CN110431173A - 用于制备热塑性聚氨酯膜的方法和由此制备的热塑性聚氨酯膜 - Google Patents

用于制备热塑性聚氨酯膜的方法和由此制备的热塑性聚氨酯膜 Download PDF

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Publication number
CN110431173A
CN110431173A CN201880018745.7A CN201880018745A CN110431173A CN 110431173 A CN110431173 A CN 110431173A CN 201880018745 A CN201880018745 A CN 201880018745A CN 110431173 A CN110431173 A CN 110431173A
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polyurethane resin
isocyanates
thermoplastic polyurethane
curing agent
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CN201880018745.7A
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CN110431173B (zh
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李相圪
洪周希
朴世贞
金相还
金章淳
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LG Chem Ltd
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LG Chem Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

本发明涉及用于制备具有大的厚度和优异的耐久性的热塑性聚氨酯膜的方法以及由此制备的热塑性聚氨酯膜。

Description

用于制备热塑性聚氨酯膜的方法和由此制备的热塑性聚氨 酯膜
技术领域
本说明书要求于2017年3月20日向韩国知识产权局提交的韩国专利申请第10-2017-0034801号的优先权和权益，其全部内容通过引用并入本文。
本发明涉及具有大的厚度的热塑性聚氨酯膜及其制备方法。
背景技术
热塑性聚氨酯(TPU)膜在诸如强度、拉伸特性、韧性和耐磨性的机械特性方面是优异的，并因此主要用于汽车领域。
通常，通过将挤出并模制的聚氨酯丸粒溶解在溶剂中来制备聚氨酯溶液，并通过将聚氨酯溶液施加在基底上来制备热塑性聚氨酯膜。然而，由于具有高分子量的聚氨酯丸粒无法很好地溶解在溶剂中，因此制备的聚氨酯溶液的固体内容物的含量为约15％或更低的低值。由于可能无法将具有低含量的固体内容物的聚氨酯溶液施加在基底上以具有预定的厚度或更大的厚度，因此存在难以制备厚的聚氨酯膜的问题。此外，由于难以在聚氨酯丸粒上进行另外的聚合反应，因此存在不易控制由聚氨酯溶液制备的热塑性聚氨酯膜的物理特性的问题，并且存在为了使具有高分子量的聚氨酯丸粒溶解而必须使用剧毒溶剂的问题。
此外，在汽车领域中需要具有优异的耐久性和使用寿命特性的热塑性聚氨酯膜。
