CN114379175A - 一种水性环保高阻燃无溶剂压花吸纹合成革及其制备方法 - Google Patents

一种水性环保高阻燃无溶剂压花吸纹合成革及其制备方法 Download PDF

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CN114379175A
CN114379175A CN202210059234.8A CN202210059234A CN114379175A CN 114379175 A CN114379175 A CN 114379175A CN 202210059234 A CN202210059234 A CN 202210059234A CN 114379175 A CN114379175 A CN 114379175A
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solvent
free
flame
synthetic leather
retardant
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邵晨旭
王新垚
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Zhejiang Changfeng New Material Co ltd
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Abstract

本发明涉及一种水性环保高阻燃无溶剂压花吸纹合成革，包括面层、发泡层、基布，所述发泡层包括无溶剂A组分、无溶剂B组分和阻燃剂，无溶剂A组分包括聚醚多元醇、小分子扩链剂、发泡剂、稳泡剂、催化剂，无溶剂B组分包括异氰酸酯预聚体，本发明使用的聚醚多元醇是由分子量3000‑4000基于甘油的聚醚多元醇和分子量1000‑2000基于丙二醇的聚醚多元醇按一定比例混合，分子量3000‑4000基于甘油的聚醚多元醇在无溶剂A组分和无溶剂B组分扩链反应中形成网状交联给无溶剂层提供更好的韧性及物理性能，分子量1000‑2000基于丙二醇的聚醚多元醇使得无溶剂A组分和无溶剂B组分进一步扩链，大分子直链更多，压纹时经过高温能够更容易软化便于压纹。

Description

一种水性环保高阻燃无溶剂压花吸纹合成革及其制备方法
技术领域
本发明涉及水性聚氨酯合成革技术领域，尤其涉及一种水性环保高阻燃无溶剂压花吸纹合成革及其制备方法。
背景技术
随着大众的环保意识的逐步提高，水性聚氨酯树脂因为不含各种有毒有害溶剂，以及其不易燃耐水解性能优异等特点，逐步取代传统的溶剂型聚氨酯，成为一种全新水性绿色环保的合成革新技术。
但是因为水性聚氨酯树脂是以水做溶剂，合成革在生产过程中要烘掉多余的水分需要消耗大量的能耗，导致制作成本大幅提高；而无溶剂聚氨酯合成革在生产过程中无需加入溶剂，也不会产生任何有毒有害的物质，且使用无溶剂材料制作出来的合成革，手感丰满拥有剥离高，物理性能优异等功能，因此采用面层中层使用水性树脂，底层贴合使用无溶剂树脂，成为一种更加高效环保产品。
