201000713 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種人造皮 用基材時，可製造具有緻密性 發色性亦優異，耐剝離性等之 柔軟、膨賬感之質感的絨毛狀 有微細皺折之表面，且兼具高的 脹感之質感的粒面狀人造皮革。 【先前技術】 以往，在由纖維束與高分子 上形成有由該纖維束所形成的滅 正絨牛皮革（Nub uck)狀人造皮革 爲已知。絨毛狀人造皮革，不僅 革之表面感）、質感（兼具柔軟的 或充實感）、發色性（顏色鮮明或 求耐光性、耐剝離性、耐摩擦性 ί / 水準，遂有爲解決此等之各種提 爲滿足外觀或質感之要求時 人造皮革之纖維形成極細纖維的 形成的人造皮革的一方法，係廣 合型等之複合纖維予以分割、或 除去，變成極細纖維束的方法。 的極細纖維束所形成的不織布中 皮革用基材的絨毛狀人造皮革或 用基材。使用該人造皮革 高的優美絨毛狀外觀，且 面摩擦耐久性優異，兼具 造皮革，或平滑性高、具 黏合剝離強力與柔軟、膨 彈性體所形成的基材表面 毛之絨毛狀人造皮革等或 等之絨毛狀人造皮革，係 要求外觀（較爲接近天然皮 手觸摸感與適當的膨脹感 濃度感）等之感性面，且要 等之物性面，全部滿足高 案。 ，一般而言例如使用構成 方法。製造由極細纖維所 泛採用使海島型或多層貼 使一成分藉由分解或萃取 使用在由該複合纖維所得 含有高分子彈性體之人造 :粒面狀人造皮革，在外觀 201000713 或質感上得到非常高的評價。然而’伴隨纖度予以細化時， 會有發色性降低且鮮明度或濃度感顯著惡化的缺點，特別 是爲絨毛狀人造皮革時無法滿足全部的高品質要求。 製造人造皮革用基材所使用的不織布構造體之方法， 一般係使經紡紗的纖維形成切成1 〇〇mm以下長度之短纖 維’使該物藉由紋版法或抄紙法等，形成企求的單位面積 重量之不織纖維網，視其所需使複數張該不織纖維網積層 後’藉由針刺法或不織布法等以使纖維絡合的方法最爲普 遍。藉由此等方法所製造具有企求的大體積性或絡合程度 之不織布構造體，製造人造皮革用基材。使用該人造皮革 用基材之絨毛狀人造皮革或粒面狀人造皮革，特別是就質 感而言可得高的評價。然而，構成不織布構造體之短纖維， 藉由纖維間之絡合處理或所含的高分子彈性體固定於基材 內，惟與絨毛狀人造皮革之絨毛面或粒面狀人造皮革之粒 面層的黏合界面上，由於纖維長度短，無法避免較爲容易 自不織布構造體拔落、或脫落的傾向。藉由該傾向，會有 絨毛面之摩擦耐久性、或粒面層之黏合剝離強力等之重要 表面物性降低的情形。爲解決該問題時，一般而言例如爲 使不織布構造體之絡合度增大、且使纖維間黏合，或使纖 維間之拘束增強時，採用含有多量高分子彈性體的方法。 然而，使絡合度變大、且使高分子彈性體之含量增加時， 會有人造皮革之質感顯著惡化，無法同時滿足外觀或質感 與表面物性。 有關改善絨毛狀人造皮革之絨毛纖維的耐剝離性之典 201000713 型表面摩擦耐久性，例如提案藉由使由產生0.8旦尼爾以 下之極細纖維所形成的極細纖維束之海島型纖維所形成的 針刺絡合不織布浸漬於聚乙烯醇（以下簡稱爲PVA)水溶液 中、且予以乾燥，以使不織布之形狀予以假固定；藉由使 海島型纖維之海成份溶解的有機溶劑以萃取除去海成份； 含浸聚胺基甲酸酯之二甲基甲醯胺（以下簡稱爲DMF)溶液 予以凝固；然後，藉由使表面起毛所得的絨毛狀人造皮革 (參照專利文獻1 )。提案在該極細纖維中具有大於纖維直徑 之4分之一的直徑，且對纖維而言添加惰性的粗大粒子。 於專利文獻2中，藉由在由海島型纖維所形成的針刺 絡合不織布中，含浸聚胺基甲酸酯之DMF溶液且予以凝 固，然後’使海成份進行萃取除去所得的皮革用基材予以 起毛處理，製造絨毛狀人造皮革。構成該基材之纖維束， 係由0 · 0 2〜0.2旦尼爾之細纖維（A )、與細纖維（a )之平均纖 度的1 / 5以下且低於0.0 2旦尼爾之纖度的極細纖維（B )所形 成，其條數之比例（A/B)爲2/1〜2/3。在纖維束內部中實質 上不含高分子彈性體’絨毛纖維中之細纖維（A)與極細纖維 (B)之條數比例（A/B)爲3/1以上。 另外’提案有使部分以溶劑存在於絨毛纖維之根部的 高分子彈性體予以溶解’且藉由絨毛纖維根部固定，以改 善絨毛人造皮革之耐剝離性的方法（參照專利文獻3 )。 於專利文獻4中’亦提案藉由可轉換成極爲微細的表 面觸摸感之絨毛狀人造皮革的長纖維不織布時，藉由針刺 處理予以絡合時’積極切斷長纖維，在不織布表面上發現 201000713 5〜1 00個/mm2之纖維的切斷端部，於長纖維不織布中藉由 特徵的絡合處理，以解決變形問題。此外，於與不織布之 厚度方向平行的任意截面中，在每lcm寬度中存在5〜70 條纖維束之範圍（換言之，於與不織布之厚度方向平行的任 意截面中，藉由針刺處理在厚度方向配向的纖維，在每1 c m 寬度中存在5〜7 0條之範圍），且纖維束所佔有的總面積在 垂直於不織布厚度方向的任意截面上，爲該截面積之5〜 70%的範圍。 於專利文獻5中，提案由可變換成0.5旦尼爾以下之 極細纖維的長纖維所形成，該長纖維之捲縮度爲1 〇%以 下，且不織布之纖維密度爲0.25〜0.50 g/cm3之長纖維絡合 不織布。 然而，於專利文獻1中記載的方法中，由於使海島型 纖維之海成分萃取除去後，使聚胺基甲酸酯之DMF溶液進 行含浸凝固處理，聚胺基甲酸酯侵入極細纖維束之內部， 無法避免質感硬化的情形。而且，由於在纖維中添加粗大 粒子，故無法得到柔軟質感或手觸摸感。 於專利文獻2中記載的方法，由於在萃取除去海島型 纖維之海成份前，使聚胺基甲酸酯之D M F溶液含浸凝固， 在極細纖維束之外周部分及內部實質上不存在有聚胺基甲 酸酯下’可得柔軟質感或手觸摸感。然而，由於極細纖維 束沒有以聚胺基甲酸酯予以固定，故耐剝離性不充分。 於專利文獻3中記載的方法，由於使部分在如皮革之 基材的最表面上存在的高分子彈性體溶解’僅使絨毛纖維 201000713 之根部固定’缺乏皮革用基材內部纖維的固定效果，對纖 維之高分子彈性體的固定能力低，對〇. 〇 1旦尼爾以上之纖 維而言，無法得到良好的耐剝離性之改良效果。 專利文獻4中爲製得長纖維不織布構造的方法，在不 會使物性極力降低至目的水準以下，具有切斷端部。然而， 實際問題係由於有相當數量之長纖維被切斷，因長纖維優 點之纖維連續性導致不織布強力物性的改善效果降低，無 法充分產生長纖維之特徵。而且，專利文獻4之絡合處理， 不是爲使長纖維自長纖維不織布之表面通過內部、及相反 面予以絡合，在沒有使長纖維滿遍於表面下予以切斷，作 成5〜1 0 0個/mm2之極多數的切斷端部予以進行。因此， 採用一般的絡合處理時，必須以相當強的條件進行針刺處 理，不僅纖維間不易進行絡合處理，且大多數原爲長纖維 之纖維變化成短纖維，不織布構造形成與長纖維直接予以 絡合者不同的狀態’結果容易變成接近由習知短纖維不織 布所得的人造皮革之質感·品質者，不易製得本發明目的 之高品質的人造皮革。 於專利文獻5中記載的方法，僅觀察纖維密度之數値 時，可得緻密性較高的長纖維不織布，惟由於緻密化的方 法僅爲針刺處理及壓製處理’所得的不織布構造僅散在有 約百μιη大〜數百Mm大的程度之空隙，無法製得本發明目 的之高品質的人造皮革。更詳言之，視纖維直徑或針刺條 件而定’針剌處理後之不織布構造中本質上具有約數百μ m 大〜數mm大的空隙，然後，使纖維之一成分進行熱軟化 201000713 處理且朝厚度方向予以壓製處理時，在厚度方向呈崩塌的 狀態下同時進行海成分之硬化且僅使形狀固定下，空隙本 身直接殘留。因此’由於使海成分除去時無法藉由海成分 固定下’經崩塌的空隙大小回復至原有的大小，結果形成 散在有約百μιη大〜數百μίη大之空隙的構造。 專利文獻1 :日本特開昭53-34903號公報（第3〜4頁） 專利文獻2 :日本特開平7 _丨7 3 7 7 8號公報（第i〜2頁） 專利文獻3 :日本特開昭5 7- 1 54468號公報（第1〜2頁） 專利文獻4:日本特開2000-273769號公報（第3〜5頁） 專利文獻5:日本特開平11-200219號公報（第2〜3頁） 【發明內容】 以往’絨毛狀人造皮革無法兼具有優美、緻密的絨毛 感與極細纖維絨毛的發色性；柔軟的膨脹感與充實感；極 細纖維絨毛的柔軟表面觸感與耐剝離性之典型的表面摩擦 耐久性等。於粒面狀人造皮革中，無法兼具粒面部與基材 部之平衡性、例如平滑性高、具有緻密的皺摺之硬的性質、 及與柔軟性高的基材部分具有一體感之軟的性質之平衡 性；具有柔軟的膨脹感與充實感之粒面部與基材部的質 感；藉由基材部之高柔軟性、具有柔軟的質感，與粒面-基 材界面之黏合剝離強力的典型表面機械物性等。 本發明提供一種人造皮革用基材，係於人造皮革用基 材中，兼具有高水準與習知相反性能之感性面的性能與物 性面之性能。藉由使用本發明之基材，可製得兼具有習知 沒有的高品質與高物性之人造皮革。 -1 0 - 201000713 爲達成上述課題時，本發明人等再三深入硏究檢討的 結果’遂而完成本發明。換言之，本發明係有關一種人造 皮革用基材，同時滿足下述（1)〜（4): (1 )極細長纖維束係使8〜70條截面形狀約爲圓形之 極細長纖維所集束者， (2)極細長纖維束係截面積17〇〜7〇〇μΓη2、扁平率4.0 以下， (3 )於與不織布構造體之厚度方向平行的任意截面 中，極細長纖維束之截面爲1500〜3000個/mm2之範圍存 在，及 (4)於與不織布構造體之厚度方向平行的任意截面 中，極細纖維束間之空隙尺寸爲7 0 μηι以下。 本發明另外有關一種人造皮革用基材之製造方法，其 特徵爲順序實施下述步驟（a)〜（d)， (a) 使島成分使用熱收縮性聚合物、海成分使用水溶 性聚合物、島數爲8〜70個、海與島之截面積比爲5 : 95 〜60 : 40、截面積爲70〜3 5 0μιη2之海島型長纖維進行熔融 紡紗處理，使該物在沒有被切斷下、在捕集面上以無規的 配向狀態聚集，以製造薄片狀長纖維纖維網的步驟’ (b) 使長纖維纖維網視其所需數個重疊組合’在至少 使用6根針鈎的織針，且使該織針的至少1條以上之針鈎 爲貫穿的條件下，自兩面進行針刺並使海島型長纖維彼此 進行三次元絡合，以製造不織布構造體的步驟’ (c) 使不織布構造體在海成分聚合物爲可塑化、且島 -11- 201000713 成分聚合物爲收縮的條件下進行濕熱處理’且視其所需進 行乾熱壓製處理，在與厚度方向平行的截面中使海島型長 纖維之截面成爲1000〜3500個/mm2的範圍爲止之緻密化 步驟， (d)藉由水或水溶液從海島型長纖維去除海成分’以 變成極細長纖維束之步驟。 本發明之人造皮革用基材，由於極細纖維素集合成習 知沒有的緻密狀態，故可得緻密性極高、平滑性優異的表 面狀態。使用本發明之人造皮革用基材時，可製得質感勝 過天然皮革且具有沒有惡化的平滑且優美的外觀或觸摸 感，發色性、具有膨脹感之質感及耐剝離性等之表面摩擦 耐久性優異的絨毛狀人造皮革。而且，可製得勝過天然皮 革且具有不會惡化、平滑且柔軟之膨脹感的質感及黏合剝 離強力等之表面強度優異的粒面狀人造皮革。 【實施發明之最佳形態】 本發明之人造皮革用基材，例如可藉由順序實施下述 步驟（a)〜（d)製得。 步驟（a) 使島成分使用熱收縮性聚合物，海成分使用水溶性聚 合物，使海成分聚合物與島成分聚合物自複合紡紗用噴嘴 押出，且使海島型長纖維予以熔融結紗處理。 複合紡紗用噴嘴’以可形成在海成分聚合物中分散有 島成分聚合物爲8〜70個之範圍內任意個數的截面狀態之 噴嘴孔，以數個直線狀並列的並列狀複數列配置的構造者 201000713 較佳。 於所得的纖維截面中，以面積比（即聚合物體積比）在 海/島=5/95〜60/40之範圍內之任意比例下’調整海成分聚 合物與島成分聚合物之相對供應量或供應壓力’且使噴嘴 溫度爲1 8 0〜3 5 0 °C之溫度範圍內之任意溫度的溫度條件 下，以熔融狀態自噴嘴吐出。 所得的海島型長纖維之截面積爲70〜3 5 0 μηι2之範圍 內之任意値，單纖度例如島成分聚合物爲聚對苯二甲酸乙 二酯、海成分聚合物爲水溶性熱可塑性聚乙烯醇時，視複 合的聚合物之面積比例而定，以在0.9〜4.9dtex範圍內之 任意値較佳，更佳者爲1.9〜3.9dtex之範圍內之任意値。 在沒有切斷經熔融紡紗的海島型長纖維下，以無規的 配向狀態積層成網狀等之捕集面狀，製造企求的面積單位 重量（較佳者爲10〜1 000 g/m2)之長纖維纖維網。 步驟（b) 使上述長纖維纖維網視其所需使用交叉層合器等，朝 厚度方向重疊複數層後’在至少使用6根針鈎的織針，且 使該織針的至少1條以上之針鈎爲貫穿的條件下、自兩面 同時或交互進行針刺處理’使纖維予以三次元絡合，並於 與厚度方向平行的截面上使海島型長纖維以400〜2000個 /mm2之範圍內任意的密度存在，製得海島型長纖維極爲緻 密、經集合的不織布構造體。長纖維纖維網於製造後 '至 絡合處理爲止之任何階段’可賦予單獨或數種具有抗靜電 效果之油劑或爲控制與織針之摩擦阻力時之油劑、爲控制 201000713 纖維間之摩擦阻力時之油劑等。 步驟（C) 使藉由步驟（b)所得的不織布構造體在海成分聚合物 爲可塑化、且島成分聚合物爲收縮的條件下進行濕熱處 理，且視其所需追加進行熱壓製處理，在與厚度方向平行 的截面上使海島型長纖維之截面成爲1000〜3500個/mm: 的範圍爲止予以緻密、集合。上述之濕熱處£里，例如導λ 連續供應飽和水蒸氣的環境中之方法；使海成分聚合；f:勿胃 至企求的程度爲止，對不織布構造體而言賦予可· @ Θ g _ •可塑化處理時的充分量之水後，藉由加熱氣體或紅外# 等之電磁波，使不織布構造體中之水分加熱的方法；_ Μ 合此等之方法等。上述熱壓製處理，除使纖維構造予以糸致 密化的效果外，可期待具有使不織布構造體之形態予以gj 定化的效果，或使表面予以平滑化的效果。 藉由步驟（C)之緻密化處理後的不織布構造體之平 表觀密度，例如島成分聚合物爲聚對苯二甲酸乙二酯、海 成分聚合物爲水溶性熱可塑性聚乙烯醇時，以 0.3〜 〇.8g/cm3範圍內之任意値較佳。而且，平均表觀密度藉由 在沒有施加壓縮的荷重之方法，例如藉由以電子顯微鏡等 之截面觀察方法。不織布構造體之單位面積重量，通常爲 100 〜2000 g/cm3 較佳。 步驟（d) (d)藉由水或水溶液從構成不織布構造體之海島型長 纖維萃取除去海成分聚合物，以變成極細長纖維束。 -14- 201000713 造皮革用基材，藉由順序實施下 .有本發明之效果，且更爲適合於 皮革狀等天然皮革、沒有惡化的 造皮革的人造皮革用基材。 之一面上塗布易萃取性高分子之 且使易萃取性高分子進行硬化處 子彈性體之水分散液，使高分子 易萃取性高分子。 處理塗布高分子彈性體之面，且 厚度方向平行的任意截面之硏磨 圍內，極細纖維束間之平面空隙 S內予以緻密化處理。 皮革用基材的製造方法中，藉由 步驟（d)後，視其所需進行下述步 之效果，且更適合於與塗布層之 狀人造皮革之人造皮革用基材。 有關如上述所得的人 述步驟（e)〜（h)，可製得具 具備勝過絨毛狀、正絨牛 外觀或觸摸感之絨毛狀人 工程⑷ 在至少不織布構造體 溶液、水分散液或熔液， 理。 步驟（0 在相同面上塗布筒分 彈性體予以硬化。 步驟（g ) 自不織布構造體除去 步驟（h) 一面加壓 '一面硏磨 使在自與不織布構造體之 處理側表面至200μιη的範 尺寸成爲10〜40 的範G 另外，於上述之人造 於進行步驟（d)前、或進行 驟（i)，可製得具有本發明 一體感等質感優異的粒面 步驟（i) 在不織布構造體中含浸高分子彈性體之溶液或水分散 201000713 液’且使高分子彈性體硬化。 於下述中，更詳細地說明有關爲達成本發明之方法。 構成本發明不織布構造體之海島型纖維’係爲至少由 2種聚合物所形成的多成分紗複合纖維，於纖維截面上以 纖維外周部爲主所構成的海成分聚合物中，分布有與該物 不同種類之島成分聚合物的截面形態之纖維。本發明之島 成分聚合物，藉由表面張力之作用、及適當選擇海成分聚 合物與島成分聚合物之比例，以約爲圓形之截面形狀分 布。而且，此處所指的約爲圓形，係指如文字、接近圓形 的形狀，係指接近圓形之多角形形狀或橢圓形形狀。該海 島型纖維可藉由形成具有企求緻密性之不織布構造體後， 再視其所需含浸高分子彈性體時，在處理前或後之適當階 段，藉由使海成分聚合物進行萃取或分解予以除去，可生 成使由殘留的島成分聚合物所形成、較原有的海島型纖維 更細之複數條纖維集束的纖維束。該海島型纖維可使用習 知的粗製混合物（混合紡紗）方式或複合紡紗方式之典型多 成分紗複合纖維的紡紗方法製得。海島型纖維由於纖維截 面中海成分聚合物以纖維外周部爲主所構成，與使纖維外 周在複數種成分交互構成下形成花瓣形狀或重疊形狀等之 剝離分割型複合纖維相比時，可使以針剌處理爲典型的纖 維絡合處理時產生的破裂、彎曲 '切斷等之纖維損傷情形 極少’即可藉由絡合處理更爲提高緻密化程度。而且，海 島型纖維與剝離分割型複合纖維相比時’由於在垂直於纖 維軸之面內方向的各向異性更少，且可製得各極細纖維之 201000713 纖度、即截面積之均勻性高的極細纖維束，爲 體時可使非常多的纖維束以習知沒有的緻密 此，本發明之不織布構造體’爲在不會製得花 疊形狀等之剝離分割型複合纖維下可得此等效 海島型纖維予以製造。 構成海島型纖維之島成分的聚合物’熱收 爲重要。例如聚對苯二甲酸乙二酯（以下簡稱I 對苯二甲酸伸丙二酯（以下簡稱爲ptt)、聚對 二酯（以下簡稱爲PBT)、聚酯彈性體等之聚酯 等之改性物；熱收縮性聚醯胺系樹脂、熱收縮 脂或此等之改性物等、具有習知之纖維形成能 縮聚合物。於此等之中，藉由使用pET、PTT、 等改性聚酯等之聚酯系樹脂’可製得藉由熱收 發明目的之極細纖維束緻密地集合的不織布構 的人造皮革用基材，就可形成具有緻密的表面 之質感等感性面的特徵、或耐摩擦性、耐光性 t 定性等之實用性能良好的人造皮革製品而言更 聚合物以熔點（以下簡稱爲Tm)爲160 °C以上較〃 1 8 0〜3 3 0 °C之纖維形成性結晶性樹脂更佳。島 之T m低於1 6 0 °C時，所得的極細纖維之形態安 到本發明目的之水準，特別是人造皮革製品之 言不佳。於本發明中，Tm係採用使用示差掃3 下簡稱爲DSC)，在氮氣氣體環境下、以昇溫每 分鐘、自室溫、視其所需昇溫至300〜3 5 0 °C後 不織布構造 性集合。因 瓣形狀或重 果時，使用 縮聚合物係 i PET)、聚 苯二甲酸丁 系樹脂或此 聚烯烴系樹 力的各熱收 P B T、或此 縮製得使本 造體所形成 感、充實感 、或形態安 佳。島成分 [圭，以Tm爲 成分聚合物 定性無法達 實用性能而 苗熱量§十（以 I度爲1 〇 °c / ，然後冷卻 -17- 201000713 至室溫，再以昇溫速度爲1 0 °C /分鐘、昇溫至3 0 0〜3 5 0 °c時 所觀察的聚合物之吸熱波峰的峰頂溫度。於本發明中，在 構成極細纖維之聚合物中，亦可在紡紗階段添加著色劑、 紫外線吸收劑、熱安定劑、消臭劑、防黴劑、抗菌劑之其 他各種安定劑等。 構成海島型纖維之海成份的聚合物，爲水溶性聚合物 係爲重要。而且’由於必須使海島型纖維變成極細纖維束， 必須使採用的島成分聚合物對溶劑或分解劑而言之溶解性 或分解性各不同’就紡紗安定性而言，島成分聚合物爲親 和性小的聚合物，且在紡紗條件下熔融黏度較導成分聚合 物更小的聚合物’或表面強力較島成分聚合物更小的聚合 物較佳。較佳的具體例’以使含有聚乙烯醇、聚乙二醇、 或磺酸鹼金屬鹽之化合物等共聚合的改性聚酯、聚氧化乙 嫌等之水溶性聚合物較佳，最適合的海成分聚合物爲聚乙 烯醇同元聚合物、聚乙烯醇系共聚物等之聚乙烯醇系樹脂 (以下總稱爲p VA)。此處，水溶性聚合物係指藉由水或鹼 水溶液、酸性水溶液等之水溶液’於加熱、加壓等之條件 下可溶解除去或分解除去之聚合物。使用此等之水溶性聚 合物作爲海成分，使不織布構造體進行濕熱處理時，海成 分聚合物於瞬間進行膨脹.可塑化，且幾乎完全沒有阻害 島成分聚合物之收縮能力下，可製得由本發明目的之極細 纖維束經緻密集合的不織布構造體所形成的人造皮革用基 材，就可製得具有緻密表面感、充實感之質感等感性面的 特徵、或耐摩擦性、耐光性、或形態安定性等之實用性能 -18- 201000713 良好的人造皮革製品而言更佳。 上述PVA可藉由使具有乙嫌酯單位爲主要構成單位的 樹脂進行皂化、製得。爲形成乙烯酯單位時之乙烯基化合 物單體，例如甲酸乙烯酯、醋酸乙烯酯、丙酸乙烯酯、戊 酸乙烯酯、己酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯、 苯甲酸乙烯酯、三甲基乙酸乙烯酯及十碳酸乙烯酯等，於 此等之中’就容易製得p v A而言以醋酸乙烯酯較佳。 上述PVA可爲均勻的PVA，亦可爲導入有共聚合單位 之改性PVA ’就熔融紡紗性、水溶性、纖維物性而言，以 使用改性P VA較佳。藉由適當選擇改性時所使用的共聚合 單體之種類’在沒有使PVA之水溶性降低下，可安定地製 造海島型纖維。共聚合單體之種類，就共聚合性、熔融紡 紗性及纖維之水溶性而言，以乙烯、丙烯、1 - 丁烯、異戊 烯等之碳數爲4以下之α-烯烴類；及甲基乙烯醚、乙基乙 稀醚、正丙基乙烯醚、異丙基乙嫌醚、正丁基乙烯醚等之 乙烯醚類較佳。PVA中之共聚合單位含量，以1〜2〇莫耳 %較佳，以4〜1 5莫耳％更佳，以6〜1 3莫耳。/。最佳。另外， 共聚合單位爲乙烯時，由於纖維物性變高，故以乙烯改性 P VA更佳。乙烯改性P VA中之乙烯單位含量，以4〜丨5莫 耳％較佳，以6〜1 3莫耳％更佳。 上述P VA以塊狀聚合法、溶液聚合法、懸濁聚合法、 乳化聚合法等之習知方法製造。於此等之中，通常採用在 無彳谷劑或醇等之溶劑中進行聚合的塊狀聚合法或溶液聚合 法。作爲溶液聚合的溶劑所使用的醇，例如甲醇、乙醇、 -1 9 - 201000713 丙醇等之低元醇。於共聚合時，使用a，a’-偶氮雙異丁腈、 2，2’-偶氮雙（2，4-二甲基戊腈）、過氧化苯甲醯、η-丙基過氧 化碳酸酯等之偶氮系引發劑或過氧化物系引發劑等之習知 引發劑。有關聚合溫度，沒有特別的限制，以〇〜1 5 〇 °C之 範圍爲宜。 上述PVA之黏度平均聚合度（以下簡稱爲聚合度），以 200〜500較佳，以250〜470更佳，以300〜450最佳。聚 合度爲200以上時，由於熔融黏度安定地被複合化，具有 充分的高値，聚合度爲5 0 0以下時，由於熔融黏度容易自 紡紗噴嘴吐出，具有充分的低値。此外，藉由使用聚合度 爲5 00以下、即低聚合度PVA，具有使藉由水或水溶液除 去時之溶解速度變快的優點。P V A之聚合度以J I S - K 6 7 2 6 爲基準，藉由下式求取。 Ρ = ([η] X 1 0 3 / 8.2 9)(|/0'62) (Ρ爲黏度平均聚合度，[η]爲使PVA予以再皂化且精 製後’在3 0 °C之水中測定的特性黏度） ί ‘ 上述PVA之皂化度，以90〜99.99莫耳％較佳、以93 〜99.77莫耳。/。更佳、以95〜99.55莫耳％尤佳、以97〜99.33 莫耳％最佳。皂化度爲9 0莫耳％以上時，熱安定性良好， 於溶融紡紗時不易進行熱分解或皂化處理，皂化度爲9 9.9 9 旲耳％以下時，可安定地製造PVA。 上述P VA之T m ’就考慮紡紗性時以1 6 0。(：以上較佳， 以170〜230。(：更佳，以175〜225 〇C尤佳，以180〜220。(：最 佳。Tm爲1 6 〇它以上時’可藉由降低結晶性以避免pvA之 -20 -。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 007 007 007 007 007 007 007 007 007 007 007 007 007 007 007 007 007 【 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 A grain-like artificial leather that has a finely creased surface and a texture of high swell. [Prior Art] Conventionally, a Nubuck-like artificial leather formed of the fiber bundle is formed of a fiber bundle and a polymer. Fluffy artificial leather, not only the surface of the leather), texture (both soft or full), color (light color or light resistance, peel resistance, abrasion resistance ί / level, 遂 to solve this A method of forming an artificial leather in which fine fibers are formed into fibers of artificial leather when the appearance or texture is required, and a method of dividing or removing the composite fibers such as a wide-type type into a fine fiber bundle. A pile-like artificial leather or a base material for a base material for leather in a non-woven fabric formed of an ultrafine fiber bundle. The artificial leather has a high-quality fluffy appearance and is excellent in surface friction durability, and has both leather-making properties and high smoothness. The fluff-like artificial leather with the adhesive peeling strength and the soft, swellable elastomer surface of the substrate surface, such as fluffy artificial leather, etc., is required to have an appearance (closer to the natural leather hand touch feeling and appropriate swelling feeling density) ), etc., and the physical surface, etc., all of which satisfy the high case. In general, for example, the composition method is used. An artificial: grain-like artificial leather containing a polymeric elastomer obtained by the composite fiber by decomposing or extracting a sea-island type or a plurality of layers is used, and the appearance is highly evaluated in terms of appearance 201000713 or texture. When the fineness is refined, there is a disadvantage that the color developability is lowered and the sharpness or the concentration feeling is remarkably deteriorated, and in particular, the high-quality requirements cannot be satisfied in the case of the fluff-like artificial leather. The non-woven fabric used for the substrate for artificial leather is manufactured. In the method of constructing a structure, generally, the spun fiber is formed into a short fiber which is cut into a length of 1 mm or less, so that the object is formed into a nonwoven fabric having a basis weight per unit area by a stencil method or a papermaking method. According to the need to make a plurality of sheets of the nonwoven web, it is most common to use a needle punching method or a non-woven method to complex the fibers. The method is thus manufactured to have a large volume or A nonwoven fabric structure having a degree of complexation, and a base material for artificial leather is produced. The pile-like artificial leather or the grain-like artificial leather of the base material for artificial leather is used, in particular The texture can be highly evaluated. However, the short fibers constituting the nonwoven fabric structure are fixed in the substrate by the complexation treatment between the fibers or the contained polymer elastomer, but with the fluffy surface of the fluffy artificial leather. Or, at the bonding interface of the grain layer of the grain-like artificial leather, since the fiber length is short, it is unavoidable that it is easy to pull off or fall off from the non-woven structure. With this tendency, there is a frictional durability of the pile surface. Or, in the case where the important surface physical properties such as the adhesion peel strength of the grain layer are lowered, in order to solve this problem, generally, for example, the degree of complexation of the nonwoven fabric structure is increased, and the fibers are bonded or interfiber-bonded. When the restraint is enhanced, a method of containing a large amount of a polymer elastomer is used. However, when the degree of complexation is increased and the content of the polymer elastomer is increased, the texture of the artificial leather is remarkably deteriorated, and the appearance or texture cannot be satisfied at the same time. Physical properties with surface. The surface friction durability of the model 201000713 for improving the peeling resistance of the pile fibers of the fluffy artificial leather is, for example, proposed by the island-type fiber which is formed by the ultrafine fiber bundle formed by the ultrafine fibers of 0.8 denier or less. The needle-punched non-woven fabric is immersed in an aqueous solution of polyvinyl alcohol (hereinafter abbreviated as PVA) and dried to pseudo-fix the shape of the non-woven fabric; and the sea component is extracted by extracting an organic solvent in which sea components of the sea-island type fiber are dissolved. A solution of dimethylformamide (hereinafter abbreviated as DMF) impregnated with a polyurethane is solidified; and then, a fluffy artificial leather obtained by raising the surface (see Patent Document 1). It is proposed to have a diameter larger than one-fourth of the fiber diameter in the ultrafine fibers, and to add inert coarse particles to the fibers. In Patent Document 2, a leather base is obtained by impregnating a DMF solution of a polyurethane in a needle-punched nonwoven fabric formed of sea-island type fibers, and then solidifying the sea component. The material is raised to produce fluffy artificial leather. The fiber bundle constituting the substrate is a fine fiber (A) of 0·0 2 to 0.2 denier, and a fineness of 1 / 5 or less and less than 0.0 2 denier of the average fineness of the fine fiber (a). The ultrafine fibers (B) are formed, and the ratio (A/B) thereof is 2/1 to 2/3. The ratio of the number of the fine fibers (A) to the ultrafine fibers (B) (A/B) in the fiber bundles which are substantially free of the polymeric elastomer's fluff fibers is 3/1 or more. In addition, a method of dissolving a part of the polymer elastic body in which the solvent is present in the root portion of the pile fiber is prepared, and the root portion of the pile fiber is fixed to improve the peeling resistance of the pile artificial leather (see Patent Document 3). In Patent Document 4, when a long-fiber non-woven fabric of fluffy artificial leather which can be converted into a very fine surface touch feeling is also proposed, when the needle is treated by the needling treatment, the long fibers are actively cut off on the surface of the non-woven fabric. It was found that the cut ends of the fibers of 201000713 5 to 100 pieces/mm2 were subjected to the complexing treatment in the long fiber nonwoven fabric to solve the deformation problem. Further, in any cross section parallel to the thickness direction of the non-woven fabric, there are 5 to 70 fiber bundles per 1 cm width (in other words, in any cross section parallel to the thickness direction of the non-woven fabric, by needle punching in thickness) The direction-aligned fibers have a range of 5 to 70 in a width of 1 cm, and the total area occupied by the fiber bundles is 5 to 70% of the cross-sectional area on any cross section perpendicular to the thickness of the nonwoven fabric. range. Patent Document 5 proposes a long fiber which can be converted into an ultrafine fiber of 0.5 denier or less, the long fiber has a crimp of 1% or less, and the non-woven fabric has a fiber density of 0.25 to 0.50 g/cm3. The long fiber is woven with non-woven fabric. However, in the method described in Patent Document 1, since the sea component of the sea-island type fiber is extracted and removed, the DMF solution of the polyurethane is subjected to impregnation and solidification treatment, and the polyurethane invades the ultrafine fiber bundle. Internally, the texture hardening cannot be avoided. Further, since coarse particles are added to the fibers, a soft texture or a hand touch feeling cannot be obtained. In the method described in Patent Document 2, since the DMF solution of the polyurethane is impregnated and solidified before extracting and removing the sea-based component of the sea-island type fiber, substantially no polyamine is present in the outer portion and the inner portion of the ultrafine fiber bundle. Under the carbamate, a soft texture or a hand touch can be obtained. However, since the ultrafine fiber bundle is not fixed by the polyurethane, the peeling resistance is insufficient. In the method described in Patent Document 3, since the polymer elastomer which is partially present on the outermost surface of the substrate such as leather is dissolved, 'only the root portion of the pile fiber 201000713 is fixed' lacks the fixing effect of the inner fiber of the substrate for leather. The fixing ability of the polymer elastomer of the fiber is low, and the fiber having a denier of 〇1 or more does not have a good effect of improving the peeling resistance. Patent Document 4 is a method for producing a long-fiber nonwoven fabric structure, and has a cut end portion without lowering the physical properties below the target level. However, the practical problem is that a considerable amount of long fibers are cut, and the fiber continuity due to the long fiber advantage causes the improvement of the strength property of the nonwoven fabric to be lowered, and the characteristics of the long fibers cannot be sufficiently produced. Further, in the complexation treatment of Patent Document 4, the long fibers are not entangled from the surface of the long-fiber non-woven fabric through the inside and the opposite surface, and the long fibers are not cut over the surface to be cut, and 5 to 1 0 is formed. A large number of cut ends of 0/mm2 are performed. Therefore, when a general complexing treatment is used, the needling treatment must be carried out under relatively strong conditions, and not only the fibers are difficult to be complexed, but most of the fibers which are originally long fibers are changed into short fibers, and the non-woven fabric is formed into long fibers. It is easy to change the texture and quality of the artificial leather obtained by the conventional short fiber non-woven fabric, and it is difficult to obtain the high-quality artificial leather which is the object of the present invention. In the method described in Patent Document 5, when only the number of fiber densities is observed, a long-fiber non-woven fabric having high denseness can be obtained, but the method of densification is only a needle punching treatment and a pressing treatment, and the resulting non-woven fabric structure is scattered only. There is a gap of about 100 μm to a large extent of several hundred Mm, and high-quality artificial leather for the purpose of the present invention cannot be obtained. More specifically, depending on the fiber diameter or the needling condition, the non-woven fabric structure after the needle-punching treatment essentially has a gap of about several hundred μm large to several mm, and then one of the fibers is thermally softened. 