CN111704879A - 一种透气性皮革胶粘剂及其制备方法 - Google Patents

一种透气性皮革胶粘剂及其制备方法 Download PDF

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CN111704879A
CN111704879A CN202010710915.7A CN202010710915A CN111704879A CN 111704879 A CN111704879 A CN 111704879A CN 202010710915 A CN202010710915 A CN 202010710915A CN 111704879 A CN111704879 A CN 111704879A
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宋小群
杨文华
陈文胜
陈杰
单志华
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Xuzhou Hongfeng High Molecular Material Co ltd
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Abstract

本发明公开了一种透气性皮革胶粘剂及其制备方法，由以下原料制备而成：多元醇，多异氰酸酯，胶原蛋白，扩链剂，偶联剂，致孔剂和增强剂。通过如下步骤制得皮革胶粘剂，首先将多元醇与胶原蛋白混炼获得单体，其次与多异氰酸酯和扩链剂反应制备预聚体；第三将中和、乳化获得乳液；最后与致孔剂、偶联剂反应获得胶黏剂。本发明通过牛皮粘合实验表明，采用发明的胶黏剂与商品胶黏剂比较下，除剥离强度略低外，透气性显著增加。

Description

一种透气性皮革胶粘剂及其制备方法
技术领域
本发明涉及一种透气性皮革胶粘剂及其制备方法，属于黏合剂工程技术领域。
背景技术
胶粘剂是皮具加工过程中必不可少的化工产品之一。传统胶粘剂成膜后不透气的缺点极大的影响了皮具产品的卫生性能。随着经济的发展，消费者对透气性皮具产品的需求越来越高。因此，提高胶粘剂透气性对于提升皮具产品卫生性能具有积极意义。传统胶粘剂不透气是因为生产过程中选用的都是内聚能较高的原料导致成膜规整性好、结晶度高、强度高，缺点则是透气性差。对胶粘剂进行改进，在保证物理强度的前提下尽可能提高其透气性是皮革胶粘剂未来的发展方向。在胶粘剂中加入多相组分，通过相分离使胶膜内部形成透气性通道是一种有效途径。同时，为了弥补强度下降的缺陷，在配方中加入增强剂以保证粘接强度。
发明内容
本发明的目的是针对现有聚氨酯胶黏剂透气性不足，经过胶粘后的皮革制品缺乏必要的透气而失去了天然皮革的最重要特性，为了增加透气性，已有的报道是物理掺杂，但是掺杂部分不仅本身不透气还会降低粘合强度。本申请将废弃皮革提取的胶原降解物直接接入聚氨酯分子，干燥后随着蛋白的收缩及亲水性使粘合胶膜获得透气及透水汽双重功能，最大化地提高了黏合皮革的卫生性能。为实现上述目的，本发明的技术方案如下：一种透气性皮革胶粘剂，包括如下的重量份数组成：30~50份多元醇，30~40份多异氰酸酯、10~20份胶原蛋白、0.5~2份偶联剂、5~10份致孔剂和10~25份增强剂。
一种透气性皮革胶粘剂的制备方法，其特征包括以下步骤：
1）30~50份多元醇与 10~20 份胶原蛋白 80~130℃ 获得混炼单体；
2）混炼单体与 30~40 份多异氰酸酯在 70~95℃ 反应制备预聚体；
3）将预聚体用三乙胺在5~10℃ 中和、乳化获得预聚体乳液；
4）将聚氨酯乳液与 5~ 10 份致孔剂、0.5~2 份偶联剂在30~50℃下反应60min，获得胶粘剂组分；
5）将10~25 份增强剂在20~30℃下与胶黏剂组分混合获得胶粘剂产品 。
在本发明中：所述的混炼单体中多元醇为二羟甲基丁酸、二羟甲基丙酸中的一种与聚碳酸酯二醇、聚己二醇己二酸酯二醇、甘油聚醚三醇、聚丁二醇丁二酸酯二醇中的一种，两类多元醇按照各50%比率混合。
在本发明中：所述的混炼单体中胶原蛋白为废弃皮革提取胶原蛋白降解物，分子量8000~10000。
在本发明中：所述的多异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六次甲基二异氰酸酯中的一种或多种的混合物。
在本发明中：所述的致孔剂为中空二氧化钛微球、纳米二氧化硅中的一种或多种的混合物。
在本发明中：所述的偶联剂为γ-氨丙基三乙氧基硅烷、γ-（2，3-环氧丙氧）丙基三甲氧基硅烷、γ-（甲基丙烯酰氧）丙基三甲氧基硅烷、γ-巯丙基三甲氧基硅烷中的一种或多种的混合物。
在本发明中：所述的增强剂为环氧树脂EP-12、EP-13、EP-16和EP-20中的一种或多种的混合物。
通过上述技术方案，本发明的有益效果如下：本发明奖弃皮革提取的胶原降解物直接接入聚氨酯分子，干燥后随着蛋白的收缩及亲水性使粘合胶膜获得透气及透水汽双重功能，最大化地提高了黏合皮革的卫生性能，得到的产品稳定，粘接强度高，透气性好。
附图说明
图1为本发明的实施例的透气性比较示意图；
图2为本发明的实施例的剥离强度比较示意图。
具体实施方式
为使本发明实现的技术手段、创作特征、达成目的的功效易于明白了解，下面结合具体实施例，进一步阐述本发明。
实施例 1
一种透气性皮革胶粘剂的制备方法，其特征包括以下步骤：
1）40份多元醇（二羟甲基丁酸+聚碳酸酯二醇）与20 份胶原蛋白 100℃ 获得混炼单体；
2）混炼单体与 40 份异佛尔酮二异氰酸酯在 85℃ 反应制备预聚体；
3）将预聚体用三乙胺在10℃ 中和、乳化获得预聚体乳液；
4）聚氨酯乳液与 5份中空二氧化钛微球致孔剂、0.5份 γ-氨丙基三乙氧基硅烷偶联剂在40℃下反应60min，获得胶粘剂组分；
5）将20 份EP-12作为增强剂在30℃下与胶黏剂组分混合获得胶粘剂产品。
实施例 2
一种透气性皮革胶粘剂的制备方法，其特征包括以下步骤：
1）30份多元醇（二羟甲基丙酸+聚丁二醇丁二酸酯二醇）与 10 份胶原蛋白 110℃ 获得混炼单体；
2）混炼单体与 35 份六次甲基二异氰酸酯在 90℃ 反应制备预聚体；
3）将预聚体用三乙胺在0℃ 中和、乳化获得预聚体乳液；
4）聚氨酯乳液与 8 份纳米二氧化硅致孔剂、1 份 γ-(甲基丙烯酰氧)丙基三甲氧基硅烷偶联剂在50℃下反应60min，获得胶粘剂组分；
5）将15 份EP-16作为增强剂在30℃下与胶黏剂组分混合获得胶粘剂产品。
实施例 3
一种透气性皮革胶粘剂的制备方法，其特征包括以下步骤：
1）50份多元醇（二羟甲基丁酸+甘油聚醚三醇）与 20 份胶原蛋白 130℃ 获得混炼单体；
2）混炼单体与40 份甲苯二异氰酸酯在95℃ 反应制备预聚体；
3）将预聚体用三乙胺在10℃ 中和、乳化获得预聚体乳液；
4）聚氨酯乳液与10 份纳米二氧化硅致孔剂、2 份 γ-(2，3-环氧丙氧)丙基三甲氧基硅烷偶联剂在50℃下反应60min，获得胶粘剂组分；
5）将25 份EP-20作为增强剂在30℃下与胶黏剂组分混合获得胶粘剂产品。
应用实例
与商品HN-8209同类胶粘剂比较，材料为牛皮二层革（1.3mm厚）与布基粘结，用量为120g/m2时，粘合结果见图1-2，尽管在剥离强度稍低于商品胶粘剂外，在透气性上的优势显著。
以上对本发明的具体实施方式进行了描述，但本发明并不限于以上描述。对于本领域的技术人员而言，任何对本技术方案的同等修改和替代都是在本发明的范围之中。因此，在不脱离本发明的精神和范围下所作的均等变换和修改，都应涵盖在本发明的范围内。

