CN109594355A - 一种高强度无溶剂聚氨酯再生皮及其制备方法 - Google Patents

一种高强度无溶剂聚氨酯再生皮及其制备方法 Download PDF

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CN109594355A
CN109594355A CN201811459504.4A CN201811459504A CN109594355A CN 109594355 A CN109594355 A CN 109594355A CN 201811459504 A CN201811459504 A CN 201811459504A CN 109594355 A CN109594355 A CN 109594355A
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regenerated bark
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赵伟栋
邢高瞻
李童
罗运东
程艳西
陈茂祥
黄万里
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Anhui Anli Material Technology Co Ltd
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Abstract

本发明公开了一种高强度无溶剂聚氨酯再生皮，由内至外依次为再生皮基布层、补强层、无溶剂发泡层、无溶剂面层。本发明同时公开了上述高强度无溶剂聚氨酯再生皮的制备方法，通过后续加工处理方式可以明显提高再生皮基布的物理强度，和无溶剂环保节能加工方式完美结合，同时提高无溶剂聚氨酯合成革与针刺无纺布和机织布的结合能力，明显提高产品的剥离强度，满足运动休闲鞋物理性质的无溶剂聚氨酯再生皮产品，实现真皮加工过程中的废料再利用。

Description

一种高强度无溶剂聚氨酯再生皮及其制备方法
技术领域
本发明涉及再生皮领域，具体涉及一种高强度无溶剂聚氨酯再生皮及其制备方法。
背景技术
目前，市场上传统运动休闲鞋用合成革的生产方式基本为湿法底坯经干法贴面获得。生产过程中不可避免的需要添加大量的有机溶剂DMF等，由此获得的合成革产品溶剂残留量高、气味重。其次，虽然大部分的DMF能够回收再利用，但回收能耗高。总得来说，目前的生产方式越来越难以满足人们对节能环保方面的要求，而无溶剂聚氨酯合成革就是一个很好的选择。
再生皮是将动物的废皮及真皮下脚料粉碎后，调配成化工原料加工制作而成，其特点是皮张边缘较整齐、利用率高、价格便宜，纵切面纤维组织均匀一致，再生皮具有无与伦比的质感、弹性、坚韧度、抗湿能力。但是，目前再生皮相关产品具有拉断和撕裂强度差等物理性能相对较差的缺点，很难直接作为运动休闲鞋的鞋面材料。
无溶剂聚氨酯合成革作为一种环保性的新型聚氨酯合成革，很受市场的喜爱。但是，常规的再生皮基布与无溶剂聚氨酯合成革的结合性能较差，且产品的剥离强度低，很难达到运动休闲鞋的鞋面材料的强度要求。
发明内容
针对上述不足，本发明提供了一种高强度无溶剂聚氨酯再生皮及其制备方法，通过后续加工处理方式可以明显提高再生皮基布的物理强度，和无溶剂环保节能加工方式完美结合，同时提高无溶剂聚氨酯合成革与针刺无纺布和机织布的结合能力，明显提高产品的剥离强度，满足运动休闲鞋物理性质的无溶剂聚氨酯再生皮产品，实现真皮加工过程中的废料再利用。
为了实现上述目的，本发明采用以下技术方案：
一种高强度无溶剂聚氨酯再生皮，其特征在于：由内至外依次为再生皮基布层、补强层、无溶剂发泡层、无溶剂面层，所述高强度无溶剂聚氨酯再生皮的剥离强度达到75 N/3cm以上，拉断强度达到600 N/3cm以上，撕裂强度达到70 N以上。