201000713 When it is processed and pressed in the thickness direction, the sea component is simultaneously hardened in a state where the thickness direction is collapsed, and only the shape is fixed, and the void itself remains directly. Therefore, the size of the collapsed void which cannot be fixed by the sea component when the sea component is removed is restored to the original size, and as a result, a structure having a gap of about 100 μm to a few hundreds μ μη is formed. Patent Document 1: Japanese Laid-Open Patent Publication No. SHO 53-34903 (pages 3 to 4) Patent Document 2: Japanese Patent Laid-Open No. 7-丨7 3 7 7 8 (pp. i to 2) Patent Document 3: Japanese Special Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. ~3 pages) [Summary of the Invention] In the past, the 'fleece-like artificial leather could not have the beautiful, dense fluffy feel and the color development of the ultrafine fiber fluff; the soft expansion feeling and the fullness; the soft surface feel of the ultrafine fiber fluff and Typical surface friction durability such as peel resistance. In the grain-like artificial leather, it is not possible to balance the balance between the granule portion and the base portion, for example, it has high smoothness, hard properties with dense wrinkles, and softness with the substrate portion having high flexibility. The balance of the nature; the texture of the grain surface and the base portion with a soft feeling of expansion and fullness; the high flexibility of the base portion, the soft texture, and the adhesion to the grain-substrate interface Typical surface mechanical properties and so on. The present invention provides a base material for artificial leather which is used in a base material for artificial leather and which has both a high level and a performance of an inductive surface having opposite properties and a property of a physical surface. By using the substrate of the present invention, it is possible to obtain an artificial leather having both high quality and high physical properties which are not conventionally known. -1 0 - 201000713 In order to achieve the above-mentioned problem, the inventors of the present invention have further intensively studied the results of the review. In other words, the present invention relates to a substrate for artificial leather, which satisfies the following (1) to (4): (1) a very elongated fiber bundle system which bundles 8 to 70 extremely elongated fibers having a cross-sectional shape of about a circular shape. (2) The extremely long fiber bundle has a cross-sectional area of 17 〇 to 7 〇〇 μ Γ 2 and an tying ratio of 4.0 or less. (3) In any cross section parallel to the thickness direction of the nonwoven fabric structure, the cross section of the extremely elongated fiber bundle is 1500. In the range of ~3000 pieces/mm2, and (4) in any cross section parallel to the thickness direction of the nonwoven fabric structure, the gap size between the ultrafine fiber bundles is 70 μm or less. Further, the present invention relates to a method for producing a substrate for artificial leather, which comprises the following steps (a) to (d), (a) using a heat-shrinkable polymer for an island component and a water-soluble polymer for a sea component; The number of islands is 8 to 70, and the sea-island cross-sectional area ratio is 5: 95 to 60: 40. The island-type long fiber with a cross-sectional area of 70 to 3 5 0 μιη2 is melt-spun, so that the object is not The step of arranging in a random alignment state on the collecting surface to produce a flaky long fiber web [b] making the long fiber web as many overlapping combinations as needed] at least 6 a step of producing a non-woven fabric structure by needle-punching the needles of the needles and inserting at least one of the needles into the needles, and performing the three-dimensionally complexing of the island-in-the-sea long fibers with each other. ' (c) The non-woven fabric is subjected to a wet heat treatment under the condition that the sea component polymer is plasticized and the island-11-201000713 component polymer is shrinked, and the dry heat pressing treatment is performed as needed, in the thickness direction Island-type long fiber in parallel cross section The densification step up cross section having a range of 1000~3500 / mm2 sum of, (d) water or aqueous solutions by removal of the sea component from the sea-island filaments' to become the bundle of elongated pole step. In the base material for artificial leather of the present invention, since the ultrafine cellulose is aggregated into a dense state which is not conventionally known, it is possible to obtain a surface state which is extremely dense and excellent in smoothness. When the base material for artificial leather of the present invention is used, surface friction which is superior to natural leather and has a smooth and elegant appearance or touch feeling without deterioration, color developability, texture with a feeling of expansion, and peeling resistance can be obtained. Fluffy artificial leather with excellent durability. Further, it is possible to obtain a grain-like artificial leather which is superior to the natural leather and which has a texture which is not deteriorated, smooth and soft, and has excellent surface strength such as a strong peeling strength. [Best Mode for Carrying Out the Invention] The substrate for artificial leather of the present invention can be obtained, for example, by sequentially performing the following steps (a) to (d). Step (a) using the heat-shrinkable polymer for the island component, and using the water-soluble polymer for the sea component, the sea component polymer and the island component polymer are extruded from the composite spinning nozzle, and the sea-island long fiber is melt-knotted. deal with. The nozzle for composite spinning is a nozzle hole which can be formed in a cross-sectional state in an arbitrary number of ranges of 8 to 70 in which the island component polymer is dispersed in the sea component polymer, and is arranged in parallel in a plurality of linear parallel rows. The constructor 201000713 is preferred. In the obtained fiber cross section, the relative supply of the sea component polymer and the island component polymer is adjusted at an arbitrary ratio of the area ratio (ie, the polymer volume ratio) in the range of sea/island = 5/95 to 60/40. The amount or supply pressure is discharged from the nozzle in a molten state at a temperature of any temperature within a temperature range of 1 to 80 to 350 °C. The cross-sectional area of the obtained island-type long fiber is any range within the range of 70 to 3 5 0 μηι 2 , and the single-denier degree, for example, the island component polymer is polyethylene terephthalate, and the sea component polymer is water-soluble thermoplastic polymer. In the case of vinyl alcohol, depending on the area ratio of the composite polymer, any enthalpy in the range of 0.9 to 4.9 dtex is preferable, and more preferably any enthalpy in the range of 1.9 to 3.9 dtex. In the case of the island-type long fibers which have been melted and spun, the surface area of the mesh is formed by laminating in a random alignment state, and the desired unit weight is produced (preferably 10 to 1 000 g/m 2 ). Long fiber web. Step (b): using the cross-layer laminate or the like as described above, and using a cross layer in the thickness direction, after using at least six needles, and at least one of the needles is used. The needle hook is under the condition of penetration, and the needle-punching treatment is performed simultaneously or alternately from both sides', so that the fiber is three-dimensionally complexed, and the island-type long fiber is in the range of 400 to 2000/mm2 in the cross section parallel to the thickness direction. The density of any of the islands is extremely dense and the assembled non-woven fabric structure is obtained. The long fiber fiber web can be given to any oil agent with antistatic effect or oil agent for controlling the frictional resistance with the knitting needle at any stage after the production to the complex treatment, in order to control the fiber between 201000713 Oil agent when frictional resistance. Step (C) The non-woven fabric obtained by the step (b) is subjected to a wet heat treatment under the condition that the sea component polymer is plasticized and the island component polymer is shrunk, and the hot press treatment is additionally added as needed. In the cross section parallel to the thickness direction, the cross section of the sea-island type long fibers is made dense and gathered until the range of 1000 to 3500 pieces/mm: is obtained. In the above-mentioned hot and humid place, for example, a method in which the λ is continuously supplied with saturated steam; the sea component is polymerized; f: the stomach is not required, and the non-woven structure is given. @ Θ g _ • After a sufficient amount of water in the plasticizing treatment, a method of heating the water in the nonwoven fabric structure by heating an electromagnetic wave such as a gas or infrared #; _ combines the methods and the like. In addition to the effect of densifying the fiber structure, the hot pressing treatment is expected to have an effect of setting the shape of the nonwoven fabric structure or smoothing the surface. The flat apparent density of the nonwoven fabric structure after the densification treatment in the step (C), for example, when the island component polymer is polyethylene terephthalate or the sea component polymer is water-soluble thermoplastic polyvinyl alcohol, Any 値 in the range of 0.3 to 8.8 g/cm 3 is preferred. Further, the average apparent density is obtained by a method of observing a load without applying compression, for example, by a cross section observation method using an electron microscope or the like. The basis weight of the nonwoven fabric structure is usually from 100 to 2,000 g/cm3. Step (d) (d) The sea component polymer is extracted from the sea-island type long fibers constituting the nonwoven fabric structure by water or an aqueous solution to become a very elongated fiber bundle. -14-201000713 The base material for leathermaking, which is carried out in the order of the present invention, is more suitable for a natural leather such as a leather or a base material for artificial leather which is not deteriorated. The extractable polymer is coated on one side, and the easily extractable polymer is subjected to an aqueous dispersion of the hardened elastomer, so that the polymer is easily extracted. The surface of the surface of the polymer elastic body coated with the polymer elastic body and the arbitrary cross section of the parallel direction is densified, and the plane gap S between the ultrafine fiber bundles is densified. In the method for producing a substrate for leather, the step (d) is carried out, and the effect of the following step is required, and it is more suitable for a substrate for artificial leather of artificial leather having a coating layer. With regard to the steps (e) to (h) obtained as described above, it is possible to produce a villus-like person having a shape superior to that of a fluffy, nubuck or touch (4) in at least a non-woven structure solution, an aqueous dispersion or Melt, rational. Step (0) Coating the tube on the same surface to separate the elastomer to be hardened. Step (g) From the non-woven structure removing step (h) One side pressurizing 'one side honing to make the surface from the treated side surface of the non-woven fabric structure to 200 μm The dimension G is 10 to 40. Further, before the step (d) or the step (i), the grain surface having excellent texture such as the integral feeling of the present invention can be obtained (i) in the nonwoven fabric structure. The body is impregnated with a solution of a polymeric elastomer or water-dispersed 201000713 liquid and hardens the polymeric elastomer. In the following, the method for achieving the present invention will be described in more detail. The island-in-the-sea fiber constituting the non-woven fabric of the present invention ' is a multicomponent yarn composite fiber formed of at least two kinds of polymers, and a sea component polymer mainly composed of the outer peripheral portion of the fiber in the fiber cross section is distributed with an island component polymer different from the material. The fiber of the cross-sectional shape. The island component polymer of the present invention is approximated by the action of surface tension and the ratio of the sea component polymer to the island component polymer. The cross-sectional shape distribution, and the term "circular shape" as used herein refers to a shape that is close to a circle, and refers to a polygonal shape or an elliptical shape that is close to a circle. The sea-island type fiber can be formed by After obtaining a dense non-woven fabric structure, when it is required to impregnate the polymer elastomer, it may be removed by extraction or decomposition of the sea component polymer at an appropriate stage before or after the treatment. A fiber bundle formed by a plurality of fiber bundles formed by an island component polymer which is thinner than the original sea-island type fiber. The sea-island type fiber can be used in a conventional coarse mixture (mixed spinning) method or a composite spinning method. In the sea-island type fiber, the sea-component polymer in the fiber cross-section is mainly composed of the outer peripheral portion of the fiber, and the outer periphery of the fiber is formed by the interaction of a plurality of components to form a petal shape or an overlapping shape. When the split type composite fiber is compared, it is possible to treat the fiber which is broken, bent, etc. which is generated during the fiber complexing treatment by the needle-punching treatment. The degree of densification is increased by the complex treatment. Moreover, the island-in-the-sea fiber has less anisotropy in the in-plane direction perpendicular to the fiber axis when compared with the peel-off type composite fiber. Moreover, the ultrafine fiber bundle of the 201000713 fineness, that is, the uniformity of the cross-sectional area of each of the ultrafine fibers can be obtained, and when the body is a body, a very large number of fiber bundles can be made dense without the conventional one, and the non-woven fabric structure of the present invention is This equivalent island-in-the-sea fiber can be produced without peeling off the split type composite fiber, etc. The heat of the polymer which constitutes the island-type fiber island component is important. For example, polyethylene terephthalate a modified product of an ester (hereinafter referred to as I-butylene terephthalate (hereinafter referred to as ptt), a poly-p-diester (hereinafter abbreviated as PBT), a polyester elastomer, or the like; heat-shrinkable polyfluorene An amine-based resin, a heat-shrinkable grease, or a modified product thereof, etc., has a conventional fiber-forming energy-shrinkable polymer. Among these, a base material for artificial leather which is densely gathered by a very fine fiber bundle for heat collection purposes can be obtained by using a polyester resin such as pET, PTT or the like modified polyester. In addition, it is possible to form a characteristic of a sensitive surface such as a dense surface, or an artificial leather product having good practical properties such as abrasion resistance and light resistance t-characteristics. The melting point of the polymer (hereinafter abbreviated as Tm) is 160 °. A fiber-forming crystalline resin having a C content of more than 1 80 0 to 3 3 ° C is more preferable. When the T m of the island is lower than 160 ° C, the form of the obtained ultrafine fibers is attained to the level of the object of the present invention, particularly the artificial leather product. In the present invention, the Tm is a non-woven structural set after using a differential sweep 3 (referred to as DSC) in a nitrogen gas atmosphere at a temperature rise per minute, from room temperature, and depending on the temperature required to reach 300 to 350 ° C. . When the shape of the valve or the fruit is heavy, the shrinkable polymer system i PET), the polybutylene phthalate resin or the heat-receiving PBT of the polyolefin-based resin is used, or the shrinkage is used to form the feeling of the original body. Fullness, or good form. Island composition [Guide, Tm as a component of the polymer qualitative can not reach practical performance and seedling heat § 10 (I degree is 1 〇 °c /, then cooling -17-201000713 to room temperature, then the heating rate is 10 ° C / min, the peak top temperature of the endothermic peak of the polymer observed when the temperature is raised to 300 to 350 ° C. In the present invention, in the polymer constituting the ultrafine fiber, it may be added in the spinning stage. Coloring agent, ultraviolet absorber, heat stabilizer, deodorant, antifungal agent, various other stabilizers for antibacterial agents, etc. The polymer constituting the sea component of the island-type fiber is important for the water-soluble polymer system. Since it is necessary to make the sea-island type fiber into a very fine fiber bundle, it is necessary to make the solubility or decomposition property of the island component polymer used for the solvent or the decomposing agent different. In terms of spinning stability, the island component polymer is affinity. A small polymer, and a polymer having a lower melt viscosity than a component polymer under spinning conditions, or a polymer having a surface strength smaller than that of the island component polymer is preferred. Vinyl alcohol, polyethyl b A modified polyester having a copolymer of an alcohol or an alkali metal sulfonate, a water-soluble polymer such as polyoxyethylene or the like is preferred, and the most suitable sea component polymer is a polyvinyl alcohol homopolymer or polyethylene. A polyvinyl alcohol-based resin such as an alcohol-based copolymer (hereinafter collectively referred to as p VA). Here, the water-soluble polymer means an aqueous solution such as water or an aqueous alkali solution or an acidic aqueous solution, under conditions of heating or pressurization. A polymer which can be dissolved or removed by decomposition. When such a water-soluble polymer is used as a sea component, when the nonwoven fabric structure is subjected to a wet heat treatment, the sea component polymer expands instantaneously. It can be plasticized and has almost no islanding resistance. Under the shrinkage ability of the polymer, a substrate for artificial leather formed by the densely-formed nonwoven fabric structure of the ultrafine fiber bundle of the present invention can be obtained, and an inductive surface having a dense surface feeling and a feeling of fullness can be obtained. Practical properties such as characteristics, or abrasion resistance, light resistance, or form stability -18- 201000713 Better for good artificial leather products. The above PVA can be A resin in which a resin having a main constituent unit is saponified, and is obtained by forming a vinyl compound unit such as vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, and caproic acid. Vinyl ester, vinyl laurate, vinyl stearate, vinyl benzoate, trimethyl vinyl acetate and ethylene carbonate, etc., in which it is easy to produce pv A for vinyl acetate Preferably, the PVA may be a uniform PVA or a modified PVA having a copolymerization unit introduced therein. In terms of melt spinning property, water solubility, and fiber properties, it is preferred to use a modified PVA. The type of copolymerized monomer used in the modification is selected. The sea-island type fiber can be stably produced without lowering the water solubility of the PVA. The type of the copolymerized monomer, the copolymerization property, the melt spinning property, and the fiber In terms of water solubility, α-olefins having a carbon number of 4 or less such as ethylene, propylene, 1-butene, and isopentene; and methyl vinyl ether, ethyl ether ether, n-propyl vinyl ether, Isopropyl propylene, n-butyl vinyl ether, etc. Vinyl ethers are preferred. The content of the copolymerization unit in the PVA is preferably from 1 to 2 mol%, more preferably from 4 to 15 mol%, and from 6 to 13 mol. /. optimal. Further, when the copolymerization unit is ethylene, since the physical properties of the fiber become high, it is more preferable to modify P VA with ethylene. The ethylene unit content in the ethylene-modified PVA is preferably 4 to 丨5 mol%, more preferably 6 to 13 mol%. The P VA is produced by a conventional method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method. Among these, a bulk polymerization method or a solution polymerization method in which polymerization is carried out in a solvent such as no glutinous agent or alcohol is usually employed. The alcohol used as the solvent for solution polymerization, such as methanol, ethanol, or a lower alcohol such as -1 9 - 201000713 propanol. For copolymerization, use a, a'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), benzammonium peroxide, η-propyl peroxidation A conventional initiator such as an azo initiator such as a carbonate or a peroxide initiator. Regarding the polymerization temperature, there is no particular limitation, and it is preferably in the range of 〇~1 5 〇 °C. The viscosity average degree of polymerization of the above PVA (hereinafter referred to as the degree of polymerization) is preferably 200 to 500, more preferably 250 to 470, and most preferably 300 to 450. When the degree of polymerization is 200 or more, the melt viscosity is stably combined, and it has a sufficiently high enthalpy. When the degree of polymerization is 500 or less, the melt viscosity is easily discharged from the spinning nozzle, and is sufficiently low. Further, by using a polymerization degree of 500 or less, i.e., a low degree of polymerization PVA, there is an advantage that the dissolution rate when water or an aqueous solution is removed becomes faster. The degree of polymerization of P V A is determined by the following formula based on J I S - K 6 7 2 6 . Ρ = ([η] X 1 0 3 / 8.2 9)(|/0'62) (Ρ is the viscosity average degree of polymerization, [η] is the re-saponification of PVA and refined] in water at 30 ° C The intrinsic viscosity of the PVA is preferably 90 to 99.99 mol%, and 93 to 99.77 m. /. More preferably, it is preferably 95~99.55 mol%, and the best is 97~99.33 mol%. When the degree of saponification is 90% by mole or more, the heat stability is good, and it is difficult to carry out thermal decomposition or saponification treatment at the time of melt spinning, and when the degree of saponification is 99.99% or less, the PVA can be stably produced. The T m ' of the above P VA is 1 60 in consideration of the spinning property. (: The above is better, with 170~230. (: Better, 175~225 〇C is better, to 180~220. (: Best. Tm is 1 6 〇 when it is above) can be reduced by crystallinity To avoid pvA -20 -
