CN110409191B - 一种基于热固化的无溶剂聚氨酯-有机硅合成革及其制造方法 - Google Patents

一种基于热固化的无溶剂聚氨酯-有机硅合成革及其制造方法 Download PDF

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CN110409191B
CN110409191B CN201910762028.1A CN201910762028A CN110409191B CN 110409191 B CN110409191 B CN 110409191B CN 201910762028 A CN201910762028 A CN 201910762028A CN 110409191 B CN110409191 B CN 110409191B
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范浩军
孙哲
陈意
颜俊
向均
文嘉婷
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Abstract

本发明公开了一种基于热固化的无溶剂聚氨酯‑有机硅合成革及其制造方法，其特征是将由活性官能团封端的无溶剂聚氨酯预聚体、异氰酸酯基封端的聚硅氧烷及助剂组成的混合浆料涂覆于离型纸上，经热固化成膜；然后再涂覆热熔胶粘合剂，与合成革基材热压贴合，经热烘箱固化，纸革分离，制得无溶剂聚氨酯‑有机硅合成革。本发明将不含任何溶剂的聚氨酯‑有机硅浆料经热固化形成合成革涂层，实现了聚氨酯和有机硅材料性能的优势互补，赋予合成革更为优异的使用性能，其制造工艺简单、能耗低、效率高，从源头消除有机溶剂污染，产品不含VOC，大大提升了合成革的生态等级、成品档次和国际市场竞争力。

Description

一种基于热固化的无溶剂聚氨酯-有机硅合成革及其制造 方法
技术领域
本发明涉及一种基于热固化的无溶剂聚氨酯-有机硅合成革及其制造方法，属于合成革制造领域。
背景技术
我国是世界合成革生产和消费大国，目前国内已有人造革、合成革企业1100多家，规模以上企业470余家，是我国轻工行业的支柱产业之一。
近几年，随着人们生活水平和环保意识的不断提高，消费者对于高品质、高性能生态环保合成革的需求量持续上升，仅国内市场对高档生态合成革的需求量已达2亿平方米/年。此外，欧美市场对合成革的生态性也提出了更高的要求，特别是家居装饰革、汽车内饰革、沙发革等高档产品要求零甲醛、零重金属残留，同时可挥发性有机溶剂含量（VOC含量）≤5 mg/Kg（革）。由此可见，合成革行业的清洁化生产势在必行。
然而，目前国内合成革的制造主要采用溶剂型聚氨酯，而这些树脂中通常含有大量的N,N-二甲基甲酰胺、甲苯和丁酮等有机溶剂。一方面，大量的有机溶剂造成严重的资源浪费和环境污染；另一方面，有机溶剂易燃易爆、毒性大、气味大、严重危害劳动者的身心健康，且DMF在成品革中的残留问题也将对消费者的身心健康构成威胁，限制产品进入欧美市场。显然，传统溶剂型树脂的合成革制造技术已无法满足国内外市场需求，要想实现从合成革生产大国向合成革生产强国的跨越，必须确定从量的扩大向重视收益性转移的“高附加值化”战略，提高产品档次及生态等级，以增强在国际市场上的竞争力。