因此，需要能够通过在使用具有高分子量的聚氨酯树脂的同时使用低毒性溶剂制备具有大的厚度和优异的耐久性的热塑性聚氨酯膜的技术。
发明内容
技术问题
本发明致力于提供具有大的厚度和优异的耐久性的热塑性聚氨酯膜及其制备方法。
然而，本发明要解决的技术问题不限于上述问题，并且本领域技术人员从以下描述中可以清楚地理解未提及的另一些问题。
技术方案
本发明的一个示例性实施方案提供了用于制备热塑性聚氨酯膜的方法，所述方法包括：制备包含聚氨酯树脂、第一基于异氰酸酯的固化剂和有机溶剂的聚氨酯树脂组合物；通过将聚氨酯树脂组合物施加在基底膜上以及对聚氨酯树脂组合物进行热处理来制备包括聚氨酯树脂层的层合体；提供两个层合体以使其接合，使得层合体中的各自的聚氨酯树脂层彼此面对；以及通过使接合的层合体老化来形成包括彼此直接接触的两个聚氨酯树脂层的热塑性聚氨酯膜，其中两个聚氨酯树脂层之间的界面粘合强度为14MPa至18MPa。
本发明的另一个示例性实施方案提供了热塑性聚氨酯膜，其包括彼此直接接触的两个聚氨酯树脂层，其中两个聚氨酯树脂层之间的界面粘合强度为14MPa至18MPa，以及聚氨酯树脂层包含聚氨酯树脂组合物的固化产物，所述聚氨酯树脂组合物包含聚氨酯树脂、第一基于异氰酸酯的固化剂和有机溶剂。
有益效果
根据本发明的一个示例性实施方案的用于制备热塑性聚氨酯膜的方法可以容易地制备具有大的厚度和优异的耐久性的热塑性聚氨酯膜。
根据本发明的一个示例性实施方案的热塑性聚氨酯膜可以具有大的厚度和优异的耐久性。
本发明的效果不限于上述效果，并且本领域技术人员从本申请的说明书和附图中将清楚地理解未提及的效果。
附图说明
图1是示出根据本发明的一个示例性实施方案的用于制备热塑性聚氨酯膜的方法的示意图。
图2是示意性地示出根据本发明的一个示例性实施方案的测量聚氨酯树脂层之间的界面粘合强度的实验的视图。
具体实施方式
在本申请的整个说明书中，当一个部分“包括”一个构成要素时，除非另外具体描述，否则这并不意指排除另外的构成要素，而是意指还可以包括另外的构成要素。
在本申请的整个说明书中，当一个构件设置在另一个构件“上”时，这不仅包括一个构件与另一个构件接触的情况，而且还包括在这两个构件之间存在又一构件的情况。
在本申请的整个说明书中，单位“重量％”可以意指构件中包含的组分基于构件的总重量的重量比。
在本申请的整个说明书中，单位“重量份”可以意指相应组分之间的重量比。
在本申请的整个说明书中，术语“聚合单元”可以意指单体在聚合物中反应的形式，并且具体地，可以意指聚合物进行聚合反应以形成聚合物的骨架(例如，主链或侧链)的形式。
在本申请的整个说明书中，化合物的“重均分子量”和“数均分子量”可以通过使用化合物的分子量和分子量分布来计算。具体地，通过将四氢呋喃(THF)和化合物放入1ml玻璃瓶来制备其中化合物的浓度为1重量％的样品试样，将标准试样(聚苯乙烯)和样品试样通过过滤器(孔径为0.45mm)过滤，然后通过将试样注入GPC注射器中来将样品试样的洗脱时间与标准试样的校准曲线进行比较，从而获得化合物的分子量和分子量分布。在这种情况下，可以使用Infinity II 1260(由Agilent Inc.制造)作为测量装置，并且流量和柱温可以分别设定为1.00mL/分钟和40.0℃。
在下文中，将更详细地对本说明书进行描述。