201000713 纖維強度降低。而且，PVA之熱安定性良 良好。Tm爲2 3 0 °C以下時，可使熔融紡紗 較PVA之分解溫度更低的溫度，可安定地 形成性長纖維。 海島型纖維中所佔有的海成分聚合物= 維截面之面積比例設定爲5〜6 0 %之範圍 要’以1〇〜50%較佳。海島型纖維中之海戶 小於5 %時，由於海島型纖維之紡紗安定性 產性不佳。另外，藉由使海成分變少，使转 濕熱收縮時，使島成分之摩擦或干涉緩和& 無法得到目的之收縮狀態、緻密化，且在巧 含浸高分子彈性體之溶液或水分散液、予B 成分除去後，在極細纖維束與高分子彈性| 空隙不充分。結果，無法製得膨脹感或充| 面感等之本發明目的效果。另外，海成分聚 60%時’海島型纖維截面上島成分形狀或分 安定’不僅品質安定性不佳，且使海島型纖 縮時，具有收縮能力之島成分相對性不足， 的之收縮狀態、密緻化。結果，無法得到本 果。而且，海成分聚合物之比例愈高時，除 人造皮革用基材中極細纖維量愈少，爲使形 求的水準時必須含有的高分子彈性體量有 向’爲回收經除去的海成分聚合物時，就必 本而言會增大工業生產上之負荷，且對地球 :，纖維形成性 .度充分降低至 ;造極細纖維束 比例，以使纖 的比例係爲重 ,分聚合物比例 ;低，工業上生 島型纖維予以 效果不充分， 織布構造體中 硬化時，使海 之間所形成的 感、緻密的表 合物比例大於 布狀態變得不 維予以濕熱收 或無法得到目 發明目的之效 去海成分後之 態安定性爲企 顯著增大的傾 要的能量或成 環境之負荷當 201000713 然亦會增大。因此，在上述各種要因所容許的範圍，以使 海成分聚合物之比例設定爲更低者較佳。 於本發明中，海島型纖維使用長纖維之形態。一般而 言，長纖維係爲沒有如短纖維切斷成約1 〇〜5 〇mtn之纖維 長度之纖維，長纖維之纖維長度無法以一槪之。惟爲達成 本發明效果時，極細化前之長纖維的纖維長度以1 00mm以 上較佳，且技術上可製造、且在物理上無法切斷時，可爲 數m、數百m、數km、或此等以上之纖維長度。 '海島型纖維之紡紗處理時，使用複合紡紗用噴嘴。對 1個噴嘴孔而言具有8〜7 0個範圍內之任何個數予以平均 配置的島成分聚合物用流路、與圍住該島成分聚合物用流 路下所配置的海成分聚合物流路之複數個噴嘴孔，以直線 狀或圓形狀等間隔配置，而且，爲直線時以並列狀、或爲 圓形狀時以同心圓狀予以複數列配置。使由海成分聚合物 與島成分聚合物所形成的熔融狀態之海島型複合纖維自各 噴嘴孔連續吐出。自噴嘴孔下方至下述吸引裝置之間的任 t ^ 何階段’藉由冷卻風實質上予以冷卻硬化，且使用噴氣. 噴嘴等之吸引裝置使高速氣流作用，複合纖維在目的纖度 下予以均勻地拉伸細化。高速氣流爲一般紡紗之機械的引 取速度之平均紡紗速度爲1 000〜6000m/分鐘範圍內之任意 速度下予以作用。另外，視所得纖維網之質感而言使複合 纖維藉由衝突板或氣流等予以開纖處理，且在輸送帶狀移 動式網子等之捕集面上、自網子之相反側吸引且捕集.堆 積，形成長纖維纖維網。 -22 - 201000713 複合紡紗用噴嘴爲同心圓狀配置時’一般而言對1個 噴嘴而言使用1個噴嘴狀吸引裝置。因此’於吸引時多數 海島型纖維集束成同心圓之中心點。一般而言，由於使複 數個噴嘴以直線狀並列’製得企求的紡紗量，自相鄰的噴 嘴所吐出的海島型纖維束之間幾乎完全沒有纖維存在。因 此，爲使纖維網之質感爲均勻的狀態時，進行開纖處理係 爲重要。複合紡紗用噴嘴爲並列狀配置時，使用對向於噴 嘴之直線的隙縫狀吸引裝置。因此’吸引來自並列配置的 列間之海島型纖維時予以集束’於採用同心圓狀配置之噴 嘴相比時，可製得更爲均句質感之纖維網。此點係與同心 圓狀配置相比時，以並列狀配置者更佳。 所得的長纖維纖維網，以於繼後步驟中視其所需之形 態安定性而定，繼續藉由壓製、壓花處理等進行部份加熱 或冷卻且壓熔較佳。海成分聚合物之熔融黏度較島成分聚 合物更小時，藉由沒有施加直至熔融溫度之高溫，且在約 6 0〜1 2 0 °C溫度範圍內之任何溫度下進行加熱或冷卻，在沒 有使構成長纖維纖維網之海島型纖維的截面形狀大爲損失 下，在繼後之步驟中仍可充分保持長纖維纖維網之質感。 另外，可使長纖維纖維網之形態安定性提高至可捲取等處 理性之水準。 習知的人造皮革係爲一般所採用的使短纖維藉由_ 機裁成纖維網的方法，不僅使用紋版機，且必須使用陚予 適合通過紋版機之油劑及捲縮處理、裁成所定的纖維胃 度、切斷後原綿之搬送及開纖等一連串的大型設備，就& -23 - 201000713 產速度、安定生產、成本等而言會有問題。而且，經由短 it維的其他方法爲抄紙法，惟由於該方法亦必須具備裁斷 機設備等之附帶設備，仍會有與上述方法相同的問題，由 於可製造的不織布單位面積重量停留於約高達2 〇〇g/m2之 値’故可適用於人造皮革製品之用途非常受到限制。對使 用此等短纖維之方法而言，本發明之製造方法，係自紡紗 形成纖維網在沒有被途切下，作爲1步驟予以實施，設備 非常緻密、簡單，生產速度或成本優異。此外，由於不會 產生藉由組合習知的各種步驟、設備而產生複合的問題， 故安定生產性亦優異。另外，與藉由習知纖維間的絡合或 高分子彈性體之拘束所成的短纖維使用之不織布構造體相 比時’由長纖維所得的不織布構造體、使用該物之人造皮 革用基材或人造皮革，就形態安定性、即機械強度或表面 摩擦耐久性、粒面之黏合剝離強力等之物性面而言可發揮 優異的特性。 藉由本發明之製造方法，可使用藉由採用習知紋版機 f "1 之方法無法使用的纖維直徑極細的纖維，此外，由於不需 賦予捲縮處理、纖維本身無法使體積變大，自機械性堆積 的階段，可安定地製得較習知不織布構造體更極爲緻密的 狀態，且藉由組合下述方法，可製得習知人造皮革不可能 實現的極高品質之人造皮革。 有關纖維直徑’於製造使用習知短纖維之不織布構造 體時，必須爲適合於開纖裝置或紋版機之一定以上的纖維 直徑。具體而言，截面積必須爲2 0 0 μ m2以上之粗細，就考 -24 - 201000713 慮工業的安全生產性時，一般而言採用約3 Ο 0〜6 0 0 μ m 2粗 度之纖維。本發明之製造方法，由於使用的纖維粗度不會 受設備所限制，亦可使用截面積爲1 Ο Ο μ m 2以下之極細纖 維，惟爲製得本發明目的之不織布構造的緻密性時，截面 積必須爲7 0〜3 5 Ο μ m 2，就繼後步驟之形態安定性、處理性 而言，以80〜300μιη2較佳。藉由使用該截面積之長纖維， 所得的長纖維網於與厚度方向平行的任意截面上，可得與 截面幾乎垂直的纖維之截面以100〜600個/mm2(較佳者爲 150〜5 00個/mm2)範圍之平均數密度存在的纖維分布狀 態，藉由繼後步驟之絡合或收縮等，最後可製得本發明之 緻密的不織布構造體。 本發明中，構成所得的人造皮革用基材之不織布構造 體的緻密性，係爲重要，換言之，必須提高構成人造皮革 用基材表層部之不織布構造的緻密性。因此，藉由自海島 型纖維除去海成分聚合物所得的極細長纖維束之截面積， 必須至少爲7 0 0 μηι2以下。7〇〇μηι2以下之截面積，例如構 成極細長纖維之聚合物爲對苯二甲酸乙二酯時，極細纖維 束之纖度大約相當於dt ex以下。爲形成可製得極高品質 的絨毛調人造皮革、或緻密皺折之粒面狀人造皮革的人造 皮革用基材時，必須具有藉由該粗度之纖維束所得的不織 布構造體之緻密性。換言之’以使正絨牛皮革狀極細纖維 絨毛變短、具有緻密表面感之人造皮革爲目的時，極細長 纖維束之截面積以500μιη2以下較佳’以400μιη2以下更佳。 極細長纖維束之截面積的下限値’不像上述的上限値會影 -25 - 201000713 響人造皮革用基材之特性者，惟由於過細時會顯著降低人 造皮革之強度或表面摩擦耐久性等，及在人造皮革之製造 步驟上會受到限制等，於本發明中極細長纖維束之截面積 必須至少爲170μιη2以上，較佳者爲180μπι2以上，更佳者 爲190μηι2以上。 於本發明中，構成一束極細纖維束之極細長纖維的條 數’就極細長纖維束之易彎曲性、即不織布構造體內之易 絡合性或最終所得的人造皮革用基材之易彎曲性等而言爲 8條以上，就極細長纖維束之易彎曲性或截面形狀之變形 性' 及最終所得的人造皮革用基材之發色性等而言爲7 0條 以下。另外，極細長纖維之條數，以1 0〜6 0條較佳，以 1 2〜45條更佳。極細長纖維之條數爲7條以下時，由於不 僅極細長纖維束之易彎曲性不佳，且在不織布構造體中含 有高分子彈性體時之拘束條數率、即極細長纖維束之構成 條數所佔有的最外周上所配置的條數比例變多時，視高分 子彈性體而定，極細長纖維束之易彎曲性容易受到阻害’ 少量的高分子彈性體之質感容易硬化。因此，由於高分子 彈性體之含有狀態的斑點，容易作爲人造皮革用基材之質 感予以顯示化，不易確認具有作爲工業製品之價値。另外， 極細長纖維之條數大於7 0條時，1條1條之極細長纖維本 身的易彎曲性優異，惟由於極細長纖維束內之極細長纖維 間的接觸面積增大、被相抵觸，會有易彎曲性惡化的傾向。 而且，於極細長纖維束之截面形狀中，藉由自與纖維軸垂 直的壓縮力而變形，即容易引起扁平化，且構成纖維束之 -26 - 201000713 纖維間變寬’纖維束容易變得鬆散，纖維束之大體積性增 高’不織布構造體之緻密化的臨界値變低。該大體積性於 '海島型纖維之階段時亦相同，由於纖維爲截面形狀容易扁 平化’不織布構造體之纖維截面的塡充效果降低，於海成 分除去前會阻害緻密化。 由該理由可知，在纖維束不易扁平化下，必須至少爲 7 〇條以下，最終所得的人造皮革用基材之極細長纖維束的 扁平率必須爲4.0以下，較佳者爲3 _ 0以下。而且，藉由極 細長纖維束扁平化之缺點，特別是人造皮革用基材之表面 顯著’自表面觀察時纖維束之寬度、即極細長纖維束之投 影尺寸以1 0〜6 0 μ m較佳，以1 5〜4 5 μ m更佳。極細長纖維 束之投影尺寸大於6 0 μ m時，纖維束之緻密化不充分，特 別是作爲絨毛狀人造皮革時可形成絨毛的織纖維束變少， 僅可得外觀品質不高的絨毛表面。另外，極細長纖維束之 投影尺寸低於1 〇 μπι時，纖維束雖極爲容易緻密化，惟纖 維束沒有全面扁平化，纖維束之直徑本身低於1 Ομηι時， 爲非常細者，特別是即使形成絨毛狀人造皮革之絨毛時， 由於藉由起毛處理容易產生纖維束之切斷情形，絨毛變 少，不易得到良好的外觀品質，表面之耐摩擦性不佳。 藉由形成具有上述特徵之極細長纖維束，構成人造皮 革用基材之不織布構造體時，可製得與其厚度方向平行的 任意截面中，與截面幾乎垂直的極細長纖維束之截面個數 爲1 5 0 0〜3 0 0 0個/ m m2、習知所不具的極爲緻密的纖維集合 構造。低於1 5 〇 〇個/ m m 2時，僅極細纖維束之緻密性變少， -27 - 201000713 會產生沒有存在極細纖維束的空間，而且容易存在有區分 爲極細纖維束之數密度變少時，在沒有均勻分散下、幾乎 完全沒有存在密集範圍之疏鬆範圍的傾向，由於在極細纖 維束間所產生的空間變大時，形成厚的高分子彈性體之連 續皮膜’人造皮革之質感變硬’藉由極大的粗密斑導致形 成表面外觀或表面物性惡化者。大於3 0 0 0個/ m m 2時，所 觀察者爲藉由本發明之人造皮革用基材所形成的緻密的纖 維集合體，惟藉由熱壓製處理等時，僅使不織布構造體在 厚度方向強制壓縮，且藉由貼合於不織布構造體之收縮性 的編織物等之收縮力，僅朝長度方向或寬度方向強制壓縮 之構造，朝使極細纖維束壓縮的方向崩塌、扁平化，會使 物性降低或反而會有質感變硬，較佳者爲2〇00〜27〇0個 /mm 〇 採用習知不織布構造體之人造皮革用基材，在使不織 布構造體以絡合處理等予以緻密化的階段開始，纖維之粗 度係變成如極細纖維束時的截面積爲3 00〜600 /zm2左右的 粗度，所以直至變成極細纖維束之階段，不織布構造體之 緻密化不充分，使該物變成極細纖維束的結果所得的極細 纖維束截面之數密度約高達200〜600個/mm2,亦有約多達 7 5 0個/mm2。假設習知技術中製得極細纖維束之數密度大 於7 5 0個/mm2之不織布構造體時，藉由進行過度的針刺處 理導致纖維束本身受損，藉由上述之熱壓製等強制進行壓 縮處理，會使纖維束之截面形狀大爲變形，或僅藉由該處 理予以緻密化的結果，會有在纖維束間之空隙中斑點大的 形態，所得的人造皮革用基材與本發明目的者完全不同。 -28 - 201000713 而且，纖維束之數密度約高達2 00〜6〇〇個/mm2 織布構造體，在其內部含有高分子彈性體時，視售 由於僅極細纖維束之數密度變少下、極細纖維束 的高分子彈性體之連續皮膜，不僅作爲不織布構 分子彈性體之複合構造的質感變成必要以上之硬 各處散在有纖維或高分子彈性體緻密地集合存在 及纖維與高分子彈性體幾乎完全不存在的範圍下 到具有極大的粗密斑者。對此而言，本發明之不 體由於具有極細纖維束極爲緻密且均勻地集合的 造，在不織布構造體內含有高分子彈性體時，可 纖維束間所形成的高分子彈性體之連續皮膜的厚 且高分子彈性體所爲成的元件亦更小，可予以均 故可抑制人造皮革用基材內部產生顯著的粗密斑 本發明藉由滿足上述要件之極細長纖維束構 構造體時，極細長纖維本身之纖維直徑沒有特別 形成具有本發明目的之優美外觀或觸感的絨毛面 ^ 於絨毛部分中極細長纖維以0.8〜15μηι較佳，更隹 〜13μηι，尤佳者爲1.2〜ΙΟμπι，最佳者爲1.5〜8 細長纖維之纖維直徑大於1 5 μ m時，對作爲絨毛 革時之外觀品質有不良影響，例如表面之絨毛 點’觸摸感之平滑性受損，故不爲企求。另外， 維之纖維直徑低於1 · 0 μ m時，作爲絨毛狀人造皮 絨毛感雖爲緻密者’惟全體而言對外觀品質或表 生不良的影響。例如，表面之絨毛色產生白化情 之習知不 ί量而定， 間形成厚 造體與高 質感，且 的範圍、 ，無法得 織布構造 超緻密構 使在極細 度變薄， 勻分布， 〇 成不織布 限制，爲 時，至少 巨者爲1 .0 .5 μ m。極 狀人造皮 色產生斑 極細長纖 革時雖爲 面特性產 形，且耐 -29 - 201000713 剝離性等之表面耐摩擦性亦產生惡化情形。 所得的長纖維纖維網之單位面積重量或厚度不充分 時，在企求的單位重量面積、厚度下進行調整摩擦處理（對 步驟之流動方向而言垂直的方向供應1張長纖維纖維網、 且幾乎全部朝寬度方向摺疊，或使自對步驟之流動方向而 言平行的方向供應的纖維網朝其長度方向摺疊）或體積重 量（使數張長纖維纖維網重疊）。由海島型纖維所形成的不 織布構造體之形態安定性或纖維之緻密性不充分時，調整 不織布構造體之海島型纖維朝厚度方向的配向情形時，藉 由針刺法等之習知方法進行機械性絡合處理。藉此可使構 成長纖維纖維網之纖維間、特別是經摩擦或積層的層狀長 纖維纖維網相鄰的層間進行三次元絡合處理。藉由針刺法 進行絡合處理時’適當選擇織針之種類（織針之形狀或編 號、繭絲之形狀或深度、繭絲之數目或位置等）、織針之針 刺數（織針空隙中經植針的織針密度與使該空隙在長纖維 纖維網之每單位面積作用的冲程數之每單位面積之針刺處 、/ 理密度）、織針之針刺深度（對長纖維纖維網而言使織針作 用的深度）等各種處理條件予以實施。 織針的種類’可適當使用與使用習知短纖維製造人造 皮革時所使用相同者’惟就可得本發明之效果而言，織針 之編號、蘭絲之丨木度、鋪絲之數特別重要，以使用以下述 種類之織針爲主較佳。 織針的編號，係爲使處理後所得的緻密性或表面品質 受到影響的因素，至少使刀片部分（形成織針前端之繭絲的 -30 - 201000713 部分）之尺寸必須爲小於3〇號（細者）（截面形狀爲正三角形 時之筒度 '或爲圓形時之直徑約爲0.73〜0_75mm)，較佳者 爲32號（約0.68〜〇_7〇rnrn)〜46號（約0.33〜0_35mm)之範 圍’更佳者爲36號（約〇58〜〇.60mm)〜43號（約0.38〜 0.40mm)之範圍。刀片部分之尺寸大於3〇號（粗者）的織針， W絲之形狀或深度的自由度高，織針之強度或耐久性較 佳’ I隹相反地在不織布構造體之表面上殘留有大孔徑之織 隹十刺？L痕跡’無法製得本發明目的之緻密的纖維集合狀態 或表面品質。而且，由於長纖維纖維網中之纖維與織針的 摩擦力變得過大’必須賦予過多的針刺處理用油劑，故不 爲企求。另外’刀片部分之尺寸小於46號之織針，有關強 度或耐久性’不僅無法在工業上生產，且於本發明中無法 設定適當深度之繭絲。刀片部分之截面形狀，就纖維之容 易拉伸性或摩擦力小等而言，於本發明中以正三角形較佳。 本發明之繭絲深度，係爲自繭絲之最深部分至繭絲前 端之高度。一般形狀之繭絲，係指符合自織針側面突出於 外側的繭絲則端之局度（亦稱爲向上彎曲）、與自織針側面 至在內側所形成的繭絲之最深部分的深度（亦稱爲狹口深 度）之高度。繭絲深度係至少爲海島型纖維之直徑以上，較 佳者爲1 2 0 μ m以下。繭絲深度低於海島型纖維之直徑時， 海島型纖維極爲不易予以鈎絲成繭絲，故不爲企求。此外， 繭絲深度大於1 2 0 μ m時’纖維容易予以鈎絲，反之，在不 織布構造體之表面上容易殘留有大孔徑之針剌痕跡，不易 得到本發明目的之緻密的纖維集合狀態或表面品質。而 201000713 且，繭絲深度對海島型纖維之直徑而言以〗7〜1〇2倍範圍 內之任意倍數較佳’更佳者選自2 · 〇〜7 〇倍之範圍。繭絲 深度低於1 _ 7倍時’海島型纖維不易予以鈎絲成繭絲，即 使增加針刺數，仍無法得到符合的絡合效果，此外，大於 1 0.2倍時’藉由提尚海島型纖維之钩絲容易性，當然會有 海島型纖維之切斷或破裂等情形之損傷增加的傾向，故不 爲企求。 本發明之繭絲數，係在1〜9根針鈎之範圍內可得企求 的絡合效果下予以適當選擇’爲製得本發明必要的緻密不 織布構造體時，針刺絡合處理時主要使用的織針、即下述 針刺數之至少5 0 °/。以上的針刺處理時所使用的織針，繭絲 數必須爲6根針鈎。而且，於本發明中，針刺絡合處理時 所使用的織針之繭絲數不一定必須爲1種，例如可適當組 合1根針鈎與6根針鈎、3根針鈎與6根針鈎、6根針鈎與 9根針鈎、1根針鈎與6根針鈎與9根針鈎等不同繭絲數之 織針’可以任意順序使用。具有數根針鈎繭絲之織針中， 各繭絲之位置與自織針前端之距離完全不同者，及具有數 個相同距離之繭絲者。後者之織針，例如刀片部分之截面 形狀爲正二角形’ 3個頂點之各繭絲係自各1根針鈎前端、 在相同距離上附有織針等。於本發明中，絡合處理時主要 使用的織針，係使用前者之織針。此係在相同距離上具有 複數根針鉤的繭絲之織針，由於觀察時具有織針之刀片部 分粗’且繭絲厚度大的效果，故絡合效果雖高，惟會有刀 片部分過粗且繭絲過深的顯著缺點。另外，使用後者之織 -32 - 201000713 針過分進行針刺處理時，由於在1處上十數條〜數十條之 多數纖維形成束，朝不織布構造體之厚度方向配向的地方 變得過多’故會有不易製得本發明目的之緻密構造的傾 向。換言之，於與不織布構造體之厚度平行的任意截面上， 會有存在多數與截面幾乎平行的纖維，與截面垂直的纖維 之數密度極端減少的傾向。惟由於即使少數的繭絲數，仍 可得強的絡合效果，在部分絡合處理時亦以使用後者之織 針較佳。例如，自絡合處理之初期階段至中期階段的任意 f :r 1 階段，在不會損害目標之緻密構造下以後者之織針進行絡 合處理，然後，使用前者之織針形成目標之緻密構造的方 法爲較佳形態之一。而且，於本發明中繭絲數爲6根針鈎 時，係爲使織針前端之不織布構造體貫通的繭絲至沒有貫 通且實質上作用於不織布構造體之繭絲爲止的合計個數， 不包含沒有作用於不織布構造體之部分的繭絲。例如，織 針中所形成的繭絲數爲 9根針鈎時，織針突刺於最深處 時，採用在不織布構造體外殘留有3根針鈎繭絲之絡合處 4- ... I 理條件時，實質上具有與繭絲數爲6根針鈎之針刺處理相 等的效果。 織針之合計針剌數，以在8 0 0〜4 〇 〇 0針刺/ c m 2之範圍 的任意値較佳，更佳者爲1 000〜35〇〇針刺/ cm2之範圍。在 上述相同距離具有數個繭絲的織針時，該針刺處理之針刺 數，約爲3 0 〇針刺/c m 2以下 '較佳者約爲1 0〜2 5 0針刺/ c m2 之範圍。使用在上述相同距離具有數個繭絲的織針’進行 大於3 0 0針刺/cm2之針刺處理時，由於纖維多數朝厚度方 -33 - 201000713 向進行配向，即使進行使用繼後另外的織針之針刺處理或 熱收縮處理、壓製處理等’不易使不織布構造體之數密度 高的傾向變強。織針之合計針刺數低於800針刺/cm2時’ 不僅緻密化不充分，特別是藉由在長纖維纖維網之異層間 的纖維絡合處理之不織布構造體的一體化不充分的傾向變 強，另外，大於4000針刺/cm2以下時，視上述織針的形狀 而定，藉由纖維之織針會有切斷或破裂等之損傷情形，纖 維之損傷情形特別嚴重時，不織布構造體之形態安定性大 f 1 幅降低且緻密性亦降低。 所得的不織布構造體及人造皮革用基材之形態安定性 或拉伸強力等之力學物性、厚度方向之纖維的配向性等而 言，經過長纖維纖維網之全部厚度，較織針之繭絲更有作 用者較佳。因此，織針之針刺深度，以設定爲至少在織針 最前端側之繭絲通過長纖維纖維網之全部厚度下的深度較 佳。特別是於本發明必要的繭絲爲6根針鈎之織針中，爲 使本發明目的之絡合效果發揮至最大極限時，全部的繭絲 沒有貫通係爲重要。換言之，距離前端最遠的繭絲，係以 在長纖維纖維網中殘留的針刺深度使織針予以作用。使全 部繭絲通過時’由於6根針鈎的繭絲經鈎絲的長纖維自全 部長纖維纖維網內突出，無法製得本發明目的之緻密構 造。沒有通過長纖維纖維網之繭絲個數，以6根針鈎的繭 絲內之2根針鈎〜5根針鈎較佳，更佳者爲3根針鈎或4 根針钩。而且’爲貫現習知所沒有的緻密構造時，上述針 刺數的5 0 %以上之針刺處理’必須使織針前端之繭絲設定 -34- 201000713 爲貫通長纖維纖維網之針刺深度，使7 0 %以上之針刺處理 在織針前端的繭絲設定爲通過長纖維纖維網之針刺處理深 度下進行較佳。惟針刺處理深度過深時，繭絲爲6根針鈎 織針時，不僅如上所述無法製得上述之緻密構造，且繭絲 爲1根針鈎、2根針鈎' 3根針鈎、4根針鈎、5根針鈎、 或7根針鈎、8根針鈎、9根針鈎、或1 〇根針鈎以上之織 針時’即沒有視繭絲之個數而定，藉由繭絲導致纖維之損 害顯著，爲極端時纖維有被切斷的傾向、或針刺痕跡容易 殘留於不織布構造體之表面上的傾向，故於設定針刺條件 時’必須特別留意此等情形。 爲藉由針刺處理以抑制纖維之損傷或切斷情形，且抑 制藉由織針與纖維之強力摩擦作用所產生的帶電或發熱等 情形時’以於長纖維纖維網之製造步驟後、絡合處理步驟 前之任何階段中賦予油劑者較佳。賦予的方法，可採用噴 霧塗布法、可逆輥塗布法、接觸輥塗布法、隙縫塗布法等 t習知塗布法’其中噴霧塗布法係對長纖維纖維網而言爲 非接觸’且可使用在長纖維纖維網內層中以短時間浸透的 低·黏度 '油劑最佳。而且，此處所指的長纖維纖維網製造步 ，驟後’係指使海島型纖維進行熔融紡紗處理，在移動式網 子等之捕集面上捕集.堆積的階段後。於本發明中，於實 施絡合處理前賦予的油劑，可爲由1種成分所形成的油 劑’亦可以爲使用具有不同效果之數種油劑、使此等混合 W予’或順序賦予。本發明所使用的油劑，係爲使織針與 @ Μ之摩擦、即使金屬與聚合物摩擦緩和的平滑效果高的 -35- 201000713 油劑’具體而言，以礦物油系油劑或聚石: 爲後者時，以二甲基矽氧烷爲主體之油 氧烷系、平滑效果高的油劑時，平滑效 絲之鈎絲作用、會導致絡合效果局部顯 抑制因纖維間之摩擦係數顯著降低，無 目的時’以使用組合摩擦效果高的油劑 油劑更佳。惟由於本發明中海島型纖維 性聚合物’使纖維變成極細纖維束時使 別是聚矽氧烷系油劑沒有在變成極細纖 去’直至人造皮革用基材之階段爲止， 細纖維表面或高分子彈性體表面上。因 皮革用基材使用於絨毛狀人造皮革時， 染色處理典型的水浴中處理時所殘留 (例如染色狀態爲斑狀）、或於浴中處理 有被完全除去下，殘留的油劑使絨毛纖 上的固定狀態變弱，容易予以剝離等之 留意使用聚矽氧烷系油劑。除礦物油系 油劑倂用外’藉由摩擦導致靜電顯著時 劑（例如聚氧化烯系界面活性劑等作爲技 於由海島型纖維形成階段之不織布 要的平均數密度（與厚度方向平行的截 直的纖維截面之每單位面積的個數） /mm2’較佳者爲11〇〇〜3000個/mm2,更 個/mm2範圍內之任意値。爲製得具有該 ?氧烷系油劑較佳， 劑更佳。使用聚矽 果過強時，藉由繭 著降低，特別是以 法維持絡合狀態爲 、例如礦物油系之 之海成分使用水溶 用水或水溶液，特 維束時同時予以除 容易多數殘留於極 此，使所得的人造 由於產生藉由進行 的油劑形成處理斑 等之加工處理後沒 維在不織布構造體 缺點，特別是必須 油劑與聚矽氧烷系 ，以倂用界面活性 ί靜電劑）較佳。 構造體中，最終必 面中幾乎與截面垂 爲 1000〜3500個 佳者爲1200〜2500 平均數密度範圍之 -36 - 201000713 緻密構造時，在針刺處理等之絡合處理後，倂用藉由棄 溫水' 蒸氣等之熱收縮處理。藉由組合丨種或數種此 處理’最後可製得本發明目的之緻密構造。當然，除 處理或收縮處理外，以進行壓製處理較佳。倂用壓製 與絡合處理時，可於絡合處理前或後進行，亦可同時 壓製處理與絡合處理。而且，與收縮處理倂用時，可 縮處理前或後進行，惟壓製處理與收縮處理同時進行 法’收縮狀態變得不均勻，故不爲企求。 於針刺處理後進行熱收縮處理，於本發明中必須 進行濕熱處理。濕熱處理係爲使針刺絡合處理後之不 構造體、或於高溫高濕氣體環境中、在所企求的緻密 進行熱收縮處理。例如，製得平均數密度約爲8 00〜 個/mm2之不織布構造體的緻密性時，首先藉由針刺處 至3 5 0〜75 0個/mm2爲止予以緻密化後，進行目標緻 之熱收縮處理。爲進行熱收縮處理時，長纖維纖維網 以含有熱收縮性成分之海島型纖維予以形成，另外， ' 除海島型纖維外、倂用收縮性纖維所製造的長纖維 網，積層另外製造的收縮性纖維網較佳。爲製得熱收 海島型纖維時，可採用熱收縮性聚合物作爲海成分 物、島成分聚合物中任何一種、或兩者予以紡紗，惟 發明中，至少使用上述之熱收縮性聚合物作爲島成分 物。濕熱收縮處理之條件，只要是至少使島成分聚合 有充分的收縮作用，且使海成分聚合物予以膨脹. 化、沒有溶出下之溫度條件即可，沒有特別的限制， V風、 等之 絡合 處理 進行 在收 的方 至少 織布 性下 1100 理直 密性 必須 使用 纖維 縮性 聚合 於本 聚合 物具 可塑 視採 -37 - 201000713 用的熱收縮處理方法或處理對象物之處理量等而定予以適 當設定，例如藉由連續供應飽和水蒸氣，在控制於溫度65 〜l〇〇°C、相對濕度70〜100%範圍內之任何溫濕度的環境 中導入的方法，或使在不織布構造體中爲使海成分聚合物 膨脹•可塑化時供應充分量之水後、或供應時以繼後的任 何方法使島成分聚合物之收縮與海成分聚合物之膨脹•可 塑化時所需的熱連續作用於不織布構造體的方法，爲較佳 例。對賦予有水分之不織布構造體使熱予以作用的方法， 係爲導入控制於企求溫度之環境中的方法、使企求溫度之 空氣直接於不織布構造體上作用的方法、或使紅外線等之 電磁波在不織布構造體上作用、使不織布構造體昇溫成企 求溫度的方法係爲較佳之例。不織布構造體由於面積變廣 時’視其本身重量之影響等而定容易在熱收縮狀態下產生 斑點，以控制收縮之開始點或收縮速度爲目的時，視片狀 不織布構造體之長度方向、寬度方向之位置而定，控制不 同的溫度條件爲較佳的形態。 ή 除藉由上述針刺處理之絡合處理或熱收縮處理外，爲 使以由海島型纖維所形成的不織布構造體爲目的予以徽密、 化時’預先進行下述高分子彈性體之含浸處理，視# m _ 採用壓製處理較佳。例如，以不織布構造體之平均數密度 約爲1 00 0〜1 2 00個/mm2之緻密性爲目標時，首先可直至 熱收縮處理，緻密化至600〜900個/mm2後，壓製處理成 目標之緻密性。採用壓製處理時之具體例，如以上述濕熱 收縮處理後之濕潤狀態下直接予以壓製的方法、& _ _ @ -38 - 201000713 縮處理、乾燥的狀態下予以壓製的方法、在完全沒有乾燥 下殘留部分水分的狀態下予以壓製的方法等。例如，壓製 處理的溫度，係於濕熱收縮處理或乾燥處理之熱冷卻前， 在較不織布構造體之表面溫度更低的溫度下使軟化成分予 以硬化且壓製處理的方法、較不織布構造體之表面溫度更 高的溫度下使一成分更爲軟化，再使含有水分予以蒸發且 壓製處理的方法等。藉由採用該處理方法，由於除熱收縮 處理外，幾乎同時進行藉由壓製處理之緻密化，故僅藉由 實施壓製處理，可製得均勻的緻密化狀態，且可得優異的 生產效率。於構成不織布構造體之海島型纖維中，海成分 聚合物之軟化溫度較島成分聚合物之軟化溫度更低2 0 °C以 上、較佳者更低3 0°C以上時，倂用熱收縮處理之壓製處理 藉由緻密化更爲有效。此時，藉由自接近海成分聚合物之 軟化溫度加熱成較島成分聚合物之軟化溫度更低、且島成 分聚合物之收縮溫度更高的溫度範圍，僅海島型纖維中之 海成分聚合物在軟化或接近軟化的狀態，島成分之自由度 ' 變高的狀態下，使收縮性島成分聚合物予以收縮。該收縮 充分進行後，海成分聚合物之軟化溫度在溫度沒有降低的 狀態下使不織布構造體進行壓製處理時，在使不織布構造 體壓縮成更爲緻密的狀態，使該物冷卻至室溫時，可製得 在企求的緻密狀態下固定的不織布構造體。除壓製處理之 緻密化以外之優點，例如可使不織布構造體之表面固定在 更爲平滑化的狀態的效果。藉由平滑化處理，本發明之人 造皮革用基材中最大特徵之極細纖維束的極爲緻密的集合 -39- 201000713 狀態，可更爲有效地製得。換言之，由於可使人造皮革用 基材之表面更爲平滑’可於製造絨毛狀人造皮革時以摩擦 處理等之絨毛形成處理的硏磨量更少，且於製造粒面狀人 造皮革時，在沒有使基材表面進行加熱壓製或摩擦處理 等’可安定地形成平滑且厚度爲50μιη以下之極薄的粒面 層。 該所得的數密度爲1000〜3500個/mm2，較佳者爲1300 〜3 000個/mm2範圍之緻密不織布構造體中，在海成分聚合 物除去前或除去後’視其所需含有高分子彈性體。所含有 的方法’例如含浸高分子彈性體之溶液或分散液，且藉由 習知的乾式法或濕式法予以凝固的方法。含浸方法可採用 使不織布構造體浸漬於以高分子彈性體液體塡滿的浴中 後’以壓製輥等進行1次或數次所定的含液狀態下扭轉的 處理’即浸漬法、或棒塗布法、刀塗布法、輥塗布法、豎 立型塗布法、噴霧塗布法等習知的各種塗布法等中任一 種。可爲1種之方法，亦可組合數種的方法。 在不織布構成體中所含的高分子彈性體，只要是人造 皮革用基材之習知使用者即可，任何皆可使用，具體例如 聚胺基甲酸酯彈性體、丙烯腈彈性體、烯烴彈性體、聚酯 彈性體、丙烯酸彈性體，較佳者爲至少一種選自聚胺基甲 酸酯彈性體、丙烯酸彈性體。聚胺基甲酸酯彈性體係可將 選自於聚酯二醇、聚醚二醇、聚醚酯二醇、聚碳酸酯二醇 等之至少1種平均分子量爲500〜3000之聚合物多醇，與 至少一種選自4,4’-二苯基甲烷二異氰酸酯、異佛爾酮二異 -40 - 201000713 氰酸醋、六亞甲基二異氰酸醋等之芳香族系、脂環族系、 脂肪族系二異氰酸酯等之聚異氰酸酯組合做爲主成分’再 以所定莫耳比組合至少一種乙二醇、乙二胺等之具有2個 以上活性氫原子的低分子化合物’使此等以一段式或多段 式、藉由熔融聚合法、塊狀聚合法、溶液聚合法等予以聚 合反應所得的各種聚胺基甲酸酯彈性體’聚胺基甲酸酯彈 性體中所佔有的聚合物多醇成分之含量，以1 5〜9 0質量％ 較佳。而且，丙烯酸彈性體’其同元聚合物的玻璃轉移溫 度爲-90〜-5 T：之範圍，較佳者爲非交聯性之單體’例如至 少一種選自丙烯酸甲酯、丙烯酸正丁酯、丙烯酸異丁酯、 丙烯酸異丙酯、（甲基）丙烯酸正己酯、（甲基）丙烯酸2 -乙基 己酯等之軟質成分，與其同元聚合物之玻璃轉移溫度爲50 〜2 5 0 °C之範圍、較佳者爲非交聯性之單體、例如至少一種 選自甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸異丙 酯、甲基丙烯酸異丁酯、甲基丙烯酸環己酯、（甲基）丙烯 酸等之硬質成分，與形成交聯構造所得的單官能或多官能 乙烯性不飽和單體單位、或導入聚合物鏈之乙烯製不飽和 單體單位進行反應，形成交聯構造所得之化合物，例如至 少一種選自乙二醇二（甲基）丙烯酸酯、三乙二醇二（甲基） 丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、1，4 -丁二醇二（甲 基）丙烯酸酯等之交聯形成性成分所形成的乙烯性不飽和 單體進行聚合反應所得的各種丙烯酸彈性體。採用聚胺基 甲酸酯彈性體作爲主體之高分子彈性體所得的人造皮革用 基材，質感或力學物性之平衡性優異，且包含耐久性之平 -41- 201000713 衡性亦優異而言較佳。而且，採用丙烯酸彈性體所得的人 造皮革用基材，丙烯酸彈性體與聚胺基甲酸酯彈性體相比 時’由於對極細長纖維束之黏合性低，缺乏絨毛形成時之 絨毛固定效果，不易形成絨毛狀人造皮革，由於對含量而 言可抑制質感之硬化程度，形成粒面狀人造皮革時更佳。 高分子彈性體中混合含有不同的種類，亦可分數次含有不 同的種類，且除含有主體之高分子彈性體外，亦可含有視 其所需添加有合成橡膠、聚酯彈性體等之高分子彈性體的 f 高分子彈性體組成物。 藉由在不織布構造體中含浸高分子彈性體之溶液或分 散液等之高分子彈性體液，然後，使高分子彈性體藉由習 知的乾式法或濕式法予以凝固，使高分子彈性體固定於不 織布構造體內。此處所指的乾式法，係指全部使溶劑或分 散劑藉由乾燥處理等除去，使高分子彈性體固定於不織布 構造體內的方法。而且，此處所指的濕式法，係指全部藉 由含浸高分子彈性體液之不織布構造體以高分子彈性體之201000713 Fiber strength is reduced. Moreover, the thermal stability of PVA is good. When the Tm is 2,300 ° C or less, the melt spinning can be made at a temperature lower than the decomposition temperature of the PVA, and the long fibers can be formed stably. The sea component polymer which is occupied by the island-type fiber = the area ratio of the cross-section is set to a range of 5 to 60%. It is preferable to be '1 to 50%. When the sea-shell type of the island-type fiber is less than 5%, the spinning stability of the island-type fiber is poor. In addition, when the sea component is reduced, the friction or interference of the island component is alleviated when the heat is contracted, and the shrinkage state and the densification of the target are not obtained, and the solution or the aqueous dispersion of the polymer elastomer is impregnated. After the removal of the B component, the voids in the ultrafine fiber bundle and the polymer elasticity are insufficient. As a result, the effects of the present invention such as a feeling of expansion, a feeling of filling, and the like cannot be obtained. In addition, when the sea component is 60%, the shape of the island component or the sub-stable on the sea-island fiber cross-section is not only poor in quality stability, but also the contraction state of the island component having shrinkage ability when the sea-island type is slender. Meticulous. As a result, the results were not obtained. In addition, the higher the proportion of the sea component polymer, the less the amount of the ultrafine fibers in the base material for the artificial leather, and the amount of the polymer elastomer which must be contained in order to obtain the level of the shape, the sea component to be recovered. When polymer is used, it will increase the load on industrial production, and on the earth: fiber formation. The degree is sufficiently reduced; the ratio of the fine fiber bundle is made so that the proportion of the fiber is heavy, and the proportion of the polymer is low; the industrial island fiber is insufficiently applied, and when the woven fabric is hardened, the sea is interposed. The formed sensation and the proportion of the dense composition are larger than the state of the cloth, which is not suitable for the wet heat collection or the effect of the purpose of the invention. The stability of the sea component is a significant increase in energy or environmental environment. The load will increase when 201000713. Therefore, it is preferable to set the ratio of the sea component polymer to be lower in the range allowed by the above various factors. In the present invention, the sea-island type fiber is in the form of long fibers. In general, the long fiber is a fiber which is not cut into a fiber length of about 1 〇 5 〇 mtn, and the fiber length of the long fiber cannot be smashed. However, in order to achieve the effect of the present invention, the fiber length of the long fiber before the ultrafine refining is preferably 100 mm or more, and is technically manufacturable and physically impossible to cut, and may be several m, several hundred m, several km. Or the fiber length of these or more. In the spinning process of the island-type fiber, a nozzle for composite spinning is used. An island component polymer flow path having an average of any number of 8 to 70 in one nozzle hole, and a sea component polymer flow disposed under the flow path surrounding the island component polymer The plurality of nozzle holes of the road are arranged at equal intervals in a straight line or a circular shape, and are arranged in a plurality of rows in a concentric shape when they are in a straight line or in a circular shape. The island-in-sea type composite fiber in a molten state formed by the sea component polymer and the island component polymer is continuously discharged from each nozzle hole. From the bottom of the nozzle hole to any of the following suction devices, the stage is cooled and hardened by the cooling air, and the jet is used. The suction device such as a nozzle acts on the high-speed air stream, and the conjugate fiber is uniformly stretched and refined at the desired fineness. The high-speed airflow acts at any speed in the range of the sampling speed of the general spinning machine at an average spinning speed of 1 000 to 6000 m/min. Further, depending on the texture of the obtained fiber web, the composite fiber is opened by a collision plate or a gas flow, and is attracted to the opposite side of the net on the collecting surface of the conveyor belt-like movable net or the like. set. Stacking to form a long fiber web. -22 - 201000713 When the nozzles for composite spinning are arranged in a concentric shape, generally, one nozzle-shaped suction device is used for one nozzle. Therefore, most of the island-in-the-sea fibers are bundled into the center point of the concentric circle at the time of attraction. In general, since a plurality of nozzles are arranged in parallel in a straight line to obtain a desired amount of spinning, almost no fibers exist between the sea-island type fiber bundles discharged from adjacent nozzles. Therefore, in order to make the texture of the fiber web uniform, it is important to perform the fiber opening treatment. When the nozzles for composite spinning are arranged in parallel, a slit-like suction device that faces a straight line of the nozzle is used. Therefore, when the island-type fibers between the columns arranged in parallel are attracted to be bundled, a more uniform texture web can be obtained when the nozzles are arranged in a concentric arrangement. This point is better in a side-by-side configuration when compared to a concentric circular configuration. The resulting long fiber web is preferably subjected to partial heating or cooling by compression, embossing or the like in a subsequent step depending on its desired shape stability. The sea component polymer has a lower melt viscosity than the island component polymer, and is heated or cooled at any temperature within a temperature range of about 60 to 120 ° C without applying a high temperature up to the melting temperature. When the cross-sectional shape of the sea-island type fiber constituting the long fiber web is largely lost, the texture of the long fiber web can be sufficiently maintained in the subsequent steps. In addition, the form stability of the long fiber web can be improved to a level of rationality such as reelability. The conventional artificial leather is a generally used method for cutting short fibers into a fiber web by using a machine, and not only using a pattern machine, but also using an oil agent and a crimping treatment suitable for passing through a pattern machine. A series of large-scale equipment such as the predetermined fiber stomach, the original cotton transfer after cutting, and the opening of the fiber