因此，合成革的发展方向将从传统的有机溶剂型合成革生产向绿色、生态环保的水性聚氨酯、无溶剂聚氨酯、有机硅合成革方向转变。硅是地球上含量最丰富的元素，基于有机硅合成革涂层具有耐高低温、电气绝缘、耐氧化稳定性、耐候性、难燃、憎水、耐腐蚀、无毒无味以及生理惰性等优异特性，制造过程不使用、不产生任何有机溶剂，因此，以有机硅作为合成革的涂层材料替代油性聚氨酯，是合成革清洁生产的方向之一。中国专利CN105670298A提供了一种加成型硅橡胶配方及粘接方法，该方法中将乙烯基聚硅氧烷、含氢聚硅氧烷、填料、铂系催化剂和延迟剂的混合物涂覆在需要粘接的基材上，放入烘箱烘烤，即可完成将加成型硅橡胶涂层在基材上的粘接和成膜。
然而，由于有机硅材料成膜强度偏低(≤5 MPa)，延伸率偏小(≤400 %)，且具有表面张力小、表面能低的特点，因此成膜后底面与基材粘接力不足，在其表面再进行表面处理如改色、印花、压花、增光、消光、抛光、烫亮、湿气固化等后处理操作时存在表处层润湿性、流平性、再涂性差的特点，降低了通过后处理工序改善产品美学视觉效果的可行性；另外，有机硅原料价格昂贵，目前有机硅合成革的价格是水性聚氨酯合成革价格的3-4倍、是油性聚氨酯合成革价格的5-6倍，价格高的问题也削弱了有机硅生态革的国际市场竞争力。
利用聚氨酯来改性有机硅树脂制造合成革，由于两类材料极性差异大（相容性差）、聚合物形成机理不同（聚氨酯属逐步聚合，有机硅属配位聚合），至今未见有相关报导。
发明内容
本发明的目的是针对上述现有技术的不足而提供一种基于热固化的无溶剂聚氨酯-有机硅合成革及其制造方法。将由羟基或胺基封端的无溶剂聚氨酯预聚体、异氰酸酯基封端的聚硅氧烷及助剂组成的混合浆料涂覆于离型纸上，热固化成膜，然后再涂覆热溶胶粘合剂，与合成革基材热压贴合，经热烘箱固化，制得半成品，再经真空吸纹或热压成纹，得到无溶剂聚氨酯-有机硅合成革产品。本发明将不含任何溶剂的聚氨酯-有机硅浆料经热固化形成合成革涂层，实现了聚氨酯和有机硅材料性能的优势互补，聚氨酯组分降低了成革的成本，提高了涂层的表面张力和再涂性，弥补了单纯有机硅涂层在机械强度和与基布间粘接力上的不足，而有机硅组分则能够有效提升合成革的耐寒性、耐磨型、疏水性和阻燃性等性能。此外，该发明在生产过程中不含有任何有机溶剂，符合绿色、环保的需求，为高品质生态合成革的开发提供了新的思路。
本发明提供的一种基于热固化的无溶剂聚氨酯-有机硅合成革及其制造方法，其特征在于包括以下步骤，所用物料的份数均为重量份数：
（1）活性官能团封端的无溶剂聚氨酯预聚体的制备：
将经脱水处理后的液态聚酯或聚醚二元醇45~75份加入反应釜中，再依次加入异氰酸酯12~20份，有机铋催化剂0~0.1份，升温至75~85 ℃，反应2 h后加入小分子扩链剂6.0~10份，45~85 ℃继续反应1~2 h，控制体系-NCO和-OH或-NH2摩尔比在1:2，获得羟基或胺基封端的聚氨酯预聚体，密封备用；
（2）异氰酸酯基封端的聚硅氧烷的制备：
反应釜中加入含氢聚硅氧烷5~10份、液态二异氰酸酯10~20份，升温至40~60 ℃，反应2 h后，控制体系-NCO和活性H的摩尔比在2:1，获得异氰酸酯基封端的聚硅氧烷，密封备用；
（3）无溶剂涂层浆料的制备：将（1）制备的无溶剂聚氨酯预聚体80~100份、（2）制备的异氰酸酯基封端的聚硅氧烷20~30份、填料7.0~15份、有机铋催化剂0~0.1份、色粉2.0~5.0份混合均匀；
（4）无溶剂合成革的制造：
将步骤（3）中制备的无溶剂涂层浆料涂覆于离型纸上，涂膜厚度控制在0.8~1.0mm，然后进入90~130 ℃烘箱熟化，烘箱长度60~80 m，固化温度一区90~100 ℃，二区100~110 ℃，三区110~130 ℃，车速8~10 m/min，熟化后再涂覆聚氨酯热熔胶，与合成革基材热压贴合，进入90~130 ℃烘箱熟化1~2 min，冷却，纸革分离，制得无溶剂聚氨酯-有机硅合成革。再经表面处理、吸纹或压纹、揉革工艺，丰富无溶剂聚氨酯-有机硅合成革的花色品种。
