CN111718646A - 一种水性聚氨酯皮革光亮剂及其制备方法 - Google Patents

一种水性聚氨酯皮革光亮剂及其制备方法 Download PDF

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CN111718646A
CN111718646A CN202010649324.3A CN202010649324A CN111718646A CN 111718646 A CN111718646 A CN 111718646A CN 202010649324 A CN202010649324 A CN 202010649324A CN 111718646 A CN111718646 A CN 111718646A
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polyurethane
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赵旭忠
严建林
李梅芳
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Shanghai Gold Lion Chemical Co ltd
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Abstract

本发明提供了一种水性聚氨酯皮革光亮剂及其制备方法，包括如下步骤：制备聚氨酯型的成膜表面组分A；制备聚氨酯型的成膜底层组分B；以及将成膜表面组分A与成膜底层组分B共混搅拌得自然光水性聚氨酯光亮剂。本发明的制备方法通过制备具有较大支链结构和较大体积的胶束粒子的聚氨酯型成膜表面组分A和聚氨酯型的成膜底层组分B，使在成膜过程中聚氨酯型的成膜表面组分A能够上浮在膜表面，使膜表面具有较高的表面粗糙度，起到降低光泽度的效果，达到自然光效果。组分A由有机硅二元醇类单体合成，具有皮革光亮剂所要求的舒适表面触感，同时组分A和组分B均为聚氨酯结构，折光系数接近，提高了成膜透明度和产品的储存稳定性。

Description

一种水性聚氨酯皮革光亮剂及其制备方法
技术领域
本发明涉及一种皮革涂饰剂技术领域，且特别涉及一种水性聚氨酯皮革光亮剂及其制备方法。
背景技术
皮革涂饰剂作为皮革的顶层涂饰材料，对皮革制品的外在观感、卫生性能及物理机械性能有至关重要的影响。水性聚氨酯涂饰剂以水为溶剂，消除了溶剂型聚氨酯生产、储运和使用过程中易燃易爆等危险，能够满足安全、健康及环保的要求。水性聚氨酯皮革光亮剂作为皮革的顶层涂饰，需要具有较好的物理性能及合适的光泽。在光泽度选择上，相对于亮光和消光而言，目前光泽度中等的自然光逐渐被主流市场所接受。为使水性聚氨酯光亮剂达到自然光泽，通常需要在水性聚氨酯中加入消光组分，现有技术中主要通过向水性聚氨酯树脂中添加适量消光粉或消光蜡来实现。
本申请人发现现有技术中至少存在以下技术问题：现有技术中所添加的消光剂其物质结构与聚氨酯分子有较大的差别，因此，两者的相容性较差，在储存过程中容易出现分层现象。另外，由于消光剂与聚氨酯树脂的折光系数存在较大差别，其涂饰成膜后容易出现成膜通透性较差的现象，造成皮革色彩鲜艳度不够。
发明内容
本发明的目的在于提供一种水性聚氨酯皮革光亮剂的制备方法，此制备方法所制备的水性聚氨酯皮革光亮剂无需添加消光剂，其成膜表面组分和成膜底层组分均为聚氨酯结构，可提高产品的储存稳定性，而且折光系数接近，能够提高成膜透明度，不会影响涂饰后皮革的色彩鲜艳度。
本发明解决其技术问题是采用以下技术方案来实现的。
本发明提出一种水性聚氨酯皮革光亮剂的制备方法，包括如下步骤：
制备聚氨酯型的成膜表面组分A；
制备聚氨酯型的成膜底层组分B；以及