will have problems in terms of production speed, stable production, and cost. Moreover, the other method of short-dimensional dimension is the papermaking method, but since the method must also have the accompanying equipment such as the cutting machine equipment, there is still the same problem as the above method, since the unit area weight of the non-woven fabric that can be manufactured stays at about as high as 2 〇〇g/m2 値', so the use of artificial leather products is very limited. For the method of using such short fibers, the production method of the present invention is carried out as a one-step process by forming a fiber web from a spun yarn, and the apparatus is very compact and simple, and is excellent in production speed or cost. Further, since there is no problem of recombination by combining various conventional steps and equipment, stability and productivity are also excellent. In addition, the non-woven fabric structure obtained from the long fibers and the artificial leather base using the same are compared with the non-woven fabric structure used for the short fibers formed by the conventional fibers or the restraint of the polymer elastic body. The material or the artificial leather exhibits excellent characteristics in terms of physical stability such as form stability, mechanical strength, surface friction durability, and adhesion strength of the grain surface. According to the production method of the present invention, it is possible to use a fiber having a very small fiber diameter which cannot be used by a conventional patterning machine f "1, and further, since the crimping treatment is not required, the fiber itself cannot be made bulky. From the stage of mechanical accumulation, a state in which the conventional non-woven fabric structure is more extremely dense can be stably obtained, and by combining the following methods, an extremely high-quality artificial leather which is impossible for conventional artificial leather can be obtained. The fiber diameter must be a fiber diameter suitable for a fiber opening device or a patterning machine when manufacturing a nonwoven fabric structure using conventional short fibers. Specifically, the cross-sectional area must be a thickness of more than 200 μm 2 , and in the case of industrial safety production, generally, a fiber of about 3 Ο 0 to 600 μm 2 is used. . In the production method of the present invention, since the fiber thickness used is not limited by the apparatus, ultrafine fibers having a cross-sectional area of 1 Ο Ο μ m 2 or less may be used, but when the density of the non-woven fabric structure for the purpose of the present invention is obtained, The cross-sectional area must be 70 to 3 5 Ο μ m 2 , and it is preferably 80 to 300 μm 2 in terms of form stability and handleability in the subsequent steps. By using the long fiber of the cross-sectional area, the obtained long fiber web can be obtained in any cross section parallel to the thickness direction, and the cross section of the fiber which is almost perpendicular to the cross section can be 100 to 600 pieces/mm 2 (preferably 150 to 5). The fiber distribution state in which the average number density of 00 pieces/mm2 is in the range, and the dense non-woven fabric structure of the present invention can be finally obtained by the complexation or shrinkage of the subsequent steps. In the present invention, the compactness of the nonwoven fabric structure constituting the base material for artificial leather obtained is important, in other words, it is necessary to improve the compactness of the nonwoven fabric structure constituting the surface layer portion of the base material for artificial leather. Therefore, the cross-sectional area of the extremely elongated fiber bundle obtained by removing the sea component polymer from the sea-island type fiber must be at least 700 μm 2 or less. The cross-sectional area of 7 〇〇μηι2 or less, for example, when the polymer constituting the extremely elongated fiber is ethylene terephthalate, the fineness of the ultrafine fiber bundle is approximately equal to or less than dt ex . In order to form a substrate for artificial leather which can produce extremely high-quality fluff-toned artificial leather or densely creased grain-like artificial leather, it is necessary to have a dense structure of the nonwoven fabric obtained by the fiber bundle of the thickness. . In other words, when the artificial leather having a dense surface texture and a dense surface is obtained, the cross-sectional area of the ultra-long fiber bundle is preferably 500 μm 2 or less and more preferably 400 μm 2 or less. The lower limit of the cross-sectional area of the extremely thin fiber bundle 不' is not like the above-mentioned upper limit -25 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - In the present invention, the cross-sectional area of the extremely elongated fiber bundle must be at least 170 μm 2 or more, preferably 180 μm 2 or more, and more preferably 190 μm 2 or more. In the present invention, the number of extremely elongated fibers constituting a bundle of ultrafine fiber bundles is such that the flexibility of the extremely elongated fiber bundle, that is, the ease of complexation in the nonwoven fabric structure or the resulting flexible substrate for artificial leather. The number of the properties is 8 or more, and the flexibility of the extremely long fiber bundle or the deformability of the cross-sectional shape and the color developability of the base material for artificial leather finally obtained are 70 or less. Further, the number of the extremely elongated fibers is preferably from 10 to 60, more preferably from 1 2 to 45. When the number of the extremely thin fibers is seven or less, the flexibility of the extremely long fiber bundle is not good, and the ratio of the number of restraint strips, that is, the composition of the extremely elongated fiber bundle, when the polymer elastic body is contained in the nonwoven fabric structure is not preferable. When the ratio of the number of the strips disposed on the outermost circumference of the number of the strips is large, depending on the polymer elastomer, the flexibility of the extremely long fiber bundle is easily prevented. A small amount of the polymer elastomer is easily cured. Therefore, the spots in the state of the polymer elastomer are easily displayed as the texture of the base material for artificial leather, and it is difficult to confirm the price as an industrial product. In addition, when the number of extremely elongated fibers is more than 70, one of the extremely long fibers is excellent in flexibility, but the contact area between the extremely elongated fibers in the extremely elongated fiber bundle is increased and is contradicted. There is a tendency for the flexibility to deteriorate. Further, in the cross-sectional shape of the extremely elongated fiber bundle, it is deformed by a compressive force perpendicular to the fiber axis, that is, it is easy to cause flattening, and the fiber bundle -26 - 201000713 becomes widened between the fibers. Loose, the bulkiness of the fiber bundle increases. The critical threshold of densification of the non-woven fabric is low. This bulkiness is also the same at the stage of the island-in-the-sea fiber, and the fiber is easily flattened in cross-sectional shape. The fiber cross-section effect of the non-woven fabric structure is lowered, and the densification is prevented before the sea component is removed. For this reason, it is understood that the fiber bundle must be at least 7 strands or less, and the flatness of the extremely elongated fiber bundle of the final artificial leather substrate must be 4. 0 or less, preferably 3 _ 0 or less. Moreover, by the disadvantage of flattening the extremely elongated fiber bundle, in particular, the surface of the substrate for artificial leather is significantly 'the width of the fiber bundle when viewed from the surface, that is, the projected size of the extremely elongated fiber bundle is 10 to 60 μm. Good, preferably 1 5~4 5 μ m. When the projection size of the extremely long fiber bundle is larger than 60 μm, the densification of the fiber bundle is insufficient, and in particular, as the pile-like artificial leather, the bundle of woven fibers which can form the pile is reduced, and only the surface of the pile having a low appearance quality can be obtained. . In addition, when the projection size of the extremely thin fiber bundle is less than 1 〇μπι, the fiber bundle is extremely easy to densify, but the fiber bundle is not completely flattened, and the diameter of the fiber bundle itself is less than 1 Ομηι, which is very fine, especially Even when the fluff of the fluff-like artificial leather is formed, since the fiber bundle is easily cut by the raising process, the pile is reduced, and it is difficult to obtain a good appearance quality, and the surface is not excellent in abrasion resistance. When the non-woven fabric structure of the base material for artificial leather is formed by forming the extremely elongated fiber bundle having the above characteristics, the number of cross-sections of the extremely elongated fiber bundle which is almost perpendicular to the cross section can be obtained in any cross section parallel to the thickness direction thereof. 1 5 0 0~3 0 0 / m m2, an extremely dense fiber assembly structure that is not known in the prior art. When it is less than 15 〇〇 / mm 2 , only the density of the ultrafine fiber bundle becomes small, and -27 - 201000713 produces a space where there is no ultrafine fiber bundle, and there is a tendency that the density of the ultrafine fiber bundle is reduced. In the case where there is no uniform dispersion, there is almost no tendency to have a loose range of a dense range, and the texture of the continuous film forming a thick polymer elastomer is artificially changed due to the space generated between the ultrafine fiber bundles becoming large. Hard 'is caused by the appearance of surface appearance or deterioration of surface properties by extremely thick spots. When it is more than 3,000 / mm 2 , the observed fiber assembly is a dense fiber assembly formed by the substrate for artificial leather of the present invention, but only by the heat pressing treatment or the like, only the nonwoven fabric structure is in the thickness direction. By the contraction force of the woven fabric or the like which is bonded to the non-woven fabric structure, the structure is forced to compress only in the longitudinal direction or the width direction, and collapses and flattens in the direction in which the ultrafine fiber bundle is compressed. The physical properties are lowered or the texture is hardened, and it is preferably 2 〇 00 to 27 〇 0 pieces/mm. The base material for artificial leather using a conventional non-woven fabric structure is densified by a non-woven fabric structure by a complexing treatment or the like. At the beginning of the stage, the thickness of the fiber becomes a thickness of about 300 to 600 /zm 2 when the fiber bundle is in the form of an ultrafine fiber bundle. Therefore, the densification of the nonwoven fabric is insufficient at the stage of becoming a very fine fiber bundle. As a result of the formation of the ultrafine fiber bundle, the number density of the cross section of the ultrafine fiber bundle is as high as about 200 to 600 pieces/mm2, and also about as much as 750 pieces/mm2. Assuming that a non-woven fabric having a number density of the ultrafine fiber bundles of more than 750/mm2 is produced in the prior art, the fiber bundle itself is damaged by excessive needling treatment, and is forced by the above-described hot pressing or the like. The compression treatment causes the cross-sectional shape of the fiber bundle to be greatly deformed, or the densification by the treatment alone, and there is a large spot in the gap between the fiber bundles, and the obtained substrate for artificial leather and the present invention The target is completely different. -28 - 201000713 Moreover, the number density of the fiber bundle is about 200 to 6 〇〇/mm2. The woven fabric structure contains a polymer elastomer, and the number density of the ultrafine fiber bundles is reduced. The continuous film of the polymer elastic body of the ultrafine fiber bundle not only becomes a texture of the composite structure of the non-woven fabric molecular elastic body but also becomes harder and harder, and the fiber or the polymer elastic body is densely gathered and the fiber and the polymer elastic are dispersed. The body is almost completely absent from the range to the one with a large rough spot. On the other hand, the present invention has a structure in which the ultrafine fiber bundles are extremely densely and uniformly assembled, and when the non-woven fabric structure contains the polymeric elastomer, the continuous elastic film of the polymeric elastomer formed between the fiber bundles can be used. The thick and high-molecular elastomer is also made of a smaller element, and the same can be used to suppress the occurrence of significant coarse spots on the inside of the substrate for artificial leather. The present invention is extremely fine by the extremely elongated fiber bundle structure satisfying the above requirements. The fiber diameter of the long fiber itself does not particularly form a fluffy surface having a beautiful appearance or tactile sensation for the purpose of the present invention. 8~15μηι is better, more 〜~13μηι, especially better. 2~ΙΟμπι, the best one is 1. When the fiber diameter of the elongated fiber is more than 15 μm, the appearance quality of the elongated fiber is adversely affected. For example, the smoothness of the touch point of the surface is impaired, so it is not desirable. In addition, when the fiber diameter of the dimension is less than 1.0 μm, the fluffy artificial leather has a fluffy feel, which is a dense one, but the overall effect on the appearance quality or the appearance is poor. For example, the villus color of the surface is determined by the amount of whitening, and the thickness of the body and the high texture are formed, and the range of the texture is not obtained, so that the ultra-fine structure of the woven fabric can be made thinner and evenly distributed. It is not limited by the weaving, so at least the giant is 1. 0 . 5 μ m. Extremely artificial leather color produces plaques. Although extremely thin and fine fibers are produced in the form of surface properties, the surface abrasion resistance such as peeling resistance of -29 - 201000713 is also deteriorated. When the weight per unit area or thickness of the obtained long fiber web is insufficient, the rubbing treatment is performed at a desired unit weight area and thickness (a long fiber web is supplied in a direction perpendicular to the flow direction of the step, and almost All are folded in the width direction, or the web supplied in a direction parallel to the flow direction of the step is folded toward its length) or the volume is made to overlap a plurality of long fiber webs. When the form stability of the non-woven fabric structure formed by the sea-island type fiber or the denseness of the fiber is insufficient, when the sea-island type fiber of the non-woven fabric structure is aligned in the thickness direction, the conventional method such as a needle punching method is used. Mechanical complexation treatment. Thereby, a three-dimensional complexing treatment can be carried out between the fibers of the constituting fiber web, in particular, the layers adjacent to the layered long fiber web which is rubbed or laminated. When performing the complexing treatment by the needle punching method, 'the type of knitting needle (the shape or number of the needle, the shape or depth of the thread, the number or position of the thread), and the number of needles of the needle (needle) The needle density of the needle in the void and the needling area per unit area of the number of strokes acting on the unit area of the long fiber web, and the needle depth of the needle (for long fibers) Various processing conditions such as the depth of the action of the knitting needle in the fiber web are carried out. The type of the knitting needle can be appropriately used in the same manner as when the artificial leather is produced by using the conventional short fiber. However, in terms of the effect of the present invention, the number of the knitting needle, the eucalyptus of the blue silk, and the number of the silking It is particularly important to use a knitting needle of the following type. The number of the knitting needle is such that the density or surface quality obtained after the treatment is affected, and at least the size of the blade portion (the portion of the -30 - 201000713 of the crepe forming the front end of the knitting needle) must be less than 3 〇 ( Fine) (the degree of the tube when the cross-sectional shape is an equilateral triangle) or the diameter of the circle is about 0. 73~0_75mm), preferably 32 (about 0. 68~〇_7〇rnrn)~46 (about 0. The range of 33~0_35mm) is better than 36 (about 〇58~〇. 60mm) ~ 43 (about 0. 38~ 0. 40mm) range. The size of the blade portion is larger than the size of the 3 ( (thick) needle, the W shape has a high degree of freedom of shape or depth, and the strength or durability of the needle is better 'I 隹 contrary to the surface of the nonwoven structure Large aperture woven ten thorns? The L trace 'cannot produce a dense fiber assembly state or surface quality for the purpose of the present invention. Further, since the friction between the fibers in the long fiber web and the knitting needle becomes too large, it is not necessary to provide an excessive amount of the oil for needling treatment. Further, the knitting needle having a size of the blade portion smaller than 46, the strength or durability is not only industrially produced, and it is impossible to set a twist of a proper depth in the present invention. The cross-sectional shape of the blade portion is preferably an equilateral triangle in the present invention in terms of the ease of stretching of the fiber or the low frictional force. The depth of the crepe of the present invention is the height from the deepest portion of the crepe to the front end of the crepe. The general shape of the filature refers to the degree of the end of the crepe which protrudes from the side of the self-woven needle on the outer side (also referred to as upward bending), and the depth of the deepest part of the crepe formed from the side of the self-woven needle to the inner side. (also known as the depth of the slit). The depth of the silk is at least the diameter of the island-type fiber, and preferably less than 120 μm. When the depth of the silk is lower than the diameter of the island-type fiber, the island-type fiber is extremely difficult to be hooked into a silk, so it is not desirable. In addition, when the depth of the filature is more than 120 μm, the fiber is easily hooked, and on the other hand, the needle of the large-diameter is likely to remain on the surface of the nonwoven structure, and the dense fiber state of the object of the present invention is not easily obtained or Surface quality. Further, in 201000713, the depth of the crepe is preferably any number in the range of 7 to 1 〇 2 times for the diameter of the island-type fiber. The more preferable one is selected from the range of 2 · 〇 to 7 〇. When the depth of the silk is less than 1 _ 7 times, the island-type fiber is not easy to be hooked into a silk, and even if the number of needles is increased, the complexing effect cannot be obtained, and more than 1 0. When it is twice as large, the ease of hooking of the island-type fiber is increased, and of course, there is a tendency that the damage of the island-type fiber is severed or broken, so that it is not desired. The number of twisted yarns of the present invention is appropriately selected under the effect of the desired complexing effect within the range of 1 to 9 hooks. When the dense non-woven fabric structure necessary for the present invention is obtained, the needle-punching complex treatment is mainly used. The needle used, that is, at least 50 °/ of the number of needles described below. For the needles used in the above acupuncture treatment, the number of threads must be 6 needle hooks. Further, in the present invention, the number of threads of the knitting needle used in the needle-punching treatment is not necessarily one, and for example, one needle hook and six needle hooks, three needle hooks, and six needles may be appropriately combined. Needle hooks, 6 needle hooks and 9 needle hooks, 1 needle hook and 6 needle hooks and 9 needle hooks, etc., can be used in any order. In a needle having a plurality of needle hooks, the position of each thread is completely different from the distance from the front end of the needle, and the number of strands having the same distance. The knitting needle of the latter, for example, the cross-sectional shape of the blade portion is a regular double-angle. Each of the three vertices is attached to the front end of each of the hooks, and the knitting needle is attached to the same distance. In the present invention, the knitting needle mainly used in the complexing treatment is the knitting needle of the former. This is a knitting needle with a plurality of needle hooks at the same distance. Since the blade portion of the knitting needle has a thick portion and a large thickness of the thread, the complexing effect is high, but the blade portion is excessive. Significant