CN109072544A - 由原液染色的聚酯纤维组成的人造革及其制备方法 - Google Patents
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Abstract
本发明涉及一种由原液染色的聚酯纤维组成的人造革，其包含在人造革的生产过程中海岛复合纤维的岛成分中的炭黑以及聚氨酯聚合物弹性体。根据本发明，可以改善中等色和深色时的耐光牢度和耐摩擦牢度，同时表现出奢华的高质量，并减少人造革生产过程中使用的染料量。
Description
技术领域
本发明涉及通过使用原液染色的聚酯海岛型复合纱线而具有改进的牢度和染色生产率的人造革。
背景技术
通过将聚合物弹性体浸渍在由三维交织的超细纤维形成的非织造织物中，然后进行磨绒和染色来制备人造革。人造革具有光滑的纹理和独特的外观，与天然皮革相似，并且广泛应用于诸如鞋、服装、手套、杂货、家具和汽车内饰等各个领域。
传统的超细纱非织造人造革在均匀染色和超细纱的深色显色存在困难，由于聚氨酯弹性体的不可染性使纤维和聚氨酯弹性体彼此染色不同，会发生双色或不均匀染色，并且引入用于深色显色的过量染料使染色成本增加，由于牢度降低而难以实现高质量。
为了解决上述问题，已经开发了使用原液染色纤维的技术。
作为其示例，韩国专利公开No.1996-0023482公开了一种具有优异牢度和触感的人造革的生产方法。
根据该文献，描述了通过将聚氨酯树脂浸渍到由聚酰胺原液染色超细纱线制成的非织造织物并用还原染料进行染色的方法改进人造革的染色牢度。然而，根据该方法，使用还原染料与使用分散染料相比导致耐光性较低，并且因聚酰胺纤维的耐候性低而难以应用于汽车内部材料。
作为另一个例子，韩国专利公开No.2012-0021665公开了一种使用黑色原液染色的海岛型复合纱或黑色原液染色的分体型复合纱的人造革及其制备方法。
根据该文献，描述了通过使用圆形针织物改进人造革的牢度，通过用黑色原液染色的聚酯超细变形纱编织高收缩率的聚酯并制备变形纱线来生产该圆形针织物。
然而，根据该方法，由于聚酯原液染色纱限于生产圆形针织物，并且与由非织造织物制成的绒面革型人造革相比，其产品质量较差，因此存在在诸如家具、汽车内饰材料或奢侈品等高附加值产品中使用受限的问题。
在使用原液染色纱对超细纱非织造人造革的生产中使用聚酰胺纤维的情况下，必须使用金属络盐染料或还原染料，这引起与分散染料相比人造革的耐光性降低的问题。
另外，在使用原液染色纱对超细纱非织造人造革的生产中使用聚酰胺纤维的情况下，生产经编针织物或圆形针织物，这引起与非织造人造革相比产品质量差的问题。
发明内容
技术问题
为了解决上述问题，本发明通过使用原液染色的聚酯海岛型复合纱线并改善原液染色成分和人造革的制造工艺，提供具有改进的牢度和奢华的外观品质的人造革。
技术方案
为了解决上述问题，本发明提供一种由原液染色的聚酯纤维组成的人造革，其中，在包含海岛型复合纤维的非织造织物中浸渍黑色聚合物弹性体并用分散染料染色，所述海岛型复合纤维的岛成分为黑色原液染色聚酯。
此外，本发明提供一种由原液染色的聚酯纤维组成的人造革的制备方法，包括：由海岛型复合纤维长丝制备短纤维，所述海岛型复合纤维长丝由作为岛成分的包含0.08至3.00重量％的炭黑的黑色原液染色的聚酯组成；用短纤维针刺制备非织造织物；在所述非织造织物中浸渍包含1至6重量％炭黑的聚合物弹性体；通过从所述非织造织物中洗脱所述海岛型复合纤维的海成分以生产超细纤维并研磨所述非织造织物的表面来形成磨绒；以及使用分散染料对所述非织造织物进行染色。
有益效果
根据本发明，通过将黑色聚氨酯弹性体浸渍到由黑色原液染色的聚酯海岛型复合纤维制成的非织造织物中并用分散染料染色来制备人造革，因此人造革的中等色或深色时的耐光牢度和耐摩擦牢度得到改善，表现出奢华的品质，并且其可应用于诸如汽车内部材料等高级应用。
另外，在制造人造革的过程中减少的染料的量降低了成本。
具体实施方式
