CN106147689A - 一种鞋用高柔韧性、高粘接强度双组份聚氨酯粘合剂及其制备方法和应用 - Google Patents
一种鞋用高柔韧性、高粘接强度双组份聚氨酯粘合剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种鞋用高柔韧性、高粘结强度双组份聚氨酯粘合剂及其制备方法和应用，具体的技术方案为：所述粘合剂有A、B组分组成，A组分与B组分的质量比为2‑4：1；所述A组分包括由超支化聚酯多元醇、聚醚多元醇和六亚甲基异氰酸酯反应得到羟基封端聚氨酯组分；所述B组分包括由蓖麻油、超支化异氰酸酯和甲苯二异氰酸酯反应得到异氰酸酯封端聚氨酯组分。A组分或B组分至少一个组分含有丁腈橡胶微球和/或足球烯。最终产品具有优异的柔韧性和粘接强度的聚氨酯粘合剂，适用于鞋业生产中使用。
Description
技术领域：
本发明涉及一种鞋用粘合剂领域，特别涉及一种高柔韧性、高粘结强度双组份聚氨酯粘合剂领域。
背景技术：
聚氨酯粘合剂是现有技术中使用十分普遍、应用领域广泛的一种粘合剂，其具有优异的莪耐低温性、低的固化温度、良好的柔韧性、耐冲击性，对材料的浸润效果好，粘结性优异，其常用在室温粘接的领域。
鞋子生产过程中，鞋底和鞋帮等多处需要使用粘合剂进行粘接，但鞋子最容易损坏部分就是粘接处，粘接不牢和粘接处僵硬是存在的两个粘接技术中的难题。现有使用的粘合剂有效的解决该问题，难以同时满足两个要求，为了解决该问题，本发明就生产了一种具有高柔韧性、高粘结强度双组份聚氨酯粘合剂，其在鞋子粘接过程中可以安祖柔韧性和粘接强度的要求。
发明内容：
发明目的：本发明提供了一种鞋用高柔韧性、高粘结强度双组份聚氨酯粘合剂，通过对原料多元醇、异氰酸酯以及添加填料的选择，最终得到性能优异的聚氨酯粘合剂。
同时，本发明还提供了一种鞋用高柔韧性、高粘结强度双组份聚氨酯粘合剂的制备方法以及在鞋子生产中的应用。
具体的技术方案：
一种鞋用高柔韧性、高粘接强度双组份聚氨酯粘合剂的制备方法，粘合剂包括A、B组分，A组分与B组分的质量比为2-4：1；
所述A组分包括由超支化聚酯多元醇、聚醚多元醇和六亚甲基异氰酸酯反应得到羟基封端聚氨酯组分；
所述B组分包括由蓖麻油、超支化异氰酸酯和甲苯二异氰酸酯反应得到异氰酸酯封端聚氨酯组分。
超支化结构具有多个分支，具有三维的类球型，众多的端基团，超支化聚合物黏度低、溶解性良好、柔韧性和抗冲击性等优异的特点。本发明采用了超支化聚酯多元醇、超支化异氰酸酯，分别在组分A和组分B中配合聚醚多元醇或蓖麻油，延长了超支化外端的链长。研究还惊奇的发现，同时使用超支化聚酯多元醇和超支化异氰酸酯比使用其中任意一种达到的柔韧性效果要好，提高幅度明显。
作为优选技术方案，组分A中所述聚醚多元醇为高分子量二官能聚醚多元醇和低分子量三官能团聚醚多元醇以3-5：1的质量比组成。高分子量二官能度聚醚多元醇交联程度较低，低分子量三官能团聚醚多元醇的交联程度高，且二异氰酸酯组分采用的具有长链的异氰酸酯，其最终形成的结构中为柔性链段为主，并借助超支化聚酯多元醇形成的柔性交联点，应力可以有效的分散。
所述高分子量二官能聚醚多元醇分子量在12000-22000之间，低分子量三官能聚醚多元醇分子量在1200-2200之间，高分子量二官能聚醚多元醇分子量为低分子量三官能聚醚多元醇分子量的10倍以上。通过分子量的控制和分子量比例的变化，可以保证整体柔韧性，且分子量的控制也保证了粘接力达到实际使用的要求。
作为进一步优选技术方案，所述组分A中，NCO：OH的摩尔比在1：1.5-2.1之间，且组分A中超支化聚酯多元醇提供OH摩尔量占组分A中总OH摩尔量的50%-75%。
限定超支化聚酯多元醇提供OH摩尔量就限定了在交联中所占比例，如果不在该范围内，最终产品或者柔韧性不能满足高端的要求，或者太软，难以满足对粘接力高的要求。
作为进一步优选技术方案，所述组分B中，NCO：0H的摩尔比在1：0.75-0.8，且组分B中超支化异氰酸酯提供NCO占组分B中总NCO含量的70-99%。
组分B中超支化异氰酸酯提供NCO决定了最终结构的交联问题，如果超支化异氰酸酯含量过少，非柔性连接点过多，最终硬度过大；如果全部为超支化异氰酸酯提供NCO，那最终产品粘接力不足或硬度过低，难以满足高端使用要求。
作为优选技术方案，A组分或B组分至少一个组分含有丁腈橡胶微球，丁腈橡胶具有优异的韧性，其加入起到了应力分散点的作用，大幅提升了柔韧性。
在实际使用中发现运动鞋或负重较大的鞋，长时间处于高压力的穿着条件下，丁腈橡胶微球难以实现长期应力分散，应力会对微球自身结构产生损害；故进一步优选丁腈橡胶微球结构为丁腈橡胶为壳，二氧化硅微粒为核，二氧化硅作为一个力学承受点，且可以保持丁腈效果基本的外形不受到破坏，又可以进一步提升柔韧性和使用寿命。