本发明的一个示例性实施方案提供了用于制备热塑性聚氨酯膜的方法，所述方法包括：制备包含聚氨酯树脂、第一基于异氰酸酯的固化剂和有机溶剂的聚氨酯树脂组合物；通过将聚氨酯树脂组合物施加在基底膜上并对聚氨酯树脂组合物进行热处理来制备包括聚氨酯树脂层的层合体；提供两个层合体以使它们接合，使得层合体中的各自的聚氨酯树脂层彼此面对；以及通过使接合的层合体老化来形成包括彼此直接接触的两个聚氨酯树脂层的热塑性聚氨酯膜，其中两个聚氨酯树脂层之间的界面粘合强度为14MPa至18MPa。
根据本发明的一个示例性实施方案的用于制备热塑性聚氨酯膜的方法可以容易地制备具有大的厚度和优异的耐久性的热塑性聚氨酯膜。具体地，通过提供彼此直接接触的两个聚氨酯树脂层，可以制备具有更大厚度和改善的耐久性的热塑性聚氨酯膜。此外，彼此直接接触的两个聚氨酯树脂层之间的界面粘合强度为14MPa至18MPa，并且可以有效地抑制两个聚氨酯树脂层彼此剥离。包括具有优异的界面粘合强度的两个聚氨酯树脂层的热塑性聚氨酯膜可以具有优异的耐久性和使用寿命特性。
根据本发明的一个示例性实施方案，基于100重量份的聚氨酯树脂，第一基于异氰酸酯的固化剂的含量可以大于5重量份且小于7.5重量份，或者为5.5重量份至7.25重量份。通过将第一基于异氰酸酯的固化剂的含量调节在上述范围内，可以改善两个聚氨酯树脂层之间的界面粘合强度和热塑性聚氨酯膜的耐久性。
根据本发明的一个示例性实施方案，第一基于异氰酸酯的固化剂可以包含二至六个异氰酸酯官能团。例如，第一基于异氰酸酯的固化剂可以包括以下中的至少一者：H12MDI，其是Evonik Industries制造的双官能的基于异氰酸酯的固化剂；MHG-80B，其是Asahi Kasei Chemicals Corporation制造的六官能的基于异氰酸酯的固化剂；MFA-100，其是Asahi Kasei Chemicals Corporation制造的六官能的基于异氰酸酯的固化剂；和TKA-100，其是Asahi Kasei Chemicals Corporation制造的三官能的基于异氰酸酯的固化剂。
根据本发明的一个示例性实施方案，聚氨酯树脂可以通过在有机溶剂中进行混合物的共聚反应来制备，所述混合物包含：数均分子量为1800g/mol至2200g/mol的多元醇；含有具有4至10个碳原子的二醇的扩链剂；和第二基于异氰酸酯的固化剂。
根据本发明的一个示例性实施方案，聚氨酯树脂可以是包含软链段和硬链段的嵌段共聚物。具体地，聚氨酯树脂的软链段可以包含衍生自多元醇和第二基于异氰酸酯的固化剂的聚合单元，以及聚氨酯树脂的硬链段可以包含衍生自扩链剂和第二基于异氰酸酯的固化剂的聚合单元。
根据本发明的一个示例性实施方案，多元醇的数均分子量可以为1800g/mol至2200g/mol、1950g/mol至2050g/mol、或1900g/mol至2100g/mol。当多元醇的数均分子量在上述范围内时，可以抑制热塑性聚氨酯膜的伸长率降低。
根据本发明的一个示例性实施方案，多元醇可以是含有两个羟基的二醇。具体地，多元醇可以包括聚碳酸酯二醇、聚己内酯二醇、聚酯二醇和聚醚二醇中的一种或更多种。
根据本发明的一个示例性实施方案，基于混合物的重量，多元醇的含量可以为45重量％至55重量％。具体地，基于混合物的重量，多元醇的含量可以为48重量％至54重量％或50重量％至53重量％。通过将混合物中多元醇的含量调节在上述范围内，可以稳定地进行聚氨酯树脂的聚合反应，并且可以改善热塑性聚氨酯膜的可加工性。
根据本发明的一个示例性实施方案，扩链剂可以包含具有4至10个碳原子的二醇、或具有4至6个碳原子的二醇。包含具有在上述范围内的碳原子的二醇的扩链剂可以有效地使第二基于异氰酸酯的固化剂的链延伸。具体地，扩链剂可以包括以下中的至少一者：1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、1,10-癸二醇、1,1-环己烷二甲醇和1,4-环己烷二甲醇。