shortcomings of thick and silky. In addition, when the needle is excessively subjected to the needling treatment by the woven fabric of the latter, the number of the fibers in the thickness direction of the non-woven fabric structure becomes excessive. Therefore, there is a tendency that it is difficult to obtain a dense structure for the purpose of the present invention. In other words, in any cross section parallel to the thickness of the nonwoven fabric structure, there are many fibers which are almost parallel to the cross section, and the number density of fibers perpendicular to the cross section tends to be extremely reduced. However, since a strong complexing effect can be obtained even with a small number of twisted yarns, it is preferable to use the latter knitting needle in the partial complexing treatment. For example, in any f:r 1 stage from the initial stage to the middle stage of the complexation treatment, the knitting needles are subjected to complexation treatment under the dense structure which does not impair the target, and then the needle of the former is used to form the dense object of the target. The method of construction is one of the preferred forms. Further, in the present invention, when the number of twisted yarns is six needle hooks, the total number of twisted yarns that pass through the nonwoven fabric structure at the tip end of the needle to the twisted yarn that does not penetrate and substantially acts on the nonwoven fabric structure is obtained. It does not contain silk which does not act on the portion of the nonwoven structure. For example, when the number of filatures formed in the knitting needle is 9 needle hooks, when the needle is spurted to the deepest point, the complex where the three needle hook crepe remains in the non-woven fabric structure is used. . . In the case of the I condition, the effect is substantially the same as the needling treatment with six needle hooks. The total number of needles of the needles is preferably in the range of 800 to 4 〇 〇 0 needles / c m 2 , and more preferably in the range of 1 000 to 35 inches of acupuncture / cm 2 . When the knitting needle having a plurality of twisting wires at the same distance is used, the number of needles in the needling treatment is about 30 〇 acupuncture/cm 2 or less. Preferably, the number of needles is about 10 to 2 50 needles/c. The range of m2. When a needle punching process of more than 300 needle punches/cm2 is performed using the knitting needles having a plurality of twists at the same distance as described above, since the fibers are mostly aligned toward the thickness side -33 - 201000713, even after use, another The needle punching treatment, the heat shrinkage treatment, the pressing treatment, and the like of the knitting needles tend to make it difficult to increase the number density of the nonwoven fabric structure. When the total number of needles of the knitting needle is less than 800 needles/cm2, not only the densification is insufficient, but the integration of the nonwoven fabric structure by the fiber complexing treatment between the different layers of the long fiber web tends to be insufficient. When it is more than 4,000 needles/cm2 or less, depending on the shape of the needle, the needle of the fiber may be damaged by cutting or cracking, and when the damage of the fiber is particularly serious, the nonwoven fabric structure The shape stability of the body is large and the density is reduced and the compactness is also reduced. The obtained nonwoven fabric structure and the substrate for artificial leather have mechanical properties such as dimensional stability and tensile strength, and alignment properties of fibers in the thickness direction, and the thickness of the long fiber web is higher than that of the needle. More effective is better. Therefore, the needle-punching depth of the needle is set to be at least the depth of the filament at the most front end side of the needle passing through the entire thickness of the long fiber web. In particular, in the knitting needle in which the twisted yarn which is necessary for the present invention is six needle hooks, in order to maximize the complexing effect of the object of the present invention, it is important that all of the twisted yarns have no through-seam. In other words, the filament that is furthest from the front end acts on the needle by the depth of the needle stuck in the long fiber web. When all the filatures are passed, the dense fibers of the purpose of the present invention cannot be obtained because the filaments of the six hooks are protruded from the entire fiber web by the hooked long fibers. It is preferable that the number of the filaments passing through the long fiber web is 2 needle hooks to 5 needle hooks of the 6 needle hooks, and more preferably 3 needle hooks or 4 needle hooks. Moreover, 'in the case of a dense structure that is not conventionally known, the above-mentioned needling of more than 50% of the number of needlings must be set at the front end of the needle. -34-201000713 is a needle punch through the long fiber web. The depth is such that the twisting of more than 70% of the needles at the front end of the needle is preferably set by the depth of the needled web of the long fiber web. However, when the depth of the acupuncture treatment is too deep, when the silk thread is 6 needle-crocheted needles, not only the above-mentioned dense structure cannot be obtained as described above, but the silk thread is one needle hook and two needle hooks '3 needle hooks. , 4 needle hooks, 5 needle hooks, or 7 needle hooks, 8 needle hooks, 9 needle hooks, or 1 needle needle hook or more, the needle is not depending on the number of silk, Since the damage of the fiber is remarkable by the twisted yarn, the fiber tends to be cut at an extreme time, or the needle streak tends to remain on the surface of the nonwoven fabric structure. Therefore, when setting the needling condition, it is necessary to pay special attention to such a condition. situation. In order to suppress the damage or cutting of the fiber by the needling treatment, and to suppress the charging or heat generated by the strong friction between the knitting needle and the fiber, the manufacturing process of the long fiber web is followed by It is preferred to impart an oil agent in any stage prior to the combination of the treatment steps. The method of imparting can be carried out by a spray coating method, a reversible roll coating method, a contact roll coating method, a slit coating method, etc., where the spray coating method is non-contact to the long fiber web and can be used. The low-viscosity 'oil agent which is impregnated in the inner layer of the long fiber web for a short time is the best. Further, the term "long fiber web" as referred to herein is a step in which the sea-island type fiber is subjected to melt spinning treatment and captured on a collecting surface of a mobile net or the like. After the stage of accumulation. In the present invention, the oil agent applied before the complexation treatment may be an oil agent formed of one component', or may be a plurality of oil agents having different effects, such that the mixture is mixed with or Give. The oil agent used in the present invention is a friction effect between the knitting needle and the @Μ, and the smoothing effect of the friction between the metal and the polymer is high. -35-201000713 Oil agent 'Specifically, mineral oil type oil or poly Stone: In the latter case, when the oxyalkylene oxide is the main component of dimethyloxane and the oil agent with high smoothing effect, the hook effect of the smoothing effect wire will cause the complexing effect to be locally suppressed due to the friction between the fibers. The coefficient is significantly reduced, and it is better to use an oil agent having a high combined friction effect when there is no purpose. However, since the sea-island type fiber-like polymer in the present invention causes the fiber to become a very fine fiber bundle, the polyoxyalkylene-based oil agent does not become a fine fiber to the stage of the substrate for artificial leather, the surface of the fine fiber or On the surface of the polymeric elastomer. When the leather substrate is used for fluffy artificial leather, it is left in the typical water bath treatment (for example, the staining state is spotted), or it is completely removed in the bath, and the residual oil agent is used to make the fluffy fiber. The fixed state on the upper side is weakened, and it is easy to peel off, etc., and the polyoxyalkylene-based oil agent is used. In addition to mineral oil-based oils, the use of friction-induced significant static agents (such as polyoxyalkylene-based surfactants, etc. as the average number density of non-woven fabrics formed by the island-type fiber formation stage (parallel to the thickness direction) The number of pieces per unit area of the cross section of the cut fiber is preferably from 11 〇〇 to 3,000 pieces/mm 2 , and any 値 in the range of /mm 2 . To obtain the oxyalkylene oil agent. Preferably, the agent is more preferable. When the use of the capsule is too strong, the water is dissolved in water or the aqueous solution by using a hydration reduction, in particular, a method of maintaining the complex state, for example, a mineral oil system. It is easy to remove most of them, and the obtained artificial product is not defective in the nonwoven structure after the processing of the oil-forming treatment spot or the like by the production, and in particular, the oil agent and the polyoxyalkylene system are required.界面Use interface activity 静电 electrostatic agent) is preferred. In the structure, the final surface is almost 1000~3500 with the section perpendicular to 1200~2500. The average density range is -36 - 201000713. In the dense structure, after the complex treatment of acupuncture treatment, etc. It is treated by heat shrinkage of discarded warm water 'vapor. The dense structure for the purpose of the present invention can be finally obtained by combining one or several such treatments. Of course, in addition to the treatment or shrinkage treatment, it is preferred to carry out the pressing treatment. When pressing and complexing treatment, it may be carried out before or after the complexation treatment, or may be simultaneously subjected to pressing treatment and complexation treatment. Further, when it is used in the shrinking treatment, it is carried out before or after the shrinking treatment, but the pressing process and the shrinking process are simultaneously performed, and the shrinkage state becomes uneven, so that it is not desired. The heat shrinkage treatment is carried out after the needling treatment, and it is necessary to carry out the wet heat treatment in the present invention. The wet heat treatment is a heat shrinkage treatment in which the acupuncture is subjected to a complex treatment or a high temperature and high humidity gas atmosphere in a desired high density. For example, when the density of the non-woven fabric having an average density of about 800 ft/mm2 is obtained, the densification is first performed by acupuncture to 305 to 750/mm2, and then the target is obtained. Heat shrinkage treatment. In the case of the heat shrinkage treatment, the long fiber web is formed of a sea-island type fiber containing a heat-shrinkable component, and a long fiber web made of a shrinkable fiber other than the sea-island type fiber, and a shrinkage produced by the laminate. A fibrous web is preferred. In order to obtain a heat-receiving island-type fiber, a heat-shrinkable polymer may be used as the sea component, the island component polymer, or both, but in the invention, at least the above-mentioned heat-shrinkable polymer is used. As an island ingredient. The conditions of the wet heat shrinkage treatment are as long as at least the island component is polymerized to have sufficient shrinkage action, and the sea component polymer is expanded. The temperature condition without dissolution is not particularly limited, and the complex treatment of V wind, etc. is carried out at least 100% of the weaving property on the receiving side, and the fiber shrinkage polymerization must be used in the polymer. Plastically tempered -37 - 201000713 The heat shrinkage treatment method or the processing amount of the object to be treated is appropriately set, for example, by continuously supplying saturated water vapor at a temperature of 65 〜 l 〇〇 ° C, relative humidity a method of introducing into any environment of temperature and humidity within the range of 70 to 100%, or for supplying a sufficient amount of water in the non-woven structure to expand the sea component polymer, or plasticizing, or any subsequent supply The method is a preferred embodiment in which the shrinkage of the island component polymer and the expansion of the sea component polymer and the heat required for plasticization are continuously applied to the nonwoven fabric structure. The method of imparting heat to the non-woven fabric structure to which moisture is applied is a method of introducing a temperature controlled environment, a method of causing air of a temperature to directly act on the nonwoven fabric structure, or an electromagnetic wave such as infrared rays. A method in which the nonwoven fabric structure acts and the nonwoven fabric structure is heated to a desired temperature is a preferred example. When the area is widened, the non-woven fabric structure is likely to cause spots in the heat-shrinking state depending on the influence of its own weight, and the purpose of controlling the shrinkage start point or the shrinking speed is to determine the length direction of the sheet-like nonwoven fabric structure. Depending on the position in the width direction, it is preferable to control different temperature conditions. In addition to the complexing treatment or the heat shrinkage treatment by the above-mentioned needling treatment, the following polymer elastomer is impregnated in advance for the purpose of densifying and tempering the nonwoven fabric structure formed by the sea-island type fiber. Processing, depending on #m _ is better by pressing. For example, when the average density of the non-woven fabric is about 1000 to 12,000/mm2, the heat treatment can be performed until the heat shrinkage treatment is performed until the densification is 600 to 900/mm2. The compactness of the target. Specific examples of the pressing treatment, such as a method of directly pressing in a wet state after the above-mentioned wet heat shrinkage treatment, & _ _ @ -38 - 201000713 shrinking treatment, drying in a dry state, without drying at all A method of pressing under a state in which a part of water remains. For example, the temperature of the press treatment is a method of hardening the softening component at a temperature lower than the surface temperature of the nonwoven fabric structure and pressing the surface before the heat cooling of the wet heat shrinkage treatment or the drying treatment, and the surface of the nonwoven fabric structure. A method of softening a component at a higher temperature, and then evaporating and compressing the water. By this treatment method, since the densification by the press treatment is performed almost simultaneously with the heat shrinkage treatment, the uniform densification state can be obtained only by performing the press treatment, and excellent production efficiency can be obtained. In the sea-island type fiber constituting the non-woven fabric structure, the softening temperature of the sea component polymer is lower than the softening temperature of the island component polymer by 20 ° C or more, preferably lower than 30 ° C. The pressing treatment of the treatment is more effective by densification. At this time, by heating from the softening temperature of the near-sea component polymer to a temperature range lower than the softening temperature of the island component polymer and the contraction temperature of the island component polymer is higher, only the sea component polymerization in the sea-island type fiber The shrinkable island component polymer is shrunk in a state where the object is softened or nearly softened, and the degree of freedom of the island component is increased. When the shrinkage is sufficiently performed, when the nonwoven fabric structure is subjected to a pressing treatment in a state where the softening temperature of the sea component polymer is not lowered, the nonwoven fabric structure is compressed to a more dense state, and the article is cooled to room temperature. A nonwoven fabric structure fixed in a desired dense state can be obtained. In addition to the advantages of densification of the press treatment, for example, the surface of the nonwoven fabric structure can be fixed in a smoother state. By the smoothing treatment, the extremely dense collection of the extremely fine fiber bundles of the largest characteristics of the leather substrate of the present invention can be more effectively produced. In other words, since the surface of the base material for artificial leather can be made smoother, the amount of honing of the pile forming treatment by the rubbing treatment or the like can be reduced when the pile-like artificial leather is produced, and when the granular artificial leather is produced, The surface of the substrate is not subjected to heat pressing or rubbing treatment, etc., and a very fine grain layer having a smooth thickness of 50 μm or less can be stably formed. In the dense non-woven fabric structure having a number density of 1000 to 3500 pieces/mm2, preferably 1300 to 3,000 pieces/mm2, the polymer is required to be contained before or after removal of the sea component polymer. Elastomer. The method contained therein is, for example, a method of impregnating a solution or dispersion of a polymeric elastomer, and solidifying by a conventional dry method or wet method. The impregnation method may be a method in which a non-woven fabric structure is immersed in a bath filled with a polymer elastomer liquid and then subjected to a torsion in a liquid-containing state by a pressing roll or the like, that is, a dipping method or a bar coating. Any of various conventional coating methods such as a method, a knife coating method, a roll coating method, a vertical coating method, and a spray coating method. There may be one method or a combination of several methods. The polymer elastomer contained in the nonwoven fabric structure may be any conventional user of the substrate for artificial leather, and may be used, for example, a polyurethane elastomer, an acrylonitrile elastomer, or an olefin. The elastomer, the polyester elastomer, the acrylic elastomer, preferably at least one selected from the group consisting of polyurethane elastomers and acrylic elastomers. The polyurethane elastic system may be at least one polymer polyol selected from the group consisting of polyester diol, polyether diol, polyether ester diol, polycarbonate diol, etc., having an average molecular weight of 500 to 3,000. And at least one aromatic, alicyclic selected from the group consisting of 4,4'-diphenylmethane diisocyanate, isophorone diiso-40 - 201000713 cyanate vinegar, hexamethylene diisocyanate, and the like A combination of a polyisocyanate such as an aliphatic diisocyanate as a main component and a combination of at least one low molecular compound having two or more active hydrogen atoms such as ethylene glycol or ethylenediamine at a predetermined molar ratio Polymerization of various polyurethane elastomer 'polyurethane elastomers obtained by polymerization by one-stage or multi-stage polymerization by a melt polymerization method, a bulk polymerization method, a solution polymerization method, or the like The content of the polyol component is preferably from 1 5 to 90% by mass. Further, the acrylic elastomer's glass transition temperature of the homopolymer is in the range of -90 to -5 T: preferably a non-crosslinkable monomer, for example, at least one selected from the group consisting of methyl acrylate and butyl acrylate. a soft component such as an ester, isobutyl acrylate, isopropyl acrylate, n-hexyl (meth)acrylate or 2-ethylhexyl (meth)acrylate, and a glass transition temperature of the homopolymer thereof is 50 to 2 5 a range of 0 ° C, preferably a non-crosslinkable monomer, for example at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, A The hard component such as cyclohexyl acrylate or (meth)acrylic acid is reacted with a monofunctional or polyfunctional ethylenically unsaturated monomer unit obtained by forming a crosslinked structure or an ethylenically unsaturated monomer unit introduced into the polymer chain. a compound obtained by reacting to form a crosslinked structure, for example, at least one selected from the group consisting of ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4 -butanediol II Various acrylic elastomers obtained by polymerization of an ethylenically unsaturated monomer formed of a crosslinking-forming component such as (meth) acrylate. The base material for artificial leather obtained by using a polyurethane elastomer as a main body elastomer is excellent in balance of texture or mechanical properties, and includes durability - 41-201000713 good. Further, in the base material for artificial leather obtained by using an acrylic elastomer, when the acrylic elastomer is compared with the polyurethane elastomer, the adhesion to the extremely thin fiber bundle is low, and the pile fixing effect at the time of formation of the pile is lacking. It is not easy to form a fluffy artificial leather, and since the degree of hardening of the texture can be suppressed in terms of content, it is more preferable to form a grain-like artificial leather. The polymer elastomer may be mixed with different types, or may be different in number, and may contain a polymer such as a synthetic rubber or a polyester elastomer as needed in addition to the polymer elastic body containing the main body. The elastomeric f elastomer elastomer composition. The polymer elastomer liquid such as a solution or a dispersion of a polymer elastomer is impregnated into the nonwoven fabric structure, and then the polymer elastomer is solidified by a conventional dry method or a wet method to form a polymer elastomer. Fixed in the body of the non-woven fabric. The dry method referred to herein means a method in which all of the solvent or the dispersing agent is removed by a drying treatment or the like, and the polymeric elastomer is fixed in the nonwoven fabric structure. Further, the wet method referred to herein means a non-woven fabric structure in which all of the polymer elastomer liquid is impregnated with a polymer elastomer.
