CN115537139B - 防水透气tpu高低温膜及其制备方法 - Google Patents

防水透气tpu高低温膜及其制备方法 Download PDF

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CN115537139B
CN115537139B CN202211273773.8A CN202211273773A CN115537139B CN 115537139 B CN115537139 B CN 115537139B CN 202211273773 A CN202211273773 A CN 202211273773A CN 115537139 B CN115537139 B CN 115537139B
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tpu
film
low temperature
parts
film layer
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CN115537139A (zh
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李锋
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Guangdong Zhongding Technology Development Co ltd
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Abstract

本发明涉及TPU技术领域，具体涉及一种防水透气TPU高低温膜及其制备方法。防水透气TPU高低温膜包括由上至下依次设置的透气防水膜层、TPU发泡膜层、网状热熔胶层和离型膜层；所述TPU发泡膜层设置有多个间隔设置的过气通孔，所述过气通孔贯穿TPU发泡膜层的上表面和下表面。本发明的TPU发泡高低温膜结构简单，具有良好的透气防水性能，力学性能佳，使用方便，实用性强；其制备方法操作简便，易于控制，生产成本低，产品质量稳定，利于工业化大生产。

Description

防水透气TPU高低温膜及其制备方法
技术领域
本发明涉及TPU技术领域，具体涉及一种防水透气TPU高低温膜及其制备方法。
背景技术
现有技术中的TPU高低温膜主要包括熔点较高的高温层和熔点较低的低温层，高温侧主要用于表面，低温侧主要用于与其他材料粘接。目前，TPU高低温膜已经被广泛应用于鞋材、服饰、箱包等各种面料中，也可应用于医用产品等领域。然而现有的TPU高低温膜，在使用于一些产品如鞋面或者其他织物上时，不能很好地兼顾防水透气性，使得产品兼具良好的防水性和透气性，有待进一步改进。
发明内容
为了克服现有技术中存在的缺点和不足，本发明的目的在于提供一种具有透气功能的TPU发泡高低温膜，该具有透气功能的TPU发泡高低温膜结构简单，具有良好的透气防水性能，使用方便。
本发明的另一目的在于提供一种防水透气TPU高低温膜的制备方法，该制备方法操作简便，易于控制，生产成本低，利于工业化大生产。
本发明的目的通过下述技术方案实现：一种防水透气TPU高低温膜，包括由上至下依次设置的透气防水膜层、TPU发泡膜层、网状热熔胶层和离型膜层；所述TPU发泡膜层设置有多个间隔设置的过气通孔，所述过气通孔贯穿TPU发泡膜层的上表面和下表面。
