame retardant component and not containing a flame retardant component An entangled nonwoven fabric (A ₀ ) in which an elastic body (c) containing a flame retardant imparting component is contained inside the nonwoven fabric, and a flame retardant polyester ultrafine fiber having a single fiber fineness of 0.5 dtex or less containing the flame retardant imparting component Each of the entangled nonwoven fabrics (B ₀ ) in which the elastic polymer (c) containing the flame retardant imparting component is contained in the entangled nonwoven fabric constituted by (b);
(Ii) laminating the entangled nonwoven fabric (A ₀ ) and the entangled nonwoven fabric (B ₀ ) obtained in the step (i);
A method for producing a flame-retardant leather-like sheet base material. Suede-like artificial leather using the flame-retardant leather-like sheet base material according to any one of claims 1 to 7. Silver-finished artificial leather using the flame-retardant leather-like sheet base material according to any one of claims 1 to 7. Chairs or vehicle seats using the suede-like artificial leather according to claim 10 or the silver-like artificial leather according to claim 11 as an upholstery material.