Claims (8)

1.一种透气性皮革胶粘剂，其特征在于：包括如下的重量份数组成：30~50份多元醇，30~40份多异氰酸酯、10~20份胶原蛋白、0.5~2份偶联剂、5~10份致孔剂和10~25份增强剂。
2.一种制备如权利要求1所述的透气性皮革胶粘剂的方法，其特征在于：包括以下步骤：
1）30~50份多元醇与 10~20份胶原蛋白在80~130℃制得混炼单体；
2）混炼单体与 30~40份多异氰酸酯在70~95℃反应制备预聚体；
3）将预聚体用三乙胺在5~10℃中和、乳化获得预聚体乳液；
聚氨酯乳液与5~10 份致孔剂，0.5~2 份偶联剂在30~50℃下反应60min，获得胶粘剂组分；
将10~25 份增强剂在20~30℃下与胶黏剂组分混合获得胶粘剂产品。
3.根据权利要求 2所述的一种透气性皮革胶粘剂的制备方法，其特征在于：
所述的混炼单体中多元醇为二羟甲基丁酸、二羟甲基丙酸中的一种与聚碳酸酯二醇、聚己二醇己二酸酯二醇、甘油聚醚三醇、聚丁二醇丁二酸酯二醇中的一种，两类多元醇按照各50%比率混合。
4.根据权利要求 2所述的一种透气性皮革胶粘剂的制备方法，其特征在于：所述的混炼单体中胶原蛋白为废弃皮革提取胶原蛋白降解物，分子量8000~10000。
5.根据权利要求 2所述的一种透气性皮革胶粘剂的制备方法，其特征在于：所述的多异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六次甲基二异氰酸酯中的一种或多种的混合物。
6.根据权利要求 2所述的一种透气性皮革胶粘剂的制备方法，其特征在于：所述的致孔剂为中空二氧化钛微球、纳米二氧化硅中的一种或多种的混合物。
7.根据权利要求 2所述的一种透气性皮革胶粘剂的制备方法，其特征在于：所述的偶联剂为γ-氨丙基三乙氧基硅烷、γ-（2，3-环氧丙氧）丙基三甲氧基硅烷、γ-（甲基丙烯酰氧）丙基三甲氧基硅烷、γ-巯丙基三甲氧基硅烷中的一种或多种的混合物。
8.根据权利要求 2所述的一种透气性皮革胶粘剂的制备方法，其特征在于：所述的增强剂为环氧树脂EP-12、EP-13、EP-16和EP-20中的一种或多种的混合物。
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