传统合成革制作生成纹路主要通过离型纸转移贴面以及压花的方法，离型纸转移贴面制作的合成革纹路相对于压花来说花纹不够清晰立体感不强，而且离型纸价格昂贵又有使用次数限制无形中大大增加制作合成革的制作成本，因此使用压纹方法越来越受到市场欢迎。但是现有的压花产品均是采用贝斯贴面然后再经过高温软化压花，这种工艺制作的合成革一般剥离强度、耐水解、撕裂强度、等物理性能不足，也无法满足对阻燃效果有更高要求的产品。
发明内容
本发明要解决上述现有技术存在的问题，提供一种水性环保高阻燃无溶剂压花吸纹合成革方案，用一种高阻燃特性且利于压花的无溶剂树脂作为合成革的发泡层以及粘接层，来达到可压花效果。
本发明解决其技术问题采用的技术方案：这种水性环保高阻燃无溶剂压花吸纹合成革，包括面层、发泡层、基布，所述发泡层包括无溶剂A组分、无溶剂B组分和阻燃剂，无溶剂A组分包括聚醚多元醇、小分子扩链剂、发泡剂、稳泡剂、催化剂，无溶剂B组分包括异氰酸酯预聚体。
为了进一步完善，所述面层包括芳香族聚醚型树脂、脂肪族聚醚型树脂、色浆、润湿流平助剂、氮丙啶类交联剂、增稠剂，芳香族聚醚型聚氨酯树脂拥有良好的高温软化可塑性强等优点，脂肪族聚醚型聚氨酯可与无溶剂树脂更好的进行粘接达到高剥离要求。
进一步完善，所述阻燃剂是磷系阻燃剂和氢氧化镁阻燃剂进行复配，磷系阻燃剂包括二乙基次膦酸铝、三聚氰胺氰尿酸盐、三聚氰胺磷酸盐，氢氧化镁阻燃剂主要成分是氢氧化镁，其中磷系阻燃剂受热时能产生结构更趋稳定的交联状固体物质或碳化层。碳化层的形成一方面能阻止聚合物进一步热解，另一方面能阻止其内部的热分解产生物进入气相参与燃烧过程，氢氧化镁是一种新型填充型阻燃剂，其受热会分解并释放出结合水，从而吸收大量的热量，来降低它所填充的合成材料在火焰中的表面温度，具有抑制聚合物分解和对所产生的可燃气体进行冷却的作用，两种阻燃剂通过一定比例复配后添加到无溶剂中来达到高阻燃特性需求。
进一步完善，所述聚醚多元醇是由分子量3000-4000基于甘油的聚醚多元醇和分子量1000-2000基于丙二醇的聚醚多元醇组成。
进一步完善，所述小分子扩链剂为丙二醇、乙二醇、1,4丁二醇、甘油中一种或一种以上。
进一步完善，所述稳泡剂是一种有机硅油类产品，发泡剂主要成分是去离子水，催化剂是金属铋类和胺类型催化剂。
一种水性环保高阻燃无溶剂压花吸纹合成革的制备方法，包括以下步骤：
步骤一：无溶剂发泡树脂准备
将无溶剂A组分添加到配料桶中，再加入阻燃剂，在真空脱泡条件下充分混合均匀得到无溶剂A料；无溶剂B组分为异氰酸酯与聚醚多元醇部分扩链形成的异氰酸酯预聚体，是合成反应，本发明中的无溶剂B组分主要从原材料厂采购的无溶剂B料；
步骤二：面层水性聚氨酯树脂的制备
将芳香族聚醚型树脂和脂肪族聚醚型树脂按8:2混合，在其中加入1-3%色浆、0.5-1%润湿流平助剂、0.5-1%氮丙啶类交联剂、0.5-1%增稠剂并充分混合均匀，得到的配置好树脂粘度为3000-6000cps；
步骤三：生产操作工艺
（1）将步骤二中的面层水性聚氨酯树脂以一定间隙涂覆在平纹纸上，进烘箱烘干得到面层；
（2）将步骤一准备好的无溶剂A料和无溶剂B料分别加入干法线浇注机A料罐B料罐中，在浇注机搅拌头中充分搅拌均匀，并通过刮涂的方式涂布在涂好面层的平纹纸上，进入烘箱后，经过预烘50-80S，混合的A组分和B组分料预聚物之间会发生快速的反应，使聚合物分子质量迅速增加，粘度大幅提高，直至表面由透明低粘度状变成乳白色有黏性状，然后与丝光绒基布贴合，再继续熟化直至烘干；