本发明的TPU发泡高低温膜通过由上至下依次设置透气防水膜层、TPU发泡膜层、网状热熔胶层和保护层，透气防水膜层、TPU发泡膜层、网状热熔胶层均具有良好的透气功能，保护层可对网状热熔胶层实现良好的保护作用，使用时可以去除保护膜，将TPU发泡高低温膜通过网状热熔胶层贴合于鞋面材料或者其他产品上；本发明的TPU发泡高低温膜结构简单，在具有柔软、弹性好等优点的同时，具有良好的透气防水性能，使用方便，实用性强。
进一步的，所述透气防水膜层为PU防水透气防水膜层。
进一步的，所述网状热熔胶层为TPU网状胶层、EVA网状胶层、PA网状胶层或PES网状胶层中的至少一种。网状热熔胶层可将TPU发泡高低温膜稳固粘合于鞋面或者其他产品表面，同时网状热熔胶层具有的网纹孔又具有良好的透气性。
进一步的，所述离型膜为PE离型膜或OPP离型膜。在TPU发泡高低温膜使用前，采用离型膜，可对网状热熔胶层进行保护，使用时可方便地撕除离型膜，使得TPU发泡高低温膜便于运输、储藏和使用，可靠性好。
进一步的，所述透气防水膜层的制备方法包括如下步骤：
(S1)将聚氨酯颗粒、聚偏二氟乙烯颗粒和改性二氧化硅颗粒添加到混合液A中，搅拌10-15h，制得静电纺丝溶液；所述混合液A为氯化钙和N,N-二甲基甲酰胺混合液；所述聚氨酯颗粒、聚偏二氟乙烯颗粒、改性二氧化硅与混合液A的质量比为14-19:4-7:3-6:100；
(S2)对静电纺丝溶液进行静电纺丝处理，制得膜初品；
(S3)将膜初品放入处理室中并通入氮气，采用等离子体设备对膜初品进行等离子表面活化；
(S4)将经过活化处理的膜初品放入混合物B中浸泡18-26h，所述混合液B为十二氟庚基丙基三甲氧基硅烷和甲醇混合液；
(S5)将经过浸泡处理的膜初品取出，在55-65℃真空干燥箱中干燥18-26h，得到透气防水膜层。
进一步的，所述步骤(S1)中，所述混合液A中氯化钙的浓度为0.01-0.03wt％。
进一步的，所述步骤(S2)中，所述混合液B中十二氟庚基丙基三甲氧基硅烷的浓度为1-2.5wt％。
进一步的，所述步骤(S2)中，纺丝流率为0.5-0.8mL/h，纺丝电压为10-15kV，温度为22-28℃，喷丝头到收集器之间的距离为12-15cm。
进一步的，所述步骤(S3)中，等离子处理功率为80-130W，压力为10-50Pa，处理时间为90-150s。
本发明通过将聚氨酯颗粒、聚偏二氟乙烯颗粒和改性二氧化硅颗粒相配合，并采用氯化钙、N,N-二甲基甲酰胺、十二氟庚基丙基三甲氧基硅烷等原料处理，制得具有优异防水透气性能的透气防水膜层，且使得该透气防水膜层具有良好的机械性能，实用性强，可应用于鞋材、箱包等各种面料中，也可用用于医用防护服等产品。
进一步的，所述改性二氧化硅的制备方法包括如下步骤：按重量份计，取纳米二氧化硅颗粒10-15份加入到30-40份的乙醇溶液中，然后再加入全氟十二烷基三氯硅烷1.6-2份，采用盐酸将pH值调节至3.0-5.0，于20-30℃温度下超声搅拌处理5-10h，得到混合液；再用氨水将经过超声处理的混合液的pH值调节至6.0-7.0，超声搅拌30-90min后，进行超声雾化，再置于75-95℃温度下干燥，得到改性二氧化硅。所述纳米二氧化硅颗粒的粒径为20-40nm。
本发明通过采用上述方法制得具有良好疏水性的改性二氧化硅颗粒，制得的改性二氧化硅颗粒应用于制备透气防水膜，与其他原料相配合，有助于提高具有微孔的透气防水膜的疏水性能并增加了透气防水膜承受静水压的能力。
