CN101331265B - 具有优异的强度和伸长率性质的绒面状人造革 - Google Patents

具有优异的强度和伸长率性质的绒面状人造革 Download PDF

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CN101331265B
CN101331265B CN2006800477137A CN200680047713A CN101331265B CN 101331265 B CN101331265 B CN 101331265B CN 2006800477137 A CN2006800477137 A CN 2006800477137A CN 200680047713 A CN200680047713 A CN 200680047713A CN 101331265 B CN101331265 B CN 101331265B
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fabric
artificial leather
yarn
suede
woven fabric
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CN101331265A (zh
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黄永男
金元俊
姜盛元
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Kolon Industries Inc
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    • D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
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Abstract

本发明涉及一种具有优异的强度和伸长率性质的绒面状人造革。所述绒面状人造革包含在其中填充有聚氨酯的复合片材，所述复合片材包含：相互缠结并且细度小于0.3旦尼尔的超细短纤维的非织造织物；以及被置于所述非织造织物中的机织物或针织物，所述机织物或针织物与非织造织物的超细短纤维缠结，并且在8kgf的负载下具有10至30％的恒定负载伸长率，其中在纵向和横向上的拉伸强度为35至60kgf/50mm，并且在纵向和横向上的恒定负载伸长率为8至25％。由于其优异的拉伸强度和恒定负载伸长率，所述绒面状人造革可用作用于需要耐久性的家具和车辆的材料。