将所述聚氨酯型的成膜表面组分A与所述聚氨酯型的成膜底层组分B共混搅拌制得自然光水性聚氨酯光亮剂。
根据一种优选实施方式，所述制备聚氨酯型的成膜表面组分A的步骤包括：采用至少包括有机硅二元醇类单体的原料合成聚氨酯型的成膜表面组分A。
根据一种优选实施方式，所述制备聚氨酯型的成膜表面组分A的步骤还包括：
将三羟甲基丙烷、脂肪族二异氰酸酯、小分子亲水单体、有机硅二元醇类单体及催化剂在50-90℃下混合反应2-7h；
向上述反应物中加入丙酮降粘，并降温至30-50℃，加入三乙胺反应5-30min；以及
向上述预聚体中加入去离子水，搅拌分散0.5-3h得到阴离子水性聚氨酯乳液成膜表面组分A。
根据一种优选实施方式，所述脂肪族二异氰酸酯为IPDI，所述小分子亲水单体为DMPA，所述有机硅二元醇类单体为聚醚改性有机硅二元醇。
根据一种优选实施方式，所述脂肪族二异氰酸酯与所述有机硅二元醇类单体的摩尔比为3-6:1；所述小分子亲水单体的用量为固体份质量的2-9％；所述三羟甲基丙烷的用量为固定份质量的1-4％；所述丙酮的用量为单体总量的20-60％；所述三乙胺的摩尔数为所述小分子亲水单体摩尔数的80-120％。
根据一种优选实施方式，所述制备聚氨酯型的成膜底层组分B的步骤包括：
将脂肪族二异氰酸酯、小分子亲水单体、大分子二元醇类单体和催化剂在50-90℃下混合反应2-7h；
向上述反应物中加入丙酮降粘，然后降温至30-50℃，加入三乙胺反应5-30min；以及
向上述预聚物中加入去离子水，搅拌分散0.5-3h得到阴离子水性聚氨酯乳液成膜底层组分B。
根据一种优选实施方式，所述脂肪族二异氰酸酯为IPDI，所述小分子亲水单体为DMPA，所述大分子二元醇类单体选自聚己内酯二元醇、聚碳酸酯二元醇、聚四氢呋喃醚二元醇或聚丙二醇的一种或几种。
根据一种优选实施方式，所述脂肪族二异氰酸酯与所述大分子二元醇类单体的摩尔比为2.5-4.5:1；所述小分子亲水单体的用量为固体份质量的3-7％；所述丙酮的用量为单体总量的20-60％，所述三乙胺的摩尔数为小分子亲水单体摩尔数的80-120％。
根据一种优选实施方式，所述将所述聚氨酯型的成膜表面组分A与所述聚氨酯型的成膜底层组分B共混搅拌制得自然光水性聚氨酯光亮剂的步骤包括：
将质量分数为15-35％的所述聚氨酯型的成膜表面组分A和质量分数为65-85％的所述聚氨酯型的成膜底层组分B共混，在搅拌状态下加入增稠剂，调节共混物的粘度至100-1000mPa·s，制得自然光水性聚氨酯光亮剂。
本发明还提供了一种水性聚氨酯皮革光亮剂，所述水性聚氨酯皮革光亮剂是由所述的制备方法制备而成。
基于上述技术方案，本发明的水性聚氨酯皮革光亮剂的制备方法至少具有如下技术效果：
本发明的制备方法通过制备具有聚氨酯型的成膜表面组分A和聚氨酯型的成膜底层组分B，使所制备的水性聚氨酯乳液在成膜过程中聚氨酯型的成膜表面组分A能够上浮在膜表面，使膜表面具有较高的表面粗糙度，起到降低光泽度的效果，使薄膜达到自然光效果。同时由于组分A和组分B均属于聚氨酯型树脂，具有相似的物化性质及官能团结构，因此，两者具有较好的相容性，从而有效解决了储存稳定性的问题，成膜后折光率较为接近，在涂饰后具有较好的通透度，在达到降低光泽效果的同时不会影响皮革本身的色彩。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
下面对本发明实施例的水性聚氨酯皮革光亮剂的制备方法进行具体说明。
本发明提供了一种水性聚氨酯皮革光亮剂的制备方法，包括如下步骤：
(1)制备聚氨酯型的成膜表面组分A。
优选的，制备聚氨酯型的成膜表面组分A的步骤包括：采用至少包括有机硅二元醇类单体的原料合成聚氨酯型的成膜表面组分A。采用有机硅二元醇类单体所合成的聚氨酯型的成膜表面组分A，其分子结构中支链较多，交联结构较大，胶束粒子具有较大体积，比重较轻，在成膜过程中能够上浮至膜表面，可赋予皮革滑爽、舒适的表面触感。