进一步的，所述TPU发泡膜层采用TPU发泡材料制成，所述TPU发泡材料包括如下重量份的原料：聚氨酯乳液50-60份、硅丙乳液5-10份、聚偏二氟乙烯4-8份、十二烷基苯磺酸钠0.3-0.8份、纳米二氧化硅3-6份、羟乙基纤维素3-8份、聚乙二醇2-5份、乙烯基三(β-甲氧乙氧基)硅烷2-4份、氮丙啶1-2份、催化剂0.1-0.3份、溶剂15-20份。
本发明通过将聚氨酯乳液、硅丙乳液、聚偏二氟乙烯与其他原料配合制得TPU发泡材料，使得TPU发泡材料中形成气孔和气泡，且制得的TPU发泡膜层具有较佳的透气透湿性和力学性能。
进一步的，所述溶剂为乙酸乙酯、乙酸丁酯、丙二醇甲醚或乙酰丙酮中的至少一种。
进一步的，所述催化剂为异辛酸铋、月桂酸铋或新癸酸铋中的至少一种。
进一步的，所述TPU发泡材料的制备方法为：将各原料按比例后混合，采用空气发泡机进行发泡，发泡比为1:1.8-2.4，进行发泡，制得TPU发泡材料。
本发明还提供上述防水透气TPU高低温膜的制备方法，包括如下步骤：
(1)取离型膜，在离型膜的表面复合网状热熔胶层；取透气防水膜层，将TPU发泡材料涂布于透气防水膜层，烘干，在透气防水膜层的表面形成TPU发泡膜层；
(2)将网状热熔胶层与TPU发泡膜层贴合，制得防水透气TPU高低温膜。
本发明防水透气TPU高低温膜的制备方法操作简便，易于控制，通过控制各原料配比，并控制具体步骤，制得综合性能优越的防水透气TPU高低温膜，该TPU高低温膜具有良好的透气防水性能，力学性能佳；其制备方法生产成本低，产品质量稳定，利于工业化大生产。
本发明的有益效果在于：本发明的TPU发泡高低温膜通过由上至下依次设置透气防水膜层、TPU发泡膜层、网状热熔胶层和保护层，透气防水膜层、TPU发泡膜层、网状热熔胶层均具有良好的透气功能，保护层可对网状热熔胶层实现良好的保护作用，使用时可以去除保护膜，将TPU发泡高低温膜通过网状热熔胶层贴合于鞋面材料或者其他产品上；本发明的TPU发泡高低温膜结构简单，具有良好的透气防水性能，力学性能佳，使用方便，实用性强。该防水透气TPU高低温膜的制备方法操作简便，易于控制，生产成本低，产品质量稳定，利于工业化大生产。
具体实施方式
为了便于本领域技术人员的理解，下面结合实施例对本发明作进一步的说明，实施方式提及的内容并非对本发明的限定。
在本发明的实施方式中，一种防水透气TPU高低温膜，包括由上至下依次设置的透气防水膜层、TPU发泡膜层、网状热熔胶层和离型膜层；所述TPU发泡膜层设置有多个间隔设置的过气通孔，所述过气通孔贯穿TPU发泡膜层的上表面和下表面。
在本发明的一种实施方式中，所述透气防水膜层为PU防水透气防水膜层。
在本发明的一种实施方式中，所述网状热熔胶层为TPU网状胶层、EVA网状胶层、PA网状胶层或PES网状胶层中的至少一种。
在本发明的一种实施方式中，所述离型膜为PE离型膜或OPP离型膜。
在本发明的一种实施方式中，所述透气防水膜层的制备方法包括如下步骤：
(S1)将聚氨酯颗粒、聚偏二氟乙烯颗粒和改性二氧化硅颗粒添加到混合液A中，搅拌10-15h，制得静电纺丝溶液；所述混合液A为氯化钙和N,N-二甲基甲酰胺混合液；所述聚氨酯颗粒、聚偏二氟乙烯颗粒、改性二氧化硅与混合液A的质量比为14-19:4-7:3-6:100；
(S2)对静电纺丝溶液进行静电纺丝处理，制得膜初品；
