CN114907545A - 一种特柔软合成革干法机械发泡涂层用高固含水性聚氨酯 - Google Patents

一种特柔软合成革干法机械发泡涂层用高固含水性聚氨酯 Download PDF

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CN114907545A
CN114907545A CN202210629807.6A CN202210629807A CN114907545A CN 114907545 A CN114907545 A CN 114907545A CN 202210629807 A CN202210629807 A CN 202210629807A CN 114907545 A CN114907545 A CN 114907545A
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戴家兵
郭文鹤
李维虎
赵曦
朱保凌
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Lanzhou Ketian Waterborne Polymer Material Co ltd
Hefei Ketian Waterborne Technology Co ltd
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Hefei Ketian Waterborne Technology Co ltd
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Abstract

本发明公开了一种特柔软合成革干法机械发泡涂层用高固含水性聚氨酯及其制备方法，涉及水性聚氨酯技术领域，本发明制备的水性聚氨酯合成革树脂有效解决了水性聚氨酯树脂固含量低、机械发泡过程中泡沫稳定性差、烘干过程中树脂开裂分层等问题，对PET等极性基材有较好的附着力，该水性聚氨酯发泡后泡沫细腻，手感柔软，模量较低，可以添加适量填充粉体，降低成本，剥离强度高，肤感佳，回弹性好。

