CN113544325A - 粒面皮革状片 - Google Patents

粒面皮革状片 Download PDF

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Publication number
CN113544325A
CN113544325A CN202080019027.9A CN202080019027A CN113544325A CN 113544325 A CN113544325 A CN 113544325A CN 202080019027 A CN202080019027 A CN 202080019027A CN 113544325 A CN113544325 A CN 113544325A
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China
Prior art keywords
polyurethane
grain
leather
sheet
intermediate layer
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Granted
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CN202080019027.9A
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English (en)
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CN113544325B (zh
Inventor
芦田哲哉
原宽齐
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Kuraray Co Ltd
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Kuraray Co Ltd
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Abstract

本发明提供一种粒面皮革状片，其具备：纤维基材、层叠于纤维基材的聚氨酯中间层、以及直接或夹隔其它聚氨酯层而层叠于聚氨酯中间层的聚氨酯表面被膜，聚氨酯表面被膜包含有机硅改性聚氨酯，所述粒面皮革状片具有凹凸表面，所述凹凸表面的基于ISO25178的表面粗糙度的偏度(Ssk)、峰度(Sku)及最大高度(Sz)满足60μm≤Sz≤150μm、‑0.4≤Ssk≤‑0.2及3≤Sku≤4。

Description

粒面皮革状片
技术领域
本发明涉及耐划痕性优异的粒面皮革状片。
背景技术
作为皮包、衣料、鞋等的表皮材料，已知具有与天然皮革相似的粒面外观的粒面皮革状片。在用锋利的物体刮擦这样的粒面皮革状片的表面时，会产生划痕(擦伤、scratch)。这样的划痕有损粒面皮革状片的外观。以往，提出了一些使粒面皮革状片不易产生划痕、或使产生的划痕不明显的技术。
例如，在下述专利文献1中，作为耐划痕性得到改进的皮革状成型品，公开了一种皮革样成型品，其在将胶原蛋白添加至合成树脂原材料或与合成树脂原材料发生了局部反应而得到的成型品上层叠有最上层、或者在设置了使胶原蛋白分散于基材上而成的合成树脂层的基础上层叠了最上层，该最上层由未添加胶原蛋白或未发生局部反应的合成树脂原材料构成。
另外，下述专利文献2公开了一种具有表面的平滑感和光泽度、颜色的鲜明感、且耐划性、耐擦伤性及耐折痕性优异、手感良好的粒面皮革状片。具体而言，公开了一种粒面皮革状片，其依次层叠有纤维基材层、聚氨酯无孔层、包含粘结剂聚氨酯和粒径1～50μm的聚氨酯微粒的聚氨酯表面层，聚氨酯无孔层和该聚氨酯表面层的总厚度为150μm以上，该聚氨酯表面层含有相对于该粘结剂聚氨酯100质量份为10～40质量份的该聚氨酯微粒，该聚氨酯微粒未露出至聚氨酯表面层的表面。