(S3)将膜初品放入处理室中并通入氮气，采用等离子体设备对膜初品进行等离子表面活化；
(S4)将经过活化处理的膜初品放入混合物B中浸泡18-26h，所述混合液B为十二氟庚基丙基三甲氧基硅烷和甲醇混合液；
(S5)将经过浸泡处理的膜初品取出，在55-65℃真空干燥箱中干燥18-26h，得到透气防水膜层。
在本发明的一种实施方式中，所述步骤(S1)中，所述混合液A中氯化钙的浓度为0.01-0.03wt％。
在本发明的一种实施方式中，所述步骤(S2)中，所述混合液B中十二氟庚基丙基三甲氧基硅烷的浓度为1-2.5wt％。
在本发明的一种实施方式中，所述步骤(S2)中，纺丝流率为0.5-0.8mL/h，纺丝电压为10-15kV，温度为22-28℃，湿度为35-45％，喷丝头到收集器之间的距离为12-15cm。
在本发明的一种实施方式中，所述步骤(S3)中，等离子处理功率为80-130W，压力为10-50Pa，处理时间为90-150s。
在本发明的一种实施方式中，所述改性二氧化硅的制备方法包括如下步骤：按重量份计，取纳米二氧化硅颗粒10-15份加入到30-40份的乙醇溶液中，然后再加入全氟十二烷基三氯硅烷1.6-2份，采用盐酸将pH值调节至3.0-5.0，于20-30℃温度下超声搅拌处理5-10h，得到混合液；再用氨水将经过超声处理的混合液的pH值调节至6.0-7.0，超声搅拌30-90min后，进行超声雾化，再置于75-95℃温度下干燥，得到改性二氧化硅。所述纳米二氧化硅颗粒的粒径为20-40nm。
在本发明的一种实施方式中，所述TPU发泡膜层采用TPU发泡材料制成，所述TPU发泡材料包括如下重量份的原料：聚氨酯乳液50-60份、硅丙乳液5-10份、聚偏二氟乙烯4-8份、十二烷基苯磺酸钠0.3-0.8份、纳米二氧化硅3-6份、羟乙基纤维素3-8份、聚乙二醇2-5份、乙烯基三(β-甲氧乙氧基)硅烷2-4份、氮丙啶1-2份、催化剂0.1-0.3份、溶剂15-20份。
在本发明的一种实施方式中，所述溶剂为乙酸乙酯、乙酸丁酯、丙二醇甲醚或乙酰丙酮中的至少一种；所述催化剂为异辛酸铋、月桂酸铋或新癸酸铋中的至少一种。
进一步的，所述TPU发泡材料的制备方法为：将各原料按比例后混合，采用空气发泡机进行发泡，发泡比为1:1.8-2.4，进行发泡，制得TPU发泡材料。TPU发泡材料的发泡方法可采用现有技术中的发泡步骤。
本发明还提供上述防水透气TPU高低温膜的制备方法，包括如下步骤：
(1)取离型膜，在离型膜的表面复合网状热熔胶层；取透气防水膜层，将TPU发泡材料涂布于透气防水膜层，在透气防水膜层的表面形成TPU发泡膜层；
(2)将网状热熔胶层与TPU发泡膜层贴合，制得防水透气TPU高低温膜。网状热熔胶层与TPU发泡膜层贴合可采用现有技术中的复合方式。
实施例1
本实施例中，一种防水透气TPU高低温膜，包括由上至下依次设置的透气防水膜层、TPU发泡膜层、网状热熔胶层和离型膜层；所述TPU发泡膜层设置有多个间隔设置的过气通孔，所述过气通孔贯穿TPU发泡膜层的上表面和下表面。所述透气防水膜层为PU防水透气防水膜层。所述网状热熔胶层为PA网状胶层。所述离型膜为OPP离型膜。
实施例2
本实施例中，一种防水透气TPU高低温膜，包括由上至下依次设置的透气防水膜层、TPU发泡膜层、网状热熔胶层和离型膜层；所述TPU发泡膜层设置有多个间隔设置的过气通孔，所述过气通孔贯穿TPU发泡膜层的上表面和下表面。所述透气防水膜层为PU防水透气防水膜层。所述网状热熔胶层为TPU网状胶层。所述离型膜为PE离型膜。