（3）将熟化完全的无溶剂合成革从平纹纸上剥离并收卷得到半成品，然后进行后段压纹，压纹所需温度在190-220℃，压纹后再与0.5-0.7mm厚度的TC布复合，得到纹路与花纹饱满清晰，立体感强的阻燃型无溶剂合成革。
进一步完善，所述骤三所述面层树脂涂覆厚度为0.12-0.15mm，通过烘箱烘干温度控制在80-90℃之间。
进一步完善，所述无溶剂A组分和无溶剂B组分按比例52%-60%在浇筑机头中充分分散均匀并涂覆在带有面层树脂的平纹纸上，厚度为0.25-0.35mm，然后通过90-110℃的烘箱预熟化至表面成乳白色并带有很强的黏性后贴合丝光绒基布，继续在温度120-130℃烘箱中熟化完全。
进一步完善，所述步骤三制作的合成革半成品压纹所需温度为190-220℃，压纹间隙为0.1-0.3mm。
本发明有益的效果是：1、本发明使用纯水性聚氨酯树脂做面层，具有无毒、无味、环保等特点，且由于两种树脂复配，既可以满足跟无溶剂层更好的剥离性能同时也有着高温可塑性强便于压纹的优点；
2、本发明使用的聚醚多元醇是由分子量3000-4000基于甘油的聚醚多元醇和分子量1000-2000基于丙二醇的聚醚多元醇按一定比例混合，分子量3000-4000基于甘油的聚醚多元醇在无溶剂A组分和无溶剂B组分扩链反应中形成网状交联给无溶剂层提供更好的韧性及物理性能，分子量1000-2000基于丙二醇的聚醚多元醇使得无溶剂A组分和无溶剂B组分进一步扩链，大分子直链更多，压纹时经过高温能够更容易软化便于压纹；
3、本发明使用去离子水作为发泡剂，水在催化剂作用下会与异氰酸酯快速反应产生大量的二氧化碳气体，在无溶剂层中形成稳定的泡孔结构，使得压纹时纹路更加清晰饱满；
4、本发明使用的磷系阻燃剂和氢氧化镁阻燃剂具有低烟、无毒、无卤等特点。其阻燃机理如下：磷系阻燃剂，燃烧受热时能产生结构更趋稳定的交联状固体物质或碳化层。碳化层的形成一方面能阻止聚合物进一步热解，另一方面能阻止其内部的热分解产生物进入气相参与燃烧过程；氢氧化镁在受热时(340-490℃)发生分解吸收燃烧物表面的热量起到阻燃作用；同时释放出大量水分稀释燃物表面的氧气，分解生成的活性氧化镁附着于可燃物表面又进一步阻止了燃烧的进行。氢氧化镁在整个阻燃过程中不但没有任何有害物质产生，而且其分解的产物在阻燃的同时还能够大量吸收合成革燃烧所产生的有害气体和烟雾。经实验研究两种阻燃剂添加总量占A组分的30-40%，且磷系阻燃剂占总阻燃剂量的65-85%阻燃效果最佳。
具体实施方式
下面通过具体实施例对本发明作进一步说明：
本发明所采用的其他原料和设备若非特指，均可从市场购得或是本领域常用的，实施例中的方法，如无特别说明，均为本领域的常规方法。
实施例1
无溶剂A组分制备：将聚醚多元醇WANOL®F3156和聚醚多元醇WANOL®F2030按7:3混合，添加5%小分子扩链剂、0.8%发泡剂、2%稳泡剂、0.07%催化剂、10%氢氧化镁、20%磷系阻燃剂NP1060，添加在配料桶中，在真空脱泡条件下充分混合均匀；无溶剂B组分为异氰酸酯预聚体；将无溶剂A组分和无溶剂B组分加入到干法线无溶剂浇注机AB储料罐中，设定流量及搅拌转速以及A组分B组分比例参数；
将芳香族聚醚型树脂JF-PDY-841A和脂肪族聚醚型树脂Tekspro®5215按8:2混合，在其中加入3%色浆、1%润湿流平助剂SY-8009A、0.5%氮丙啶类交联剂ST100、0.5%增稠剂VesmodyTM506，并充分混合均匀，得到的配置好树脂粘度为4500cps，配好的面层树脂在平纹纸上涂覆厚度为0.12mm，并匀速12m/min通过温度90℃烘箱烘干；
