CN116836684A - 抗皱型tpu薄膜、抗皱型tpu复合面料及其制备方法 - Google Patents

抗皱型tpu薄膜、抗皱型tpu复合面料及其制备方法 Download PDF

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CN116836684A
CN116836684A CN202310785234.0A CN202310785234A CN116836684A CN 116836684 A CN116836684 A CN 116836684A CN 202310785234 A CN202310785234 A CN 202310785234A CN 116836684 A CN116836684 A CN 116836684A
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tpu
wrinkle
epoxy resin
polyurethane prepolymer
fabric
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CN116836684B (zh
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李振林
王青海
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Kunming Red Apple Plastic Cement New Material Co ltd
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Kunming Red Apple Plastic Cement New Material Co ltd
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    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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Abstract

本申请涉及面料制造技术领域，具体公开了一种抗皱型TPU薄膜、抗皱型TPU复合面料及其制备方法。抗皱型TPU薄膜包括TPU基膜层和涂覆在TPU基膜层上的粘结层；粘结层包括由以下重量份的原料制成：丙烯酸/环氧树脂改性聚氨酯预聚体100份、固化剂2‑5份和催化剂0.1‑0.5份。本申请通过对聚氨酯进行改性处理，使得粘接层具备高延展性以及粘接性，实现了使TPU薄膜快速、稳定且平整的粘接于面料上的效果，进而使TPU薄膜自身不易产生褶皱，使用该TPU薄膜的面料的抗皱性能亦可提高。

Description

抗皱型TPU薄膜、抗皱型TPU复合面料及其制备方法
技术领域
本申请涉及面料制造技术领域，更具体地说，它涉及一种抗皱型TPU薄膜、抗皱型TPU复合面料及其制备方法。
背景技术