实施例3
本实施例中，所述透气防水膜层的制备方法包括如下步骤：
(S1)将聚氨酯颗粒、聚偏二氟乙烯颗粒和改性二氧化硅颗粒添加到混合液A中，搅拌12h，制得静电纺丝溶液；所述混合液A为氯化钙和N,N-二甲基甲酰胺混合液；所述聚氨酯颗粒、聚偏二氟乙烯颗粒、改性二氧化硅与混合液A的质量比为16:5:4:100；所述聚氨酯颗粒为巴斯夫聚氨酯1185A，所述聚偏二氟乙烯颗粒为Kynar 720；
(S2)对静电纺丝溶液进行静电纺丝处理，制得膜初品；
(S3)将膜初品放入处理室中并通入氮气，采用等离子体设备对膜初品进行等离子表面活化；
(S4)将经过活化处理的膜初品放入混合物B中浸泡24h，所述混合液B为十二氟庚基丙基三甲氧基硅烷和甲醇混合液；
(S5)将经过浸泡处理的膜初品取出，在60℃真空干燥箱中干燥24h，得到透气防水膜层。
进一步的，所述步骤(S1)中，所述混合液A中氯化钙的浓度为0.015wt％。
进一步的，所述步骤(S2)中，所述混合液B中十二氟庚基丙基三甲氧基硅烷的浓度为2wt％。
进一步的，所述步骤(S2)中，纺丝流率为0.6mL/h，纺丝电压为13kV，温度为26℃，湿度为38％、喷丝头到收集器之间的距离为14cm。
进一步的，所述步骤(S3)中，等离子处理功率为110W，压力为30Pa，处理时间为120s。
进一步的，所述改性二氧化硅的制备方法包括如下步骤：按重量份计，取纳米二氧化硅颗粒12份加入到35份的乙醇溶液中，然后再加入全氟十二烷基三氯硅烷1.8份，采用盐酸将pH值调节至4.0，于25℃温度下超声搅拌处理7h，得到混合液；再用氨水将经过超声处理的混合液的pH值调节至6.6，超声搅拌60min后，进行超声雾化，再置于78℃温度下干燥，得到改性二氧化硅。所述纳米二氧化硅颗粒的粒径为20-40nm。
进一步的，所述TPU发泡膜层采用TPU发泡材料制成，所述TPU发泡材料包括如下重量份的原料：聚氨酯乳液55份、硅丙乳液7份、聚偏二氟乙烯6份、十二烷基苯磺酸钠0.5份、纳米二氧化硅4份、羟乙基纤维素5份、聚乙二醇3份、乙烯基三(β-甲氧乙氧基)硅烷3份、氮丙啶1.5份、催化剂0.2份、溶剂18份。所述聚氨酯乳液为HEBEN A-539聚氨酯乳液。所述硅丙乳液为SD-5281硅丙乳液。
进一步的，所述TPU发泡材料的制备方法为：将各原料按比例后混合，采用空气发泡机进行发泡，发泡比为1:2，进行发泡，制得TPU发泡材料。
进一步的，所述溶剂为乙酸乙酯、乙酸丁酯和丙二醇按照质量比1:1.5:3组成。所述催化剂为月桂酸铋。
上述防水透气TPU高低温膜的制备方法，包括如下步骤：
(1)取离型膜，在离型膜的表面复合网状热熔胶层；取透气防水膜层，将TPU发泡材料涂布于透气防水膜层，烘干，在透气防水膜层的表面形成TPU发泡膜层；
(2)将网状热熔胶层与TPU发泡膜层贴合，制得防水透气TPU高低温膜。
本实施例的其余部分与实施例1相同，此处不再赘述。
实施例4
本实施例中，所述透气防水膜层的制备方法包括如下步骤：
(S1)将聚氨酯颗粒、聚偏二氟乙烯颗粒和改性二氧化硅颗粒添加到混合液A中，搅拌10-15h，制得静电纺丝溶液；所述混合液A为氯化钙和N,N-二甲基甲酰胺混合液；所述聚氨酯颗粒、聚偏二氟乙烯颗粒、改性二氧化硅与混合液A的质量比为14:4.5:4:100；
(S2)对静电纺丝溶液进行静电纺丝处理，制得膜初品；