开启浇注机启动开关，通过刮涂的方式将充分混合的无溶剂A料和无溶剂B料均匀涂布在涂好面层的平纹纸上，进入烘箱后，经过预烘55S，混合的无溶剂A料和无溶剂B料预聚物之间会发生快速的反应，使聚合物分子质量迅速增加，粘度大幅提高，直至表面由透明低粘度状变成乳白色有黏性状，然后与丝光绒基布贴合，再继续熟化直至烘干；
将熟化完全的无溶剂合成革从离型纸上剥离并收卷得到半成品，然后进行后段压纹，压纹所需温度在190-220℃，压纹后再与0.7mm厚度的含棉量35%以上的TC布复合，得到纹路与花纹饱满清晰，立体感强的阻燃型无溶剂合成革。
实例2
无溶剂A组分制备：将聚醚多元醇WANOL®F3156和聚醚多元醇WANOL®F2030按7:3混合，添加5%小分子扩链剂、0.8%发泡剂、2%稳泡剂、0.07%催化剂、30%磷系阻燃剂NP1060，添加在配料桶中，在真空脱泡条件下充分混合均匀；B组分为异氰酸酯预聚体；将无溶剂A组分和无溶剂B组分加入到干法线无溶剂浇注机AB储料罐中，设定流量及搅拌转速以及A组分B组分比例参数；
将芳香族聚醚型树脂JF-PDY-841A和脂肪族聚醚型树脂Tekspro®5215按8:2混合，在其中加入3%色浆、1%润湿流平助剂SY-8009A、0.5%氮丙啶类交联剂ST100、0.5%增稠剂VesmodyTM506，并充分混合均匀，得到的配置好树脂粘度为4500cps。配好的面层树脂在平纹纸上涂覆厚度为0.12mm，并匀速12m/min通过温度90℃烘箱烘干。
开启浇注机启动开关，通过刮涂的方式将充分混合的无溶剂A料和无溶剂B料均匀涂布在涂好面层的平纹纸上，进入烘箱后，经过预烘55S，混合的无溶剂A料和无溶剂B料预聚物之间会发生快速的反应，使聚合物分子质量迅速增加，粘度大幅提高，直至表面由透明低粘度状变成乳白色有黏性状，然后与丝光绒基布贴合，再继续熟化直至烘干。
将熟化完全的无溶剂合成革从离型纸上剥离并收卷得到半成品，然后进行后段压纹，压纹所需温度在190-220℃，压纹后再与0.7mm厚度的含棉量35%以上的TC布复合，得到纹路与花纹饱满清晰，立体感强的阻燃型无溶剂合成革。
实例3
无溶剂A组分制备：将聚醚多元醇WANOL®F3156和聚醚多元醇WANOL®F2030按6:4混合，添加5%小分子扩链剂、0.8%发泡剂、2%稳泡剂、0.07%催化剂、10%氢氧化镁、20%磷系阻燃剂NP1060，添加在配料桶中，在真空脱泡条件下充分混合均匀；无溶剂B组分为异氰酸酯预聚体。将无溶剂A组分和无溶剂B组分加入到干法线无溶剂浇注机AB储料罐中，设定流量及搅拌转速以及A组分B组分比例参数。
将芳香族聚醚型树脂JF-PDY-841A和脂肪族聚醚型树脂Tekspro®5215按8:2混合，在其中加入3%色浆、1%润湿流平助剂SY-8009A、0.5%氮丙啶类交联剂ST100、0.5%增稠剂VesmodyTM506，并充分混合均匀，得到的配置好树脂粘度为4500cps；配好的面层树脂在平纹纸上涂覆厚度为0.12mm，并匀速12m/min通过温度90℃烘箱烘干；