所述的一种基于热固化的无溶剂聚氨酯-有机硅合成革及其制造方法，其特征在于所述的液态聚酯或聚醚二元醇为相对分子质量在1000~2000的聚己二酸-1,3-丁二醇酯二醇、聚碳酸亚丙酯二醇、聚丙二醇、聚乙二醇中的至少一种。
所述的一种基于热固化的无溶剂聚氨酯-有机硅合成革及其制造方法，其特征在于所述异氰酸酯为常温呈液态的异佛尔酮二异氰酸酯、2,4-甲苯二异氰酸酯、六亚甲基二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯中的至少一种。
所述的一种基于热固化的无溶剂聚氨酯-有机硅合成革及其制造方法，其特征在于所述小分子扩链剂为1,4-丁二醇、1,6-己二醇、1,3-丙二醇、乙二醇或乙二胺、己二胺、1,4-己二胺中的至少一种。
所述的一种基于热固化的无溶剂聚氨酯-有机硅合成革及其制造方法，其特征在于所述含氢聚硅氧烷为含氢量为0.18~1.6 %的含氢聚硅氧烷，所述氢原子位于聚硅氧烷的链端或侧链，粘度100-1500 cps。
所述的一种基于热固化的无溶剂聚氨酯-有机硅合成革及其制造方法，其特征在于所述填料为轻质碳酸钙、白炭黑或硅藻土中的至少一种。
所述的一种基于热固化的无溶剂聚氨酯-有机硅合成革及其制造方法，其特征在于所述合成革基材为机织布、无纺布、超纤布中的一种。
本发明与现有技术相比，具有以下积极效果：
（1）针对非极性有机硅组分与极性聚氨酯组分相容性差，不易混合均匀问题，本发明首先用异氰酸酯对聚硅氧烷进行极性改性，确保了双组分体系聚氨酯和聚硅氧烷的相容性；
（2）将不含任何溶剂的聚氨酯/改性聚硅氧烷双组分经热固化形成合成革涂层，实现了聚氨酯和有机硅材料性能的优势互补，聚氨酯组分降低了成革的综合成本60 %以上，提高了涂层的表面张力和再涂性，弥补了单纯有机硅涂层在机械强度和与基布间粘接力上的不足，而有机硅组分则能够有效提升合成革的耐寒性、耐磨型、疏水性和阻燃性等性能；
（3）本发明在合成过程中不使用任何有机溶剂，可实现生产过程的清洁化、低能耗，所制得的无溶剂聚氨酯-有机硅涂层为环保产品，符合行业发展趋势，并且符合消费者的绿色、健康需求。
具体实施方式
下面通过实施例对本发明进行具体的描述，有必要指出的是以下实施例只是用于对本发明进行进一步的说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员可根据上述发明的内容做出一些非本质的改进和调整，仍属于本发明的保护范围。
实施例1：无溶剂聚氨酯-有机硅沙发革的制造
（1）羟基封端的无溶剂聚氨酯预聚体的制备：
将经脱水处理后的数均分子量2000的聚己二酸-1,3-丁二醇酯二醇50份、数均分子量1000聚碳酸亚丙酯二醇15份、数均分子量2000的聚乙二醇10份加入反应釜中，再依次加入六亚甲基二异氰酸酯10份、异佛尔酮二异氰酸酯10份，有机铋催化剂0.1份，升温至85℃，反应2 h后加入1,4-丁二醇10份， 85 ℃继续反应2 h，控制体系-NCO和-OH摩尔比在1:2，获得羟基封端的聚氨酯预聚体，密封备用；
（2）异氰酸酯基封端的聚硅氧烷的制备：
反应釜中加入含氢量为1.6 %的含氢聚硅氧烷10份、异佛尔酮二异氰酸酯20份，升温至60 ℃，反应2 h后，控制体系-NCO和活性H的摩尔比在2:1，获得异氰酸酯基封端的聚硅氧烷，密封备用；
（3）无溶剂涂层浆料的制备：将（1）制备的无溶剂聚氨酯预聚体100份、（2）制备的异氰酸酯基封端的聚硅氧烷30份、轻质碳酸钙15份、有机铋催化剂0.1份、色粉5.0份混合均匀；