由于上述微球与基体聚氨酯作用力较大，属于固定性应力分散点，本发明进一步提供了一个动态应力分散，优选所述A组分和B组分至少一个组分中含有足球烯，足球烯与基体聚氨酯作用力很小，可以随着压力的变化位置发生变化，达到应力分散，提升承受能力，同时还可以一定程度上提高力学强度。
鞋用高柔韧性、高粘接强度双组份聚氨酯粘合剂在鞋子粘接中的应用，具体指鞋帮与鞋底之间的连接，或者鞋子中各种附属部件的粘接。
技术效果：本发明通过使用超支化聚酯多元醇和超支化异氰酸酯，大幅提升了粘合剂最终的柔韧性；配合使用聚醚多元醇、蓖麻油，延长了超支化外端的长度，提高了柔韧性；同时，下的宁了多元醇具体种类、用量以及分子量比例等，都提高了柔韧性，并提高了粘接力。另一个发明点在于采用丁腈橡胶微球，尤其是丁腈橡胶为壳，二氧化硅微粒为核，有效的起到静态交联、应力分散，且二氧化硅为核提升了耐压能力；使用足球烯作为体系中的动态应力分散点，提高了应力承受能力、提高了力学性能。
具体实施方式：
以下对本发明的原理和特征进行描述，所举实例只是用于解释本发明，并非用于限定本发明的范围。
双组份粘合剂制备为常规制备方法，A组分和B组分分别反应完全，A组分和B组分按照质量比3:1进行混合，搅拌均匀后即可使用。
实施例1-7和对比例1-6的各组分主要组分投料比以及效果见下表（投料单位为中两份）：
实施例1为最佳实施例，其余实施例相对于实施例1为：
实施例2未使用足球烯；实施例3使用非丁腈橡胶为壳、SiO2为核的微球；实施例4为不满足高分子量二官能聚醚多元醇分子量为低分子量三官能团聚醚多元醇分子量的10倍以上；实施例5为不满足超支化聚酯多元醇提供OH摩尔量占组分A中总OH摩尔量的50%-75%；实施例6为组分B仅使用超支化异氰酸酯；实施例7为不适用任何丁腈微球。
对比例1为组分A不使用低分子量三官能聚醚多元醇；对比例2为组分A不使用高分子量二官能聚醚多元醇；对比例3为不使用超支化聚酯多元醇；对比例4为不使用超支化异氰酸酯；对比例5组分B不使用蓖麻油、使用聚酯多元醇代替；对比例6为组分A不使用聚醚多元醇。
*1：分子量20000，结构为每个超支化聚酯多元醇结构中具有12个端基羟基；
*2：聚酯多元醇为2官能度，分子量1000；
*3：分子量1200，结构为每个超支化异氰酸酯结构中具有6个NCO基团。
Claims (10)
1.一种鞋用高柔韧性、高粘接强度双组份聚氨酯粘合剂的制备方法，其特征在于：所述粘合剂包括A组分和B组分，A组分与B组分的质量比为2-4：1；
所述A组分包括由超支化聚酯多元醇、聚醚多元醇和六亚甲基异氰酸酯反应得到羟基封端聚氨酯组分；
所述B组分包括由蓖麻油、超支化异氰酸酯和甲苯二异氰酸酯反应得到异氰酸酯封端聚氨酯组分。
2.如权利要求1所述的鞋用高柔韧性、高粘接强度双组份聚氨酯粘合剂的制备方法，其特征在于：A组分或B组分至少一个组分含有丁腈橡胶微球。
3.如权利要求1所述的鞋用高柔韧性、高粘接强度双组份聚氨酯粘合剂的制备方法，其特征在于：所述聚醚多元醇为高分子量二官能聚醚多元醇和低分子量三官能聚醚多元醇以3-5：1的质量比组成。
4.如权利要求2所述的鞋用高柔韧性、高粘接强度双组份聚氨酯粘合剂的制备方法，其特征在于：所述丁腈橡胶微球结构为丁腈橡胶为壳，二氧化硅微粒为核。
5.如权利要求1所述的鞋用高柔韧性、高粘接强度双组份聚氨酯粘合剂的制备方法，其特征在于：所述组分A中，NCO：OH的摩尔比在1：1.5-2.1之间，且组分A中超支化聚酯多元醇提供OH摩尔量占组分A中总OH摩尔量的50%-75%。
6.如权利要求1所述的鞋用高柔韧性、高粘接强度双组份聚氨酯粘合剂的制备方法，其特征在于：所述组分B中，NCO：0H的摩尔比在1：0.75-0.8，且组分B中超支化异氰酸酯提供NCO占组分B中总NCO含量的70-99%。
7.如权利要求3所述的鞋用高柔韧性、高粘接强度双组份聚氨酯粘合剂的制备方法，其特征在于：所述高分子量二官能聚醚多元醇分子量在12000-22000之间，低分子量三官能团聚醚多元醇分子量在1200-2200之间，高分子量二官能聚醚多元醇分子量为低分子量三官能聚醚多元醇分子量的10倍以上。
8.如权利要求1所述的鞋用高柔韧性、高粘接强度双组份聚氨酯粘合剂的制备方法，其特征在于：所述A组分和B组分至少一个组分中含有足球烯。
9.权利要求1-8中任一种方法制备得到的鞋用高柔韧性、高粘接强度双组份聚氨酯粘合剂。
10.权利要求9中鞋用高柔韧性、高粘接强度双组份聚氨酯粘合剂在鞋子粘接中的应用。
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