(S3)将膜初品放入处理室中并通入氮气，采用等离子体设备对膜初品进行等离子表面活化；
(S4)将经过活化处理的膜初品放入混合物B中浸泡22h，所述混合液B为十二氟庚基丙基三甲氧基硅烷和甲醇混合液；
(S5)将经过浸泡处理的膜初品取出，在58℃真空干燥箱中干燥20h，得到透气防水膜层。
进一步的，所述步骤(S1)中，所述混合液A中氯化钙的浓度为0.01wt％。
进一步的，所述步骤(S2)中，所述混合液B中十二氟庚基丙基三甲氧基硅烷的浓度为2.5wt％。
进一步的，所述改性二氧化硅的制备方法包括如下步骤：按重量份计，取纳米二氧化硅颗粒10份加入到30份的乙醇溶液中，然后再加入全氟十二烷基三氯硅烷1.6份，采用盐酸将pH值调节至3.0，于20℃温度下超声搅拌处理10h，得到混合液；再用氨水将经过超声处理的混合液的pH值调节至6.0，超声搅拌90min后，进行超声雾化，再置于85℃温度下干燥，得到改性二氧化硅。所述纳米二氧化硅颗粒的粒径为20-40nm。
上述防水透气TPU高低温膜的制备方法，包括如下步骤：
(1)取离型膜，在离型膜的表面复合网状热熔胶层；取透气防水膜层，将TPU发泡材料涂布于透气防水膜层，在透气防水膜层的表面形成TPU发泡膜层；
(2)将网状热熔胶层与TPU发泡膜层贴合，制得防水透气TPU高低温膜。
进一步的，所述TPU发泡膜层采用TPU发泡材料制成，所述TPU发泡材料包括如下重量份的原料：聚氨酯乳液50份、硅丙乳液5份、聚偏二氟乙烯4份、十二烷基苯磺酸钠0.3份、纳米二氧化硅3份、羟乙基纤维素3份、聚乙二醇2份、乙烯基三(β-甲氧乙氧基)硅烷2份、氮丙啶1份、催化剂0.1份、溶剂15份。所述溶剂为乙酸乙酯、乙酸丁酯和丙二醇按照质量比1:1.5:4组成。所述催化剂为月桂酸铋。
本实施例的其余部分与实施例1相同，此处不再赘述。
实施例5
本实施例中，所述透气防水膜层的制备方法包括如下步骤：
(S1)将聚氨酯颗粒、聚偏二氟乙烯颗粒和改性二氧化硅颗粒添加到混合液A中，搅拌10-15h，制得静电纺丝溶液；所述混合液A为氯化钙和N,N-二甲基甲酰胺混合液；所述聚氨酯颗粒、聚偏二氟乙烯颗粒、改性二氧化硅与混合液A的质量比为19:3:6:100；
(S2)对静电纺丝溶液进行静电纺丝处理，制得膜初品；
(S3)将膜初品放入处理室中并通入氮气，采用等离子体设备对膜初品进行等离子表面活化；
(S4)将经过活化处理的膜初品放入混合物B中浸泡24h，所述混合液B为十二氟庚基丙基三甲氧基硅烷和甲醇混合液；
(S5)将经过浸泡处理的膜初品取出，在60℃真空干燥箱中干燥24h，得到透气防水膜层。
进一步的，所述步骤(S1)中，所述混合液A中氯化钙的浓度为0.02wt％。
进一步的，所述步骤(S2)中，所述混合液B中十二氟庚基丙基三甲氧基硅烷的浓度为2.2wt％。
进一步的，所述改性二氧化硅的制备方法包括如下步骤：按重量份计，在氮气氛围下，取纳米二氧化硅颗粒15份加入到甲苯溶液中，然后再加入全氟十二烷基三氯硅烷2份，于32℃温度下超声搅拌处理8h，得到混合物，过滤除去多余的甲苯后，再置于85℃温度下真空干燥，得到改性二氧化硅。所述纳米二氧化硅颗粒的粒径为20-40nm。
上述防水透气TPU高低温膜的制备方法，包括如下步骤：
(1)取离型膜，在离型膜的表面复合网状热熔胶层；取透气防水膜层，将TPU发泡材料涂布于透气防水膜层，在透气防水膜层的表面形成TPU发泡膜层；