热塑性聚氨酯弹性体(TPU)是由硬段和软段材料组成的共聚物，其具有较高的拉伸性能和耐磨性能、以及具有优异的弹性和生物相同性。TPU薄膜是在TPU颗粒料的基础上，通过压延、流延、吹膜、涂覆等工艺制程的薄膜。TPU薄膜是一种功能性薄膜，具有其他塑胶材料无法比拟的强度高、韧性好、耐寒、耐油、耐老化、耐气候、环保无毒、可分解等特性，同时具有高防水、防风、防寒、抗菌、保暖、抗紫外线及能量释放等优异功能，使得其被广泛地应用于服饰面料行业。
TPU复合织物通常是将TPU薄膜和织物粘合而成，目前市面上的TPU薄膜虽具有优异的弹性，但其应用在TPU复合织物上抗皱性表现欠佳，存在不能适应纺织品大幅度伸缩的问题。
针对上述中的相关技术，发明人认为TPU薄膜应用在纺织品上时存在抗皱性能差的问题，因此限制了其使用与发展。
发明内容
为了提高TPU薄膜的抗皱性能，本申请提供抗皱型TPU薄膜、抗皱型TPU复合面料及其制备方法。
第一方面，本申请提供的抗皱型TPU薄膜，采用如下的技术方案：
抗皱型TPU薄膜，包括TPU基膜层和涂覆在TPU基膜层上的粘接层；
所述粘接层包括由以下重量份的原料制成：丙烯酸/环氧树脂改性聚氨酯预聚体100份、固化剂2-5份和催化剂0.1-0.5份。
通过采用上述技术方案，由于丙烯酸/环氧树脂改性聚氨酯预聚体中，丙烯酸或丙烯酸酯基团的存在可增加粘接层在TPU基膜层表面的润湿性，同时提高聚氨酯与TPU基膜层间的相容性；环氧树脂改性聚氨酯不仅有环氧基团，同时具有氨酯基以及羟基、酚基等活性基团，可提高聚氨酯的稳定性和粘接性；在丙烯酸与环氧树脂的共同作用下得到的丙烯酸/环氧树脂改性聚氨酯预聚体具有高延展性和粘接性，提高了TPU基膜层与粘接层的粘接强度，可使形成的TPU薄膜快速、平稳且平整的粘接于面料上，提高TPU薄膜自身的抗皱性能。
在一个具体的可实施方案中，所述丙烯酸/环氧树脂改性聚氨酯预聚体的制备方法为：将聚碳酸酯二醇与异佛尔酮二异氰酸酯混合反应后，经熟化，得到聚氨酯预聚体；将所述聚氨酯预聚体与丙烯酸类单体在引发剂作用下，于有机溶剂中反应得到丙烯酸改性聚氨酯预聚体；将环氧树脂加入所述丙烯酸改性聚氨酯预聚体中，反应得到丙烯酸/环氧树脂改性聚氨酯预聚体；
所述聚碳酸酯二醇与异佛尔酮二异氰酸酯的质量比为100：(10-35)；
所述聚氨酯预聚体、丙烯酸类单体与引发剂的质量比为10：(0.5-4)：(0.02-0.1)；
所述环氧树脂与丙烯酸/环氧树脂改性聚氨酯的质量比为1：(4-6)。
通过采用上述技术方案，制备方法简单，聚氨酯、丙烯酸和环氧树脂三种组分在材料中彼此网间互穿和存在着三维的“机械缠结”；同时通过聚氨酯中异氰酸酯NCO与环氧树脂和丙烯酸树脂的羟基(氨基)反应，制得接枝互传网络丙烯酸/环氧树脂改性聚氨酯预聚体；且制备过程中用丙烯酸单体替代部分溶剂，通过用引发剂引发自由基聚合，制备出了以丙烯酸树脂为核，以改性聚氨酯为壳的丙烯酸/环氧树脂改性聚氨酯预聚体，具有聚氨酯、丙烯酸和环氧树脂三者的优点，具有良好的机械强度、耐磨性、稳定性和附着性等综合性能优异等特点，同时能够降低成本。
在一个具体的可实施方案中，所述固化剂为多异氰酸酯与多元醇的加成物或多异氰酸酯三聚体；所述催化剂为有机金属类催化剂或叔胺类催化剂。
通过采用上述技术方案，粘接层在使用过程中，固化剂中的异氰酸酯基团和丙烯酸改性聚氨酯中的氨基甲酸酯基团发生固化交联，实现膜TPU薄膜与基布的粘接，同时满足耐溶剂型、耐水解性、柔韧性、耐摩擦性、耐弯折性等方面的要求。