另外，在下述专利文献3中，作为在带有划痕、压痕时通过进行加热而能够容易地修复伤痕的皮革状片，公开了一种具有包含形状记忆性聚氨酯弹性体的粒面层的皮革状片。
另外，下述专利文献4公开了一种兼具对涂膜伤痕的自修复性和耐久性的自修复性优异、且包含丙烯酸类树脂、多异氰酸酯及添加剂的自修复型形成性涂敷组成物。
现有技术文献
专利文献
专利文献1：日本特开平5-279967号公报
专利文献2：国际公开2006/137394号
专利文献3：日本特开2016-211129号公报
专利文献4：日本特开2012-107101号公报
发明内容
发明所要解决的课题
对于粒面皮革状片而言，存在容易残留划痕的问题。本发明的目的在于提供不易残留划痕的粒面皮革状片。
用于解决课题的方法
本发明人等为了获得耐划痕性优异的粒面皮革状片，发现了不易残留划痕的粒面皮革状片的表面状态，从而想到了本发明。
即，本发明的一个方面为一种粒面皮革状片，其具备纤维基材、层叠于纤维基材的聚氨酯中间层、以及直接或夹隔其它聚氨酯层而层叠于聚氨酯中间层的聚氨酯表面被膜，聚氨酯表面被膜包含有机硅改性聚氨酯，所述粒面皮革状片具有凹凸表面，所述凹凸表面的基于ISO25178的表面粗糙度的最大高度(Sz)、偏度(Ssk)、以及峰度(Sku)满足60μm≤Sz≤150μm、-0.4≤Ssk≤-0.2、以及3≤Sku≤4。这样的粒面皮革状片具有凹凸表面，具有包含有机硅改性聚氨酯的聚氨酯表面被膜的表面，所述凹凸表面如60μm≤Sz≤150μm所示那样高度差大、如-0.4≤Ssk≤-0.2所示那样细的谷多、并且如3≤Sku≤4所示那样在表面具有很多尖锐的峰、谷。根据这样的表面，成为不易带有划痕、且因微细的凹凸表面而不易残留划痕的粒面皮革状片。从缓冲性优异、且弯折时不易残留皱褶的观点考虑，优选聚氨酯中间层为聚氨酯多孔层。
另外，粒面皮革状片的凹凸表面优选最大峰高度(Sp)满足20μm≤Sp≤70μm、最大谷深度(Sv)满足20μm≤Sv≤100μm、算术平均高度(Sa)满足2≤Sa≤10、或均方根高度(Sq)满足1≤Sq≤10。
发明的效果
根据本发明，可以得到不易残留划痕的粒面皮革状片。
附图说明
图1是对实施方式的粒面人造革10的厚度方向的截面进行示意性说明的剖面示意图。
图2是对实施方式的其它例的粒面人造革20的厚度方向的截面进行示意性说明的剖面示意图。
图3是用于说明实施例的评价结果的粒面皮革状片的表面的照片。
具体实施方式
本实施方式的粒面皮革状片具备纤维基材、层叠于纤维基材的聚氨酯中间层、以及直接或夹隔其它聚氨酯层而层叠于聚氨酯中间层的聚氨酯表面被膜，聚氨酯表面被膜包含有机硅改性聚氨酯，所述粒面皮革状片具有凹凸表面，所述凹凸表面的基于ISO25178的表面粗糙度的最大高度(Sz)、偏度(skewness)(Ssk)、以及峰度(kurtosis)(Sku)满足60μm≤Sz≤150μm、-0.4≤Ssk≤-0.2、以及3≤Sku≤4。
图1是对作为本实施方式的粒面皮革状片的一例的粒面人造革10的厚度方向的截面进行示意性说明的剖面示意图。粒面人造革10具备：纤维基材1、层叠于纤维基材1的聚氨酯中间层2、以及粘附于聚氨酯中间层2的聚氨酯表面被膜3。聚氨酯表面被膜包含有机硅改性聚氨酯。此外，在聚氨酯表面被膜3的表面形成有微细的凹凸表面3a。
另外，微细的凹凸表面的基于ISO25178的表面粗糙度的最大高度(Sz)、偏度(Ssk)、以及峰度(Sku)满足60μm≤Sz≤150μm、-0.4≤Ssk≤-0.2、以及3≤Sku≤4。
这里，基于ISO25178的表面粗糙度的最大高度(Sz)是表示相对于平均面从最高点至最低点的距离的参数。通过使本实施方式的粒面皮革状片的表面为60μm≤Sz≤150μm，形成了相对于平均面的峰的最高点与谷的最低点之差大的表面。当Sz＜60μm时，划痕难以隐藏于峰、谷中而变得明显。另外，当Sz＞150μm时，在表面较高地显现出的峰部分变得容易带有划痕。