进一步的，所述再生皮基布层由真皮废旧原料加工处理制成，其具体的制备工艺可参考专利公开号CN 108265397 A的鞋材装饰用再生皮基布制造方法中的方法。将动物真皮纤维重复利用，节约资源，制成布基和真皮效果基本一致，性价比高。
进一步的，所述无溶剂发泡层为双组份聚醚型无溶剂发泡层，无溶剂发泡层生产过程不使用DMF，同时可以有效降低生产能耗以及湿法生产过程中水的使用量，是一个节能环保型生产工艺。其中，所述无溶剂面层由以下组份按重量份制备而成：
聚醚多元醇组份A料 50~160份，
异氰酸组份B料 50~160份，
有机锡类催化剂 0~0.05份
颜料 0~10份；
所述无溶剂发泡层由以下组份按重量份制备而成：
聚醚多元醇组份A料 50~160份，
异氰酸组份B料 50~160份，
超细碳酸钙 0~20份，
有机锡类催化剂 0~0.03份，
颜料 0~10份。
这里的颜料可以为色浆，也可以为色粉。
进一步的，所述补强层由补强材料组成，所述补强材料为机织布、水刺无纺布、针刺无纺布的一种或两种以上的组合。将真皮废旧原料经过加工处理后形成高真皮含量的再生皮基布，与补强材料复合，一方面将废旧真皮重复利用，在保持再生皮真皮手感的同时，大幅度提高了再生皮的物理强度，尤其是剥离强度和抗撕裂强度的提高。
优选的，所述机织布为棉、锦纶、涤纶、氨纶中的一种或两种以上共织形成的高强度机织布。
本发明的另一个目的在于提供一种高强度无溶剂聚氨酯再生皮的制备方法，包括以下步骤：
a、将再生皮基布层经过复合工艺复合补强层，得到基材；
b、经过干法转移无溶剂面层，按照配比制得无溶剂发泡浆料，将无溶剂发泡浆料涂覆在无溶剂面层上，涂覆厚度为0.3mm~0.6mm，得到无溶剂发泡层后，于70℃~130℃预烘至黏合状态，将无溶剂发泡层与基材贴合，于130℃~170℃固化定型，收卷，室温熟化至少24h后剥离，制得高强度无溶剂聚氨酯再生皮；
c、将高强度无溶剂聚氨酯再生皮经过有机硅类柔软剂含浸揉纹处理，同时将再生皮基布面依次封毛，磨皮起毛。
进一步的，所述的复合工艺为湿气固化反应型聚氨酯（PUR）复合或高低温胶膜复合的一种或者两种。
进一步的，所述封毛采用水性聚氨酯刀涂工艺涂敷封毛。
优选的，所述水性聚氨酯为阴离子热固型聚醚类水性聚氨酯树脂，所述阴离子热固型聚醚类水性聚氨酯树脂中的阴离子基团为羧酸根基团或磺酸根基团。
进一步的，所述磨皮起毛采用砂纸目数100目和150目组合工艺通过卧式双辊磨皮机磨皮起毛。
与现有技术相比，本发明具有以下有益效果：
1、本发明制备的高强度无溶剂聚氨酯再生皮产品，将真皮废旧原料经过加工处理后形成高真皮含量的再生皮基布，经过复合补强，物理性质强度明显提高，再生皮基布与无溶剂聚氨酯合成革的结合性能提高，产品的剥离强度高，满足运动休闲鞋的鞋面材料的强度要求；同时实现了真皮原料的重复利用，可以作为再运动休闲鞋的鞋面材料。
2、本发明制备的一种高强度无溶剂聚氨酯再生皮产品生产过程完全不使用有机溶剂，生产过程节能环保，产品低VOC，是一支理想的环保型运动休闲鞋用再生皮产品。
3、本发明制备的一种高强度无溶剂聚氨酯再生皮，经过有机硅类柔软剂含浸揉纹处理，同时背面采用水性聚氨酯刀涂工艺涂覆封毛工艺，卧式双辊磨皮机磨皮起毛，具有真皮效果好，手感丰满、有弹性、皱折回复性好。
附图说明
图1为本发明高强度无溶剂聚氨酯再生皮的侧面剖视示意图。
图中：1.再生皮基布层，2.补强层，3.无溶剂发泡层，4.无溶剂面层。
具体实施方式
如图1所示，本发明公开的高强度无溶剂聚氨酯再生皮由内至外依次为再生皮基布层1补强层，2无溶剂发泡层，3无溶剂面层，4再生皮基布经过复合补强，物理性质强度明显提高，同时实现了真皮原料的重复利用，尤其是剥离强度和抗撕裂强度的提高使其可以作为再运动休闲鞋的鞋面材料，满足运动休闲的各项物性要求。