Description

一种特柔软合成革干法机械发泡涂层用高固含水性聚氨酯
技术领域：
本发明涉及水性聚氨酯技术领域，具体涉及一种特柔软合成革干法机械发泡涂层用高固含水性聚氨酯及其制备方法。
背景技术：
传统合成革生产用聚氨酯都为有机溶剂型，有机溶剂对人们身体有害，所以淘汰是必然趋势。水性聚氨酯具有绿色、环保、无毒、低VOC等特性，是代替溶剂型聚氨酯的理想材料。市场上水性聚氨酯合成革一般只是面层用水性聚氨酯，发泡层树脂大多以溶剂型发泡层树脂为主。因此，水性聚氨酯发泡涂层树脂有很大的发展前途。
聚酯类聚氨酯手感硬，结晶性强，不常做柔软类树脂；聚醚类聚氨酯手感柔软，发泡后液膜弹性好，更有利于发泡与稳泡，但是聚醚类树脂耐热差，强度小，尺寸稳定性差。如果树脂固含量较低，那么成膜所需能耗大，发泡与稳泡性差，树脂烘干时开裂，分层，手感僵硬，剥离强度低，粉体添加量少，粉体与树脂基材粘接力小。
发明内容：
本发明所要解决的技术问题在于提供一种高固含、成膜性好、发泡及稳泡效果好、对无机粉体包裹性好，在PET等极性基材上附着力强的水性聚氨酯树脂，通过使用聚醚多元醇赋予水性聚氨酯良好的柔软性与起泡稳泡性；多官能度内交联TMP提高树脂耐热性与乳液分散乳化稳定性，提高涂膜回弹性与力学性能；小分子扩链剂调节树脂分子结构与结晶性，更好地成膜；硅烷偶联剂提高树脂与无机粉体在基材上的附着力；较大的分子量可以保证良好的基础物性，较大的乳液粒径以及高固含可以降低树脂发泡烘干排液速度，防止形成较大的气泡，更利于形成更小更稳定的泡沫，使合成革手感更柔软。
本发明所要解决的技术问题采用以下的技术方案来实现：
本发明的目的之一在于提供一种特柔软合成革干法机械发泡涂层用高固含水性聚氨酯，包括以下重量份的原料：
Figure BDA0003679282030000021
所述聚醚多元醇包括聚乙二醇、聚丙二醇二元醇、聚氧化丙烯二醇、聚四氢呋喃二醇中的一种或两种。
所述多异氰酸酯包括异佛尔酮二异氰酸酯、甲苯二异氰酸酯、1,6己基二异氰酸酯中的一种或多种。
所述亲水扩链剂包括二羟甲基丙酸(DMPA)、二羟甲基丁酸中的一种或多种。
所述小分子扩链剂包括环己二甲醇、1,4-丁二醇、甲基丙二醇、一缩二乙二醇中的一种或多种。
所述内交联剂为TMP(三羟甲基丙烷)。
所述中和剂为三乙胺。
所述后扩链剂为异佛尔酮二胺，乙二胺，二正丁胺、二乙烯三胺中的一种或多种。
所述偶联剂为硅烷偶联剂，优选硅烷偶联剂KH550、KH791、WD56中的一种或多种。
本发明的目的之二在于提供一种特柔软合成革干法机械发泡涂层用高固含水性聚氨酯的制备方法，包括以下步骤：将聚醚多元醇投入反应釜，105℃下真空脱水，降温至50～60℃，投入多异氰酸酯，升温至90℃反应，降温至50-60℃，投入小分子扩链剂和降粘丙酮，升温至80～85℃反应，然后降温至50-55℃，加入内交联剂、催化剂和降粘丙酮，75℃反应，降至常压，加入降粘丙酮，降至20℃进行中和，加入去离子水高速乳化，乳化打开后加后扩链剂与硅烷偶联剂，搅拌，减压脱溶，得到水性聚氨酯。
本发明的有益效果是：本发明制备的水性聚氨酯合成革树脂有效解决了水性聚氨酯树脂固含量低、机械发泡过程中泡沫稳定性差、烘干过程中树脂开裂分层等问题，对PET等极性基材有较好的附着力，该水性聚氨酯发泡后泡沫细腻，手感柔软，模量较低，可以添加适量填充粉体，降低成本，剥离强度高，肤感佳，回弹性好。
具体实施方式：
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体实施例，进一步阐述本发明。
实施例1
1)制备预聚体：将18份聚丙二醇(分子量2000)升温至100-105℃抽真空(-0.1MPa)脱水至二元醇水含量0.03％以下，降温至50～60℃，投入8份异佛尔酮二异氰酸酯升温至90℃氮气保护反应3h，然后降温至50-55℃，加入2.8份丙酮、0.6份DMPA、0.4份一缩二乙二醇，80℃保温搅拌2h，降温到50℃加入0.07份TMP与少量丙酮，75℃反应3h，降至常压，加丙酮降粘度，降温20℃，加0.3份三乙胺中和30min，得到预聚体。
2)乳化：将预聚体转移至乳化器中，在转速2000r/min的条件下将23份去离子水加入预聚体中，搅拌2min，然后将转速降至200～400r/min，加入0.7份乙二胺和0.8份硅烷偶联剂KH550搅拌360min，在旋转蒸发仪上50-60℃减压蒸馏脱去丙酮，获得乳液。
实施例2
1)制备预聚体：将16份聚丙二醇(分子量2000)升温至100-105℃抽真空(-0.1MPa)脱水至二元醇水含量0.03％以下，降温至50～60℃，投入9份六亚甲基二异氰酸酯升温至90℃氮气保护反应3h，然后降温至50-55℃，加入2.8份丙酮、0.6份DMPA、0.5份甲基丙二醇，80℃保温搅拌2h，降温到50℃加入0.09份TMP反应，75℃反应3h，降至常压，加丙酮降粘度，降温20℃，加0.4份三乙胺中和30min，得到预聚体。
2)乳化：将预聚体转移至乳化器中，在转速2000r/min的条件下将25份去离子水加入预聚体中，搅拌2min，然后将转速降至200～400r/min，加入0.7份乙二胺和0.9份硅烷偶联剂KH550搅拌360min，在旋转蒸发仪上50-60℃减压蒸馏脱去丙酮，获得乳液。
测试结果：
将上述实施例制备的水性聚氨酯与市售一三七化工科技有限公司的水性聚氨酯MR-875发泡树脂分别按照以下质量配比配置浆料：
100质量份水性聚氨酯，加入20质量份重钙，0.3质量份色浆，5质量份非离子稳泡剂，0.3质量份聚氨酯类增稠剂，0.5质量份氮丙啶交联剂，在高速分散机发泡搅拌至体积增加2.5倍，粘度20000cps刮涂0.40mm于离型纸，120℃烘箱烘干，得到水性聚氨酯发泡料干燥涂层，再在上面刮涂0.40mm料浆，贴合0.3mm麂皮绒，烘干，得到水性聚氨酯机械发泡层。
1)剥离、耐曲折测试
在耐曲折测试机上分别测试，设定测试曲折次数为100000次。结果显示：采用本发明实施例制备的水性聚氨酯，耐折100000次不破，剥离强度30N/3cm；采用市售水性聚氨酯，耐折50000次破，剥离15N/3cm。
2)泡沫稳定性以及成膜性测试
本发明实施例制备的水性聚氨酯相比市售水性聚氨酯发泡速率较快，泡沫直径较小至30-40um，泡沫半小时稳定性好，泡沫弹性较好，树脂快速烘干过程中收缩小，成膜性好，不开裂。
3)手感回弹性测试以及基础物性
本发明实施例制备的水性聚氨酯相比市售水性聚氨酯手感柔软，丰满，肤感强，回弹性好。树脂基础物性如下：100％拉伸强度1MPa，拉伸强度13MPa.断裂伸长率1300％。
4)固含测试
本发明实施例制备的水性聚氨酯固含可达55％，远高于市场聚氨酯树脂。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。