（4）无溶剂合成革的制造：
将步骤（3）中制备的无溶剂涂层浆料涂覆于离型纸上，涂膜厚度控制在1.0 mm，然后进入130 ℃烘箱熟化，烘箱长度80 m，固化温度一区100 ℃，二区110 ℃，三区130 ℃，车速10 m/min，熟化后再涂覆聚氨酯热熔胶，与无纺布热压贴合，进入130 ℃烘箱熟化2 min，冷却，纸革分离，再经吸纹、揉革工艺制得无溶剂聚氨酯-有机硅合成革。
与普通无溶剂聚氨酯合成革相比，采用本专利技术制造的无溶剂聚氨酯-有机硅沙发革具有优异的耐磨和防水性，合成革表面水接触角从89°提高至110°，耐磨性由5.8mg/r提高至2.8 mg/r。
实施例2：无溶剂聚氨酯-有机硅服装革的制造
（1）羟基封端的无溶剂聚氨酯预聚体的制备：
将经脱水处理后的数均分子量2000的聚己二酸-1,3-丁二醇酯二醇50份、数均分子量2000聚碳酸亚丙酯二醇7份、数均分子量2000的聚乙二醇10份加入反应釜中，再依次加入4,4’-二环己基甲烷二异氰酸酯15份，有机铋催化剂0.1份，升温至85 ℃，反应2 h后加入1,3-丙二醇6.0~10份，75 ℃继续反应2 h，控制体系-NCO和-OH摩尔比在1:2，获得羟基封端的聚氨酯预聚体，密封备用；
（2）异氰酸酯基封端的聚硅氧烷的制备：
反应釜中加入含氢量0.78 %含氢聚硅氧烷7.5份、六亚甲基二异氰酸酯15份，升温至50 ℃，反应2 h后，控制体系-NCO和活性H的摩尔比在2:1，获得异氰酸酯基封端的聚硅氧烷，密封备用；
（3）无溶剂涂层浆料的制备：将（1）制备的无溶剂聚氨酯预聚体90份、（2）制备的异氰酸酯基封端的聚硅氧烷25份、轻质碳酸钙8.0份、有机铋催化剂0.05份、色粉3.0份混合均匀；
（4）无溶剂合成革的制造：
将步骤（3）中制备的无溶剂涂层浆料涂覆于离型纸上，涂膜厚度控制在0.8 mm，然后进入110 ℃烘箱熟化，烘箱长度60 m，固化温度一区90 ℃，二区110 ℃，三区120 ℃，车速9 m/min，熟化后再涂覆聚氨酯热熔胶，与超纤布热压贴合，进入110 ℃烘箱熟化1 min，冷却，纸革分离，再经表面处理、揉革制得无溶剂聚氨酯-有机硅合成革。
与普通无溶剂聚氨酯合成革相比，采用本专利技术制造的无溶剂聚氨酯-有机硅服装革具有优异的耐寒性（低温耐折牢度）。低温耐曲折牢度（-25 ℃）由120000次提高至150000次。
实施例3：无溶剂聚氨酯-有机硅汽车内饰革的制造
（1）氨基封端的无溶剂聚氨酯预聚体的制备：
将经脱水处理后的数均分子量为2000的聚乙二醇45份加入反应釜中，再依次加入六亚甲基二异氰酸酯12份，有机铋催化剂0份，升温至85 ℃，反应2 h后加入乙二胺6.0份，45 ℃继续反应1 h，控制体系-NCO和-NH2摩尔比在1:2，获得氨基封端的聚氨酯预聚体，密封备用；
（2）异氰酸酯基封端的聚硅氧烷的制备：
反应釜中加入含氢量为0.18 %的含氢聚硅氧烷5份、2,4-甲苯二异氰酸酯10份，升温至40 ℃，反应2 h后，控制体系-NCO和活性H的摩尔比在2:1，获得异氰酸酯基封端的聚硅氧烷，密封备用；
（3）无溶剂涂层浆料的制备：将（1）制备的无溶剂聚氨酯预聚体80份、（2）制备的异氰酸酯基封端的聚硅氧烷20份、白炭黑7.0份、有机铋催化剂0份、色粉2.0份混合均匀；
（4）无溶剂合成革的制造：
将步骤（3）中制备的无溶剂涂层浆料涂覆于离型纸上，涂膜厚度控制在0.8 mm，然后进入90 ℃烘箱熟化，烘箱长度60 m，固化温度一区90 ℃，二区100℃，三区110 ℃，车速8m/min，熟化后再涂覆聚氨酯热熔胶，与机织布热压贴合，进入90 ℃烘箱熟化1 min，冷却，纸革分离，制得无溶剂聚氨酯-有机硅合成革。