开启浇注机启动开关，通过刮涂的方式将充分混合的无溶剂A料和无溶剂B料均匀涂布在涂好面层的平纹纸上，进入烘箱后，经过预烘55S，混合的无溶剂A料和无溶剂B料预聚物之间会发生快速的反应，使聚合物分子质量迅速增加，粘度大幅提高，直至表面由透明低粘度状变成乳白色有黏性状，然后与丝光绒基布贴合，再继续熟化直至烘干；
将熟化完全的无溶剂合成革从离型纸上剥离并收卷得到半成品，然后进行后段压纹，压纹所需温度在190-220℃，压纹后再与0.7mm厚度的含棉量35%以上的TC布复合，得到纹路与花纹饱满清晰，立体感强的阻燃型无溶剂合成革。
相关性能测试结果如下：
马丁戴尔耐磨 耐折牢度 剥离强度 GBBS5852阻燃 耐水解测试（丛林） 表面纹路清晰度
实例1 10万次 15万次 大于70N 35秒 8周 较清晰
实例2 10万次 15万次 大于70N 25秒 8周 较清晰
实例3 10万次 15万次 大于60N 35秒 7周 很清晰
（1）无溶剂压纹PU合成革马丁代尔耐磨测试采用GBT2726-2005《皮革物理和机械实验耐磨性能的测定》方法测定。
（2）无溶剂压纹PU合成革耐折性能的测定采用QBT3812.9-1999《皮革耐折牢度的测定》的规定测试。
（3）无溶剂压纹PU合成革剥离强度按GB8949-1995中5.8条规定测试。
（4）无溶剂压纹PU合成革阻燃性能按照英标BS5852中5号火源测试方法测试，5cm火焰垂直燃烧革产品表面一定时间，火源离开革表面5秒内火焰是否自己熄灭。
（5）无溶剂压纹PU合成革耐水解性能按（丛林测试：95%RH，70℃）标准。测试周数可对应革产品使用年限。
上述实施例中的原料来源说明：
1、芳香族聚醚型树脂（JF-PDY-841A）由华峰集团有限公司提供；
2、脂肪族聚醚型树脂（Tekspro®5215）由万华化学集团有限公司提供；
3、聚醚多元醇由万华化学集团有限公司提供，优选的聚醚多元醇为WANOL®F3156和WANOL®F2030；
4、异氰酸酯预聚体（JF-NS-6030B）由华峰集团有限公司提供；
5、磷系阻燃剂为青岛欧普瑞新材料有限公司提供的NP1060、NP0836、ADP-10、NP100中一种；
6、异氰酸酯预聚体为华峰集团有限公司提供的JF-NS-6030B、JF-NS-6020B、JF-NS-6022B中的一种；
7、色浆为达威水基聚氨酯有限公司提供水性色浆C1030、C3030、C3031、C9031中的几种；
8、润湿流平剂包括三越新材料有限公司的SY-8009A、广州市斯洛科高分子聚合物有限公司的Silok8000、Silok8022中的一种；
9、氮丙啶交联剂为宁波市赛飞特新材料有限公司提供ST100；
10、增稠剂为万华化学集团有限公司的VesmodyTM505或VesmodyTM506等。
虽然本发明已通过参考优选的实施例进行了描述，但是，本专业普通技术人员应当了解，在权利要求书的范围内，可作形式和细节上的各种水性环保高阻燃无溶剂压花吸纹合成革的制备方法各样变化。

Claims (10)

1.一种水性环保高阻燃无溶剂压花吸纹合成革，包括面层、发泡层、基布，其特征是：所述发泡层包括无溶剂A组分、无溶剂B组分和阻燃剂，无溶剂A组分包括聚醚多元醇、小分子扩链剂、发泡剂、稳泡剂、催化剂，无溶剂B组分包括异氰酸酯预聚体。
2.根据权利要求1所述的一种水性环保高阻燃无溶剂压花吸纹合成革，其特征是：所述面层包括芳香族聚醚型树脂、脂肪族聚醚型树脂、色浆、润湿流平助剂、氮丙啶类交联剂、增稠剂。