为了便于理解本发明，下面将结合具体的实施例对本发明进行更全面的描述。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施方式。相反地，提供这些实施方式的目的是使对本发明的公开内容理解的更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施方式的目的，不是旨在于限制本发明。
应当知晓的是，水性聚氨酯树脂3233和水性聚氨酯树脂3455为烟台万华聚氨酯股份有限公司产品，聚醚多元醇组分A料AL-5090A和异氰酸组份B料AL-5040B为合肥安利聚氨酯新材料有限公司产品与常规聚醚多元醇组分A料和异氰酸组分B料的主要活性成分相同，其余所用试剂均是市售产品。
实施例1
将真皮废旧原料加工处理后得到再生皮基布，将再生皮基布层经过PUR复合工艺复合针刺无纺布，得到基材；经过干法转移无溶剂面层（AL-5090A 50份、AL-5040B 160份），将AL-5090A 50份、AL-5040B 160份、超细碳酸钙10份混合制得无溶剂发泡浆料，将无溶剂发泡浆料刮涂在无溶剂面层上，涂覆厚度为0.3mm，得到无溶剂发泡层后，于70℃预烘至黏合状态，将无溶剂发泡层与基材贴合，于130℃固化定型，收卷，室温熟化至少24h后剥离得到无溶剂发泡层，制得高强度无溶剂聚氨酯再生皮；再将高强度无溶剂聚氨酯再生皮经过有机硅类柔软剂含浸揉纹处理，通过水性聚氨酯刀涂工艺涂覆封毛，所用水性聚氨酯为水性聚氨酯树脂3233，最后采用卧式双辊磨皮机采用砂纸目数100目和150目组合工艺磨皮起毛。
实施例2
将真皮废旧原料加工处理后得到再生皮基布，将再生皮基布层经过PUR复合工艺复合水刺无纺布，得到基材；经过干法转移无溶剂面层（AL-5090A 100份、AL-5040B 90份、有机锡催化剂0.05份、色浆10份），将AL-5090A 100份、AL-5040B 90份、超细碳酸钙20份、色浆10份混合制得无溶剂发泡浆料，将无溶剂发泡浆料刮涂在无溶剂面层上，涂覆厚度为0.4mm，得到无溶剂发泡层后，于100℃预烘至黏合状态，将无溶剂发泡层与基材贴合，于150℃固化定型，收卷，室温熟化至少24h后剥离，制得高强度无溶剂聚氨酯再生皮；再将高强度无溶剂聚氨酯再生皮经过有机硅类柔软剂含浸揉纹处理，通过水性聚氨酯刀涂工艺涂覆封毛，所用水性聚氨酯为水性聚氨酯树脂3455，最后采用卧式双辊磨皮机采用砂纸目数100目和150目组合工艺磨皮起毛。
实施例3
将真皮废旧原料加工处理后得到再生皮基布，将再生皮基布层经过高低温胶膜贴合复合工艺复合水刺无纺布和机织布复合材料，得到基材；经过干法转移无溶剂面层（AL-5090A160份、AL-5040B 50份、色粉5份），将AL-5090A 160份、AL-5040B 50份、有机锡催化剂0.03份、色粉5份混合制得无溶剂发泡浆料，将无溶剂发泡浆料刮涂在无溶剂面层上，涂覆厚度为0.6mm，得到无溶剂发泡层后，于130℃预烘至黏合状态，将无溶剂发泡层与基材贴合，于170℃固化定型，收卷，室温熟化至少24h后剥离，制得高强度无溶剂聚氨酯再生皮；再将高强度无溶剂聚氨酯再生皮经过有机硅类柔软剂含浸揉纹处理，通过水性聚氨酯刀涂工艺涂覆封毛，所用水性聚氨酯为水性聚氨酯树脂3455，最后采用卧式双辊磨皮机采用砂纸目数100目和150目组合工艺磨皮起毛。
对比例