本发明涉及一种通过以下步骤制备具有改善的牢度特性的人造革的制备方法：通过由海岛型复合纤维长丝制备短纤维；由海岛型复合纤维制备短纤维；通过打开、梳理、交叉和针刺短纤维来制备非织造织物；在非织造织物中浸渍包含炭黑的聚合物弹性体；通过从浸渍后的非织造织物中洗脱海岛型复合纤维的碱溶性成分来形成超细纤维；通过研磨非织造织物的表面形成磨绒；以及使用分散染料对非织造织物进行染色。
制备海岛型复合纤维的步骤包括：使用溶解在溶剂中并且洗脱的海成分的第一聚合物、以及未溶解在溶剂中的剩余岛成分的第二聚合物进行复合纺丝的步骤。
海成分的第一聚合物可以是共聚聚酯、聚苯乙烯或聚乙烯等，优选是具有优异碱溶性的共聚聚酯。
岛成分的第二聚合物可以是尼龙或聚酯等，它们不溶于碱溶剂但可以用分散染料染色，其具体例包括聚对苯二甲酸乙二醇酯、聚氧乙烯苯甲酸酯、聚对苯二甲酸丁二醇酯三亚甲基、聚对苯二甲酸丙二醇酯、聚酰胺、聚丙烯酸、聚乙烯醇、聚对苯二甲酸乙二醇酯、乙酸酯等。
在复合纺丝中，将岛成分和海成分引入各自的挤压机中并熔融和挤出。当岛成分熔融并挤出时，炭黑母料被侧面供给到岛成分中。此后，岛成分和海成分经由复合纺丝喷嘴排出并被纺丝。由此，可以生产包含岛成分、黑色第二聚合物的海岛型长丝。
此时，具有比有机颜料更好的耐光性的炭黑在第二聚合物的岛成分中的含量优选包含0.08-3.00重量％。如果含量小于0.08重量％，则染的颜色浅，并且在耐光牢度的评价中曝光后颜色变得太浅，并且不能期望使用的染料量减少。当燃料量超过3.00重量％时，黑度变得过高，因此不容易染色成特定颜色。
根据本发明的生产非织造织物的步骤包括：将海岛型长丝形成为短纤维的步骤；通过对短纤维进行梳理和交叉铺网形成网的步骤；以及针刺所形成的网的步骤。
在非织造织物中浸渍聚合物弹性体的步骤的特征在于，在将聚合物弹性体溶解在诸如二甲基甲酰胺(DMF)的有机溶剂中以制备浸渍溶液的情况下，加入炭黑使得浸渍溶液的固体含量中炭黑的含量为1至6重量％并在搅拌下均化，在均化后用有机溶剂调节粘度以获得浸渍溶液，并将非织造织物浸渍在所获得的浸渍溶液中。
如果浸渍溶液的固体含量中炭黑的含量小于1重量％，则聚合物弹性体的色密度可低于人造革中纤维的色密度，如果其含量大于6重量％，则黑度增加的效果的发生的程度变得很小。
非织造织物中包含炭黑的聚合物弹性体的浸渍量对于应用于汽车内部材料，优选为20至40重量％。如果该含量小于20重量％，则聚合物弹性体的特有弹性难以表现，并且其对构成非织造织物的纤维的抓握能力下降，并且，由于坠落在最终人造革产品上的发生，其表面外观变差，如果含量超过40重量％，则柔软感会非期望地消失。
如上所述，由于炭黑直接包含在聚合物弹性体中，因此防止炭黑在染色后的还原清洗和漂洗中再次出现，并且炭黑与聚合物弹性体一起保留在人造革中，与通常的人造革生产方法相比，可以表现出优异的牢度特性。
在将非织造织物浸入到浸渍溶液中之后，浸渍在非织造织物中的聚合物弹性体在凝固浴中固化，然后在清洗浴中被洗涤。
随后，从非织造织物中除去海岛型复合纤维的海成分，以生产具有超细短纤维的非织造织物。
该处理通过使用诸如苛性钠水溶液的碱性溶剂来洗脱作为海成分的第一聚合物而仅保留作为岛成分的第二聚合物，来生产超细短纤维。
在这种情况下，优选为超细，使得在洗脱海成分后单纱的细度为0.04至0.30旦尼尔。如果超过0.30旦尼尔，则超细纤维特有的柔软触感不能展现，如果小于0.04旦尼尔，则添加的染料量大，并且牢度特性可能下降。
然后，使非织造织物磨绒。磨绒处理是通过诸如砂纸等擦拭超细非织造织物的表面，从而在非织造织物的表面上形成大量的毛羽。
染色处理可以在磨绒后执行。
用于染色处理的染料包括偶氮类分散染料、杂环偶氮类分散染料、蒽醌类分散染料、缩合分散染料、喹啉类分散染料、香豆素类分散染料、氨基酮类分散染料和二酯分散染料等。
另外，染色可以在将染料溶液的温度保持在100至135℃的状态下执行20至60分钟。
可以进一步执行用于去除染色的人造革表面上的未固着的染料或杂质的还原清洗处理。还原清洗处理可以在40至100℃下执行10至30分钟。通过还原清洗处理，人造革的颜色可以更清楚。
还原清洗液可以是氢氧化钠或亚硫酸氢钠。
在还原清洗步骤之后，可以进一步执行使用水的漂洗处理以进行清洗。