有机金属类催化剂具有高活性，处理效率高，热稳定性和抗氧化性好，节能环保等优异特性；叔胺类催化剂对聚氨酯，尤其是聚氨酯合成中的一NCO与水和一NCO与端羟基聚酯、聚醚多元酵的两个主要反应，叔胺类催化剂都有很强的催化作用，尤其是对一NCO与一OH反应的催化作用更加明显。不仅能促进聚合物分子链迅速增长.粘度快速增加而且能促进-NCO与水反应，加快反应速率。
在一个具体的可实施方案中，所述环氧树脂为E-51、E-44、E-42双酚A环氧树脂中的一种。
通过采用上述技术方案，双酚A环氧型树脂分子结构中含芳环和侧位羟基，对提高附着力有利；另外芳环结构还赋予树脂较高的刚性、拉伸强度及热稳定性；总体而言，双酚A环氧型的主要特点包括：光固化反应速率很快，固化后硬度和拉伸强度大，膜层光泽度高，耐化学品腐蚀性能优异。
在一个具体的可实施方案中，所述TPU基膜层包括由以下重量份的原料制成：TPU母粒85-95份、增韧剂0.5-10份和抗氧化剂1.5-8份；
所述增韧剂为质量比为1：(1-1.2)的乙烯-丙烯酸甲酯共聚物和甲基丙烯酸甲酯-丁二烯-苯乙烯三元共聚物的混合物。
通过采用上述技术方案，乙烯-丙烯酸甲酯共聚物耐环境应力开裂性好，甲基丙烯酸甲酯-丁二烯-苯乙烯三元共聚物是一种具有核壳结构的弹性体粒子，与TPU有良好的掺混性，甲基丙烯酸甲酯-丁二烯-苯乙烯三元共聚物与TPU一起经过加工塑化后，以粒子状态均匀分散在TPU之中，对TPU具有很多的增韧作用，与乙烯-丙烯酸甲酯共聚物共同使用时具有协同作用，使得TPU薄膜具有优异的韧性和拉伸强度，可修复性较强。
在一个具体的可实施方案中，所述抗氧剂为抗氧剂1010和抗氧剂168中的混合物，且抗氧剂1010和抗氧剂168的重量比为1：(1-3)。
通过采用上述技术方案，抗氧剂1010能有效地防止聚合物材料在长期老化过程中的热氧化降解，同时与抗氧剂168并用具有协同效应，可有效地延长TPU薄膜的使用寿命。
在一个具体的可实施方案中，所述TPU颗粒是以二苯基甲烷-4,4-二异氰酸酯、聚四氢呋喃为基本原料进行预聚反应，在所述预聚反应时加入季铵盐类有机抗菌剂，再经过扩链反应和终止反应即得。
通过采用上述技术方案，采用具有抑菌功能的阳离子表面活性剂季铵盐加入到聚氨酯反应体系中，提高了TPU薄膜的抗菌性能。
在一个具体的可实施方案中，所述季铵盐类有机抗菌剂为双羟基季铵盐。
通过采用上述技术方案，双羟基季铵盐相比普通季铵盐抗菌剂更容易破坏菌类的细胞质膜机构，进入细胞内部，使细胞酶钝化、破坏，发生蛋白质变性，达到杀死细菌作用。
第二方面，本申请提供抗皱型TPU复合面料，采用如下的技术方案：
抗皱型TPU复合面料，采用上述的抗皱型TPU薄膜与基布复合而成，所述基布由碳纤维纱线编织而成的双层平纹织物。
通过采用上述技术方案，基布结构强度好，抗撕裂性能好，同时具有一定的抗皱性能，配合抗皱型TPU薄膜，通过平纹结构内部应力，使得复合面料实现良好的抗皱性能。
第三方面，本申请提供抗皱型TPU复合面料的制备方法，采用如下的技术方案：
抗皱型TPU复合面料的制备方法，包括以下步骤：
TPU基膜层：将TPU基膜层的原料进行混合，形成混合料；将所述混合料进行挤出、冷却、切粒得到预混颗粒；将所述预混颗粒进行挤出流延成型即可；
抗皱型TPU薄膜：将粘接层的原料进行混合并涂覆在所述TPU基膜层上即可；
抗皱型TPU复合面料：将所述抗皱型TPU薄膜与基布进行热压，冷却后即得成品。