将真皮废旧原料加工处理后得到再生皮基布，经过干法转移无溶剂面层（AL-5090A100份、AL-5040B 90份、有机锡催化剂0.05份、色浆10份），将AL-5090A 100份、AL-5040B 90份、超细碳酸钙20份、色浆10份混合制得无溶剂发泡浆料，将无溶剂发泡浆料刮涂在无溶剂面层上，涂覆厚度为0.4mm，得到无溶剂发泡层后，于100℃预烘至黏合状态，将无溶剂发泡层与基材贴合，于150℃固化定型，收卷，室温熟化至少24h后剥离，制得高强度无溶剂聚氨酯再生皮；再将高强度无溶剂聚氨酯再生皮经过有机硅类柔软剂含浸揉纹处理，通过水性聚氨酯刀涂工艺涂覆封毛，所用水性聚氨酯为水性聚氨酯树脂3455，最后采用卧式双辊磨皮机采用砂纸目数100目和150目组合工艺磨皮起毛。
将实施例1~3中制备的高强度无溶剂聚氨酯再生皮进行相关性能测试，测试结果如下表所示：
经过测试，补强后的无溶剂聚氨酯合成革的拉断、撕裂以及剥离强度明显提高，由于再生皮基布的物理强度的提高，和无溶剂环保节能加工方式完美结合，同时提高了无溶剂聚氨酯合成革与针刺无纺布和机织布的结合能力，从而明显提高产品的剥离强度，满足运动休闲鞋物理性质的无溶剂聚氨酯再生皮产品，实现真皮加工过程中的废料再利用。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

1.一种高强度无溶剂聚氨酯再生皮，其特征在于：由内至外依次为再生皮基布层、补强层、无溶剂发泡层、无溶剂面层，所述高强度无溶剂聚氨酯再生皮的剥离强度达到75 N/3cm以上，拉断强度达到600 N/3cm以上，撕裂强度达到70 N以上。
2.如权利要求1所述的高强度无溶剂聚氨酯再生皮，其特征在于：所述再生皮基布层由真皮废旧原料加工处理制得。
3.如权利要求1所述的高强度无溶剂聚氨酯再生皮，其特征在于：所述无溶剂面层由以下组份按重量份制备而成：
聚醚多元醇组份A料 50~160份，
异氰酸组份B料 50~160份，
有机锡类催化剂 0~0.05份
颜料 0~10份；
所述无溶剂发泡层由以下组份按重量份制备而成：
聚醚多元醇组份A料 50~160份，
异氰酸组份B料 50~160份，
超细碳酸钙 0~20份，
有机锡类催化剂 0~0.03份，
颜料 0~10份。
4.如权利要求1所述的高强度无溶剂聚氨酯再生皮，其特征在于：所述补强层由补强材料组成，所述补强材料为机织布、水刺无纺布、针刺无纺布的一种或两种以上的组合。
5.如权利要求4所述的高强度无溶剂聚氨酯再生皮，其特征在于：所述机织布为棉、锦纶、涤纶、氨纶中的一种或两种以上共织形成的高强度机织布。
6.一种制备如权利要求1~5任一项所述的高强度无溶剂聚氨酯再生皮的制备方法，其特征在于：包括以下步骤：
a、将再生皮基布层经过复合工艺复合补强层，得到基材；
b、经过干法转移无溶剂面层，按照配比制得无溶剂发泡浆料，将无溶剂发泡浆料涂覆在无溶剂面层上，涂覆厚度为0.3mm~0.6mm，得到无溶剂发泡层后，于70℃~130℃预烘至黏合状态，将无溶剂发泡层与基材贴合，于130℃~170℃固化定型，收卷，室温熟化至少24h后剥离，制得高强度无溶剂聚氨酯再生皮；
c、将高强度无溶剂聚氨酯再生皮经过有机硅类柔软剂含浸揉纹处理，同时将再生皮基布面依次封毛、磨皮起毛。
7.如权利要求6所述的制备方法，其特征在于：所述的复合工艺为湿气固化反应型聚氨酯复合或高低温胶膜复合的一种或者两种。
8.如权利要求6所述的制备方法，其特征在于：所述封毛采用水性聚氨酯刀涂工艺涂敷封毛。
9.如权利要求8所述得制备方法，其特征在于：所述水性聚氨酯为阴离子热固型聚醚类水性聚氨酯树脂，所述阴离子热固型聚醚类水性聚氨酯树脂中的阴离子基团为羧酸根基团或磺酸根基团。
10.如权利要求6所述的制备方法，其特征在于：所述磨皮起毛采用砂纸目数100目和150目组合工艺通过卧式双辊磨皮机磨皮起毛。
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