在下文中，将参考以下示例和对比例更详细地描述本发明。然而，应该注意的是，已经出于示例的目的描述了本发明的这些实施例，因此，本发明不限于此，并且对于本领域技术人员来说显而易见的是，在不脱离由以下权利要求所限定的本发明的精神和范围的情况下，可以进行修改和变型。
[示例1]
1)海岛型短纤维的制备
制备聚对苯二甲酸乙二醇酯作为岛成分，制备碱溶性共聚物聚酯作为海成分，将岛成分和海成分引入各自的挤压机中熔融并挤出，并且当岛成分熔融并挤出时，炭黑母料被侧面供给到岛成分中并经由纺丝喷嘴排出以制备在黑色聚对苯二甲酸乙二醇酯的岛成分中具有1.5重量％的炭黑的海岛型长丝。
然后，将海岛型长丝拉伸、卷曲以使卷曲数变为10/英寸，通过加热固定，然后切成51mm，以制备海岛型短纤维。
2)非织造织物的生产
通过对海岛型短纤维进行梳理和交叉铺网形成多层网，然后针刺，从而制备非织造织物。
3)浸渍有弹性体的非织造织物的生产
将非织造织物浸入到含有聚氨酯和炭黑的浸渍溶液中，使聚氨酯在甲基甲酰胺水溶液中凝固，用水洗涤，以制备黑色聚氨酯浸渍的非织造织物，在该黑色聚氨酯浸渍的非织造织物中浸渍含有5重量％炭黑的30重量％的聚氨酯弹性体。
4)人造革的生产
通过用浓度为5重量％的苛性钠水溶液处理浸渍有黑色聚氨酯的非织造织物，来洗脱海成分。由此，制备具有每根长丝分为16条纤维和0.15旦尼尔的单纱细度的黑色聚对苯二甲酸乙二醇酯纤维的非织造织物。
用粗糙度为#150的砂纸打磨非织造织物的表面以形成磨绒，然后在以下染色条件下染色。
<染色条件>
A)染料：
黑色分散染料(蒽醌类)0.8％o.w.f.(基于纤维的重量(on the weight offiber))
红色分散染料(蒽醌类)0.5％o.w.f.
蓝色分散染料(蒽醌类)1.5％o.w.f.
黄色分散染料(蒽醌类)0.5％o.w.f.
B)紫外线吸收剂：三嗪衍生物4.0％o.w.f.
C)分散剂：非离子脂肪酸酯1g/L
D)酸：乙酸1g/L
E)浴比(添加剂重量：溶剂重量)：1：20
F)染色温度和时间：125℃，50分钟
染色完成后，将染色残渣从染色机中排出，再次将水加入到染色机中，然后在还原清洗条件下还原清洗(次氯酸钠：8g/L，氢氧化钠：4g/L，浴比1：20)并干燥，从而制备具有深黑色的人造革。
[示例2和3]
除了如表1所示的海岛型长丝的岛成分中的炭黑含量、聚氨酯中的炭黑含量以及染色中的染料量以外，以与示例1相同的方式执行示例。在示例2中制备具有中等色的黑色或深灰色的人造革，在示例3中制备具有浅灰色的人造革。
[比较例1至6]
除了如表1所示的海岛型长丝的岛成分中的炭黑含量、聚氨酯中的炭黑含量以及染色中的染料量以外，通过执行与实施例1相同的方式制备人造革。
[表1]
表2显示了在上述示例和比较例中染色材料的使用CCM测量的比色值。
[表2]
从上表1和表2可以确认，示例中用于相同的色密度的染料的量小于比较例中的染料的量。
使用以下评价方法对上述示例和比较例的评价结果示于下表3中。
<评价方法>
1.耐光牢度
按照ISO 105-B06：1998中规定的方法(条件5)，用338.6KJ/m2的光量照射上面的示例和比较例中制备的人造革，并使用灰度(ISO 105A02)确定耐光牢度等级。
2.耐摩擦牢度
按照ISO 105X12方法测量耐摩擦牢度。
在耐干摩擦牢度的评价中，将与纵向方向平行的50mm宽和130mm长的两个试样固定到摩擦测试机的测试台，并且测试辊的橡胶用50mm宽和50mm长的白棉布覆盖并固定。在对橡胶施加9±0.2N的载荷后，试样表面以10次/分钟的往复速度和100mm的通过距离往复运动10次。白棉布被剥除，并且根据灰度判断白棉布的污染程度。
按照与耐干摩擦牢度相同的方式来评价耐湿摩擦牢度，白棉布中的水分为98％至100％。
3.染料量(单位：次)
其通过将比较例中染料的总使用量除以(％O.w.f.)示例中染料的总使用量(％o.w.f.)来计算。
4.表面色彩均匀度
如果人造革没有显示聚氨酯的色彩来展现二色性，其被标记为差，如果不是这样，其被标记为良好。
<评价结果>
[表3]