最大高度(Sz)是最大峰高度(Sp)与最大谷深度(Sv)之差，所述最大峰高度是距表面的平均面的高度的最大值，所述最大谷深度是距表面的平均面的高度的最小值的绝对值。作为最大峰高度(Sp)，从划痕容易隐藏于峰、谷中而变得不明显的观点考虑，优选为20μm≤Sp≤70μm，进一步优选为20μm≤Sp≤60μm。另外，作为最大谷深度(Sv)，从不易对谷产生划伤的观点考虑，优选为20μm≤Sv≤100μm，进一步优选为20μm≤Sv≤60μm。
另外，基于ISO25178的表面粗糙度的偏度(Ssk)是表示高度分布的对称性的参数。当Ssk＝0时，表示相对于平均面的高度分布是上下对称的。当Ssk＞0时，表示为相对于平均面的细的峰多的表面。当Ssk＜0时，表示为具有细的谷多的表面。通过使本实施方式的粒面皮革状片的最表层的表面为-0.4≤Ssk≤-0.2，形成了细的谷多的表面。当-0.2＜Ssk时，成为相对于平均面的高度分布上下对称或细的峰多的表面，在表面大量显现出的峰的部分容易形成划痕。另外，当Ssk＜-0.4时，细的谷变得过多而细的峰变少，在表面形成的划痕容易变得明显。
另外，基于ISO25178的表面粗糙度的峰度(Sku)是表示高度分布的尖锐程度的参数。当Sku＝3时，表示相对于平均面高度分布为正态分布。当Sku＞3时，表示相对于平均面尖锐的峰、谷多。当Sku＜3时，表示表面是平坦的。通过使本实施方式的粒面皮革状片的最表层的表面为3≤Sku≤4，从而形成了相对于平均面大量分布有尖锐的峰、谷的表面。当Sku＜3时，由于高度分布小，成为平坦的表面，因此在表面形成的划痕变得不明显。另外，当Sku＞4时，在表面尖锐的峰、谷过多，容易在尖锐的峰的部分产生划痕。
另外，基于ISO25178的表面粗糙度的算术平均高度(Sa)是表示各点相对于表面的平均面的高度差的绝对值的平均值的参数。作为本实施方式的粒面皮革状片的最表层的表面的Sa，优选为2≤Sa≤10。另外，基于ISO25178的表面粗糙度的均方根高度(Sq)是相当于距平均面的距离的标准偏差的参数。作为本实施方式的粒面皮革状片的最表层的表面的Sq，从高度的偏差适度均匀的观点考虑，优选为1≤Sq≤10。
参照图1，作为纤维基材1，可没有限定地使用无纺布、织物、编织物、或在它们中含浸赋予了聚氨酯等高分子弹性体的基材等现有公知的人造革的制造中使用的人造革基材、合成革所使用的合成革纤维基材。纤维基材的厚度没有特别限定，例如优选为300～3000μm，进一步优选为500～1500μm。
另外，形成纤维基材的纤维的种类没有特别限定。具体而言，例如可列举出：聚对苯二甲酸乙二醇酯(PET)、改性聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸三亚甲基二醇酯(PTT)、聚对苯二甲酸三乙二醇酯、聚对苯二甲酸六亚甲基二醇酯、聚对苯二甲酸丙二醇酯、聚萘二甲酸乙二醇酯等芳香族聚酯类树脂、聚乳酸、聚丁二酸乙二醇酯、聚丁二酸丁二醇酯、聚丁二酸己二酸丁二醇酯、聚羟基丁酸酯-聚羟基戊酸酯共聚物等脂肪族聚酯类树脂等聚酯纤维；聚酰胺6、聚酰胺66、聚酰胺610、聚酰胺10、聚酰胺11、聚酰胺12、聚酰胺6-12等聚酰胺类树脂；聚丙烯、聚乙烯、聚丁烯、聚甲基戊烯、氯系聚烯烃、乙烯-乙酸乙烯酯共聚物、苯乙烯乙烯共聚物等聚烯烃类树脂；由含有25～70摩尔％的乙烯单元的改性聚乙烯醇等形成的改性聚乙烯醇类树脂；以及、聚氨酯类弹性体、聚酰胺类弹性体、聚酯类弹性体等结晶性弹性体等。其中，从各种特性的平衡性优异的观点考虑，优选为聚酰胺类树脂、芳香族聚酯类树脂。
纤维的纤度、形态没有特别限定。例如，可以为纤度超过1dtex的常规纤维，也可以为低于1dtex的极细纤维。另外，纤维的形态可以为实心纤维，也可以为中空纤维、莲藕状纤维这样的具有空隙的纤维。