S 非溶劑或凝固劑處理，且採用添加有感熱凝膠化劑等之高 分子彈性體液’使含浸後之不織布構造體進行加熱處理， 預先除去溶劑或分散劑，使高分子彈性體固定於不織布構 造體內’或完全固定的方法。而且，爲使經凝固的高分子 彈性體完全固定時，以於溶劑或分散劑除去後進行加熱處 理等之硬化處理較佳。 高分子彈性體液之濃度、即高分子彈性體液中之高分 子彈性體的含量，以〇 .；!〜6 〇質量％較佳。於高分子彈性體 -42 - 201000713 液中’在不會損害最終所得的人造皮革用基材之性質的範 圍內，適當配合染料或顏料等之著色劑、凝固調整劑、抗 氧化劑、紫外線吸收劑、螢光劑、防黴劑、浸透劑、消泡 劑、平滑劑、防水劑、防油劑、增黏劑、增量劑、硬化促 進劑、發泡劑、聚乙烯醇或羧基甲基纖維素等之水溶性高 分子化合物等習知之人造皮革用基材中所含的高分子彈性 體液中所配合的各種添加劑。不織布構造體中含有的高分 子彈性體或高分子彈性體組成物之量，於目的之用途中， 視必要的力學物性、耐久性、質感等而定予以適當調整， 惟由極細纖維束所形成的不織布構造體之單位體積重量爲 1 0 0時’對此而言高分子彈性體之單位面積重量以1〜8 〇 質量％之範圍較佳，以2〜6 0質量％之範圍更佳，以5〜4 0 質量。/。之範圍最佳。高分子彈性體之含量低於1質量％時， 由於無法均勻地含有高分子彈性體，故人造皮革用基材內 部之高分子彈性體的含有斑點變得激烈，作爲人造皮革用 基材之品質不易予以安定化。另外，高分子彈性體之含量 “ 大於8 0質量％時，由於不織布構造體極爲緻密，就人造皮 革用基材之質感顯著硬化而言橡膠感變強，故不爲企求。 於本發明中，採用自於高分子彈性體含有前或含有後 之構成不織布構造體的海島型纖維除去海成分聚合物的方 法，爲島成分聚合物之非溶劑或非分散劑，使含有高分子 彈性體後予以除去時，以具有高分子彈性體之非溶劑或非 分散劑之液體、且具有海成分聚合物之溶劑或分散劑的液 體處理不織布構造體的方法。例如，使用可溶於如上述聚 -43 - 201000713 乙烯醇等之水中的聚合物作爲海成分聚合物時，只要是該 聚合物以可溶的溫度之溫水予以除去即可，另外，彳吏$ <吏 含有上述磺酸鹼金屬鹽之化合物等予以共聚合的易驗分解 性之改性聚酯作爲海成分聚合物時，係可使用使氫氧化鈉 水溶液等之鹼性分解劑的水溶液在適當溫度下予以除$。 藉由該海成分聚合物除去處理，係使海島型纖維變成由島 成分聚合物所形成的極細長纖維束，製得具有較佳者爲300 〜1 8 0 0 g/m2之單位面積重量的本發明人造皮革用基材。 藉由使海島型纖維變成極細長纖維束所得的人造皮革 用基材中，與習知的人造皮革用基材之決定性不同處，除 上述各點外，例如在極細長纖維束間所形成的空隙尺寸爲 7 0μιη以下，較佳者爲60μιη以下之極小値，且均勻、尺寸 小的斑點。此係使海島型纖維予以紡紗、積層，形成經3 次元絡合的不織布構造體之過程中，（1 )使截面積約爲 350μηι2以下、即纖維直徑約爲21μηι以下，且不易扁平化 的島數之海島型纖維進行紡紗，且在長纖維形態下直接形 成纖維網’在直至形成人造皮革用基材之間不易達到不需 的大體積性之狀態下形成不織布構造體，（2)使長纖維纖維 網進行3次元絡合處理時，於主體之針刺處理時使用6根 針鈎的繭絲之織針，在厚度方向使繭絲貫通的條件下進 行，經過廣泛範圍使相同纖維爲連續的狀態下以無規配置 的長纖維所形成的不織布構造體上，沒有於特有的纖維配 置狀態下以極佳平衡性進行緻密化與3次元絡合化處理， 藉此於不織布構造體之截面上纖維以接近充分高的數密度 -44 - 201000713 予以積層，及（3 )組合水溶性聚合物與熱收縮性聚合物作爲 海島型纖維之構成成分，且使熱收縮處理在濕熱環境下進 行，不織布構造體藉由熱收縮予以緻密化時，使海成分於 / 瞬間膨脹f可塑化，可使島成分收縮至接近理想的水準， 然而，爲使島成分之纖維直徑藉由收縮，可粗徑化至接近 理想的水準時，海島型纖維沿著纖維軸容易進行收縮，不 易達成習知的海島型纖維於收縮時藉由無規暴亂作用以排 除鄰接的纖維之效果，以及（4)爲使海成分進行溶解、分解 時，由於以較習知的有機溶劑之分子尺寸更小、具有極性 之水作爲介質，在海成分聚合物內溶劑分子之擴散速度較 爲快速，且自膨脹至溶解的狀態安定，使海成分聚合物之 溶解物順序排出於構造體外時，由於必須施加液壓或機械 硬力等之情形少，與習知相比時，爲極緻密化的本發明之 不織布構造體，不會使極細纖維束間之空隙尺寸擴大，可 容易排出海成分分解物之要因，係全部爲被複合化的結果。 於所得的人造皮革用基材中，爲製造適合於製造極細 " 纖維束間之空隙尺寸更爲均勻化、具有更爲緻密外觀品質 之絨毛狀人造皮革、或皺摺更微細的粒面狀人造皮革之人 造皮革用基材時，以先於人造皮革製品之表側的表面上塗 布易萃取性高分子之溶液、水分散液或溶液，使易萃取高 分子硬化較佳。本發明於繼後步驟之摩擦處理中，以可製 得習知不具有的緻密化的不織布構造，同時可製得更爲平 滑且均句的絨毛表面爲目的時，實施在人造皮革製品之表 側的表面上塗布高分子彈性體之水分散液，使高分子彈性 -45 - 體硬 等予 藉由 之深 100- 此外 皮革 平滑 表面 間之 緻密 性體 分子 等、 易萃 照相 輥塗 的液 如藉 察人 皮革 相同 201000713 化後’預先賦予易萃取性高分子時，使該物藉由 以除去的步驟。然後’有關賦予高分子彈性體之 進行加壓且硏磨處理’不僅使自原有表面至20〜 度的範圍進行硏磨除去，且自硏磨處理後之表面 -300μηι之深度的範圍，可使不織布構造更爲緻密 ，可預先於上述之表面上供應高分子彈性體，使 用基材之表面或裡面藉由摩擦處理或壓延處理等 化。所得的人造皮革用基材’不僅可藉由硏磨處 平滑化’且評估自表面至200μηι之範圍的極細纖 平均空隙尺寸爲10〜40μηι之範圍，形成極爲均 狀態。 易萃取性高分子之例，如聚乙烯醇、聚胺基甲酸 、丙烯酸彈性體、聚乙二醇、石蠟、聚乙烯蠟等 彈性體之例，如聚胺基甲酸酯彈性體或丙烯酸彈 與上述不織布構造體所含的高分子彈性體相同之 取性高分子、高分子彈性體之塗布方法，例如可 凹版輥塗布法、旋轉篩網塗布法、噴霧塗布法、 布法等之習知塗布法，其中以照相凹版塗布法就 體黏度與塗布量之平衡性而言較佳。硏磨處理之 由砂紙予以摩擦處理，砂紙之加壓水準，可以一 造皮革用基材之表面狀態，且一面評估處理後之 用基材之截面狀態予以適當調整，設定於最適値 使該所得的人造皮革用基材與製造上述之人造皮 地，視其所需朝厚度方向切成數張，使裏面之面 溶解 面， ^ 200 至約 化。 人造 予以 理使 維束 勻的 酯彈 〇局 性體 例。 採用 可逆 塗布 例， 面觀 人造 〇 革時 上進 -46- 201000713 行硏磨等以調整厚度，且在裏面之面或表面之面上以含有 高分子彈性體或極細纖維束之溶劑的液體進行處理。然 後’至少使表面之面藉由摩擦處理等之方法進行起毛處 理’形成以極細纖維爲主體之纖維絨毛面，可製得絨毛狀 或正絨牛皮革狀等之絨毛狀人造皮革。另外，在表面之面 上形成由高分子彈性體所形成的被覆層，可製得粒面狀人 造皮革。 於形成纖維絨毛面時，可使用任何的砂紙或針布等進 行摩擦處理、或刷毛處理等之習知方法。而且，可於該起 毛處理前或後，使高分子彈性體或極細纖維束予以溶解或 膨脹之溶劑，例如高分子彈性體爲聚胺基甲酸酯彈性體 時’可在起毛處理的表面上塗布含有二甲基甲醯胺（DMF) 等之處理液；或極細纖維束爲聚醯胺系樹脂時，可在起毛 處理的表面上塗布含有間苯二酚等之苯酚系化合物的處理 液。藉此可微調藉由高分子彈性體或極細纖維束之黏合導 致的極細纖維束之拘束狀態、絨毛狀人造皮革之極細纖維 f ... 絨毛長度、表面摩擦耐久性等。 於由高分子彈性體所形成的被覆層之形成時，可使用 直接在人造皮革用基材表面上供應含高分子彈性體之液體 的方法、或在剝離紙等之支持基材上塗布該液體後、貼合 於人造皮革用基材的方法等習知方法中之任何方法。形成 的被覆層所使用的高分子彈性體，只要是與習知高分子彈 性體中所含有的高分子彈性體相同者等、作爲習知粒面狀 人造皮革的被覆層之習知高分子彈性體即可，皆可採用。 -47 - 201000713 形成的被覆層之厚度約爲300μηι以下時，由於可製造與本 發明之人造皮革用基材之充分質感平衡的粒面狀人造皮 革，沒有特別的限制。製造本發明之人造皮革用基材的最 大特徵之藉由極細纖維束形成緻密的集合狀態所得的極爲 平滑且具有均勻表面層之粒面狀人造皮革時，厚度約爲 ΙΟΟμιη以下，較佳者約爲80μιη以下，更佳者約爲3〜50μιη 之範圍內形成被覆層，藉由形成該厚度之被覆層，可製得 具有極細的天然皮革狀之皺摺的粒面狀人造皮革。 該絨毛狀人造皮革或粒面狀人造皮革，係以在海島型 纖維變成極細長纖維束後之任何階段予以染色爲較佳的實 施形態。於本發明中，可採用任何使用視纖維之種類而定 予以適當選擇的分散染料、反應染料、酸性染料、金屬錯 鹽染料、硫化染料、硫化建染染料等爲主體之染料，使用 軋染機、卷染機、圓形機、絞染機等習知人造皮革於染色 時一般所使用的習知染色機之染色方法。而且，除染色以 外，以進行視其所需以乾式狀態予以機械搓揉處理、使用 染色機或洗濯機等濕式狀態之回縮處理、柔軟劑處理、防 燃劑或抗菌劑、消臭劑、防水防油劑等之功能性賦予處理、 聚矽氧烷系樹脂或含有絲蛋白之處理劑、賦予固定性之樹 脂等觸感改質劑賦予處理、著色劑或塗布琺瑯狀用塗布樹 脂、等除上述以外的樹脂之創意性賦予處理等加工處理較 佳。本發明之人造皮革用基材，由於爲極細纖維束非常緻 密地集合的構造，以濕式狀態之回縮處理或柔軟劑處理， 由於可顯著改善質感，於選出粒面狀人造皮革中爲較佳的 -48 - 201000713 處理。例如，爲回縮處理時，藉由以在約爲6 0〜1 4 0 °C之溫 度範圍內含有界面活性劑之水中進行處理，可製得具有勝 過天然皮革且沒有惡化的柔軟感、膨脹感，緻密構造本身 所具有的充實感不會受損之人造皮革。 【實施方式】 其次’以具體的實施例說明本發明之實施形態，本發 明不受此等實施例所限制。而且，實施例中之份及％，沒 有特別限制時係指質量。 (1)海島型纖維、或極細長纖維束之截面積、集束條數、 扁平率 有關與試料之厚度方向平行的任意截面，使用掃描型 電子顯微鏡（約100〜3 00倍）觀察，到處且隨意選出20個 自觀察方向、對截面而言幾乎垂直配向的海島型纖維、或 極細長纖維束。然後，經選出的各個海島型纖維、或極細 纖維束之集束條數、扁平率、及投影尺寸，視其所需擴大 約1000〜3000倍之倍率進行再觀察、求取。扁平率係於纖 維或纖維束之截面形狀中，測定最長部分之長度、及垂直 於該長度之方向的長度，前者除以後者之値，通常最長部 分之長度大多數爲垂直於厚度方向之方向的長度。 其次，有關選出的20個海島型纖維、或極細纖維束， 測定各截面積，去除最大截面積及最小截面積，使殘留的 1 8個截面積以算數平均法計算，求取構成試料之海島型纖 維、或極細纖維束之截面積。 而且，極細纖維束之截面積係指以構成纖維束外周之 -49 - 201000713 纖維、及連接此等纖維間之接線所圍成的面積。另外’有 關集束條數爲各纖維束之收束條數沒有一定、具有分布 時，與使截面積平均者相同地，去除最大條數與最小條數， 使1 8個極細纖維束之集束條數以算數平均法求取構成試 料之海島型纖維、或極細纖維數之集束條數。 (2)人造皮革用基材截面之海島型纖維或極細長纖維之數 密度、及海島型纖維或極細纖維束間之空隙尺寸、平均空 隙尺寸 有關與試料之厚度方向平行的任意截面，使用掃描型 電子顯微鏡（約100〜3 00倍）觀察，觀察面積合計約爲0.3 〜0.5mm2下觀察連續的截面範圍。於該觀察方向中，對海 島型纖維、或極細纖維數之長度方向而言幾乎爲垂直時， 計算所判斷的截面個數，藉由使該合計個數除以觀察面 積，求取每1 mm2上所存在的海島型纖維、或極細纖維束 截面之個數。該觀察係對1種試料而言至少進行5處以上 之觀察，以最少之値作爲該試料之數密度。 然後，於相同的觀察方向中，以除海島型纖維、或極 細纖維束之截面外的範圍全部作爲空隙，且描繪連接於海 島型纖維、或極細纖維束之截面的最大圓，測定該圓之直 徑。惟空隙連續存在於廣泛範圍時，在圓沒有重疊下、描 繪數個圓’測定所描繪的數個圓中最大直徑之圓。另外， 除去於觀察方向全體中纖維束幾乎完全密接存在者，在纖 維束密接下存在的部分空隙’自觀察方向之評估對象除 去。而且’在密接下存在’係指接近與構成纖維束之極細 -50- 201000713 纖維的纖維直徑同等以下的程度下存在者。於該經測定的 圓之直徑中，以觀察方向之最大値作爲試料之極細纖維束 間的空隙尺寸。此外，有關以於觀察方向中到處且隨意選 出的20處空隙所測定的圓直徑，以除去最大値、最小値之 1 8個的算數平均値作爲極細纖維束間之平均空隙尺寸。 (3 )絨毛狀人造皮革之外觀評估 由人造皮革領域之該業者所選出的5人評估員，藉由 目視、以下述基準評估絨毛狀人造皮革之外觀，以最多評 估員所做的評估作爲外觀之評估結果。 A :絨毛表面之緻密性全體皆極高，以手觸摸時完全沒 有不均勻感、極爲平滑。 B :絨毛表面之緻密性全體稍粗，或全體較高的部分緻 密性明顯降低，散在粗的部分，以手觸摸時稍有不均勻感。 C :全體爲粗的絨毛表面，以手觸摸時相當不均勻。 (4)絨毛狀人造皮革之質感評估 所得的絨毛狀人造皮革之厚度低於0 · 8 m m時，縫製成 高爾夫球用手套，厚度爲0.8〜1.2mm時，縫製成外套，厚 度大於1 .2mm時，縫製成沙發椅。藉由使自人造皮革領域 之該業者所選出的5人評估員穿用，以下述基準評估絨毛 狀人造皮革之質感，以最多的評估員之評估作爲質感之評 估結果。 A:具有柔軟、膨脹感且具有充分的充實感之質感，縫 製品之使用感良好。 B:柔軟感、膨脹感、充實感皆爲稍嫌不足的質感，縫 201000713 製品之使用感不充分（有關質感或使用感，具有與習知一般 絨毛狀人造皮革相同的程度）。 c :柔軟感、膨脹感、充實感大幅惡化、或皆大幅惡化 的質感，縫製品之使用感不佳（有關質感或充實感，較習知 一般的絨毛狀人造皮革更爲不佳）。 (5)絨毛狀人造皮革之表面摩擦耐久性評估 以JIS L 1 096所規定的馬丁迪魯摩擦試驗測定方法爲 基準，在荷重爲12kPa、摩擦次數爲50000次之條件下， 使所得的絨毛狀人造皮革之表面進行摩擦處理。處理前後 之質量差（摩擦減量）爲5 0 m g以下時，判斷耐摩擦性良好。 另外，處理前後之絨毛狀人造皮革表面之剝離產生狀態（增 減）藉由目觀、以下述基準進行比較。耐摩擦性良好且剝離 產生狀態爲A或B時，評估爲表面摩擦耐久性優異。 A :沒有剝離情形增加（可觀察到有因絨毛的切斷等之 剝離減少）。 B :剝離情形雖稍有增加，惟幾乎完全沒有以手觸摸時 有硬質感的剝離情形增加。 C :剝離情形明顯增加，以手觸摸時有硬質感之剝離情 形明顯增加。 【實施例】 實施例1 各使作爲海成分聚合物之乙烯改性聚乙烯醇（乙烯單 位之含量爲8.5莫耳％、聚合度爲380、皂化度爲98.7莫耳 % )、作爲島成分聚合物之異苯二甲酸改性聚對苯二甲酸乙 -52 - 201000713 二酯（異苯二甲酸單位之含量爲6.0莫耳％)予以熔融。 形成在海成分聚合物中分布有25個均勻截面積之島 聚合物的截面、多數噴嘴孔以並列狀配置的複合紡紗 嘴中，在截面中海成分聚合物與島成分聚合物之平均 比以海成分/島成分=2 5 /7 5之壓力平衡供應該熔融 物，以噴嘴溫度爲2 5 0 °C、自噴嘴孔吐出。在平均紡紗 爲3 60 0m/分下調整氣流之壓力之噴氣•噴嘴型吸引裝 以拉伸細化、平均截面積爲177μιη2(約爲2.4dtex)之海 纖維進行紡紗處理，使該物自裏面側吸引且在網上連 集。藉由調整網子之移動速度以調整堆積量，及藉由 於80°C之壓花輥以線壓 70kg/cm押入，單位面積重 3 Og/m2、與厚度方向平行的截面上存在有220〜2 5 0個 海島型纖維之截面，且可製得直至可捲取的程度爲止 態經安定化的長纖維纖維網。 藉由在壓花後之長纖維纖維網表面上噴霧賦予以 油系平滑性油劑爲主體且混合有抗靜電劑之油劑後， 交叉層合裝置，連續摺疊成長纖維纖維網，形成〗4層 狀長纖維纖維網。然後，藉由在層狀長纖維纖維網上 刺處理作用的針刺法，進行三次元絡合處理，製得海 纖維之數密度爲500個/mm2之不織布構造體。針刺處 條件，以織針編號爲40號、繭絲深度爲40 μηι、以1 鈎的繭絲數、正三角形截面之織針 A，自兩面使繭絲 度方向貫通之針刺深度，自兩面使繭絲朝厚度方向貫 針刺深度予以預備絡合、即經摺疊的長纖維纖維網沒 於可 成分 用噴 面積 聚合 速度 置予 島型 續捕 保溫 量爲 /mm2 、形 礦物 使用 之層 使針 島型 理之 根針 朝厚 通的 有剝 -53 - 201000713 離的程度進行絡合處理後，以織針編號爲4 2號、繭絲 爲4 0 μιη、以6根針鈎的繭絲數、正三角形截面之織針 自兩面使3根針鈎的繭絲朝厚度方向貫通的針刺深度 島型纖維直至企求的水準、朝厚度方向絡合進行絡 理。以織針Β之針刺處理，自兩面以合計爲1 7 〇 〇針刺 之針刺數進行。 然後’在該不織布構造體之兩面上均勻噴霧塗布 之水後’其次’使溫度爲7 5 〇C、相對濕度9 5 %之環境 朝長度方向、寬度方向之任何方向、在幾乎完全沒有 或摩擦應力作用下’以4分鐘連續通過的條件進行濕 縮處理’使海島型纖維間接近均勻。然後，使不織布 體予以乾燥前’在保溫於丨2 〇它之金屬輥間進行壓製處 使表面予以壓縮平滑化且乾燥，然後，藉由使不織布 體全體導入120 °C之環境中予以乾燥，製得單位面積重 1 125 g/m2、朝厚度方向平行的截面上海島型纖維之數 爲1900個/ mm2之極爲緻密的不織布構造體。 在所得的不織布構造體中含浸作爲高分子彈性體 碳酸酯/醚系聚胺基甲酸酯爲主體的聚胺基甲酸酯組 之水分散液（固成分濃度爲1 1質量％ )，對質量1 0 0之 布構造體而言高分子彈性體液之含液量爲5 〇下，以金 進行壓製後，再以不織布構造體的表面溫度爲8 0 °C 件，藉由使紅外線加熱器作用1分鐘進行感熱凝固處 最後導入120°C之環境中使水分乾燥，然後，直接導入1 之環境中進行硬化處理2分鐘，使聚胺基甲酸酯組成 深度 B， ，海 合處 /cm2 1 中， 張力 熱收 構造 理， 構造 量爲 密度 之聚 成物 不織 屬輥 之條 理， 5 0°C 物存 -54 - 201000713 在於海島型纖維間之空隙內。其次，在液流染色機中藉由 9 〇 °C之熱水進行處理2 0分鐘’萃取除去海島型纖維中之改 性聚乙烯醇後’藉由導入1 2 0 °C之環境中使水分乾燥，製得 在由改性聚對苯二甲酸乙二酯之極細長纖維束所形成的不 織布構造體內部含有聚胺基甲酸酯組成物、厚度約爲 1.4mm之本發明人造皮革用基材。 觀察所得的人造皮革用基材之截面中極細長纖維束 時，該截面積在 200〜400μιη2之範圍內分布的平均爲 2 5 0 μιη2 ’使2 5條具有幾乎均勻的纖維直徑、約爲圓形之截 面形狀的極細長纖維集束。纖維束沒有朝厚度方向扁平化 的情形，纖維束之扁平率最大爲2.5，幾乎皆低於2.0，投 影尺寸爲40μιη。另外，與厚度方向平行的截面中極細長纖 維束之數密度爲2500個/ mm2,極細纖維束間之空隙尺寸爲 52μηι，平均空隙尺寸爲35μιη。 實施例2 使實施例1所得的人造皮革用基材藉由切片朝厚度方 向予以二分割化，且使分割面以砂紙進行摩擦處理，符合 平均厚度爲〇.67mm之厚度。在沒有進行摩擦處理之面上， 使聚乙烯醇之 6 %水溶液以5 5篩目之照相凹版輥塗布2 次、予以乾燥，然後，與實施例1含浸時所使用者相同的 聚碳酸酯/醚系聚胺基甲酸酯爲主體之聚胺基甲酸酯組成 物的水分散液（固成分濃度爲6質量％)以75篩目之照相凹 版輥塗布3次，予以乾燥。使該聚胺基甲酸酯組成物賦予 面以繭絲機予以固定的沒有壓花之砂紙進行加壓且摩擦處 -55- 201000713 理予以起毛及整毛’形成由改性聚對苯二甲酸乙二酯之極 細纖維所形成的絨毛。另外，使用液流染色機、以分散染 料進行染色加工後’進行刷毛處理予以整毛加工’製得米 色之絨毛狀人造皮革。所得的絨毛狀人造皮革’於與厚度 方向平行的截面中自絨毛面側朝厚度方向之200μιη爲止的 範圍內，極細纖維束之數密度爲2 7 0 0個/ m m 2，緻密性極 高、具有類似天然皮革正絨牛皮革之優美絨毛外觀，質感、 表面摩擦耐久性皆極爲良好，爲具有本發明目的效果之絨 f 毛狀人造皮革。評估結果如表1所示。 比較例1 於實施例1中，除使構成長纖維纖維網之海島型纖維 之島成分聚合物更改爲耐龍6,在平均截面積爲3 0 7 μηι2 (約 3.6dtex)之條件下使海島型纖維進行紡紗以外，與實施例1 相同地製得壓花安定化的單位面積重量爲30 g/m2之長纖維 纖維網。在所得的長纖維纖維網表面上，與實施例1相同 地賦予油劑後，以交叉層合機製造層狀長纖維纖維網。其S is treated with a non-solvent or a coagulant, and the impregnated nonwoven fabric structure is heat-treated with a polymer elastomer solution containing a thermogelling agent or the like, and the solvent or dispersant is removed in advance to fix the polymer elastomer to the nonwoven fabric. Construct a 'in vivo' or a completely fixed method. Further, in order to completely fix the solidified polymer elastomer, it is preferred to carry out a curing treatment such as heating treatment after removing the solvent or the dispersant. The concentration of the polymer elastomer solution, that is, the content of the polymer elastomer in the polymer elastomer solution is preferably 〇??~6 〇 mass%. In the range of the properties of the polymer elastomer-42 - 201000713 in the liquid, the coloring agent, the coagulating agent, the antioxidant, and the ultraviolet absorber are appropriately blended with the dye or pigment. , fluorescer, antifungal agent, penetrant, defoamer, smoothing agent, water repellent, oil repellent, tackifier, extender, hardening accelerator, foaming agent, polyvinyl alcohol or carboxymethyl fiber Various additives blended in a polymer elastomer liquid contained in a conventional base material for artificial leather such as a water-soluble polymer compound such as a compound. The amount of the polymer elastomer or the polymer elastomer composition contained in the nonwoven fabric structure is appropriately adjusted depending on the necessary mechanical properties, durability, texture, etc., for the purpose of use, but is formed by a very fine fiber bundle. When the unit volume weight of the nonwoven fabric structure is 100°, the unit weight of the polymer elastomer is preferably in the range of 1 to 8 % by mass, more preferably in the range of 2 to 60% by mass. Take 5~4 0 quality. /. The range is the best. When the content of the polymer elastomer is less than 1% by mass, the polymer elastomer is not uniformly contained, and the content of the polymer elastomer in the base material for artificial leather becomes intense, and the quality of the substrate for artificial leather is high. It is not easy to stabilize. In addition, when the content of the polymer elastomer is more than 80% by mass, the nonwoven fabric structure is extremely dense, and the texture of the base material for artificial leather is significantly hardened, so that the rubber feeling is strong, and therefore it is not desired. A method of removing a sea component polymer from an island-in-sea type fiber which comprises a non-woven fabric structure before or after a polymer elastomer is contained, and is a non-solvent or non-dispersant agent of an island component polymer, and is then subjected to a polymer elastomer. When it is removed, a method of treating a nonwoven fabric structure with a liquid having a non-solvent or non-dispersant liquid of a polymeric elastomer and having a solvent or a dispersing agent of a sea component polymer. For example, it is soluble in poly-43 as described above. - 201000713 When a polymer such as vinyl alcohol is used as a sea component polymer, the polymer may be removed by warm water at a soluble temperature, and 彳吏$ <吏 contains the above sulfonic acid alkali metal salt. When the modified polyester which is copolymerized with a compound or the like is used as a sea component polymer, an alkaline decomposing agent such as an aqueous sodium hydroxide solution can be used. The aqueous solution is removed at a suitable temperature. By the sea component polymer removal treatment, the sea-island type fiber is changed into a very elongated fiber bundle formed of the island component polymer, and the preferred one is 300 to 1 800. A substrate for artificial leather of the present invention having a basis weight of 0 g/m 2 , which is a decisive difference from a conventional base material for artificial leather, which is obtained by using a sea-island type fiber into a substrate of artificial leather obtained by extremely thin fiber bundles. In addition to the above points, for example, the gap size formed between the extremely elongated fiber bundles is 70 μm or less, preferably 60 μm or less, and the uniform and small-sized spots are used. In the process of forming a three-dimensionally entangled non-woven fabric structure, (1) a sea-island type fiber having a cross-sectional area of about 350 μm 2 or less, that is, a fiber diameter of about 21 μm or less, and which is not easily flattened, is spun. Yarn, and directly forming a fiber web in a long fiber form, forming a non-woven fabric structure in a state in which it is difficult to achieve an undesirably large volume between the substrates for forming artificial leather, ( 2) When the long fiber web is subjected to the three-dimensional complexing treatment, the needles of the six needle hooks are used in the needle punching process of the main body, and the strands are passed through in the thickness direction, and the range is widened. In the non-woven fabric structure in which the same fibers are formed in a state in which the fibers are randomly arranged in a continuous state, the densification and the three-dimensional complexation treatment are performed in an excellent balance without the unique fiber arrangement, thereby making the nonwoven fabric non-woven. The fiber on the cross section of the structure is laminated to a sufficiently high number density -44 - 201000713, and (3) the water-soluble polymer and the heat-shrinkable polymer are combined as a constituent component of the island-in-the-sea fiber, and the heat shrinkage treatment is performed in the damp heat Under the environment, when the non-woven structure is densified by heat shrinkage, the sea component can be plasticized in / instantaneous expansion, and the island component can be shrunk to a near-ideal level. However, in order to shrink the fiber diameter of the island component When the diameter can be reduced to a desired level, the island-in-sea type fiber is easily contracted along the fiber axis, and it is difficult to achieve the conventional island-in-the-sea fiber by shrinking when it is contracted. The riot action acts to exclude the adjacent fibers, and (4) in order to dissolve and decompose the sea components, the sea component polymer is used as a medium with a smaller molecular size and a polar water as a medium of a known organic solvent. The diffusion rate of the internal solvent molecules is relatively fast, and the state of self-expansion to dissolution is stable, and when the dissolved matter of the sea component polymer is sequentially discharged to the outside of the structure, since it is necessary to apply a hydraulic or mechanical hard force or the like, it is conventionally known. In contrast, the non-woven fabric structure of the present invention which is extremely densified does not cause the void size between the ultrafine fiber bundles to expand, and the factor of the sea component decomposition product can be easily discharged, and all of them are composited. In the obtained base material for artificial leather, in order to produce a fine-grained artificial leather which is more uniform in the gap between the fiber bundles and has a more compact appearance quality, or a wrinkle-like finer grain shape In the case of a base material for artificial leather of artificial leather, it is preferred to apply a solution, an aqueous dispersion or a solution of an extractable polymer on the surface of the front side of the artificial leather product to harden the easily extractable polymer. In the rubbing treatment of the subsequent step, the present invention is applied to the front side of the artificial leather product in order to obtain a densified non-woven fabric structure which is conventionally not provided, and at the same time, a smoother and uniform sentence fluff surface can be obtained. The surface of the polymer is coated with an aqueous dispersion of a polymer elastomer, such that the polymer elastic-45-body is hardened by a depth of 100--in addition to the dense body between the smooth surfaces of the leather, etc. When the human leather is the same as the 201000713 after the 'improvement of the easily extractable polymer, the object is removed by the step. Then, 'the pressurization and honing treatment for imparting the polymeric elastomer' not only honing the surface from the original surface to 20 degrees, but also the range of the depth of the surface -300 μηι after the honing treatment, The nonwoven fabric structure is made denser, and the polymer elastomer can be supplied to the surface in advance, and the surface or the inside of the substrate can be treated by rubbing treatment or calendering treatment. The obtained base material for artificial leather was not only smoothed by honing, and the range of the ultrafine fiber average void size ranging from the surface to 200 μm was evaluated to be in the range of 10 to 40 μm to form an extremely uniform state. Examples of easily extractable polymers, such as polyvinyl alcohol, polyaminocarboxylic acid, acrylic elastomer, polyethylene glycol, paraffin wax, polyethylene wax, and the like, such as polyurethane elastomer or acrylic elastomer A method of applying the same as the polymer elastomer contained in the nonwoven fabric structure, and a method of applying the polymer elastomer, for example, a gravure roll coating method, a rotary screen coating method, a spray coating method, a cloth method, or the like A coating method in which the gravure coating method is preferred in terms of the balance between the body viscosity and the coating amount. The honing treatment is rubbed by sandpaper, and the pressing level of the sandpaper can be used to determine the surface state of the substrate for leather, and the surface condition of the substrate after the treatment is appropriately adjusted, and the optimum is set. For the artificial leather substrate and the artificial leather mentioned above, it is cut into several pieces in the thickness direction as needed, so that the inner surface dissolves the surface, ^200 to about. Man-made to deal with the uniformity of the ester bomb. In the case of reversible coating, when the artificial tanning is applied, the aging is carried out at -46-201000713 to adjust the thickness, and the surface of the inner surface or the surface is made of a liquid containing a solvent of a polymer elastomer or a very fine fiber bundle. deal with. Then, at least the surface of the surface is subjected to a raising treatment by a rubbing treatment or the like to form a fiber fluff surface mainly composed of ultrafine fibers, and a fluffy artificial leather such as a fluffy or nubuck leather shape can be obtained. Further, a coating layer made of a polymeric elastomer is formed on the surface of the surface to obtain a grain-like artificial leather. When a fiber fluff surface is formed, any conventional method such as rubbing treatment or brushing treatment using sandpaper or card clothing can be used. Further, a solvent which dissolves or expands the polymeric elastomer or the ultrafine fiber bundle before or after the raising treatment, for example, when the polymeric elastomer is a polyurethane elastomer, can be used on the surface of the raising treatment. When a treatment liquid containing dimethylformamide (DMF) or the like is applied, or when the ultrafine fiber bundle is a polyamide resin, a treatment liquid containing a phenol compound such as resorcin can be applied to the surface of the raising treatment. Thereby, the state of restraint of the ultrafine fiber bundle caused by the bonding of the polymeric elastomer or the ultrafine fiber bundle, the ultrafine fiber f of the fluffy artificial