Description

具有优异的强度和伸长率性质的绒面状人造革
技术领域
本发明涉及一种具有优异的强度和伸长率性质的绒面状人造革，并且更具体地，涉及一种可用作用于车辆、家具等的高耐久性材料，原因是它具有优异的拉伸强度和恒定的负载伸长率。 
现在，由具有三维交联的微纤维和浸渍在非织造织物中的聚氨酯树脂(聚氨酯弹性体)的非织造织物制成的人造革被广泛用作迅速代替用于家具或车辆的天然革的材料，原因是它具有与天然革类似的软触感以及独特的外观。 
近年来，具有高功能性以及仿造天然革的软触感以及独特外观的常规特征的人造革正在得到积极的研究。特别是，需要这样的人造革：它需要形状稳定性以在用于车辆、家具等时具有对过度的摩擦以及外力的耐久性，并且它具有适合的强度以及伸长率以当它在弯曲区域使用时使缝制和装配的可加工性变得更容易。 
背景技术
作为用于得到人造革形状稳定性的常规技术，美国专利5,112,421、美国公开专利2005/0009426 A1等提出了一种这样的方法：在非织造织物的制造中将织物***由棉花制成的料片层(web layer)之间以具有稳定的缝合强度和恒定的负载伸长率性质。 
然而，上述方法的不利之处在于尽管强度高，但是由于织物的***，恒定的负载伸长率变得远远更小，从而在这种方法用于具有许多弯曲区域的家具或者车辆时，使手动工作如座位装配变得困难。 
同时，日本专利公开2004-332173提出了下面的方法：在非织造织物的制造过程中，通过将拉伸针织物或者机织物***到短纤维料片层的中间以制造人造革，所述织物通过喷水法由聚氨酯弹性纱线制成。 
然而，根据上述方法，针织物或机织物只由聚氨酯弹性纱线制造，使得难以通过针刺***。因此，形成结合的褶，原因是结合是使用喷水法进行的，从而使表面不均匀。另外，伸长率过高并且强度弱，导致令人不满意的形状稳定性，使得织物不可以用于家具和车辆。
如上所述，通过常规方法制造的人造革具有良好的强度以及差的伸长率，或者相反，并且外观令人不满意。因此，它们不适合作为用于需要高耐久性以及漂亮外观的家具和车辆的人造革。 
发明内容
(本发明所要解决的问题) 
本发明的一个目的是提供一种人造革，所述人造革通过控制结合到料片上的机织物和针织物的强度和伸长率，以具有改善弯曲区域的缝制和装配的可加工性的强度以及伸长率，以及对过度摩擦和外力的形状稳定性，并且根据机织物和针织物的强度和伸长率适当地实现最终产品的强度和伸长率。 
(技术方案) 
为了达到上述目的，根据本发明，提供一种绒面状人造革，所述绒面状人造革包含在其中填充有聚氨酯的复合片材，所述复合片材包含：相互缠结并且细度小于0.3旦尼尔的超细短纤维的非织造织物；以及置于所述非织造织物中的机织物或针织物，所述机织物或针织物与非织造织物的超细短纤维缠结，并且在8kgf的负载下具有10至30％的恒定负载伸长率，其中在纵向和横向上的拉伸强度为35至60kgf/50mm，并且在纵向和横向上的恒定负载伸长率为8至25％。 
现在将在以下详细描述本发明。 
首先，本发明的绒面状人造革具有35至60kgf/50mm的在纵向和横向上的拉伸强度，以及8至25％的在纵向和横向上的恒定负载伸长率。 
在人造革用于家具、车辆等的材料的情况下，需要适当地延长人造革的装配加工性，以使缝制和装配工作变得更容易，以及需要用于防止过大的伸长率的形状稳定性。在形状稳定性方面，如果恒定的负载伸长率大于25％，则人造革在使用过程中继续延长，从而损害产品的永久价值。在装配可加工性方面，如果拉伸强度小于35kgf/50mm，或者恒定负载伸长率小于8％，则在装配过程中可能损害产品，并且压力和张力可能被施加到工作者的身体上。另外，如果拉伸强度大于60kgf/50mm，则恒定负载伸长率变得过低，从而导致上述问题。 
典型的人造革由小于0.3旦尼尔的超细短纤维和聚氨酯弹性体组成。然而，在本发明中，作为用于获得强度和伸长率性质的手段，将具有强度和伸长率性质的机织物或针织物作为增强材料加入到典型人造革中。机织物或针织物对于使本发明的人造革产品获得强度和伸长率性质是重要的组成部分。 
更重要的是，根据作为增强材料***的非机织物或针织物的经纱和维纱的密度及其恒定负载伸长率，产品的强度和伸长率性质大大不同。特别是，很重要的是使非织造织物中的超细短纤维与机织物或针织物整体地缠结以获得令人满意的外观和物理性能。在通过针刺法制造的情况下，机织物或针织物的经纱和纬纱的密度优选为20至100根纱线/英寸。如果密度小于20根纱线/英寸，则它太弱而不能充分地起着增强材料的作用，从而使产品的拉伸强度下降。如果密度大于100根纱线/英寸，则存在的更大可能性是在针穿过机织物或针织物的网孔时损害增强材料。在这种情况下，增强材料的恒定负载伸长率降低，从而也使产品的恒定负载伸长率劣化。 
另外，被应用于本发明的机织物或针织物在8kgf的负载下测量的恒定负载伸长率为10至30％。机织物或针织物的恒定负载伸长率是对产品的恒定负载伸长率具有最大的影响的因素。对于只包含由超细短纤维和聚氨酯填充材料组成以及在其内没有增强材料的非织造织物的典型人造革，其恒定负载伸长率太大，以致伸长率不适于作为用于车辆或家具等的材料的应用。因此，作为用于获得恒定负载伸长率的方法之一，***并且介入机织物或针织物，这使机织物或针织物的恒定负载伸长率变得很重要。当将机织物或针织物连结到非织造织物上时，机织物或针织物的恒定负载伸长率变得更小。因此，为了具有大于8％且小于25％的恒定负载伸长率，最优选机织物或针织物具有上述恒定负载伸长率。 