根据本发明的一个示例性实施方案，基于混合物的重量，扩链剂的含量可以为10重量％至15重量％，具体地为10.5重量％至14重量％、或12重量％至12.5重量％。通过将混合物中扩链剂的含量调节在上述范围内，可以有效地改善聚氨酯树脂的重均分子量。此外，当扩链剂的含量在上述范围内时，扩链剂可以与第二基于异氰酸酯的固化剂反应以有效地形成聚氨酯树脂的硬链段，并且可以改善所制备的热塑性聚氨酯膜的机械特性。
根据本发明的一个示例性实施方案，第二基于异氰酸酯的固化剂可以包含二至六个异氰酸酯官能团。具体地，第二基于异氰酸酯的固化剂可以包含两个异氰酸酯官能团。例如，第二基于异氰酸酯的固化剂可以包括以下中的至少一者：异佛尔酮二异氰酸酯(IPDI)、亚甲基二苯基-4,4'-二异氰酸酯、4,4'-亚甲基双环己基二异氰酸酯、二甲苯二异氰酸酯(XDI)、萘-1,5-二异氰酸酯和环己烷二异氰酸酯。
根据本发明的一个示例性实施方案，基于混合物的重量，第二基于异氰酸酯的固化剂的含量可以为32.5重量％至40重量％。具体地，基于混合物的重量，第二基于异氰酸酯的固化剂的含量可以为34重量％至38重量％或35重量％至36.5重量％。通过将第二基于异氰酸酯的固化剂的含量调节在上述范围内，可以有效地聚合聚氨酯树脂，并且可以改善所制备的热塑性聚氨酯膜的可加工性和耐久性。
根据本发明的一个示例性实施方案，混合物还可以包含催化剂，并且基于100重量份的混合物，催化剂的含量可以为0.005重量份至0.02重量份或0.008重量份至0.015重量份。通过将催化剂的含量调节在上述范围内，可以有效地促进聚氨酯树脂的聚合反应，并且可以在相对低的温度下聚合聚氨酯树脂。作为催化剂，可以使用本领域中使用的催化剂而没有限制，例如，可以使用二月桂酸二丁基锡(DBTDL)。
根据本发明的一个示例性实施方案，构成用作扩链剂的二醇的碳原子的数目小于构成多元醇的碳原子的数目，使得混合物中的二醇具有比多元醇的流动性更高的流动性。因此，在混合物中，扩链剂与第二基于异氰酸酯的固化剂的反应可以比多元醇与第二基于异氰酸酯的固化剂的反应更早地发生。具体地，当使用丁二醇作为扩链剂时，丁二醇的两个羟基中的一个羟基与第二基于异氰酸酯的固化剂的异氰酸酯基反应并键合，并且同时重复进行丁二醇的未反应羟基与第二基于异氰酸酯的固化剂的新的异氰酸酯基键合的过程，可以形成具有长延伸链结构的第二基于异氰酸酯的固化剂。此后，具有长延伸链结构的第二基于异氰酸酯的固化剂可以与多元醇反应以形成具有增加的重均分子量的聚氨酯树脂。
根据本发明的一个示例性实施方案，聚氨酯树脂的重均分子量可以为40000g/mol至70000g/mol。通过调节多元醇的数均分子量、用作扩链剂的二醇的碳原子数、混合物中多元醇的含量、扩链剂的含量、第二基于异氰酸酯的固化剂的含量等，可以控制聚氨酯树脂的重均分子量。通过调节聚氨酯树脂的重均分子量，可以容易地控制热塑性聚氨酯膜的物理特性例如拉伸强度和耐久性。
根据本说明书的一个示例性实施方案，共聚反应可以在50℃至70℃的温度下进行。通过将聚合反应温度调节在上述范围内，可以稳定地聚合聚氨酯树脂。此外，由于可以在相对低的温度下聚合聚氨酯树脂，因此可以降低热塑性聚氨酯膜的制备成本和制备时间。