另外，参照图1，在粒面人造革10中，聚氨酯中间层2是层叠于纤维基材1的表面的多孔的聚氨酯层。
聚氨酯多孔层例如可以通过如下方式形成：将进行湿式凝固的聚氨酯溶液涂布于纤维基材的表面后，浸渍在水中，使多孔的聚氨酯凝固。需要说明的是，粒面人造革10中示例出了聚氨酯多孔层作为聚氨酯中间层，但聚氨酯中间层也可以为非多孔的聚氨酯层。作为进行湿式凝固的聚氨酯溶液中包含的聚氨酯的具体例子，例如可列举出：以聚己二酸乙二醇酯、聚己二酸丁二醇酯、聚己二酸丙二醇酯、聚己二酸六亚甲基二醇酯、聚己内酯、聚甲基戊内酯等作为多元醇成分的聚酯二醇类聚氨酯；聚丙二醇类聚氨酯；聚四亚甲基二醇类聚氨酯；聚碳酸酯类聚氨酯；聚四亚甲基二醇-聚碳酸酯共聚物类聚氨酯等。另外，作为聚氨酯溶液中包含的溶剂，可列举出作为亲水性溶剂的例如二甲基甲酰胺(DMF)等。
聚氨酯中间层的厚度优选为100～600μm，进一步优选为200～400μm左右。
需要说明的是，为了赋予形态稳定性，聚氨酯中间层可以浸透至纤维基材的内部。作为使聚氨酯中间层浸透至纤维基材的内部的方法，可列举出：预先使聚氨酯溶液含浸于纤维基材，进一步涂敷聚氨酯溶液后，浸渍在水中使其凝固的方法。
此外，本实施方式的粒面皮革状片至少具备直接或夹隔其它聚氨酯层而层叠于聚氨酯中间层且具有微细的凹凸表面的聚氨酯表面被膜。参照图1，在粒面人造革10中，具有微细的凹凸表面3a的聚氨酯表面被膜3粘附于聚氨酯中间层2。
形成具有微细的凹凸表面的聚氨酯表面被膜3的方法只要可形成上述的表面粗糙度的偏度(Ssk)、峰度(Sku)及最大高度(Sz)的范围的凹凸表面即可，没有特别限定。作为一例，可列举出以下的方法。
首先，在层叠于纤维基材的聚氨酯中间层的表面层叠包含有机硅改性聚氨酯的聚氨酯表面被膜，形成具有平滑的粒面层的粒面皮革状片基材。
形成聚氨酯表面被膜的聚氨酯包含有机硅改性聚氨酯。通过使形成聚氨酯表面被膜的聚氨酯包含有机硅改性聚氨酯，不容易在粒面人造革的表面产生划痕。
有机硅改性聚氨酯是在聚氨酯的主链、侧链导入了硅氧烷键的聚氨酯。有机硅改性聚氨酯可以通过使用公知的聚氨酯的制造方法而制造，例如通过使多元醇、扩链剂、含活性氢基团的有机聚硅氧烷、以及多异氰酸酯进行反应而制造。
另外，作为有机硅改性聚氨酯，根据多元醇成分的不同，可以列举：有机硅改性聚碳酸酯类聚氨酯、有机硅改性聚酯类聚氨酯、有机硅改性聚醚类聚氨酯等，其中，从耐久性特别优异的观点考虑，优选为有机硅改性聚碳酸酯类聚氨酯。
聚氨酯表面被膜中可以包含除有机硅改性聚氨酯以外的有机硅未改性的聚氨酯。作为有机硅未改性的聚氨酯的具体例子，可列举出：未进行有机硅改性的聚碳酸酯类聚氨酯、聚酯类聚氨酯、聚醚类聚氨酯等。
作为形成聚氨酯表面被膜的聚氨酯中的有机硅改性聚氨酯的含有比例，在具有二甲基硅氧烷时，优选含有例如10～50质量％的二甲基硅氧烷。
在聚氨酯表面被膜中，除了包含有机硅改性聚氨酯的聚氨酯以外，还可以在不损害本发明效果的范围内含有除聚氨酯以外的合成橡胶、聚酯弹性体，有机硅弹性体等聚合物、耐光剂、分散剂等添加剂。另外，聚氨酯表面被膜优选被颜料着色。聚氨酯表面被膜可以为非发泡性(非多孔性)，也可以为发泡性(多孔性)，特别优选为非发泡性。
参照图1，在粒面人造革10中，作为将包含有机硅改性聚氨酯的聚氨酯表面被膜3粘附于聚氨酯中间层2的方法，可列举出如下方法：使用凹版辊涂机、逗点涂布机、喷涂机等将用于在聚氨酯中间层2的表面形成聚氨酯表面被膜3的聚氨酯组成物的溶液或分散液涂布用于形成目标厚度的所需量，利用干式法、湿式法使其凝固或固化。由此，可以形成具有平滑的粒面层的粒面皮革状片基材。
粘附于聚氨酯中间层的聚氨酯表面被膜的厚度没有特别限定，从容易形成具有上述微细的凹凸的表面的观点考虑，优选为2～30μm，进一步优选为5～20μm。