优选的，具体包括如下步骤：
将三羟甲基丙烷、脂肪族二异氰酸酯、小分子亲水单体、有机硅二元醇类单体及催化剂在50-90℃下混合反应2-7h；
向上述反应物中加入丙酮降粘，降温至30-50℃，加入三乙胺反应5-30min；以及
向上述预聚体中加入去离子水，搅拌分散0.5-3h得固含量为20％的阴离子水性聚氨酯乳液成膜表面组分A。
优选的，脂肪族二异氰酸酯为IPDI，小分子亲水单体为DMPA，有机硅二元醇类单体为聚醚改性有机硅二元醇。优选的，聚醚改性有机硅二元醇的分子量为500-2000。优选的，脂肪族二异氰酸酯与有机硅二元醇的摩尔比为3-6:1。小分子亲水单体的用量为固体份质量的2-9％。三羟甲基丙烷的用量为固定份质量的1-4％。丙酮的用量为单体总量的20-60％；三乙胺的摩尔数为小分子亲水单体摩尔数的80-120％。
本发明所制备的聚氨酯型的成膜表面组分A具有较大的交联结构，粒径较大，分子结构中支链较多，胶束粒子具有较大体积，其比重比聚氨酯型成膜底层组分B的比重小，在成膜过程中上浮在膜表面，使膜具有较高的表面粗糙度，从而使薄膜达到自然光效果。同时组分A具有有机硅组分，可提供爽滑的表面触感。
(2)制备聚氨酯型的成膜底层组分B。
优选的，制备聚氨酯型的成膜底层组分B的步骤包括：
将脂肪族二异氰酸酯、小分子亲水单体、大分子二元醇类单体和催化剂在50-90℃下混合反应2-7h；
向上述反应物中加入丙酮降粘，然后降温至30-50℃，加入三乙胺反应5-30min；以及
向上述预聚体中加入去离子水，搅拌分散0.5-3h得到固含量为20％的阴离子水性聚氨酯乳液成膜底层组分B。
优选的，脂肪族二异氰酸酯为IPDI，小分子亲水单体为DMPA。大分子二元醇类单体选自聚己内酯二元醇、聚碳酸酯二元醇、聚四氢呋喃醚二元醇或聚丙二醇的一种或几种。优选的，大分子二元醇类单体的分子量为500-3000。优选的，脂肪族二异氰酸酯与大分子二元醇类单体的摩尔比为2.5-4.5:1；小分子亲水单体的用量为固体份质量的3-7％；丙酮的用量为单体总量的20-60％，三乙胺的摩尔数为小分子亲水单体摩尔数的80-120％。
本发明制备的聚氨酯型的成膜底层组分B其粒径较小，能够与聚氨酯型的成膜组分A具有较好的相容性。
(3)将聚氨酯型的成膜表面组分A与聚氨酯型的成膜底层组分B共混搅拌制得自然光水性聚氨酯光亮剂。
优选的，将质量分数为15-35％的聚氨酯型的成膜表面组分A和质量分数为65-85％的聚氨酯型的成膜底层组分B共混，在搅拌状态下加入增稠剂，调节共混物的粘度至100-1000mPa·s，制得自然光水性聚氨酯光亮剂。
优选的，增稠剂选自TT935。
本发明还提供了一种水性聚氨酯皮革光亮剂，水性聚氨酯皮革光亮剂是由所述的制备方法制备而成。
以下结合实施例对本发明的特征和性能作进一步的详细描述。
实施例1
合成组分A：在装有搅拌器、冷凝回流管和热电偶的500m1四口烧瓶中，加入IPDI33克、三羟甲基丙烷3.5克、2000分子量的聚醚改性有机硅二元醇100克、二羟甲基丙酸3.4克和有机铋催化剂KAT348 0.02克在70℃下反应4小时，然后降温至60℃加入50克丙酮降粘，继续降温至45℃加入2.6克三乙胺，保温30分钟后用高速乳化分散机在1000r/min高速搅拌下将550克水加入预聚体中，分散30分钟后得到乳白色聚氨酯乳液待用。所测得乳液固含量为20％，粒径800-1000nm。