与普通无溶剂聚氨酯合成革相比，采用本专利技术制造的无溶剂聚氨酯-有机硅汽车内饰革具有优异的耐磨性，耐磨性由5.8 mg/r提高至3.6 mg/r；与单一有机硅合成革相比，涂层表面能从22 mJ/m2提高至38 mJ/m2，水接触角从131°降低至95°，涂层与基布的剥离强度从39 N/3cm提升至55 N/3 cm。

Claims (6)

1.一种基于热固化的无溶剂聚氨酯-有机硅合成革，其特征在于包括以下步骤，所用物料的份数均为重量份数：
(1)羟基或胺基封端的无溶剂聚氨酯预聚体的制备：
将经脱水处理后的液态聚酯或聚醚二元醇45～75份加入反应釜中，再依次加入异氰酸酯12～20份，有机铋催化剂0～0.1份，升温至75～85℃，反应2h后加入小分子扩链剂6.0～10份，45～85℃继续反应1～2h，控制体系-NCO和-OH或-NH2摩尔比在1:2，获得羟基或胺基封端的聚氨酯预聚体，密封备用；
(2)异氰酸酯基封端的聚硅氧烷的制备：
反应釜中加入含氢聚硅氧烷5～10份、液态二异氰酸酯10～20份，升温至40～60℃，反应2h后，控制体系-NCO和活性H的摩尔比在2:1，获得异氰酸酯基封端的聚硅氧烷，密封备用；
所述含氢聚硅氧烷为含氢量为0.18～1.6％的含氢聚硅氧烷，氢原子位于聚硅氧烷的链端或侧链，粘度100-1500cps；
(3)无溶剂涂层浆料的制备：
将(1)制备的羟基或胺基封端的无溶剂聚氨酯预聚体80～100份、(2)制备的异氰酸酯基封端的聚硅氧烷20～30份、填料7.0～15份、有机铋催化剂0～0.1份、色粉2.0～5.0份混合均匀；
(4)无溶剂合成革的制造：
将步骤(3)中制备的无溶剂涂层浆料涂覆于离型纸上，涂膜厚度控制在0.8～1.0mm，然后进入90～130℃烘箱熟化，烘箱长度60～80m，固化温度一区90～100℃，二区100～110℃，三区110～130℃，车速8～10m/min，熟化后再涂覆聚氨酯热熔胶，与合成革基材热压贴合，进入90～130℃烘箱熟化1～2min，冷却，纸革分离，制得无溶剂聚氨酯-有机硅合成革，再经表面处理、吸纹或压纹、揉革工艺，丰富无溶剂聚氨酯-有机硅合成革的花色品种。
2.根据权利要求1所述的一种基于热固化的无溶剂聚氨酯-有机硅合成革，其特征在于所述的液态聚酯或聚醚二元醇为相对分子质量在1000～2000的聚己二酸-1,3-丁二醇酯二醇、聚碳酸亚丙酯二醇、聚丙二醇、聚乙二醇中的至少一种。
3.根据权利要求1所述的一种基于热固化的无溶剂聚氨酯-有机硅合成革，其特征在于所述异氰酸酯为常温呈液态的异佛尔酮二异氰酸酯、2,4-甲苯二异氰酸酯、六亚甲基二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯中的至少一种。
4.根据权利要求1所述的一种基于热固化的无溶剂聚氨酯-有机硅合成革，其特征在于所述小分子扩链剂为1,4-丁二醇、1,6-己二醇、1,3-丙二醇、乙二醇或乙二胺、己二胺、1,4-己二胺中的至少一种。
5.根据权利要求1所述的一种基于热固化的无溶剂聚氨酯-有机硅合成革，其特征在于所述填料为轻质碳酸钙、白炭黑或硅藻土中的至少一种。
6.根据权利要求1所述的一种基于热固化的无溶剂聚氨酯-有机硅合成革，其特征在于所述合成革基材为机织布、无纺布、超纤布中的一种。
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