根据本发明的一个示例性实施方案，聚氨酯树脂的聚合反应可以在有机溶剂中进行。当使用水性溶剂以制备热塑性聚氨酯膜时，需要将氨基甲酸酯颗粒加工成直径为几十纳米至几百纳米的珠粒形式并分散在水性溶剂上。在这种情况下，由于需要使用添加剂例如各种表面活性剂和单体以有效地使氨基甲酸酯颗粒分散在水性溶剂中，因此存在制备热塑性聚氨酯膜的过程变得复杂，及其制备时间和制备成本增加的问题。
相比之下，根据本发明的一个示例性实施方案，由于聚氨酯树脂处于溶解在有机溶剂中的状态，因此不需要向氨基甲酸酯组合物中添加基于分散稳定剂的添加剂，例如另外的分散剂和表面活性剂。因此，可以降低热塑性聚氨酯膜的制备时间和制备成本。
根据本发明的一个示例性实施方案，有机溶剂可以包括以下中的至少一者：丙酮、甲基乙基酮、甲基异丁基酮、环己烷、甲苯、二甲苯、乙二醇单甲醚(甲基溶纤剂)和乙二醇单***(乙基溶纤剂)。由于在聚氨酯树脂的聚合期间使用的上述种类的有机溶剂几乎没有毒性，因此可以通过使用这些有机溶剂来防止使用者的人体和环境受到有害影响。
根据本发明的一个示例性实施方案，可以通过使混合物在有机溶剂中反应来制备包含聚氨酯树脂和有机溶剂的组合物，并且可以通过向该组合物中添加第一基于异氰酸酯的固化剂来制备聚氨酯树脂组合物。即，聚氨酯树脂组合物的有机溶剂可以是在制备聚氨酯树脂期间使用并保留的有机溶剂。此外，可以向聚氨酯树脂组合物中添加另外的有机溶剂。
根据本发明的一个示例性实施方案，基于100重量份的聚氨酯树脂，有机溶剂的含量可以为30重量份至80重量份。通过将有机溶剂的含量调节在上述范围内，可以抑制聚氨酯树脂组合物在对聚氨酯树脂组合物进行热处理的步骤中快速干燥，导致有机溶剂膨胀的现象，并且可以防止热塑性聚氨酯膜的厚度减小。
根据本发明的一个示例性实施方案，聚氨酯树脂组合物的固体内容物的含量可以为20％至70％，具体地，30％至60％、或40％至55％。在本说明书中，“固体内容物”可以意指整个溶液中除溶剂之外的溶质或固体物质，并且具体地，聚氨酯树脂组合物的固体内容物可以统称为除有机溶剂之外的聚氨酯树脂、第一基于异氰酸酯的固化剂和添加剂(例如催化剂)。当聚氨酯树脂组合物的固体内容物的含量在上述范围内时，可以将聚氨酯树脂组合物厚厚地施加在基底上，并因此，可以制备具有大的厚度的热塑性聚氨酯膜。
图1是示出根据本发明的一个示例性实施方案的用于制备热塑性聚氨酯膜的方法的示意图。参照图1，可以通过对施加在基底膜上的聚氨酯树脂组合物进行热处理来制备包括聚氨酯树脂层20和20'以及基底膜10和10'的两个层合体100和100'。可以通过将层合体100和100'中包括的两个聚氨酯树脂层20和20'布置成彼此面对并使两个层合体100和100'接合来使两个聚氨酯树脂层20和20'彼此粘附。此后，可以通过使层合体老化来制备热塑性聚氨酯膜200。此后，可以另外地除去两个基底膜10和10'。
根据本发明的一个示例性实施方案，将聚氨酯树脂组合物施加在基底膜上的方法没有特别限制，例如，可以使用以下中的任一种方法：喷涂、凹版涂覆、微凹版涂覆、辊涂、柔版涂覆、丝网涂覆、旋涂、流涂、刮刀涂覆、喷嘴涂覆、旋转丝网涂覆、反向棒涂、逗号涂覆、唇式涂覆(lip coating)和模涂(die coating)。
根据本发明的一个示例性实施方案，通过对施加在基底膜上的聚氨酯树脂组合物进行热处理来在基底膜上形成聚氨酯树脂层，从而制备层合体。具体地，可以通过将聚氨酯树脂组合物施加在基底膜上至20μm至500μm的厚度并对聚氨酯树脂组合物进行热处理来在基底膜上形成厚度为10μm至250μm的聚氨酯树脂层。在对施加在基底膜上的聚氨酯树脂组合物进行热处理的过程中，随着包含在聚氨酯树脂组合物中的有机溶剂挥发，所形成的聚氨酯树脂层的厚度可以减小。因此，可以考虑聚氨酯树脂层的厚度随着有机溶剂挥发而减小来调节施加在基底膜上的聚氨酯树脂组合物的厚度。