leather, the length of the surface friction, and the surface friction durability can be finely adjusted. In the formation of the coating layer formed of the polymeric elastomer, a method of supplying the liquid containing the polymeric elastomer directly on the surface of the substrate for artificial leather or coating the liquid on a supporting substrate such as a release paper can be used. Any of the conventional methods such as a method of bonding to a substrate for artificial leather. The polymer elastic body used for the coating layer to be formed is a conventional polymer elastic body which is a coating layer of a conventional grain-like artificial leather, as long as it is the same as the polymer elastic body contained in the conventional polymer elastic body. The body can be used, both can be used. -47 - 201000713 When the thickness of the coating layer to be formed is about 300 μm or less, the grain-like artificial leather which can balance the sufficient texture with the base material for artificial leather of the present invention is not particularly limited. When manufacturing the base material for artificial leather of the present invention, the extremely fine and uniform surface layer of the grain-like artificial leather obtained by forming the dense collection state of the ultrafine fiber bundle has a thickness of about ΙΟΟμηη or less, preferably about A coating layer is formed in a range of 80 μm or less, more preferably about 3 to 50 μm, and by forming a coating layer having the thickness, a grain-like artificial leather having an extremely fine natural leather-like wrinkle can be obtained. The pile-like artificial leather or the grain-like artificial leather is dyed in a preferred embodiment at any stage after the sea-island type fiber becomes a very long-length fiber bundle. In the present invention, any dye which is appropriately selected, such as a disperse dye, a reactive dye, an acid dye, a metal stinky dye, a sulphur dye, a vulcanization dye, or the like, which is appropriately selected depending on the kind of the optical fiber, may be used, and a pad dyeing machine is used. A dyeing method of a conventional dyeing machine generally used for dyeing a conventional artificial leather such as a jigger, a circular machine, or a dyeing machine. Further, in addition to the dyeing, it is subjected to a mechanical treatment in a dry state, a retracting treatment in a wet state such as a dyeing machine or a washing machine, a softener treatment, a flame retardant or an antibacterial agent, and a deodorant. a functional imparting treatment such as a water- and oil-repellent agent, a treatment agent for a polyoxyalkylene-based resin or a fibrin-containing resin, a tactile modifier such as a resin that imparts a fixability, a coloring agent or a coating resin for coating a coating, The processing such as the creative imparting treatment of the resin other than the above is preferable. The base material for artificial leather of the present invention has a structure in which very fine fiber bundles are densely gathered, and is treated in a wet state by a retracting treatment or a softening agent, because the texture can be remarkably improved, and the grain-like artificial leather is selected. Good -48 - 201000713 deal. For example, in the case of the retracting treatment, by treating the water containing the surfactant in a temperature range of about 60 to 140 ° C, it is possible to obtain a soft feeling that is superior to natural leather without deterioration. The artificial leather with a sense of expansion and a compact texture that does not impair the fullness of the structure itself. [Embodiment] Next, embodiments of the present invention will be described by way of specific examples, and the present invention is not limited by the embodiments. Further, the parts and % in the examples are those which are not particularly limited. (1) The cross-sectional area of the sea-island type fiber or the extremely thin fiber bundle, the number of bundles, and the flatness ratio are arbitrary cross-sections parallel to the thickness direction of the sample, and are observed using a scanning electron microscope (about 100 to 300 times). Feel free to select 20 island-in-the-sea fibers or very slender fiber bundles that are oriented perpendicularly to the cross-section. Then, the number of bundles, the flatness ratio, and the projection size of each of the selected sea-island type fibers or the ultrafine fiber bundles are re-observed and obtained as needed to expand the magnification by about 1000 to 3000 times. The flatness ratio is in the cross-sectional shape of the fiber or fiber bundle, and the length of the longest portion and the length perpendicular to the length are measured. The former is usually the longest portion, and the length of the longest portion is generally perpendicular to the thickness direction. length. Secondly, regarding the selected 20 island-type fibers or ultrafine fiber bundles, the cross-sectional area is measured, the maximum cross-sectional area and the minimum cross-sectional area are removed, and the remaining 18 cross-sectional areas are calculated by the arithmetic average method to obtain the islands constituting the sample. The cross-sectional area of the fiber or the ultrafine fiber bundle. Further, the cross-sectional area of the ultrafine fiber bundle refers to the area enclosed by the fibers constituting the outer periphery of the fiber bundle - 49 - 201000713 and the wires connecting the fibers. In addition, when the number of bundles is such that the number of bundles of each fiber bundle is not constant and has a distribution, the maximum number of strips and the minimum number are eliminated, so that the bundle of 18 ultrafine fiber bundles is removed. The number is calculated by the arithmetic average method to determine the number of bundles of island-type fibers or the number of ultrafine fibers constituting the sample. (2) The number density of the island-in-the-sea fiber or the ultra-long fiber of the cross section of the substrate for artificial leather, and the void size and the average void size between the island-in-the-sea fiber or the ultrafine fiber bundle, and any cross section parallel to the thickness direction of the sample, and scanning is used. An electron microscope (about 100 to 300 times) was observed, and a continuous cross-sectional range was observed under a total observation area of about 0.3 to 0.5 mm 2 . In the observation direction, when the length of the island-in-the-sea fiber or the number of the ultrafine fibers is almost vertical, the number of the determined cross-sections is calculated, and the total number is divided by the observation area to obtain every 1 mm 2 . The number of island-type fibers or ultrafine fiber bundles present on the top. In the observation, at least five observations were made for one sample, and the minimum density was used as the number density of the sample. Then, in the same observation direction, all the ranges except the cross-section of the island-in-the-sea fiber or the ultrafine fiber bundle are used as the voids, and the largest circle connected to the sea-island type fiber or the cross section of the ultrafine fiber bundle is drawn, and the circle is measured. diameter. When the voids are continuously present in a wide range, a circle is drawn without overlapping the circles, and the circle having the largest diameter among the plurality of circles drawn is measured. Further, except for the fact that the fiber bundles are almost completely adhered to each other in the observation direction, the partial voids existing under the close contact of the fiber bundles are removed from the evaluation target in the observation direction. Further, 'present in close contact' means that it exists to the extent that it is equal to or less than the fiber diameter of the fiber constituting the extremely fine fiber bundle -50-201000713. Among the diameters of the measured circles, the maximum enthalpy in the observation direction was used as the void size between the ultrafine fiber bundles of the sample. Further, regarding the diameter of the circle measured by the 20 spaces which are randomly selected in the observation direction, the arithmetic mean 除去 which removes the maximum 値 and the minimum 値 is taken as the average gap size between the ultrafine fiber bundles. (3) Appearance evaluation of fluff-like artificial leather The five-person assessor selected by the manufacturer in the field of artificial leather evaluated the appearance of the fluffy artificial leather by visual inspection and the following criteria, and the evaluation by the most evaluator was used as the appearance. Evaluation results. A: The compactness of the surface of the pile is extremely high, and there is no unevenness and extremely smooth when touched by the hand. B: The compactness of the surface of the pile is slightly thicker, or the density of the whole part is significantly lowered, and the thick part is scattered, and the touch is slightly uneven when touched by the hand. C: The whole is a thick pile surface, which is quite uneven when touched by a hand. (4) The texture of the fluff-like artificial leather is less than 0 · 8 mm when the thickness of the fluffy artificial leather is less than 0 · 8 mm, and it is sewn into a glove for golf balls. When the thickness is 0.8 to 1.2 mm, it is sewn into a jacket, and the thickness is more than 1.2 mm. When sewing, it is made into a sofa chair. By applying the five-person assessor selected by the manufacturer in the field of artificial leather, the texture of the fluffy artificial leather was evaluated on the basis of the following evaluation, and the evaluation by the most assessor was used as the evaluation result of the texture. A: It has a soft, swellable feeling and a feeling of fullness, and the feeling of use of the sewn product is good. B: The soft feeling, the swelling feeling, and the feeling of fullness are all slightly insufficient textures, and the seam of the 201000713 product is not sufficient (the texture or the feeling of use has the same degree as the conventional fluffy artificial leather). c: The feeling of softness, swelling, and feeling of fullness is greatly deteriorated, or the texture is greatly deteriorated, and the use of the sewn product is not good (the texture or the feeling of fullness is more unsatisfactory than the conventional fluffy artificial leather). (5) Evaluation of surface friction durability of fluff-like artificial leather The obtained fluffy shape was obtained under the conditions of a load of 12 kPa and a rubbing frequency of 50,000 times based on the Martin Diru friction test method specified in JIS L 1 096. The surface of the artificial leather is rubbed. When the mass difference (friction reduction) before and after the treatment was 50 m g or less, it was judged that the abrasion resistance was good. Further, the state of occurrence of peeling of the surface of the pile-like artificial leather before and after the treatment (increase or decrease) was compared by the following criteria. When the abrasion resistance was good and the peeling state was A or B, it was evaluated that the surface friction durability was excellent. A: No peeling was increased (a decrease in peeling due to cut of the pile, etc.) was observed. B: Although the peeling situation was slightly increased, there was almost no increase in the peeling situation with a hard feeling when touched by hand. C: The peeling situation was remarkably increased, and the peeling condition with a hard texture when touched by a hand was significantly increased. [Examples] Example 1 Each of ethylene-modified polyvinyl alcohol (having a content of ethylene unit of 8.5 mol%, a degree of polymerization of 380, and a degree of saponification of 98.7 mol%) as a sea component polymer was polymerized as an island component. The isophthalic acid modified polyethylene terephthalate-52 - 201000713 diester (the content of isophthalic acid unit is 6.0 mol%) is melted. In the composite spinning nozzle in which the cross section of the island polymer having 25 uniform cross-sectional areas distributed in the sea component polymer and the plurality of nozzle holes are arranged in parallel, the average ratio of the sea component polymer to the island component polymer in the cross section is The sea component/island component = 2 5 / 7 5 is a pressure balance supplied to the melt, and is discharged from the nozzle hole at a nozzle temperature of 250 °C. The air jet nozzle type suction device which adjusts the pressure of the air flow at an average spinning speed of 360 m/min is subjected to spinning treatment by a sea fiber having a stretched refining and an average cross-sectional area of 177 μm 2 (about 2.4 dtex). Attracted from the inside and connected on the Internet. By adjusting the moving speed of the net to adjust the amount of accumulation, and by embossing the 80 ° C embossing roller with a linear pressure of 70 kg / cm, the weight per unit area is 3 Og / m2, there is 220 ~ in the cross section parallel to the thickness direction A section of 260 island-type fibers, and a long-fiber web that is stabilized up to the extent that it can be taken up. After spraying on the surface of the long fiber web after embossing to impart an oil agent mainly composed of an oil-based smoothing oil agent and mixed with an antistatic agent, the cross-lamination device continuously folds the fiber web to form a 〗 4 Layered long fiber web. Then, by a needle punching method on the layered long fiber web, a three-dimensional complexing treatment was carried out to obtain a nonwoven fabric having a number density of 500 fibers/mm2. Acupuncture conditions, the needle depth is 40, the depth of the silk is 40 μηι, the number of twists of 1 hook, the needle A of the equilateral triangle section, the depth of the needle penetrated from the sides to the direction of the twist, from On both sides, the twisted wire is subjected to a predetermined depth of penetration in the thickness direction, that is, the folded long fiber web is not used in the polymerization rate of the sprayable area, and the island type has a continuous holding capacity of /mm2, and the layer of the mineral is used. After the needle-sharing type of needle is subjected to complexation treatment to the extent of peeling-53 - 201000713, the knitting needle number is 4 2, the silk thread is 40 μιη, and the needle is hooked with 6 needles. The needles of the number of wires and the equilateral triangle cross-section are formed by the needle-forming depth island fibers which penetrate the three needle hooks in the thickness direction from both sides until the desired level and the thickness direction are complexed. The acupuncture treatment of the needles was carried out on the two sides in total for the number of needles of 1 7 〇 〇 acupuncture. Then 'after evenly spraying the coated water on both sides of the non-woven structure, 'the second time', the environment with a temperature of 75 〇C and a relative humidity of 9.5 % is oriented in the longitudinal direction, in the width direction, in almost no direction or friction. Under the action of stress, the wet-shrinking treatment was carried out under the condition of continuous passage for 4 minutes to make the island-type fibers nearly uniform. Then, before the non-woven fabric body is dried, the surface is compressed and smoothed by pressing between the metal rolls which are kept in the crucible, and then dried, and then dried by introducing the entire non-woven fabric into an environment of 120 ° C. An extremely dense non-woven fabric structure having a surface area of 1 125 g/m 2 and a number of island-type fibers on a cross section parallel to the thickness direction of 1,900 / mm 2 was obtained. The obtained non-woven fabric structure was impregnated with an aqueous dispersion of a polyurethane group mainly composed of a polymeric elastomer carbonate/ether polyurethane, (solid content concentration was 11% by mass), In the structure of the mass of 100%, the liquid content of the polymer elastomer liquid is 5 〇, and after pressing with gold, the surface temperature of the non-woven structure is 80 ° C, and the infrared heater is used. After 1 minute, the thermosensitive solidification was introduced into the environment at 120 ° C to dry the water, and then directly introduced into the environment of 1 to carry out hardening treatment for 2 minutes to make the polyurethane composition depth B, kelp/cm2 In 1 , the tension heat shrinkage structure, the structure of the density of the aggregate is not woven into the roller, 50 ° C storage -54 - 201000713 lies in the gap between the island-type fibers. Next, in a liquid flow dyeing machine, it is treated by hot water of 9 ° C for 20 minutes to extract and remove the modified polyvinyl alcohol in the sea-island fiber, and then water is introduced by introducing an environment of 120 ° C. Drying, the base of the artificial leather of the present invention having a polyurethane composition in a nonwoven fabric structure formed of a very elongated fiber bundle of modified polyethylene terephthalate and having a thickness of about 1.4 mm is obtained. material. When observing the extremely thin fiber bundles in the cross section of the obtained substrate for artificial leather, the average cross-sectional area distributed in the range of 200 to 400 μm 2 is 2500 μm 2 '2 such that 25 pieces have an almost uniform fiber diameter, approximately a circle A very elongated fiber bundle of a cross-sectional shape. When the fiber bundle is not flattened in the thickness direction, the fiber bundle has a flattening ratio of at most 2.5, almost all of which is less than 2.0, and a projection size of 40 μm. Further, the number density of the extremely elongated fiber bundles in the cross section parallel to the thickness direction was 2,500 / mm 2 , the gap size between the ultrafine fiber bundles was 52 μm, and the average void size was 35 μm. Example 2 The base material for artificial leather obtained in Example 1 was divided into two in the thickness direction by slicing, and the divided surface was subjected to rubbing treatment with a sandpaper to have a thickness of 〇.67 mm. On the surface which was not subjected to the rubbing treatment, a 6 wt% aqueous solution of polyvinyl alcohol was applied twice by a gravure roll of 55 mesh, dried, and then the same polycarbonate as that of the user of Example 1 impregnation/ An aqueous dispersion of a polyurethane composition containing an ether-based polyurethane as a main component (solid content concentration: 6 mass%) was applied three times with a 75-mesh gravure roll and dried. The urethane-free sandpaper is used to apply the polyurethane coating to the surface without pressing the embossed sandpaper to pressurize and rub the surface -55-201000713 to raise the hair and the whole hair 'formed by the modified polyterephthalic acid The fluff formed by the ultrafine fibers of ethylene glycol. Further, a beige fluff-like artificial leather was obtained by using a liquid flow dyeing machine, performing dyeing processing with a dispersed dye, and performing a roughing process by performing a bristles treatment. The obtained fluffy artificial leather 'in the range parallel to the thickness direction is in the range of 200 μm from the side of the fluff surface to the thickness direction, and the number density of the ultrafine fiber bundle is 2,700 / mm 2 , and the density is extremely high. It has a beautiful fluffy appearance similar to natural leather nubuck cow leather, and has excellent texture and surface friction durability, and is a piled wool-like artificial leather having the effect of the present invention. The evaluation results are shown in Table 1. Comparative Example 1 In Example 1, except that the island component polymer constituting the sea-island type fiber of the long fiber web was changed to Nylon 6, the island was made under the condition that the average cross-sectional area was 30.7 μm (about 3.6 dtex). A long fiber web having an embossed and stabilized basis weight of 30 g/m 2 was obtained in the same manner as in Example 1 except that the fiber was spun. On the surface of the obtained long fiber web, an oil agent was applied in the same manner as in Example 1, and then a layered long fiber web was produced by a cross laminator. its