然后，使用在外周面具有用于形成上述那样的表面形状的凹凸的压花辊，在具有平滑的粒面层的粒面皮革状片基材的聚氨酯表面被膜的表面形成微细的凹凸(花纹)。
在压花辊的外周面形成有用于在粒面皮革状片基材的聚氨酯表面被膜的表面形成凹凸表面的凹凸，所述凹凸表面的基于ISO25178的表面粗糙度的最大高度(Sz)、偏度(Ssk)、以及峰度(Sku)满足60μm≤Sz≤150μm、-0.4≤Ssk≤-0.2、以及3≤Sku≤4。
作为压花辊的外周面的凹凸形状，例如优选为在压花处理面的整周具有10～40个/mm2的平均深度为20～100μm的凹部的微细的凹凸图案。
另外，压花辊的表面温度可根据聚氨酯表面被膜、聚氨酯中间层的厚度、组成进行调整，从容易形成满足60μm≤Sz≤150μm、-0.4≤Ssk≤-0.2、以及3≤Sku≤4的凹凸表面的观点考虑，优选为160～190℃，进一步优选为170～180℃。
另外，压花辊的线压力可根据聚氨酯表面被膜、聚氨酯中间层的厚度、组成进行调整，从容易形成满足60μm≤Sz≤150μm、-0.4≤Ssk≤-0.2、以及3≤Sku≤4的凹凸表面的观点考虑，优选为5～30kg/cm，进一步优选为10～20kg/cm。
另外，取决于压花辊的直径和转速的处理速度可根据聚氨酯表面被膜、聚氨酯中间层的厚度、组成进行调整，从容易形成满足60μm≤Sz≤150μm、-0.4≤Ssk≤-0.2、以及3≤Sku≤4的凹凸表面的观点考虑，优选为0.5～5m/分，进一步优选为1～3m/分。
由此，可以得到本实施方式的具有凹凸表面的粒面皮革状片，所述凹凸表面的基于ISO25178的表面粗糙度的最大高度(Sz)、偏度(Ssk)、以及峰度(Sku)满足60μm≤Sz≤150μm、-0.4≤Ssk≤-0.2、以及3≤Sku≤4。
以上，参照图1示例出粒面人造革10而对本实施方式的粒面皮革状片进行了详细说明，所述粒面人造革10具备纤维基材1、层叠于纤维基材1的聚氨酯中间层2、以及粘附于聚氨酯中间层2的聚氨酯表面被膜3，且具有微细的凹凸表面3a。本发明的粒面皮革状片的层结构并不限定于上述那样的层结构，只要是具有基于ISO25178的表面粗糙度的最大高度(Sz)、偏度(Ssk)及峰度(Sku)满足60μm≤Sz≤150μm、-0.4≤Ssk≤-0.2及3≤Sku≤4的凹凸表面的粒面皮革状片即可，没有特别限定。
例如，在上述例子中示例出了粒面人造革10，所述粒面人造革10具备纤维基材1、层叠于纤维基材1的聚氨酯中间层2、以及以不夹隔粘接层的方式粘附于聚氨酯中间层2的聚氨酯表面被膜3，且从聚氨酯表面被膜3的一侧用压花辊进行模压而形成了微细的凹凸表面3a。代替这样的方式，也可以是通过在表面形成有微细的花纹图案的剥离纸上形成聚氨酯表面被膜而制造的、具有满足60μm≤Sz≤150μm、-0.4≤Ssk≤-0.2及3≤Sku≤4的凹凸表面的粒面皮革状片。图2是对如此得到的粒面人造革20的厚度方向的截面进行示意性说明的剖面示意图。
粒面人造革20具备纤维基材1、层叠于纤维基材1的聚氨酯中间层2、以及夹隔粘接层4而粘接于聚氨酯中间层2的聚氨酯表面被膜13。然后，在粒面人造革20的聚氨酯表面被膜13一侧的表面形成了微细的凹凸表面13a。
这样的粒面人造革20例如可如下方式进行制造。
与粒面人造革10的制造工序同样地制造层叠有聚氨酯中间层2的纤维基材1。另一方面，在表面形成有微细的花纹图案的剥离纸上形成聚氨酯表面被膜。具体而言，在剥离纸上过量地涂布聚氨酯溶液或聚氨酯熔融树脂，例如使用刮刀涂布机、棒涂机、辊涂机等涂布机来涂布这些间隙的厚度量的聚氨酯溶液或聚氨酯熔融树脂。然后，通过利用干式法或湿式法使聚氨酯溶液或聚氨酯熔融树脂凝固或固化，从而可形成聚氨酯表面被膜。聚氨酯表面被膜可以是单层，也可以由多层构成。