通过采用上述技术方案，制备方法简单，生产效率高，可实现批量生产；选用由碳纤维纱线编织而成的双层平纹织物为基布复合抗皱型TPU薄膜复合层的面料具有不起皱，弹性好，同时具有良好的悬垂性、热塑性、尺寸稳定等优异特性。
综上所述，本申请具有以下有益效果：
1、本申请通过丙烯酸和环氧树脂对聚氨酯预聚体进行改性，制得的粘接层具备高延展性和粘接性，实现了使TPU基层膜快速，稳定且平整的连接于基布上的效果，进而使TPU薄膜自身不易产生褶皱，使用该TPU薄膜复合的面料的抗皱性能亦可提高；
2、本申请中采用具有抑菌功能的阳离子表面活性剂季铵盐加入到聚氨酯反应体系中，提高了TPU薄膜的抗菌性能；
3、选用由碳纤维纱线编织而成的双层平纹织物为基布复合抗皱型TPU薄膜复合层的面料具有不起皱，弹性好，同时具有良好的悬垂性、热塑性、尺寸稳定等优异特性。
具体实施方式
以下结合制备例和实施例对本申请作进一步详细说明。
制备例
制备例1
本制备例公开了一种丙烯酸/环氧树脂改性聚氨酯预聚体的制备方法，具体方法如下：
P1，将100g分子量为2000的聚碳酸酯二醇加入反应釜中升温至90℃，待聚碳酸酯二醇熔化后，在氮气保护下搅拌，搅拌过程中加入10g异佛尔酮二异氰酸酯反应6h后倒入容器中，放入100℃烘箱内熟化8h，冷却至室温，得到聚氨酯预聚体；
P2，将100g聚氨酯预聚体加入30g乙酸乙酯中，在80℃下缓慢搅拌，直至聚氨酯预聚体完全溶解后，在氮气保护下，边搅拌边滴加3g甲基丙烯酸甲酯、2g丙烯酸丁酯和0.2g过氧化苯甲酰的混合溶液，反应8h后得到丙烯酸改性聚氨酯预聚体；
P3，将10gE-51双酚A环氧树脂加入上述40g丙烯酸改性聚氨酯预聚体中，搅拌，水浴加热，反应温度为80℃，反应1.5h即可。其中环氧树脂选用E-51双酚A环氧树脂，在其他制备例中也可选用E-44、E-42双酚A环氧树脂。
制备例2
本制备例公开了一种丙烯酸/环氧树脂改性聚氨酯预聚体的制备方法，具体方法如下：
P1，将100g分子量为2000的聚碳酸酯二醇加入反应釜中升温至90℃，待聚碳酸酯二醇熔化后，在氮气保护下搅拌，搅拌过程中加入35g异佛尔酮二异氰酸酯反应6h后倒入容器中，放入100℃烘箱内熟化8h，冷却至室温，得到聚氨酯预聚体；
P2，将100g聚氨酯预聚体加入30g乙酸乙酯中，在80℃下缓慢搅拌，直至聚氨酯预聚体完全溶解后，在氮气保护下，边搅拌边滴加20g甲基丙烯酸甲酯、20g丙烯酸丁酯和1g过氧化苯甲酰的混合溶液，反应8h后得到丙烯酸改性聚氨酯预聚体；
P3，将10gE-51双酚A环氧树脂加入上述60g丙烯酸改性聚氨酯预聚体中，搅拌，水浴加热，反应温度为80℃，反应1.5h即可。
制备例3
本制备例公开了一种环氧树脂改性聚氨酯预聚体的制备方法，具体方法如下：
P1，在装有冷凝器的反应釜中加入10gE-51双酚A环氧树脂、5g二乙烯三胺和20gN,N-二甲基甲酰胺，加热至100℃搅拌180min反应制得氨基聚合物；
P2，将80g上述氨基聚合物、5g1,2-己二醇、10g甲苯二异氰酸酯以及50g乙酸乙酯依次加入装有冷凝器的反应釜中，常温搅拌150min反应制得。
制备例4
本制备例与制备例2基本相同，不同之处在于，省略P3，即制得丙烯酸改性聚氨酯预聚体。
制备例5
本制备例与制备例2基本相同，不同之处在于，省略P2和P3，即制得聚氨酯预聚体。
制备例6