L 次’在層狀長纖維纖維網上與實施例1相同地以織針A進 行預備絡合處理後，以織針編號爲42號、繭絲深度爲 4 0 μ m、以1根針鈎的繭絲數、正三角形截面之織針c ’使 繭絲朝厚度方向貫通的針刺深度，使海島型纖維朝厚度方 向進行絡合’自兩面以合計爲3 5 〇 〇針刺/ c m 2之針刺數進行 絡合處理。在所得的不織布構造體上，與實施例1相同地 進行濕熱處理、壓製處理，製得單位面積重量爲7〇〇g/m2 之不織布構造體。 -56 - 201000713 在所得的不織布構造體中，與實施例1相同地使聚胺 基甲酸酯組成物存在海島型纖維之空隙後，使海島型纖維 中之改性聚乙烯醇進行萃取除去後，製得在由耐龍6之極 細長纖維束所形成的不織布構造體內部含有聚胺基甲酸酯 組成物之厚度約爲1.4mm之人造皮革用基材。然後，有關 所得的人造皮革用基材’以與實施例2相同的方法進行二 分割處理、摩擦處理’形成由耐龍6之極細纖維所形成的 絨毛後，使用液流染色機 '以金屬錯鹽酸性染料，與實施 例2相同的色調進行染色加工處理，另外，藉由進行整毛 加工處理，作成米色之絨毛狀人造皮革。所得的絨毛狀人 造皮革由於緻密性不充分，就具有習知絨毛狀人造皮革可 達成的水準之粗絨毛外觀’表面摩擦耐久性沒有特別優異 而Η，爲具有硬質、骨感之質感者，無法滿足本發明目的 之水準。評估結果如表1所示。 比較例2 於實施例1中’除使用可形成分布有丨00個島成分聚 合物之截面的複合紡紗用噴嘴，使作爲構成長纖維纖維網 之海島型纖維的海島型纖維進行紡紗外，與實施例1相同 地製得壓花安定化的單位面積重量爲3 0 g / m 2之長纖維纖維 網。在所得的長纖維纖維網表面上，與實施例1相同地賦 予油劑後，以交叉層合機製造層狀長纖維纖維網。其次， 與實施例1相同地藉由針刺處理進行絡合處理。在所得的 不織布構造體上，沒有塗布水下進行熱壓製處理，製得單 位面積重量爲97 Og/m2之不織布構造體。 -57 - 201000713 在所得的不織布構造體中，與實施例1相同地使聚胺 基甲酸酯組成物存在於海島型纖維之空隙後’萃取除去海 島型纖維中之改性聚乙烯醇後，製得在由改性聚對苯二甲 酸乙二酯之極細長纖維束所形成的不織布構造體內部含有 聚胺基甲酸酯組成物、厚度約爲1.4mm之人造皮革用基 材。然後，有關所得的人造皮革用基材’以與實施例2相 同的方法進行二分割處理、摩擦處理，形成由改性聚對苯 二甲酸乙二酯之極細纖維所形成的絨毛後，以分散染料進 行染色加工處理及整毛加工處理，作成米色之絨毛狀人造 皮革。觀察所得的絨毛狀人造皮革時雖爲緻密狀，惟實際 上表層部分之纖維束朝厚度方向崩塌、扁平化’表觀密度 不會變得過高。纖維束之扁平率大於3.0者多數存在時， 最爲扁平化的纖維束爲4.7。藉由該經扁平化的纖維束予以 緻密化的表層部分，藉由摩擦處理予以起毛時，回復至與 沒有緻密化的疏鬆部分相同的緻密性，結果不僅無法得到 習知的絨毛狀人造皮革可達成的水準之粗絨毛外觀，且厚 1 度方向之中央附近對疏鬆而言僅表層部分變得極硬的構 造，質感在如內部有波紋的厚紙板表面上有硬質感，無法 滿足本發明目的之水準。評估結果如表1所示。而且，於 與實施例2之對比時，由於形成絨毛之極細纖維更細時， 染色成相同顏色者有偏白情形，顏色沒有深度，爲欠缺高 級感之外觀。 比較例3 於實施例1中，除使用可形成分布有64個島成分聚合 -58 - 201000713 物之截面的複合紡紗用噴嘴，以平均截面積爲4 8 5 μ m 2 (約 6· 6dtex)之條件使作爲構成長纖維纖維網之海島型纖維之 海島型纖維進行紡紗以外，與實施例1相同地製得壓花安 定化的單位面積重量爲3 0 g/m2之長纖維纖維網。在所得的 長纖維纖維網表面上，與實施例1相同地賦予油劑後，以 交叉層合機製造層狀長纖維纖維網。其次，在層狀長纖維 纖維網上與實施例1相同地以織針A進行預備絡合處理、 及以織針B進行絡合處理。在所得的不織布構造體上，與 實施例1相同地進行濕熱處理、壓製處理，製得單位面積 重量爲990g/m2之不織布構造體。 在所得的不織布構造體中，與實施例1相同地使聚胺 基甲酸酯組成物存在於海島型纖維之空隙後，使海島型纖 維中之改性聚乙烯醇進行萃取除去後，製得在由改性聚對 苯二甲酸乙二酯之極細長纖維束所形成的不織布構造體內 部含有聚胺基甲酸酯組成物、厚度約爲1.4mm之人造皮革 用基材。然後，有關所得的人造皮革用基材，以與實施例 2相同的方法進行二分割處理、摩擦處理，形成由改性聚 對苯二甲酸乙二酯之極細纖維所形成的絨毛後，藉由進行 以分散染料之染色加工處理及整毛加工處理，作成米色之 絨毛狀人造皮革。所得的絨毛狀人造皮革，充分存在有每 單位截面積之纖維束之數、且具有緻密性，惟纖維束之扁 平率大於4.0時，纖維束之間所存在的空隙尺寸會有顯著 的斑點，且各處存在有尺寸大的空隙，結果，不僅無法得 到習知的絨毛狀人造皮革可達成的水準之粗絨毛外觀，且 -59- 201000713 表面摩擦之減量少、剝離情形明確增加而言，有少許的芯 存在且有膨脹感不充分之質感，無法滿足本發明目的之水 準。評估結果如表1所示。 比較例4 於實施例1中’除以截面之海成分聚合物與島成分聚 合物之平均面積比爲海成分/島成分=2〇/8〇，在平均截面積 爲147μηι2 (約2.0dteX)之條件使作爲構成長纖維纖維網之 海島型纖維之海島型纖維進行結紗以外，與實施例1相同 地製得壓花安定化的單位面積重量爲30g/m2之長纖維纖維 網。在所得的長纖維纖維網表面上，與實施例1相同地賦 予油劑後，以交叉層合機製造層狀長纖維纖維網，藉由與 實施例1相同的針刺處理進行絡合處理。使所得的不織布 構造體浸漬於7 0 °C之溫水浴中，進行熱收縮處理，再於沒 有乾燥處理下浸漬於90°C之熱水浴中以萃取除去海島型纖 維中之改性聚乙烯醇。如此製得由改性聚對苯二甲酸乙二 酯之極細長纖維束所形成、不含聚胺基甲酸酯組成物、單 位面積重量爲8 4 5 g/m2之人造皮革用基材。 然後，有關所得的人造皮革用基材’以與實施例2相 同的方法進行二分割處理、摩擦處理’形成由聚對苯二甲 酸乙二酯之極細纖維所形成的絨毛後，藉由進行以分散染 料之染色加工處理及整毛加工處理’作成米色之滅毛狀人 造皮革。所得的絨毛狀人造皮革與其他例不同 '與不具聚 胺基甲酸酯組成物無關’具有紮實的充實感之較佳質感。 然而，觀察截面時，發現有纖維束非常緻密集合的部分與 -60 - 201000713 稍微疏鬆的部分混在狀態，使該纖維束中具有斑點之基材 藉由摩擦處理所形成的絨毛表面，係爲來自斑點之絨毛數 多的部分與少的部分混在之故。進行評估與厚度方向平行 的截面中極細長纖維束之數密度時，表面附近多者爲1400 個/mm2 ’極細纖維束間之空隙尺寸爲 74μιη，自表面至 200μηι爲止之範圍內平均空隙尺寸爲42μιη。結果，全體具 有粗的絨毛外觀，不具滿足本發明目的之水準。評估結果 如表1所示。 比較例5 於實施例1中，除作爲構成長纖維纖維網之海島型纖 維，使用可形成除去成分聚合物（海成分聚合物）5層與纖維 成分聚合物（相當於島成分聚合物）6層交互重疊的重疊形 狀之截面的複合紡紗用噴嘴，以與實施例1相同的乙烯改 性聚乙烯醇作爲除去成分聚合物，且以與實施例1相同的 異苯二甲酸改性聚對苯二甲酸乙二酯作爲纖維成分聚合物 個別進行熔融處理。在使截面之除去成分聚合物與纖維成 分聚合物之平均面積比爲除去成分/纖維成分=35/65之壓 力平衡下供應該熔融聚合物，以平均截面積爲3 3 0 μιη2 (約 4.4dtex)之條件使海島型纖維進行紡紗以外，與實施例1相 同地製得壓花安定化的單位面積重量爲3〇g/m2之長纖維纖 維網。在所得的長纖維纖維網表面上，與實施例1相同地 賦予油劑後，以交叉層合機製造層狀長纖維纖維網。其次， 在層狀長纖維纖維網上與實施例1相同地以織針A進行預 備絡合處理後，以織針編號爲3 2號、繭絲深度爲6 〇 μιη ' -61 - 201000713 以9根針鈎之繭絲數、正三角形截面之織針D ’使繭絲朝 厚度方向貫通的針刺深度’使複合纖維朝厚度方向進行絡 合，自兩面以合計爲6 0 0針刺/ c m2之針剌數進行絡合處理 (以針刺D、大於1 0 0 0針刺/ c m2之針刺數進行針刺處理時， 大多數產生織針折損等之問題）’其次’以織針編號爲36 號、繭絲深度爲8 0 μιη、以1根針鈎的繭絲數、正三角形截 面之織針Ε，在沒有使繭絲朝厚度方向貫通的針刺深度， 以4 0 0針刺/ c m 2之針刺數進行針刺處理。以織針Ε進行針 刺處理後，觀察不織布構造體時，截面上多數爲藉由針刺 處理、朝厚度方向配向的纖維束’且在表面上觀察到因切 斷所產生的纖維端部約爲〇 · 5〜2 · 5條/mm2的頻率。在所得 的不織布構造體上，與實施例1相同地進行濕熱處理、壓 製處理，製得單位面積重量爲6 5 0 g/m2之不織布構造體。 在所得的不織布構造體中，與實施例1相同地使聚胺 基甲酸酯組成物存在於海島型纖維之空隙後’進行萃取除 去海島型纖維中之改性聚乙烯醇後’製得在由改性聚對苯 i 二甲酸乙二酯之極細長纖維束所形成的不織布構造體內部 含有聚胺基甲酸酯組成物 '厚度約爲1 .4mm之人造皮革用 基材。然後，有關所得的人造皮革用基材’以與實施例2 相同的方法進行二分割處理、摩擦處理’形成由改性聚對 苯二甲酸乙二酯之極細纖維所形成的絨毛後，藉由進行以 分散染料之染色加工處理及整毛加工處理，作成米色之絨 毛狀人造皮革。所得的絨毛狀人造皮革’觀察截面時’纖 維束之緻密性與實施例1相比，不僅明顯地惡化’且在纖 -62 - 201000713 維束之間存在的空隙尺寸有顯著的斑點，且各處存在有尺 寸極大的空隙，故不僅無法得到習知的絨毛狀人造皮革可 達成的水準之粗絨毛外觀，且具有極硬的骨感之質感，無 法滿足本發明目的之水準。評估結果如表1所示。 【表1】L times 'after the preliminary complexing treatment with the knitting needle A on the layered long fiber web in the same manner as in Example 1, the knitting needle number was 42, the twisting depth was 40 μm, and one needle was hooked. The number of twisted yarns, the needles of the equilateral triangle section c' the depth of the needles that penetrate the filaments in the thickness direction, and the island-in-the-sea fibers are complexed in the thickness direction' from the two sides to a total of 3 5 〇〇 acupuncture / cm 2 The number of needles is subjected to complexation treatment. In the obtained nonwoven fabric structure, wet heat treatment and press treatment were carried out in the same manner as in Example 1 to obtain a nonwoven fabric structure having a basis weight of 7 〇〇g/m2. -56 - 201000713 In the obtained nonwoven fabric structure, after the polyurethane resin composition was present in the void of the sea-island type fiber in the same manner as in Example 1, the modified polyvinyl alcohol in the sea-island type fiber was subjected to extraction and removal. A base material for artificial leather having a polyurethane composition having a thickness of about 1.4 mm in a nonwoven fabric structure formed of a string of elongated fibers of Nylon 6 was obtained. Then, the obtained base material for artificial leather was subjected to two-division treatment and rubbing treatment in the same manner as in Example 2 to form a pile formed of ultrafine fibers of Nylon 6, and then a liquid flow dyeing machine was used. The hydrochloric acid dye was subjected to a dyeing treatment in the same color tone as in Example 2, and a wool-like artificial leather of beige color was produced by performing the entire hair processing. The obtained fluffy artificial leather has insufficient compactness, and has a rough fluff appearance which is achievable by the conventional fluffy artificial leather. The surface friction durability is not particularly excellent, and it is not suitable for a texture having a hard and bone texture. The level of the object of the present invention is met. The evaluation results are shown in Table 1. Comparative Example 2 In the first embodiment, except for the use of a nozzle for a composite spinning which can form a cross section of a polymer having 00 island components, the sea-island type fiber which is a sea-island type fiber constituting the long fiber web is spun. An embossed stabilized long fiber web having a basis weight of 30 g / m 2 was obtained in the same manner as in Example 1. On the surface of the obtained long fiber web, an oil agent was applied in the same manner as in Example 1, and then a layered long fiber web was produced by a cross lamination machine. Next, in the same manner as in Example 1, the complexing treatment was carried out by a needling treatment. On the obtained nonwoven fabric structure, hot press treatment was carried out without applying water to obtain a nonwoven fabric structure having a unit weight of 97 Og/m2. -57 - 201000713 In the obtained nonwoven fabric structure, after the polyurethane composition was present in the void of the sea-island type fiber in the same manner as in Example 1, after the modified polyvinyl alcohol in the sea-island type fiber was extracted and removed, A substrate for artificial leather having a polyurethane composition and a thickness of about 1.4 mm in a nonwoven fabric structure formed of a very elongated fiber bundle of modified polyethylene terephthalate was obtained. Then, the obtained base material for artificial leather was subjected to a two-division treatment and a rubbing treatment in the same manner as in Example 2 to form a pile formed of ultrafine fibers of modified polyethylene terephthalate, followed by dispersion. The dye is dyed and processed and processed into a wool-like artificial leather. When the obtained pile-like artificial leather was observed to be dense, the fiber bundle of the upper surface layer actually collapsed in the thickness direction, and the flattened 'apparent density did not become too high. When the flattening ratio of the fiber bundle is more than 3.0, the most flattened fiber bundle is 4.7. When the surface portion densified by the flattened fiber bundle is raised by rubbing treatment, it returns to the same compactness as the loose portion which is not densified, and as a result, not only the conventional fluff-like artificial leather can be obtained. The appearance of the coarse fluff of the level achieved, and the structure in which the surface layer portion is extremely hard to the looseness near the center in the direction of the thickness of 1 degree, and the texture has a hard feeling on the surface of the corrugated cardboard inside, which cannot satisfy the object of the present invention. The level. The evaluation results are shown in Table 1. Further, in comparison with Example 2, since the ultrafine fibers forming the piles are finer, those which are dyed to the same color are whitened, and the color has no depth, which is a lack of high-grade appearance. Comparative Example 3 In Example 1, except that a nozzle for composite spinning which can form a cross section of 64 island components of polymerization -58 - 201000713 was used, the average cross-sectional area was 4 8 5 μ m 2 (about 6.6 dtex). In the same manner as in Example 1, except that the sea-island type fiber constituting the sea-island type fiber of the long fiber web was spun, a long fiber web having an embossed stability of 30 g/m 2 per unit area was obtained. . On the surface of the obtained long fiber web, an oil agent was applied in the same manner as in Example 1, and then a layered long fiber web was produced by a cross laminator. Next, in the layered long fiber web, in the same manner as in the first embodiment, the preliminary stitching treatment was performed by the knitting needle A, and the knitting treatment was performed by the knitting needle B. In the obtained nonwoven fabric structure, wet heat treatment and press treatment were carried out in the same manner as in Example 1 to obtain a nonwoven fabric structure having a basis weight of 990 g/m2. In the obtained nonwoven fabric structure, in the same manner as in Example 1, the polyurethane composition was present in the void of the sea-island type fiber, and the modified polyvinyl alcohol in the sea-island type fiber was extracted and removed, and then obtained. A base material for artificial leather having a polyurethane composition and a thickness of about 1.4 mm in a nonwoven fabric structure formed of a very long fiber bundle of modified polyethylene terephthalate. Then, the obtained base material for artificial leather was subjected to a two-division treatment and a rubbing treatment in the same manner as in Example 2 to form a pile formed of the ultrafine fibers of the modified polyethylene terephthalate. The dyed processing of the disperse dyes and the processing of the whole hair are carried out to produce a beige-colored artificial leather. The obtained fluff-like artificial leather sufficiently has the number of fiber bundles per unit cross-sectional area and has compactness. However, when the flattening ratio of the fiber bundle is more than 4.0, the void size existing between the fiber bundles may have significant spots. In addition, there are large-sized voids in various places, and as a result, not only the appearance of the rough fluff which can be achieved by the conventional fluff-like artificial leather can be obtained, but also the reduction of the surface friction of -59-201000713 is small, and the peeling situation is clearly increased, A small core exists and has a texture that is insufficiently inflated, and cannot satisfy the level of the object of the present invention. The evaluation results are shown in Table 1. Comparative Example 4 In Example 1, the average area ratio of the sea component polymer to the island component polymer divided by the cross section was sea component/island component = 2 〇 / 8 〇, and the average cross-sectional area was 147 μηι 2 (about 2.0 dteX). In the same manner as in Example 1, a long fiber web having an embossed stability of 30 g/m 2 was produced in the same manner as in Example 1 except that the sea-island type fiber constituting the sea-island type fiber of the long fiber web was subjected to yarn formation. On the surface of the obtained long fiber web, an oil agent was applied in the same manner as in Example 1, and then a layered long fiber web was produced by a cross laminator, and a complexing treatment was carried out by the same needling treatment as in Example 1. The obtained non-woven fabric structure was immersed in a warm water bath at 70 ° C, subjected to heat shrinkage treatment, and immersed in a hot water bath at 90 ° C without drying treatment to extract and remove the modified polyethylene in the sea-island type fiber. alcohol. Thus, a substrate for artificial leather which was formed of a very long fiber bundle of modified polyethylene terephthalate and which did not contain a polyurethane composition and had a unit weight of 8 4 5 g/m 2 was obtained. Then, the obtained base material for artificial leather was subjected to a two-division treatment and a rubbing treatment in the same manner as in Example 2 to form a pile formed of ultrafine fibers of polyethylene terephthalate, and then The dyeing process and the whole hair processing of the disperse dyes are made into a beige-colored wool-like artificial leather. The resulting fluffy artificial leather differs from the other examples in that it has a solid feeling of solidity regardless of the absence of the polyurethane composition. However, when observing the cross section, it was found that the portion of the fiber bundle which is very densely packed is mixed with the slightly loose portion of -60 - 201000713, so that the surface of the fluffy substrate formed by the rubbing treatment in the fiber bundle is derived from the surface of the fluff formed by the rubbing treatment. The part of the spot with a large number of fluff is mixed with a small part. When evaluating the number density of extremely thin fiber bundles in a section parallel to the thickness direction, the number of voids between the extremely fine fiber bundles is 1400/mm2 in the vicinity of the surface, and the average void size in the range from the surface to 200 μηι is 42μιη. As a result, the whole has a thick fluff appearance and does not have the level of meeting the object of the present invention. The evaluation results are shown in Table 1. Comparative Example 5 In Example 1, except for the sea-island type fiber constituting the long fiber web, 5 layers of a component-removing polymer (sea component polymer) and a fiber component polymer (corresponding to an island component polymer) 6 were used. The nozzle for composite spinning in which the layers overlap the overlapped cross-sectional shape, the same ethylene-modified polyvinyl alcohol as in Example 1 was used as the component-removing polymer, and the same isophthalic acid modified poly-pair as in Example 1 was used. Ethylene phthalate is separately melted as a fiber component polymer. The molten polymer was supplied under a pressure balance of an average area ratio of the component-removing polymer of the cross section to the fiber component polymer of the removal component/fiber component = 35/65, and the average cross-sectional area was 3 3 0 μm 2 (about 4.4 dtex). In the same manner as in Example 1, except that the sea-island type fiber was spun, a long fiber web having an embossed and stabilized basis weight of 3 〇g/m 2 was obtained. On the surface of the obtained long fiber web, an oil agent was applied in the same manner as in Example 1, and then a layered long fiber web was produced by a cross laminator. Next, in the layered long fiber web, the preliminary complexing treatment was carried out with the knitting needle A in the same manner as in Example 1, and the knitting needle number was 32, and the twisting depth was 6 〇μιη ' -61 - 201000713 to 9 The number of twisted yarns of the needle hook and the needle D' of the equilateral triangle section make the composite fiber in the thickness direction by the needle-punching depth of the twisted yarn in the thickness direction, and the total of the needles from the two sides is 6,000 needles/c The number of needles of m2 is complexed (in the case of acupuncture D, acupuncture treatment of more than 1000 needles/c m2, most of the problems of needle breakage, etc.) The number of needles is 36, the depth of the thread is 80 μm, the number of twists with one hook, the needle of the equilateral triangle, and the depth of the needle without the thread passing through the thickness. The needling number of acupuncture / cm 2 was acupuncture treatment. After the needle-punching treatment with the needle-punched enamel, when the non-woven fabric structure is observed, the cross-section is mostly a fiber bundle which is needle-aligned and oriented in the thickness direction, and the end of the fiber due to the cutting is observed on the surface. For 〇·5~2 · 5 strips / mm2 of frequency. In the obtained nonwoven fabric structure, a wet heat treatment and a press treatment were carried out in the same manner as in Example 1 to obtain a nonwoven fabric structure having a basis weight of 650 g/m2. In the obtained nonwoven fabric structure, in the same manner as in Example 1, the polyurethane composition was present in the void of the sea-island type fiber, and after the extraction and removal of the modified polyvinyl alcohol in the sea-island type fiber, it was obtained. The nonwoven fabric structure formed of the extremely elongated fiber bundle of the modified polyparaphenylene dicarboxylate contains a polyurethane substrate having a thickness of about 1.4 mm. Then, the obtained base material for artificial leather was subjected to a two-division treatment and a rubbing treatment in the same manner as in Example 2 to form a pile formed of ultrafine fibers of modified polyethylene terephthalate. The dyed processing of the disperse dyes and the processing of the whole hair are carried out to produce a beige-colored artificial leather. The resulting fluffy artificial leather 'in view of the cross section' has a denseness of the fiber bundle which is not only significantly deteriorated as compared with the first embodiment, and the void size existing between the bundles of the fibers - 62 - 201000713 has significant spots, and each There is a large-sized void at that place, so that not only the appearance of the rough fluff which can be achieved by the conventional fluff-like artificial leather but also the texture of the extremely hard bone feeling cannot be obtained, and the level of the object of the present invention cannot be satisfied. The evaluation results are shown in Table 1. 【Table 1】
實施例 比較例 2 1 2 3 4 5 複合纖維種類成分 海島型 海島型 海島型 海島型 海島型 重疊形狀 島成分(纖維成分） 聚合物 改性聚對 苯二甲酸 耐龍6 改性聚對 苯二甲酸 改性聚對 苯二甲酸 改性聚對 苯二甲酸 改性聚對 苯二甲酸 乙二酯 乙二酯 乙二酯 乙二酯 乙二酯 海成分(被萃取成 改性聚乙 改性聚乙 改性聚乙 改性聚乙 改性聚乙 改性聚乙 分)聚合物 烯醇 烯醇 烯醇 烯醇 烯醇 烯醇 極細長纖維條數 25 25 100 64 25 6 極細長纖維束之 截面積(μιη2) 250 230 160 722 184 270 極細纖維束之扁 平率 2.5 2.9 4.7 4.3 2.6 3.8 極細長纖維束截 面之個數(個/mm2) 2500 1350 1900 1600 1400 450 空隙尺寸(μιη) 52 78 74 82 74 107 絨毛之緻密性、 優美感 A B B C B C 質感之柔軟性、 膨脹感 A B C B A C 表面摩擦耐久性 A B C C C C 摩擦減量(mg) 8 42 220 25 15 <1 剝離狀態 A B A C C C -63 - 201000713 【產業上之利用價値】 使用本發明之人造皮革用基材所得的人造皮革’由於 以高水準兼具外觀、表面強度、質感等之性質，故可適合 使用於以夾克或裙子、襯衫或外套爲典型的衣料用、以運 動鞋或紳士婦人用皮鞋爲典型的鞋用、以皮帶爲典型的服 飾品用、以手提包或學生背包爲典型的皮包用、以沙發椅 或辦公桌爲典型的家具用、以汽車用或列車、飛機或船舶 爲典型的運輸工具之薄片或內裝材用、以高爾夫球手套或 ： 宴會用手套、棒球手套等之運動手套或駕駛用手套、作業 用手套爲典型的各種手套用等之用途。 由本發明之人造皮革用基材所得的絨毛狀人造皮革， 緻密性極高，具有如天然絨毛狀皮革之絨毛感的外觀。而 且，發色性優異，具有柔軟膨脹感且具有充實感之質感， 以及以耐剝離性爲典型的表面摩擦耐久性等習知不易兼具 的特性皆優異。另外，由本發明之人造皮革用基材所得的 粒面狀人造皮革’平滑性高、具有如皺摺極細的天然皮革 (之粒面感的外觀。此外’具有基材與粒面層之—體感、柔 軟、膨脹感之質感及黏合剝離強力等習知不易兼具的特性 皆優異。此等之人造皮革’可適合利用於衣料用、鞋用、 手提包用、家具用、車子座椅用、高爾夫球用手套等各種 運動用手套等之用途。 【圖式簡單說明】 【主要元件符號說明】 無。 -64-EXAMPLES Comparative Example 2 1 2 3 4 5 Composite fiber type component Island-type island-type island-type island-type island-type island type overlapping shape island component (fiber component) Polymer-modified polyterephthalic acid-resistant dragon 6 modified poly-p-phenylene Formic acid modified polyterephthalic acid modified polyterephthalic acid modified polyethylene terephthalate ethylene glycol ester ethylene glycol ester ethylene glycol ester sea component (extracted into modified polyethylene modified poly B modified poly-b-modified poly-b-modified poly-b-modified polyethylene) polymer enol enol enol enol enol-eol very slender fiber number 25 25 100 64 25 6 extremely slender fiber bundle Area (μιη2) 250 230 160 722 184 270 Flat rate of very fine fiber bundles 2.5 2.9 4.7 4.3 2.6 3.8 Number of sections of extremely thin fiber bundles (pieces/mm2) 2500 1350 1900 1600 1400 450 Clearance dimensions (μιη) 52 78 74 82 74 107 Compactness and elegance of fluff ABBCBC Softness of texture, feeling of swelling ABCBAC Surface friction durability ABCCCC Friction reduction (mg) 8 42 220 25 15 <1 Peeling state ABACCC -63 - 201000713 [Industrial The use price of the artificial leather used in the artificial leather substrate of the present invention is suitable for use in a jacket or a skirt, a shirt or a jacket because it has a high level of appearance, surface strength, texture and the like. For clothing, sneakers or gentlemen's shoes for shoes, belts for typical clothing, handbags or student backpacks for typical bags, sofas or desks for furniture. For sports vehicles or trains, airplanes or ships, typical for transporting sheets or interior materials, golf gloves or sports gloves such as banquet gloves, baseball gloves, etc., and driving gloves and work gloves are typical. Various uses for gloves, etc. The pile-like artificial leather obtained from the substrate for artificial leather of the present invention has extremely high compactness and has an appearance of a fluffy texture such as natural fluffy leather. Further, it is excellent in color developability, has a feeling of softness and a feeling of fullness, and is excellent in properties such as surface friction durability which is typically excellent in peeling resistance. In addition, the grain-like artificial leather obtained from the base material for artificial leather of the present invention has high smoothness and has a natural skin which is extremely finely wrinkled (the appearance of the grainy feeling. Further, the body having the base material and the grain layer) The texture, the softness, the texture of the swell and the peeling strength are excellent, and the characteristics are excellent. These artificial leathers are suitable for use in clothing, shoes, handbags, furniture, and car seats. , golf glove, and other sports gloves, etc. [Simplified illustration] [Main component symbol description] None. -64-