需要说明的是，在聚氨酯表面被膜具有包含聚氨酯表皮中间层和粘附于聚氨酯表皮中间层的聚氨酯最表层(顶层)的层叠结构的情况下，例如，通过在剥离纸上形成聚氨酯最表层的膜，在聚氨酯最表层的膜上形成用于形成聚氨酯中间层的聚氨酯膜，从而可以形成聚氨酯最表层与聚氨酯表皮中间层的层叠结构的聚氨酯表面被膜。
作为聚氨酯表面被膜的厚度，优选为10～100μm，进一步优选为20～50μm。聚氨酯表面被膜过薄时，存在表面的耐磨损性降低的倾向。
将聚氨酯粘接剂涂布于聚氨酯表面被膜的膜，将溶剂完全或不完全地去除使其干燥。然后，将这样形成在剥离纸上的聚氨酯表面被膜的膜上层叠的聚氨酯粘接剂贴合于聚氨酯中间层的表面后，使聚氨酯粘接剂固化，由此经由聚氨酯粘接层粘接聚氨酯表面被膜。然后，通过从聚氨酯表面被膜的表面将剥离纸剥离，可以得到具有聚氨酯表面被膜13的粒面人造革20。
作为聚氨酯粘接层的厚度，优选为5～200μm，进一步优选为30～70μm。在聚氨酯粘接层过厚的情况下，存在耐弯曲性降低、粘接强度降低的倾向。
另外，作为聚氨酯表面被膜和聚氨酯粘接层的总厚度，从能够保持机械特性与手感的平衡的观点考虑，优选为10～300μm，进一步优选为30～200μm，特别优选为50～100μm左右。
以上说明的本实施方式的粒面皮革状片可用作例如皮包、衣料、鞋等的表皮材料，特别优选用作书包(学生书包)的表皮材料。
实施例
以下，通过实施例对本发明更具体地进行说明。需要说明的是，本发明的范围并不受这些实施例的任何限定。
首先，以下对本实施例的评价方法进行归纳说明。
(基于ISO25178的表面粗糙度)
使用作为非接触式的表面粗糙度/形状测定仪的“One-Shot 3D MeasuringMacroscope VR-3200”KEYENCE公司制)，依据ISO 25178(表面粗糙度测定)测定了粒面皮革状片的聚氨酯表面被膜侧的表面的表面粗糙度。具体而言，对于表面的54mm×72mm的范围，通过由高亮度LED照射的结构化照明光，用400万像素单色C-MOS照相机以12倍的倍率拍摄产生了畸变的条纹投影图像，在波纹度去除5％的条件下校正畸变后测定了表面粗糙度。然后，基于ISO25178计算出表面粗糙度的偏度(Ssk)、峰度(Sku)及最大高度(Sz)。
(耐划痕性)
使用作为线性磨损试验机的Linear Abraser5750(Tabor Industries公司制)进行了测定。具体而言，用具有直径1.0mm的半球形的顶端的碳化钨尖端，在载荷1kgf、行程长度1英寸、移动速度1英寸/秒的条件下在粒面皮革状片的聚氨酯表面被膜的表面往返1次。然后，在1小时后及1个月后，通过肉眼观察了在聚氨酯表面被膜的表面留下的划痕的状态，按照以下的基准进行了判定。需要说明的是，将判定为A～D时的图像示于图3。在图3中，(a)为A，(b)为B，(c)为C，(d)为D。
A：基本无法辨认出划痕及压痕
B：虽然没有观察到伤痕，但残留下了压痕
C：观察到很少的伤痕
D：清晰地观察到伤痕
[实施例1]
通过熔融纺丝得到了由6-尼龙45质量份(海成分)和聚苯乙烯55质量份(岛成分)构成的海岛型复合纤维。将其拉伸至3倍，赋予纤维油剂，施加机械卷曲后进行干燥。将得到的卷曲纤维切割成51mm，制成3dtex的短纤维，在形成网后，从两面交替地进行总计约500刺/cm2的针刺，得到了无纺布。该无纺布的单位面积重量为350g/m2，表观比重(表观密度)为0.17(g/cm3)。用聚乙烯醇的4％水溶液处理该无纺布，将厚度压缩固定至约1.3mm，对表面实施抛光并进行了平滑化。然后，含浸13％浓度的以聚酯类聚氨酯为主体的聚氨酯的二甲基甲酰胺(以下称为DMF)溶液。进一步，在其表面涂布以固体成分计为100g/m2量的相同的聚氨酯溶液，然后浸渍于DMF/水的混合液中，使聚氨酯湿式凝固成多孔状。然后，在热甲苯中将岛成分溶出去除，将复合纤维转化为中空纤维，由此得到了层叠有作为聚氨酯中间层的聚氨酯多孔层的纤维基材。根据基于显微镜的观察，聚氨酯多孔层的厚度为300μm。