本制备例公开了一种TPU母粒的制备方法，具体过程如下：称取1mol分子量为1800的聚四氢呋喃于三口烧瓶中，加热真空脱水，待冷却至30℃加入2.2mol二苯基甲烷二异氰酸酯，不断搅拌并将温度上升至70℃，维持此温度30min，加入1500ppmN-甲基-N-正丁基-N，N二羟乙基溴化铵，反应10min得到预聚体；在上述预聚体中加入扩链剂乙二胺，待反应液呈甘油状后，再加入0.2mol终止剂乙二胺，冷却反应液至50℃，得到抗菌聚氨酯；将抗菌聚氨酯通过双螺杆挤出机中挤出成型得到TPU母粒。
制备例7
本制备例与制备例6基本相同，不同之处在于，制备过程中不添加1500ppmN-甲基-N-正丁基-N，N二羟乙基溴化铵。
实施例
实施例1-12
如表1所述，实施例1-7的主要区别在于抗皱型TPU薄膜中TPU基膜层的原料配比不同。
如表2所述，实施例8-11与实施例6基本相同，主要区别在于抗皱型TPU薄膜中粘接层的原料配比不同。
以下以实施例1为例进行说明。本申请实施例公开了抗皱型TPU薄膜，包括TPU基膜层和涂覆在TPU基膜层上的粘接层，其中TPU基膜层以TPU母粒85Kg、乙烯-丙烯酸甲酯共聚物0.25Kg和甲基丙烯酸甲酯-丁二烯-苯乙烯三元共聚物0.25Kg、抗氧化剂10100.75Kg和抗氧剂1680.75Kg为原料制备而成；其中TPU母粒采用制备例6所得；
粘接层以丙烯酸/环氧树脂改性聚氨酯预聚体100Kg、异佛尔酮二异氰酸酯三聚体2Kg和二月桂酸二丁基锡0.1Kg为原料制备而成；其中丙烯酸/环氧树脂改性聚氨酯预聚体采用制备1所得，其中固化剂选用异佛尔酮二异氰酸酯三聚体，在其他实施例中也可选用多异氰酸酯与多元醇的加成物或其他多异氰酸酯三聚体；催化剂选用二月桂酸二丁基锡，在其他实施例中也可选用其他有机金属类催化剂或叔胺类催化剂。
本申请实施例还公开了抗皱型TPU薄膜的生产工艺：包括以下步骤：
S1，TPU基膜层的制备：
S10，按配方称取TPU基层膜的原料并置于拌料机中，在加热温度为85℃，搅拌速度为180r/min的条件下，搅拌10min，使原料充分混合，形成混合料；
S20，将混合料加入双螺杆挤出机进行挤出、冷却、切粒得到预混颗粒；其中前段温度为80-100℃，中段温度为140-150℃，后段温度为170-180℃，主机电流为70A，熔体压力为4Mpa，主机转速为300r/min，喂料转速为150r/min；
S30，将预混颗粒送入流延机挤出流延成型得到TPU基膜；其中螺杆速度为100r/min，挤出温度为200℃，模头温度为100℃，辊速为300m/min。
S2，抗皱型TPU薄膜：将粘接层的原料混合而成的粘结剂涂覆在上述TPU基膜层上形成粘接层即可，粘接层厚度为0.03mm。
本申请实施例还公开抗皱型TPU复合面料，采用上述抗皱型TPU薄膜与基布复合而成。
本申请实施例还公开抗皱性TPU复合面料的制备方法，具体过程如下：采用碳纤维编织而成的双层平纹织物作为基布，将抗皱型TPU薄膜热压在基布上，冷却后复合而成；其中粘接层设置在基布与TPU基层膜之间，热压温度为130℃，热压时间为9s，热压压力为35Pa。
表1实施例1-7中TPU基膜层中各原料配比
表2实施例6、8-11中粘接层中各原料配比
实施例12
本实施例与实施例10不同的是，丙烯酸/环氧树脂改性聚氨酯预聚体采用制备例2所得。
对比例