另外，在本发明中使用的机织物或针织物可以由一种或两种以上的纱线组成，所述纱线选自聚对苯二甲酸乙二醇酯纱线、聚对苯二甲酸丙二醇酯纱线、聚酰胺纱线、聚氨酯纱线、聚乙烯纱线和聚丙烯纱线。而且，包含机织物或针织物的纱线是长丝纱线或短纤维纱线。
增强的机织物或针织物可以通过针刺法缠结到非织造织物的短纤维料片层上，或者通过高压喷水交联到其上。 
具有优异的强度和伸长率性质的本发明的绒面状人造革的制造是通过下面一系列处理步骤实现的。 
具体而言，制备在8kgf的负载下测量的恒定负载伸长率为10至30％的机织物或针织物，然后制备在溶解或分离后细度小于0.3旦尼尔的超细短纤维料片，从而通过针刺法将机织物或针织物层和超细片幅层结合。使用其针倒刺(barb)的数量为1以下的针以防止对机织物或针织物层的损害，并且通过调节倒刺的角度，将与机织物或针织物接触的可能性最小化。结合所需的穿孔密度在每1cm2的单位面积优选为1500至3000次(time)。其中结合有机织物或针织物的复合片材的密度应当落入0.200至0.250g/cm2的范围内。 
在本发明中使用的小于0.3旦尼尔的超细短纤维可以由聚酰胺聚合物、聚酯聚合物、聚烯烃聚合物和聚氨酯聚合物中的一种或两种以上组成。 
将3至15％浓度的聚乙烯醇或羧甲基纤维素的水溶性聚合物溶液填塞在非织造织物和机织物或针织物的复合片材上，并且干燥，以相对于纤维的重量具有5至20重量％的量。这种方法对于防止最终产品的触感为坚硬是有效的，这种触感是在浸渍聚氨酯树脂的后续处理中由与转变为细纤维束的纤维过度结合的聚氨酯树脂产生的。 
接着，对复合片材进行聚氨酯湿法浸渍处理。在这个步骤中使用的聚氨酯弹性体容易溶解于由聚二醇(macroglycol)、二异氰酸酯和低分子量的二醇或二胺组成的直链聚合物材料中，或者容易溶解于一些交联聚合物材料，如二甲基甲酰胺(以下称为“DMF”)中。 
在本发明中使用的聚二醇可以包括聚醚二醇、聚酯二醇、聚醚聚酯共聚物二醇、聚碳酸酯二醇等。 
在本发明中的低分子量二醇可以包括4，4’-丁二醇、乙二醇等。还可以使用二胺碱如亚甲基-双((4，4’-苯胺)的增链剂。通过将洗涤剂、颜料、功能粒子等加入这种聚氨酯弹性体的DMF溶液中，并且稀释所得溶液，从而制备出浸渍溶液。 
将复合片材浸渍在浸渍溶液中，然后将聚氨酯在水溶液中凝结，在50至80℃热水中洗涤以完全除去临时填充的水溶性聚合物，然后干燥。相对复合片材的重量，在干燥之后的聚氨酯的含量优选为20至50重量％。 
通过用能够溶解或者分离溶解组分的溶剂或氢氧化钠水溶液除去溶解组分(海(sea)组分)，将纤维连续地转化为细纤维的束。 
在溶解组分(海组分)为共聚聚酯的情况下，使用5至15％的氢氧化钠的水溶液，通过连续或不连续的布置方法分解海组分。在溶解组分为聚乙烯或聚苯乙烯的情况下，通过用甲苯、全氯乙烯或三氯乙烯处理以除去海组分。 
例如，通过用10％的氢氧化钠水溶液在100℃处理5至10分钟，将海组分的共聚聚酯完全分解并且除去。此时，尽管由非织造织物和机织物或针织物组成的复合片材的厚度降低至某种程度，但是因为它们的溶解组分(海组分)被除去，所以通过机织物或针织物的结构将复合片材的形状保持得很好，由机械拉伸力所导致的纵向伸长程度不大，并且复合片材的表面表观密度得到提高。 
接着，通过装备有合适粗糙度的砂纸的抛光机对如此获得的皮革形式的复合片材的表面进行抛光，从而在表面上形成凸起的纤维，然后绒毛蓬松。根据其用途选择砂纸的粗糙度。通常，优选使用150至400目的砂纸。 
根据其应用，将在其中形成有绒毛的皮革形式的复合片材染色。在所用的纤维包含尼龙-6的情况下，通常使用金属配合物染料或者磨蚀型酸性染料将它染色。在聚酯的情况下，使用分散染料在高压快速印染机中将它染色。 
最后，对染色的产品进行软化和功能试剂处理，从而制备高等级的复合绒面状人造革。 
通过本发明制造的人造革使弯曲区域上的缝制和装配可加工性变得更容易，以及具有形状稳定性，该形状稳定性提供对外力的耐久性，原因是强度和伸长率性质是很优异的，即，拉伸强度为35至60kgf，并且在8kgf的负载下测量的恒定负载伸长率为8至25％。本发明的人造革适合作为用于需要形状稳定性的家具、车辆等的高耐久性材料。 
在本发明中，人造革的复合片材的各种物理性能按如下测定。 
·超细纤维的细度(旦尼尔)
取得人造革的复合片材的横截面的样品，并且对其应用制剂处理如金涂料涂覆。通过扫描电子显微镜(SEM)分析器以恒定的放大倍率拍摄样品的横截面照片。估算在照片上显示的超细纤维的一根线材的直径，并且将其转变为实际值，然后通过下式获得细度。 
细度(旦尼尔)＝9πD2ρ/4000 
在该式中，π是圆周与直径的比率，D为超细纤维的横截面的直径，并且ρ为超细纤维的密度(g/cm3)。所用的尼龙密度为1.14，并且所用的聚对苯二甲酸乙二醇酯的密度为1.38。 
·恒定负载伸长率(％)
从绒面状人造革的复合片材和从机织物或针织物中在纵向和横向上切割出各自的宽度为50mm并且长度为250mm的三个试样，并且沿着它们的中心区域标记100mm的显示线。将这些试样以150mm的夹持距离安装在疲劳实验机(*)上，并且将78.4N(8kg)的负载(包括较低的夹子的负载)仔细地悬挂在试样上达10分钟。在悬挂负载10分钟的情况下，获得在显示线之间的距离(l0)，并且通过下式计算恒定负载伸长率； 