然后，使用150目的凹印版辊，在聚氨酯多孔层的表面涂布包含黑色颜料的有机硅改性聚碳酸酯类聚氨酯(大日精化工业株式会社制NES9015-22：Si改性聚碳酸酯类PU)的二甲基甲酰胺溶液，使得干燥后的厚度为约8μm，形成了着色的表面被膜。然后，使用在具有18个/mm2的平均深度为60μm的凹部的整个面上具有微细的凹凸图案(称为图案A)的压花辊，以温度170℃、压力15kg/cm、处理速度1.5m/分进行模压，由此形成了包含凹凸表面的聚氨酯表面被膜。由此，制造了作为粒面皮革状片的粒面人造革。然后，依据上述的评价方法进行了评价。将结果示于表1。
Figure BDA0003247889000000111
[实施例2]
在实施例1中，在温度170℃、压力10kg/cm、处理速度2m/分的条件下使用压花辊进行了模压，以此代替在温度170℃、压力15kg/cm、处理速度1.5m/分的条件下使用压花辊进行模压，除此以外，与实施例1同样地制造了粒面人造革并进行了评价。将结果示于表1。
[实施例3]
在实施例1中，作为有机硅改性聚碳酸酯类聚氨酯，使用了DIC公司制的NY-324来代替大日精化工业株式会社制的NES9015-22，除此以外，与实施例1同样地制造了粒面人造革并进行了评价。将结果示于表1。
[比较例1]
在实施例1中，使用了在具有18个/mm2的平均深度为30μm的凹部的整个面具有微细的凹凸图案(称为图案B)的压花辊进行模压，以此代替使用在具有18个/mm2的平均深度为60μm的凹部的整个面具有微细的凹凸图案(图案A)的压花辊进行模压，除此以外，与实施例1同样地制造了粒面人造革并进行了评价。将结果示于表1。
[比较例2]
在实施例1中，使用了在具有23个/mm2的平均深度为20μm的凹部的整个面具有微细的凹凸图案(称为图案C)的压花辊进行模压，以此代替使用在具有18个/mm2的平均深度为60μm的凹部的整面具有微细的凹凸图案(图案A)的压花辊进行模压，除此以外，与实施例1同样地制造了粒面人造革并进行了评价。将结果示于表1。
[比较例3]
在实施例1中，作为用于形成包含凹凸表面的聚氨酯表面被膜的聚氨酯，使用了有机硅未改性的聚碳酸酯类聚氨酯(大日精化工业株式会社ME8210：聚碳酸酯类PU)来代替有机硅改性聚碳酸酯类聚氨酯，除此以外，与实施例1同样地制造了粒面人造革并进行了评价。将结果示于表1。
[比较例4]
在形成有花纹图案的剥离纸(大日本印刷株式会社制DE-125)上涂布包含有机硅改性聚碳酸酯类聚氨酯溶液(大日精化工业株式会社制NES9015-22、树脂成分25％)100质量份、颜料清漆(RESAMINE DUT4790黑(大日精化工业株式会社制))20质量份、DMF 30质量份、以及甲乙酮30质量份的溶液，使得干燥后的厚度为15μm，进行干燥，由此形成了构成聚氨酯表面被膜的顶层。
然后，在顶层涂布包含单组分型聚醚类聚氨酯(大日精化工业株式会社制RESAMINE ME8116)100质量份和颜料清漆(RESAMINE DUT4790黑)20质量份的DMF溶液，使得干燥后的厚度为20μm，进行干燥，由此形成了构成聚氨酯表面被膜的聚氨酯表皮中间层。得到的聚氨酯表面被膜的厚度以顶层和表皮中间层的总合计为35μm。
然后，在聚氨酯表面被膜的中间层的表面以130g/m2涂布聚氨酯类粘接剂溶液，在120℃下干燥15秒钟，使溶剂蒸发，形成了粘接层。然后，在层叠有与实施例1中得到的同样的聚氨酯多孔层的纤维基材上贴合粘接层，形成了层叠中间体。需要说明的是，对于聚氨酯类粘接剂溶液，作为交联型聚氨酯类粘接剂，使用了含有在TA205FT(大日精化工业株式会社制)100质量份中加入了交联剂及交联促进剂的成分作为粘接剂成分、且含有DMF 5质量份及乙酸乙酯10质量份作为溶剂的交联型聚氨酯类粘接剂。