对比例1
本对比例与实施例1不同之处在于，将粘接层中的丙烯酸/环氧树脂改性聚氨酯预聚体等替换为制备例3所得的环氧树脂改性聚氨酯预聚体。
对比例2
本对比例与实施例1不同之处在于，将粘接层中的丙烯酸/环氧树脂改性聚氨酯预聚体等替换为制备例4所得的丙烯酸改性聚氨酯预聚体。
对比例3
本实施例与实施例1不同之处在于，将粘接层中的丙烯酸/环氧树脂改性聚氨酯预聚体等替换为制备例5所得的聚氨酯预聚体。
对比例4
本实施例与实施例1不同之处在于，将TPU基膜层中的TPU母粒等量替换为制备例7所得的TPU母粒。
性能检测试验
一、抗皱性能
按照GB/T3819-1997《纺织品织物折痕回复性的测定，回复角法》进行测试。将各实施例和对比例中的面料剪成1.5㎝×2㎝的经纬向长条各5块，在温度20℃，湿度65％恒温恒湿的条件下平衡24h，测量弹性回复角，取平均值，得到抗皱回复角，折皱回复角越大，面料的抗皱性能越好，测试结果记录在表3中。
二、抗菌性能
参照GB/T15979-2002进测试，测试结果记录在表3中。
表3实施例1-12以及对比例1-4的性能检测
参照表3，结合实施例1和对比例1-3，可以看出，通过丙烯酸类单体和环氧树脂同时对聚氨酯预聚体进行改性得到的丙烯酸/环氧树脂改性聚氨酯预聚体制成的粘接层复合成的面料的抗皱性均优于丙烯酸类单体或环氧树脂对聚氨酯单体改性得到的改性预聚体得到的粘接层复合成的面料的抗皱性；同时也优于对聚氨酯预聚体不做改性处理得到的粘接层复合成的面料的抗皱性。由于丙烯酸/环氧树脂改性聚氨酯预聚体中，丙烯酸或丙烯酸酯基团的存在可增加粘接层在TPU基膜层表面的润湿性，同时提高聚氨酯与TPU基膜层间的相容性；环氧树脂改性聚氨酯不仅有环氧基团，同时具有氨酯基以及羟基、酚基等活性基团，可提高聚氨酯的稳定性和粘结性；在丙烯酸与环氧树脂的共同作用下得到的丙烯酸/环氧树脂改性聚氨酯预聚体具有高延展性和粘结性，提高了TPU基膜层与粘接层的粘结强度，可使形成的TPU薄膜快速、平稳且平整的粘结于面料上，提高TPU薄膜自身的抗皱性能，应用改TPU薄膜复合形成的面料的抗皱性也得到提高。
参照表3，结合实施例1和对比例4，可以看出，在制备TPU母粒时，添加具有抑菌功能的阳离子表面活性剂双羟基季铵盐，可提高TPU薄膜的抗菌性能，进而提高TPU复合面料的抗菌性。双羟基季铵盐可破坏菌类的细胞质膜机构，进入细胞内部，使细胞酶钝化、破坏，发生蛋白质变性，达到杀死细菌作用，达到抗菌效果。
参照表3，结合实施例1-7，可以看出，在适当的范围内改变TPU基膜层各原料配比，得到的TPU复合面料均具有良好的抗皱性能和抗菌性能。TPU薄膜是一种功能性薄膜，具有其他塑胶材料无法比拟的强度高、韧性好、耐寒、耐油、耐老化、耐气候、环保无毒、可分解等特性，同时具有高防水、防风、防寒、抗菌、保暖、抗紫外线及能量释放等优异功能，应用于服饰面料行业，可赋予面料很多优异特性。
参照表3，结合实施例6、8-12，可以看出，在适当的范围内改性粘接层各原料配比，得到的TPU复合面料的抗皱性和抗菌性均较好。改性丙烯酸/环氧树脂改性聚氨酯预聚体，具有聚氨酯、丙烯酸和环氧树脂三者的优点，具有良好的机械强度、耐磨性、稳定性和附着性等综合性能优异等特点，同时能够降低成本；异佛尔酮二异氰酸酯三聚体中的异氰酸酯基团和丙烯酸改性聚氨酯中的氨基甲酸酯基团发生固化交联，实现膜TPU薄膜与基布的粘结，同时满足耐溶剂型、耐水解性、柔韧性、耐摩擦性、耐弯折性等方面的要求；二月桂酸二丁基锡具有高活性，处理效率高，热稳定性和抗氧化性好，节能环保等优异特性。