恒定负载伸长率(％)＝l0-100 
在该式中，l0表示在悬挂8kg的负载10分钟之后，在显示线之间的距离(mm)。作为疲劳实验机的*，使用‘Marlens疲劳实验机’。 
.拉伸强度(Kgf/50mm)
分别在纵向和横向上，从样品中取出5个试样，每一个试样具有50mm宽度和250mm长度。 
将试样的上部夹紧在Densiron型或其相当的拉伸强度实验机上，并且将适当的初始负载施加到其上，使得试样是垂直的，并且与水平线一致，从而提供150mm的夹持距离。 
初始负载指将不自然的皱褶或弯曲变平所需的负载。特别是，将非特指的织物的初始负荷设定为1.96N(200gf)。 
5个试样的撕裂所需的负载(kgf/50mm)是在200200mm/min的牵引速度下测量的并且平均化。 
(有利效果) 
本发明在弯曲区域上的缝制和装配可加工性变得更容易，以及具有提供对外力的耐久性的形状稳定性，原因是强度和伸长率性质是很优异的。 
实施本发明的最佳方式 
以下，将参考实施例详细描述本发明，但不限于此。 
实施例1
通过纺丝和拉伸处理，由70重量％的作为纤维形成组分的聚对苯二甲酸乙二醇酯和30重量％的作为萃取组分的共聚物聚酯制备出海岛式的复合连续纤维，所述复合连续纤维具有75旦尼尔的总细度，并且可被转化为细纤维束。此时，连续纤维的单丝具有3.1的旦尼尔并且在其中具有16根超细纤维(纤维形成组分)。连续纤维起皱并且设定在170℃以给它提供适合的恒定负载伸长率。 
在通过在捻丝机中以650捻/分钟加捻以制造编织织物的过程中，将这样获得的复合纤维用作经纱和纬纱。将经纱和纬纱制造成编织织物，该织物具有70纱线/英寸的经纱密度和70纱线/英寸的纬纱密度。在编织织物的长度(纵向)方向上的恒定负载伸长率为20％，并且在其宽度(横向)方向上的恒定负载伸长率为22％。 
同时，通过纺丝和卷曲切割处理，由70重量％的作为纤维形成组分的聚对苯二甲酸乙二醇酯和30重量％的作为萃取组分的共聚物聚酯制备出短纤维，该短纤维具有51mm的长度、2.5旦尼尔的单丝细度、以及在单丝中为36根超细纤维(纤维形成组分)。通过梳理、交叉搭接处理，上述短纤维形成料片，并且在非织造织物的制备过程中通过针刺，将这种料片与编织织物结合，从而形成复合片材。然后，将非织造织物和编织织物的复合片材填塞在10％聚乙烯醇水溶液中，并且干燥，以使相对于纤维的重量，具有10重量％的量。然后，将复合片材浸渍在15％的浸渍溶液中，所述浸渍溶液是通过将聚醚-聚酯共聚物二醇类的聚氨酯弹性体稀释在二甲基甲酰胺(DMF)中而制备的。然后，将聚氨酯在水溶液中凝结，在70℃水热溶液中洗涤以完全除去聚乙烯醇聚合物，并且干燥。在干燥步骤后的聚氨酯的含量被发现为35重量％。通过将其在100℃的10％氢氧化钠水溶液中持续处理以完全除去海组分，即共聚物聚酯，使得只留下岛组分，即聚酯细纤维的组分，上述由纤维和聚氨酯构成的皮革形式的复合片材被转化为细纤维束。然后，将一部分超细纤维切割出来，并且通过使用#240粗砂砂纸进行抛光处理而形成凸出，以获得绒毛，从而制备了具有优异的强度和伸长率性质的皮革形式的复合片材。接着，在高压快速印染机中，用具有优异坚牢性的分散染料将所得的片材染色。然后将片材处理(reduced)、清洁并且干燥。连续进行防水剂和抗静电剂处理和绒毛尖端软化处理，从而制备用于人造革的绒面状复合片材。评价这样获得的用于人造革的复合片材的物理性能，并且结果示于表2中。 
实施例2至3以及比较例1和2
除了将在编织织物的制造中所用的经纱和纬纱的种类和细度改变为如表1那样之外，以与实施例1中相同的方式制备用于人造革的复合片材。评价物理性能，并且示于表2中。 
<表1>制备条件 
  分类   实施例1   实施例2   实施例3   比较例1   比较例2
  织物的纱线组   分   聚对苯二  甲酸丙二   醇酯   聚酰胺   聚对苯  二甲酸  乙二醇   酯   聚对苯二  甲酸乙二   醇酯   聚对苯二  甲酸乙二   醇酯
  纱线的纤维的   细度(旦尼尔)   0.14   0.24   0.06   0.14   0.14
  织物的经纱和   纬纱的密度   70×70   40×40   70×70   25×25   100×100
  织物在纵向上  的恒定负载伸  长率(％)   20   25   15   35   5
  织物在纵向上  的恒定负载伸  长率(％)   22   29   18   40   6
<表2>绒面状人造革的复合片材的物理性能的评价结果 
  分类   实施例1   实施例2   实施例3   比较例1   比较例2
  拉伸强度(纵向×  横向)(kgf/50mm)   55×56   46×43   48×45   30×29   60×56
  恒定负载伸长率   (纵向×横向)(％)   11×14   19×24   15×17   28×30   4×5
*纵向是组成用于绒面状人造革的复合片材的机织物或针织物的经纱方向，而横向是机织物或针织物的纬纱方向。 
工业可适用性
因为强度和伸长率的性质很优异，本发明使在弯曲区域上的缝制和装配可加工性变得更容易，以及具有提供对外力的耐久性的形状稳定性。由于这样，本发明有利于作为用于需要耐久性的家具和车辆的材料。 