3.根据权利要求1所述的一种水性环保高阻燃无溶剂压花吸纹合成革，其特征是：所述阻燃剂是磷系阻燃剂和氢氧化镁阻燃剂进行复配，磷系阻燃剂包括二乙基次膦酸铝、三聚氰胺氰尿酸盐、三聚氰胺磷酸盐，氢氧化镁阻燃剂主要成分是氢氧化镁。
4.根据权利要求1所述的一种水性环保高阻燃无溶剂压花吸纹合成革，其特征是：所述聚醚多元醇是由分子量3000-4000基于甘油的聚醚多元醇和分子量1000-2000基于丙二醇的聚醚多元醇组成。
5.根据权利要求1所述的一种水性环保高阻燃无溶剂压花吸纹合成革，其特征是：所述小分子扩链剂为丙二醇、乙二醇、1,4丁二醇、甘油中一种或一种以上。
6.根据权利要求1所述的一种水性环保高阻燃无溶剂压花吸纹合成革，其特征是：所述稳泡剂是一种有机硅油类产品，发泡剂主要成分是去离子水，催化剂是金属铋类和胺类型催化剂。
7.根据权利要求1-6任意一项所述的水性环保高阻燃无溶剂压花吸纹合成革的制备方法，包括以下步骤：
步骤一：无溶剂发泡树脂准备
将无溶剂A组分添加到配料桶中，再加入阻燃剂，在真空脱泡条件下充分混合均匀得到无溶剂A料；无溶剂B组分为异氰酸酯与聚醚多元醇部分扩链形成的异氰酸酯预聚体，是合成反应，本发明中的无溶剂B组分主要从原材料厂采购的无溶剂B料；
步骤二：面层水性聚氨酯树脂的制备
将芳香族聚醚型树脂和脂肪族聚醚型树脂按8:2混合，在其中加入1-3%色浆、0.5-1%润湿流平助剂、0.5-1%氮丙啶类交联剂、0.5-1%增稠剂并充分混合均匀，得到的配置好树脂粘度为3000-6000cps；
步骤三：生产操作工艺
（1）将步骤二中的面层水性聚氨酯树脂以一定间隙涂覆在平纹纸上，进烘箱烘干得到面层；
（2）将步骤一准备好的无溶剂A料和无溶剂B料分别加入干法线浇注机A料罐B料罐中，在浇注机搅拌头中充分搅拌均匀，并通过刮涂的方式涂布在涂好面层的平纹纸上，进入烘箱后，经过预烘50-80S，混合的A组分和B组分料预聚物之间会发生快速的反应，使聚合物分子质量迅速增加，粘度大幅提高，直至表面由透明低粘度状变成乳白色有黏性状，然后与丝光绒基布贴合，再继续熟化直至烘干；
（3）将熟化完全的无溶剂合成革从平纹纸上剥离并收卷得到半成品，然后进行后段压纹，压纹所需温度在190-220℃，压纹后再与0.5-0.7mm厚度的TC布复合，得到纹路与花纹饱满清晰，立体感强的阻燃型无溶剂合成革。
8.根据权利要求7所述的一种水性环保高阻燃无溶剂压花吸纹合成革的制备方法，其特征是：步骤三所述面层树脂涂覆厚度为0.12-0.15mm，通过烘箱烘干温度控制在80-90℃之间。
9.根据权利要求7所述的一种水性环保高阻燃无溶剂压花吸纹合成革的制备方法，其特征是：所述无溶剂A组分和无溶剂B组分按比例52%-60%在浇筑机头中充分分散均匀并涂覆在带有面层树脂的平纹纸上，厚度为0.25-0.35mm，然后通过90-110℃的烘箱预熟化至表面成乳白色并带有很强的黏性后贴合丝光绒基布，继续在温度120-130℃烘箱中熟化完全。
10.根据权利要求7所述的一种水性环保高阻燃无溶剂压花吸纹合成革的制备方法，其特征是：所述步骤三制作的合成革半成品压纹所需温度为190-220℃，压纹间隙为0.1-0.3mm。
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