合成组分B：在装有搅拌器、冷凝回流管和热电偶的500m1四口烧瓶中，加入IPDI28克、2000分子量的聚己内酯二醇PCL 40克、1000分子量的聚四氢呋喃醚二醇PTMEG 20克、二羟甲基丙酸5克和有机铋催化剂KAT348 0.02克在70℃下反应4小时，然后降温至60℃加入40克丙酮降粘，继续降温至45℃加入3.7克三乙胺，保温30分钟后用高速乳化分散机在1000r/min高速搅拌下将330克水加入预聚体中，分散30分钟后得到泛蓝光透明聚氨酯乳液待用。测得乳液固含量为20％，粒径40-60nm。
用高速乳化分散机在400r/min高速搅拌下将50克组分A及250克组分B搅拌混合15分钟，降低转速至300r/min加入6克TT935增稠剂，搅拌30分钟后静置消泡即得最终产品。
经测试，本实施例制备的水性聚氨酯皮革光亮剂的粘度为500mPa·s，在皮胚表面涂饰后光泽单位6.4，离心测试后无明显分层现象。
实施例2
合成组分A：在装有搅拌器、冷凝回流管和热电偶的500m1四口烧瓶中，加入IPDI18克、三羟甲基丙烷3克、2000分子量的聚醚改性有机硅二元醇100克、二羟甲基丙酸2.2克和有机铋催化剂KAT348 0.02克在90℃下反应3小时，然后降温至60℃加入40克丙酮降粘，继续降温至45℃加入1.6克三乙胺，保温30分钟后用高速
乳化分散机在1000r/min高速搅拌下将530克水加入预聚体中，分散30分钟后得到乳白色聚氨酯乳液待用。所测得乳液固含量为20％，粒径900-1100nm。
合成组分B：在装有搅拌器、冷凝回流管和热电偶的500m1四口烧瓶中，加入IPDI33克、2000分子量的聚四氢呋喃二醇PTMEG 30克、1000分子量的聚碳酸酯二元醇PCDL 30克、二羟甲基丙酸6克和有机铋催化剂KAT348 0.02克在90℃下反应3小时，然后降温至60℃加入50克丙酮降粘，继续降温至45℃加入4.5克三乙胺，保温30分钟后用高速乳化分散机在1000r/min高速搅拌下将350克水加入预聚体中，分散30分钟后得到泛蓝光透明聚氨酯乳液待用。测得乳液固含量为20％，粒径40-50nm。
用高速乳化分散机在500r/min高速搅拌下将80克A组分及220克B组分搅拌混合15分钟，降低转速至300r/min加入5.6克TT935增稠剂，搅拌30分钟后静置消泡即得最终产品。
经测试，本实施例的水性聚氨酯皮革光亮剂的粘度为450mPa·s，在皮胚表面涂饰后光泽单位5.2，离心测试后无明显分层现象。
实施例3
合成组分A：在装有搅拌器、冷凝回流管和热电偶的500m1四口烧瓶中，加入IPDI26克、三羟甲基丙烷4克、1000分子量的聚醚改性有机硅二元醇50克、二羟甲基丙酸1.8克和有机铋催化剂KAT348 0.02克在80℃下反应4小时，然后降温至60℃加入40克丙酮降粘，继续降温至45℃加入1.3克三乙胺，保温30分钟后用高速乳化分散机在1000r/min高速搅拌下将290克水加入预聚体中，分散30分钟后得到乳白色聚氨酯乳液待用。测得乳液固含量为20％，粒径700-800nm。
合成组分B：在装有搅拌器、冷凝回流管和热电偶的500m1四口烧瓶中，加入IPDI25克、2000分子量聚丙二醇PPG 60克、二羟甲基丙酸5克和有机铋催化剂KAT348 0.02克在80℃下反应4小时，然后降温至60℃加入40克丙酮降粘，继续降温至45℃加入3.8克三乙胺，保温30分钟后用高速乳化分散机在1000r/min高速搅拌下将320克水加入预聚体中，分散30分钟后得到泛蓝光透明聚氨酯乳液待用。测得乳液固含量为20％，粒径60-80nm。
用高速乳化分散机在400r/min高速搅拌下将100克A组分及200克B组分搅拌混合15分钟，降低转速至300r/min加入6.2克TT935增稠剂，搅拌30分钟后静置消泡即得最终产品。
经测试，本实施例制备的水性聚氨酯皮革光亮剂的粘度为600mPa·s，在皮胚表面涂饰后光泽单位7.2，离心测试后无明显分层现象。