Claims (4)

1.一种绒面状人造革，所述绒面状人造革包含在其中填充有聚氨酯的复合片材，所述复合片材包含：相互缠结并且细度小于0.3旦尼尔的超细短纤维的非织造织物；以及被置于所述非织造织物中的机织物或针织物，所述机织物或针织物与非织造织物的超细短纤维缠结，并且在8kgf的负载下具有10至30％的恒定负载伸长率，其中在纵向和横向上的拉伸强度为35至60kgf/50mm，并且在纵向和横向上的恒定负载伸长率为8至25％，其中所述复合片材的密度为0.200至0.250g/cm2。
2.权利要求1所述的绒面状人造革，其中所述机织物或针织物的经纱密度和纬纱密度为20至100根纱线/英寸。
3.权利要求1所述的绒面状人造革，其中所述机织物或针织物由长丝纱线或短纤维纱线组成。
4.权利要求1所述的绒面状人造革，其中所述机织物或针织物由一种或两种以上的纱线组成，所述纱线选自聚对苯二甲酸乙二醇酯纱线、聚对苯二甲酸丙二醇酯纱线、聚酰胺纱线、聚氨酯纱线、聚乙烯纱线和聚丙烯纱线。
CN2006800477137A 2005-12-19 2006-12-18 具有优异的强度和伸长率性质的绒面状人造革 Active CN101331265B (zh)

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WO2007073067A1 (en) 2007-06-28
TWI323304B (en) 2010-04-11
US20080293316A1 (en) 2008-11-27
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CN101331265A (zh) 2008-12-24
KR100658097B1 (ko) 2006-12-14

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