(2)将网状热熔胶层与TPU发泡膜层贴合，制得防水透气TPU高低温膜。
进一步的，所述TPU发泡膜层采用TPU发泡材料制成，所述TPU发泡材料包括如下重量份的原料：聚氨酯乳液60份、硅丙乳液10份、聚偏二氟乙烯8份、十二烷基苯磺酸钠0.8份、纳米二氧化硅6份、羟乙基纤维素8份、聚乙二醇5份、乙烯基三(β-甲氧乙氧基)硅烷4份、氮丙啶2份、催化剂0.2份、溶剂20份。所述溶剂为乙酸乙酯、乙酸丁酯和丙二醇按照质量比1:1.5:4组成。所述催化剂为异辛酸铋。
本实施例的其余部分与实施例1相同，此处不再赘述。
实施例6
本实施例中，所述透气防水膜层的制备方法包括如下步骤：
(S1)将聚氨酯颗粒、聚偏二氟乙烯颗粒和改性二氧化硅颗粒添加到混合液A中，搅拌15h，制得静电纺丝溶液；所述混合液A为氯化钙和N,N-二甲基甲酰胺混合液；所述聚氨酯颗粒、聚偏二氟乙烯颗粒、改性二氧化硅与混合液A的质量比为15:5.5:4:100；
(S2)对静电纺丝溶液进行静电纺丝处理，制得膜初品；
(S3)将膜初品放入处理室中并通入氮气，采用等离子体设备对膜初品进行等离子表面活化；
(S4)将经过活化处理的膜初品放入混合物B中浸泡24h，所述混合液B为十二氟庚基丙基三甲氧基硅烷和甲醇混合液；
(S5)将经过浸泡处理的膜初品取出，在60℃真空干燥箱中干燥24h，得到透气防水膜层。
进一步的，所述TPU发泡膜层采用TPU发泡材料制成，所述TPU发泡材料包括如下重量份的原料：聚氨酯乳液55份、硅丙乳液7份、聚偏二氟乙烯6份、十二烷基苯磺酸钠0.5份、纳米二氧化硅4份、羟乙基纤维素5份、聚乙二醇3份、乙烯基三(β-甲氧乙氧基)硅烷2.5份、氮丙啶1.5份、催化剂0.2份、溶剂18份。
本实施例的其余部分与实施例1相同，此处不再赘述。
对比例1
本对比例与实施例3的不同之处在于：本对比例的透气防水膜层的制备方法中，采用甲醇溶液替代混合液B，未添加改性二氧化硅。
对比例2
本对比例与实施例3的不同之处在于：本对比例的TPU发泡材料中不含有硅丙乳液、聚偏二氟乙烯和聚乙二醇，采用等量的聚氨酯乳液取代。
对实施例3-6制得的透气防水膜层控制其厚度为30±3μm，进行性能测试测试数据如下表1所示：
Figure BDA0003896221850000101
其中，耐水性采用AATCC 127-2003进行测定，透气性采用GB/T 5453-1997进行测定，透湿性采用GB/T 12704.1-2009进行测定；拉伸强度采用在拉伸试验机测量，采用单向拉伸的方式，拉伸速率为0.3cm/min，量程为10cm，待测被制成20mm×5mm的条带形状。
将实施例3的TPU高低温膜与对比例2的高低温控制TPU发泡膜层的厚度为80+5μm，撕除离型膜后，测定透气率、透湿性和拉伸强度。经测定，实施例3的透气率为33mm/s，透湿性为7.9g/(m2·24h)，拉伸强度为11.7MPa；对比例2的透气率为28mm/s，透湿性为7.4g/(m2·24h)，拉伸强度为9.4MPa。
本发明的TPU发泡高低温膜结构简单，具有良好的透气防水性能，力学性能佳，使用方便，实用性强；其制备方法操作简便，易于控制，生产成本低，产品质量稳定，利于工业化大生产。
上述实施例为本发明较佳的实现方案，除此之外，本发明还可以其它方式实现，在不脱离本发明构思的前提下任何显而易见的替换均在本发明的保护范围之内。

Claims (8)