然后，通过用设置有聚氨酯多孔层和纤维基材的总厚度达到1.5mm的约65％的1.0mm的间隙的压辊对得到的层叠中间体进行压制，从而一边压接，一边使粘接层浸透至聚氨酯多孔层。然后，在130℃下干燥3分钟后，在50℃下进行了3天熟化处理。然后，在进行熟化处理后，通过将剥离纸剥离而得到了粒面人造革。然后，依据上述的评价方法进行了评价。将结果示于表1。
[比较例5]
在比较例4中，变更为以如下方式制造顶层的工序，除此以外，与比较例4同样地制造了粒面人造革并进行了评价。将结果示于表1。
在形成有花纹图案的剥离纸(大日本印刷株式会社制R-70N)上涂布包含聚醚类聚氨酯溶液(大日精化工业株式会社制ME8116、树脂成分30％)100质量份、颜料清漆(RESAMINE DUT4790黑(大日精化工业株式会社制))20质量份、DMF 30质量份、以及甲乙酮30质量份的溶液，使得干燥后的厚度为15μm，进行干燥，由此形成了构成聚氨酯表面被膜的顶层。
[比较例6]
在比较例2中，作为用于形成包含凹凸表面的聚氨酯表面被膜的聚氨酯，使用了以未进行有机硅改性的聚己二酸乙二醇丙二醇酯(polyethylene polypropylene adipate)作为软链段的N％为4.0％的聚酯类聚氨酯，以此代替有机硅改性聚碳酸酯类聚氨酯，除此以外，与实施例1同样地制造了粒面人造革并进行了评价。将结果示于表1。
[比较例7]
在比较例6中，使用了在具有18个/mm2的平均深度为60μm的凹部的整个面具有微细的凹凸图案(图案A)的压花辊进行模压，以此代替使用在具有23个/mm2的平均深度为20μm的凹部的整个面具有微细的凹凸图案(图案C)的压花辊，除此以外，与比较例6同样地制造了粒面人造革并进行了评价。将结果示于表1。
如表1所示，对于聚氨酯表面被膜包含有机硅改性聚氨酯、且具有最大高度(Sz)、偏度(Ssk)及峰度(Sku)满足60μm≤Sz≤150μm、-0.4≤Ssk≤-0.2及3≤Sku≤4的凹凸表面的实施例1～3的粒面皮革状片而言，在划痕评价中，在1小时后及1个月后基本上无法辨认出划痕及压痕。另一方面，对于虽然聚氨酯表面被膜包含有机硅改性聚氨酯、但具有最大高度(Sz)、偏度(Ssk)及峰度(Sku)不满足60μm≤Sz≤150μm、-0.4≤Ssk≤-0.2及3≤Sku≤4的凹凸表面的比较例1、2、4的粒面皮革状片而言，在1小时后及1个月后留下了压痕或观察到划伤。另外，对于聚氨酯表面被膜不包含有机硅改性聚氨酯的比较例3、5、6的粒面皮革状片而言，在划痕评价中，在1小时后及1个月后可清晰地观察到划伤。另外，对于聚氨酯表面被膜不包含有机硅改性聚氨酯、且具有最大高度(Sz)及峰度(Sku)不满足60μm≤Sz≤150μm及3≤Sku≤4的凹凸表面的比较例7的粒面皮革状片而言，在划痕评价中，在1小时后及1个月后可清晰地观察到划伤。

Claims (6)

1.一种粒面皮革状片，其具备纤维基材、层叠于纤维基材的聚氨酯中间层、以及直接或夹隔其它聚氨酯层而层叠于所述聚氨酯中间层的聚氨酯表面被膜，
所述聚氨酯表面被膜包含有机硅改性聚氨酯，
所述粒面皮革状片具有凹凸表面，所述凹凸表面的基于ISO25178的表面粗糙度的最大高度(Sz)、偏度(Ssk)、以及峰度(Sku)满足60μm≤Sz≤150μm、-0.4≤Ssk≤-0.2、以及3≤Sku≤4。
2.根据权利要求1所述的粒面皮革状片，其具有最大峰高度(Sp)满足20μm≤Sp≤70μm的所述凹凸表面。
3.根据权利要求1或2所述的粒面皮革状片，其具有最大谷深度(Sv)满足20μm≤Sv≤100μm的所述凹凸表面。
4.根据权利要求1或2所述的粒面皮革状片，其具有算术平均高度(Sa)满足2≤Sa≤10的所述凹凸表面。
5.根据权利要求1或2所述的粒面皮革状片，其具有均方根高度(Sq)满足1≤Sq≤10的所述凹凸表面。
6.根据权利要求1～5中任一项所述的粒面皮革状片，其中，所述聚氨酯中间层为聚氨酯多孔层。
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