从表3可知，当由人造革和聚氨酯组成的超细纤维都含有炭黑(示例1、2和3)时，其耐光牢度、耐干摩擦牢度和耐湿摩擦牢度为4级或以上，被确认为优异，并且表面色彩均匀度也优异。
此外，在没有炭黑的超细纱的情况下(比较例1至6)，耐光牢度显著降低，特别是，当在超细纱和聚氨酯中都不存在炭黑时，可以确认到，为了显示相同的颜色，所使用染料的量增加。
[工业应用性]
如上所述，本发明能够解决以下问题，例如，用于绒面革家具表皮材料、包的内皮和外皮等时尚商品的非织造人造革中深色的均匀染色、以及均匀和清晰地显色的困难。通过改善为了中等色或深色的显色而添加过量染料的问题，能够节省成本并改善牢度特性。
Claims (5)
1.一种由原液染色的聚酯纤维组成的人造革，其中，包含海岛型复合纤维的非织造织物浸渍有黑色聚合物弹性体并用分散染料染色，所述海岛型复合纤维的岛成分为黑色原液染色聚酯。
2.根据权利要求1所述的由原液染色的聚酯纤维组成的人造革，其中，所述黑色原液染色聚酯包含0.08重量％至3.00重量％的炭黑。
3.根据权利要求1所述的由原液染色的聚酯纤维组成的人造革，其中，所述黑色聚合物弹性体包含1重量％至6重量％的炭黑。
4.根据权利要求1所述的由原液染色的聚酯纤维组成的人造革，按照ISO105-B06：1998方法(条件5)，具有至少4级的耐光牢度、至少4级的耐干摩擦牢度和至少4级的耐湿摩擦牢度。
5.一种由原液染色的聚酯纤维组成的人造革的制备方法，包括：
由海岛型复合纤维长丝制备短纤维，所述海岛型复合纤维长丝由作为岛成分的、包含0.08重量％至3.00重量％的炭黑的黑色原液染色聚酯组成；
通过对所述短纤维进行针刺制备非织造织物；
在所述非织造织物中浸渍包含1重量％至6重量％的炭黑的聚合物弹性体；
通过从所述非织造织物中洗脱所述海岛型复合纤维的海成分以生产超细纤维并研磨所述非织造织物的表面，来形成磨绒；以及
使用分散染料对所述非织造织物进行染色。
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| CN111041859A (zh) * | 2019-12-23 | 2020-04-21 | 明新孟诺卡(辽宁)新材料有限公司 | 一种高色牢度的涤纶超纤染色方法 |
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- 2017-12-06 US US16/097,406 patent/US20190153668A1/en not_active Abandoned
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| JP2005133256A (ja) * | 2003-10-31 | 2005-05-26 | Kuraray Co Ltd | 耐光堅牢性の良好なスエード調人工皮革およびその製造方法 |
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| CN111164258A (zh) * | 2017-09-25 | 2020-05-15 | 可隆工业株式会社 | 使用纺液染色的聚酯海-岛型复合纱线的非织造人造革及其制造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3421661A1 (en) | 2019-01-02 |
| KR20180075907A (ko) | 2018-07-05 |
| WO2018124524A1 (ko) | 2018-07-05 |
| CN109072544B (zh) | 2021-01-29 |
| JP2019511644A (ja) | 2019-04-25 |
| US20190153668A1 (en) | 2019-05-23 |
| EP3421661A4 (en) | 2019-11-06 |
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