综上所述，本发明实施例的水性聚氨酯皮革光亮剂无需添加消光剂，具有自然光光泽度的组分A为聚氨酯结构，与组分B的结构相似，成膜后不会出现分层现象，而且，折光系数接近，能够提高成膜透明度，不会影响涂饰后皮革的色彩鲜艳度。组分A由有机硅二元醇类单体合成，分子结构支链较多，胶束粒子具有较大体积，比重较轻，其在成膜过程中上浮至膜表面，可赋予皮革滑爽、舒适的表面触感。
以上所描述的实施例是本发明一部分实施例，而不是全部的实施例。本发明的实施例的详细描述并非旨在限制要求保护的本发明的范围，而是仅仅表示本发明的选定实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。

Claims (10)

1.一种水性聚氨酯皮革光亮剂的制备方法，其特征在于，包括如下步骤：
制备聚氨酯型的成膜表面组分A；
制备聚氨酯型的成膜底层组分B；以及
将所述聚氨酯型的成膜表面组分A与所述聚氨酯型的成膜底层组分B共混搅拌制得自然光水性聚氨酯光亮剂。
2.根据权利要求1所述的制备方法，其特征在于，所述制备聚氨酯型的成膜表面组分A的步骤包括：采用至少包括有机硅二元醇类单体的原料合成聚氨酯型的成膜表面组分A。
3.根据权利要求2所述的制备方法，其特征在于，所述制备聚氨酯型的成膜表面组分A的步骤还包括：
将三羟甲基丙烷、脂肪族二异氰酸酯、小分子亲水单体、有机硅二元醇类单体及催化剂在50-90℃下混合反应2-7h；
向上述反应物中加入丙酮降粘，并降温至30-50℃，加入三乙胺反应5-30min；以及
向上述预聚体中加入去离子水，搅拌分散0.5-3h得到阴离子水性聚氨酯乳液成膜表面组分A。
4.根据权利要求3所述的制备方法，其特征在于，所述脂肪族二异氰酸酯为IPDI，所述小分子亲水单体为DMPA，所述有机硅二元醇类单体为聚醚改性有机硅二元醇。
5.根据权利要求4所述的制备方法，其特征在于，所述脂肪族二异氰酸酯与所述有机硅二元醇类单体的摩尔比为3-6:1；所述小分子亲水单体的用量为固体份质量的2-9％；所述三羟甲基丙烷的用量为固定份质量的1-4％；所述丙酮的用量为单体总量的20-60％；所述三乙胺的摩尔数为所述小分子亲水单体摩尔数的80-120％。
6.根据权利要求1所述的制备方法，其特征在于，所述制备聚氨酯型的成膜底层组分B的步骤包括：
将脂肪族二异氰酸酯、小分子亲水单体、大分子二元醇类单体和催化剂在50-90℃下混合反应2-7h；
向上述反应物中加入丙酮降粘，然后降温至30-50℃，加入三乙胺反应5-30min；以及
向上述预聚物中加入去离子水，搅拌分散0.5-3h得到阴离子水性聚氨酯乳液成膜底层组分B。
7.根据权利要求6所述的制备方法，其特征在于，所述脂肪族二异氰酸酯为IPDI，所述小分子亲水单体为DMPA，所述大分子二元醇类单体选自聚己内酯二元醇、聚碳酸酯二元醇、聚四氢呋喃醚二元醇或聚丙二醇的一种或几种。
8.根据权利要求7所述的制备方法，其特征在于，所述脂肪族二异氰酸酯与所述大分子二元醇类单体的摩尔比为2.5-4.5:1；所述小分子亲水单体的用量为固体份质量的3-7％；所述丙酮的用量为单体总量的20-60％，所述三乙胺的摩尔数为小分子亲水单体摩尔数的80-120％。
9.根据权利要求1所述的制备方法，其特征在于，所述将所述聚氨酯型的成膜表面组分A与所述聚氨酯型的成膜底层组分B共混搅拌制得自然光水性聚氨酯光亮剂的步骤包括：
将质量分数为15-35％的所述聚氨酯型的成膜表面组分A和质量分数为65-85％的所述聚氨酯型的成膜底层组分B共混，在搅拌状态下加入增稠剂，调节共混物的粘度至100-1000mPa·s，制得自然光水性聚氨酯光亮剂。
10.一种水性聚氨酯皮革光亮剂，其特征在于，所述水性聚氨酯皮革光亮剂是由权利要求1至9任一项所述的制备方法制备而成。
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