本具体实施例仅仅是对本申请的解释，其并不是对本申请的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本申请的权利要求范围内都受到专利法的保护。

Claims (10)

1.抗皱型TPU薄膜，其特征在于：包括TPU基膜层和涂覆在TPU基膜层上的粘接层；
所述粘接层包括由以下重量份的原料制成：丙烯酸/环氧树脂改性聚氨酯预聚体100份、固化剂2-5份和催化剂0.1-0.5份。
2.根据权利要求1所述的抗皱型TPU薄膜，其特征在于：所述丙烯酸/环氧树脂改性聚氨酯预聚体的制备方法为：将聚碳酸酯二醇与异佛尔酮二异氰酸酯混合反应后，经熟化，得到聚氨酯预聚体；将所述聚氨酯预聚体与丙烯酸类单体在引发剂作用下，于有机溶剂中反应得到丙烯酸改性聚氨酯预聚体；将环氧树脂加入所述丙烯酸改性聚氨酯预聚体中，反应得到丙烯酸/环氧树脂改性聚氨酯预聚体；
所述聚碳酸酯二醇与异佛尔酮二异氰酸酯的质量比为100：（10-35）；
所述聚氨酯预聚体、丙烯酸类单体与引发剂的质量比为10：（0.5-4）：（0.02-0.1）；
所述环氧树脂与丙烯酸/环氧树脂改性聚氨酯的质量比为1：（4-6）。
3.根据权利要求2所述的抗皱型TPU薄膜，其特征在于：所述固化剂为多异氰酸酯与多元醇的加成物或多异氰酸酯三聚体；所述催化剂为有机金属类催化剂或叔胺类催化剂。
4.根据权利要求2所述的抗皱型TPU薄膜，其特征在于：所述环氧树脂为E-51、E-44、E-42双酚A环氧树脂中的一种。
5.根据权利要求1所述的抗皱型TPU薄膜，其特征在于：所述TPU基膜层包括由以下重量份的原料制成：TPU母粒85-95份、增韧剂0.5-10份和抗氧化剂1.5-8份；
所述增韧剂为质量比为1：（1-1.2）的乙烯-丙烯酸甲酯共聚物和甲基丙烯酸甲酯-丁二烯-苯乙烯三元共聚物的混合物。
6.根据权利要求5所述的抗皱型TPU薄膜，其特征在于：所述抗氧剂为抗氧剂1010和抗氧剂168的混合物，且抗氧剂1010和抗氧剂168的重量比为1：（1-3）。
7.根据权利要求5所述的抗皱型TPU薄膜，其特征在于：所述TPU颗粒是以二苯基甲烷-4,4-二异氰酸酯、聚四氢呋喃为基本原料进行预聚反应，在所述预聚反应时加入季铵盐类有机抗菌剂，再经过扩链反应和终止反应即得。
8.根据权利要求7所述的抗皱型TPU薄膜，其特征在于：所述季铵盐类有机抗菌剂为双羟基季铵盐。
9.抗皱型TPU复合面料，其特征在于：采用权利1-8所述的抗皱型TPU薄膜与基布复合而成，所述基布由碳纤维纱线编织而成的双层平纹织物。
10.权利要求9所述的抗皱型TPU复合面料的制备方法，其特征在于：包括以下步骤：
TPU基膜层：将TPU基膜层的原料进行混合，形成混合料；将所述混合料进行挤出、冷却、切粒得到预混颗粒；将所述预混颗粒进行挤出流延成型即可；
抗皱型TPU薄膜：将粘接层的原料进行混合并涂覆在所述TPU基膜层上即可；
抗皱型TPU复合面料：将所述抗皱型TPU薄膜与基布进行热压，冷却后即得成品。
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