Claims (10)

1.一种特柔软合成革干法机械发泡涂层用高固含水性聚氨酯，其特征在于，包括以下重量份的原料：
Figure FDA0003679282020000011
2.根据权利要求1所述的特柔软合成革干法机械发泡涂层用高固含水性聚氨酯，其特征在于：所述聚醚多元醇包括聚乙二醇、聚丙二醇二元醇、聚氧化丙烯二醇、聚四氢呋喃二醇中的一种或两种。
3.根据权利要求1所述的特柔软合成革干法机械发泡涂层用高固含水性聚氨酯，其特征在于：所述多异氰酸酯包括异佛尔酮二异氰酸酯、甲苯二异氰酸酯、1,6己基二异氰酸酯中的一种或多种。
4.根据权利要求1所述的特柔软合成革干法机械发泡涂层用高固含水性聚氨酯，其特征在于：所述亲水扩链剂包括二羟甲基丙酸、二羟甲基丁酸中的一种或多种。
5.根据权利要求1所述的特柔软合成革干法机械发泡涂层用高固含水性聚氨酯，其特征在于：所述小分子扩链剂包括环己二甲醇、1,4-丁二醇、甲基丙二醇、一缩二乙二醇中的一种或多种。
6.根据权利要求1所述的特柔软合成革干法机械发泡涂层用高固含水性聚氨酯，其特征在于：所述内交联剂为TMP。
7.根据权利要求1所述的特柔软合成革干法机械发泡涂层用高固含水性聚氨酯，其特征在于：所述中和剂为三乙胺。
8.根据权利要求1所述的特柔软合成革干法机械发泡涂层用高固含水性聚氨酯，其特征在于：所述后扩链剂为异佛尔酮二胺，乙二胺，二正丁胺、二乙烯三胺中的一种或多种。
9.根据权利要求1所述的特柔软合成革干法机械发泡涂层用高固含水性聚氨酯，其特征在于：所述偶联剂为硅烷偶联剂，优选硅烷偶联剂KH550、KH791、WD56中的一种或多种。
10.权利要求1-9任意一项所述的特柔软合成革干法机械发泡涂层用高固含水性聚氨酯的制备方法，其特征在于：将聚醚多元醇投入反应釜，105℃下真空脱水，降温至50～60℃，投入多异氰酸酯，升温至90℃反应，降温至50-60℃，投入小分子扩链剂和降粘丙酮，升温至80～85℃反应，然后降温至50-55℃，加入内交联剂、催化剂和降粘丙酮，75℃反应，降至常压，加入降粘丙酮，降至20℃进行中和，加入去离子水高速乳化，乳化打开后加后扩链剂与硅烷偶联剂，搅拌，减压脱溶，得到水性聚氨酯。
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