1.一种防水透气TPU高低温膜，其特征在于：包括由上至下依次设置的透气防水膜层、TPU发泡膜层、网状热熔胶层和离型膜层；所述TPU发泡膜层设置有多个间隔设置的过气通孔，所述过气通孔贯穿TPU发泡膜层的上表面和下表面；
所述透气防水膜层的制备方法包括如下步骤：
(S1)将聚氨酯颗粒、聚偏二氟乙烯颗粒和改性二氧化硅颗粒添加到混合液A中，搅拌10-15h，制得静电纺丝溶液；所述混合液A为氯化钙和N, N-二甲基甲酰胺混合液；所述聚氨酯颗粒、聚偏二氟乙烯颗粒、改性二氧化硅与混合液A的质量比为14-19:4-7:3-6:100；
（S2）对静电纺丝溶液进行静电纺丝处理，制得膜初品；
（S3）将膜初品放入处理室中并通入氮气，采用等离子体设备对膜初品进行等离子表面活化；
（S4）将经过活化处理的膜初品放入混合物B中浸泡，所述混合液B为十二氟庚基丙基三甲氧基硅烷和甲醇混合液；
（S5）将经过浸泡处理的膜初品取出，置于真空干燥箱中干燥，得到透气防水膜层；
所述改性二氧化硅颗粒的制备方法包括如下步骤：按重量份计，取纳米二氧化硅颗粒10-15份加入到30-40份的乙醇溶液中，然后再加入全氟十二烷基三氯硅烷1.6-2份，采用盐酸将pH值调节至3.0-5.0，于20-30℃温度下超声搅拌处理5-10h，得到混合液；再用氨水将经过超声处理的混合液的pH值调节至6.0-7.0，超声搅拌30-90min后，进行超声雾化，再置于75-95℃温度下干燥，得到改性二氧化硅颗粒；
所述TPU发泡膜层采用TPU发泡材料制成，所述TPU发泡材料包括如下重量份的原料：聚氨酯乳液50-60份、硅丙乳液5-10份、聚偏二氟乙烯4-8份、十二烷基苯磺酸钠0.3-0.8份、纳米二氧化硅3-6份、羟乙基纤维素3-8份、聚乙二醇2-5份、乙烯基三(β-甲氧乙氧基)硅烷2-4份、氮丙啶1-2份、催化剂0.1-0.3份、溶剂15-20份。
2.根据权利要求1所述的一种防水透气TPU高低温膜，其特征在于：所述网状热熔胶层为TPU网状胶层、EVA网状胶层、PA网状胶层或PES网状胶层中的至少一种。
3.根据权利要求1所述的一种防水透气TPU高低温膜，其特征在于：所述离型膜为PE离型膜或OPP离型膜。
4.根据权利要求1所述的一种防水透气TPU高低温膜，其特征在于：所述步骤（S1）中，所述混合液A中氯化钙的浓度为0.01-0.03wt%。
5.根据权利要求1所述的一种防水透气TPU高低温膜，其特征在于：所述步骤（S4）中，所述混合液B中十二氟庚基丙基三甲氧基硅烷的浓度为1-2.5wt%。
6.根据权利要求1所述的一种防水透气TPU高低温膜，其特征在于：所述步骤（S2）中，纺丝流率为0.5-0.8mL/h，纺丝电压为10-15kV，温度为22-28℃，喷丝头到收集器之间的距离为12-15cm。
7.根据权利要求1所述的一种防水透气TPU高低温膜，其特征在于：所述步骤（S3）中，等离子处理功率为80-130W，压力为10-50Pa，处理时间为90-150s。
8.一种权利要求1-7任意一项所述防水透气TPU高低温膜的制备方法，其特征在于：包括如下步骤：
（1）取离型膜，在离型膜的表面复合网状热熔胶层；取透气防水膜层，将TPU发泡材料涂布于透气防水膜层，烘干，在透气防水膜层的表面形成TPU发泡膜层；
（2）将网状热熔胶层与TPU发泡膜层贴合，制得防水透气TPU高低温膜。
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