根据本发明的一个示例性实施方案，聚氨酯树脂组合物可以在100℃至150℃的温度下进行热处理。通过将热处理温度条件调节在上述范围内，可以通过使包含在聚氨酯树脂组合物中的有机溶剂有效地挥发来形成聚氨酯树脂层。此外，通过在上述温度范围内对聚氨酯树脂组合物进行热处理，可以抑制聚氨酯树脂组合物快速干燥，导致有机溶剂膨胀的现象，并且可以抑制在所制备的聚氨酯树脂层中发生黄变现象。
根据本发明的一个示例性实施方案，可以在80℃至140℃的温度下使层合体接合。具体地，准备通过上述方法提供的两个层合体，将两个层合体堆叠使得各自的聚氨酯树脂层彼此面对，并在上述温度范围内将聚氨酯树脂层加热，从而使两个层合体接合。当将聚氨酯树脂层加热，并因此聚氨酯树脂层的温度达到玻璃化转变温度时，其中两个聚氨酯树脂层彼此接触的表面熔化，因此，粘度可以增加。因此，两个聚氨酯树脂层彼此粘附，并且两个粘附的聚氨酯树脂层可以是不容易剥离的。
因此，根据本发明的一个示例性实施方案的用于制备热塑性聚氨酯膜的方法可以在不使用粘合剂或粘合膜的情况下通过使两个聚氨酯树脂层粘附来制备具有大的厚度的热塑性聚氨酯膜。
此外，可以在80℃至140℃、80℃至130℃或100℃至120℃的温度下使层合体接合。通过将使层合体接合的温度调节在上述温度范围内，可以有效地改善两个聚氨酯树脂层之间的界面粘合强度。此外，通过在上述温度条件下使两个层合体接合，可以抑制聚氨酯树脂层过度熔化而从基底膜流出，导致热塑性聚氨酯膜的厚度减小。
根据本发明的一个示例性实施方案，可以通过本领域中使用的方法使两个层合体接合来使两个聚氨酯树脂层彼此直接粘附。例如，可以通过在使两个层合体通过在80℃至140℃下加热的两个压辊之间的同时使两个层合体接合来使两个聚氨酯树脂层彼此粘附。
根据本发明的一个示例性实施方案，可以在20℃至60℃的温度下使接合的层合体老化12小时至24小时。具体地，可以在25℃至55℃、20℃至35℃或40℃至50℃的温度下使接合的层合体老化。
通过在上述温度和时间条件下使两个聚氨酯树脂层老化，可以更有效地改善两个聚氨酯树脂层之间的界面粘合强度。在使包括两个粘附的聚氨酯树脂层的层合体老化的过程中，存在于其中两个聚氨酯树脂层彼此接触的表面上的聚氨酯树脂可以另外进行固化并彼此粘合。因此，可以更加改善两个聚氨酯树脂层之间的粘合强度。
此外，由于层合体中包括的聚氨酯树脂层是半固化的，因此可以通过使两个粘附的聚氨酯树脂层老化来制备最终固化的热塑性聚氨酯膜。在使接合的层合体老化的过程中，聚氨酯树脂层中包含的聚氨酯树脂可以与第一基于异氰酸酯的固化剂反应，使得可以增加聚氨酯树脂的重均分子量。此外，保留在半固化的聚氨酯树脂层中的少量的多元醇、扩链剂和第二基于异氰酸酯的固化剂之间可以进行另外的反应。
根据本发明的一个示例性实施方案，所述方法还可以包括在使接合的层合体老化之后，除去基底膜。
根据本发明的一个示例性实施方案，除基底之外的热塑性聚氨酯膜的厚度可以为20μm至500μm。具体地，热塑性聚氨酯膜的厚度可以为40μm至450μm、100μm至300μm或200μm至450μm。即，与现有的聚氨酯膜相比，用于制备热塑性聚氨酯膜的方法可以提供具有大的厚度的热塑性聚氨酯膜。
本发明的另一个示例性实施方案提供了包括彼此直接接触的两个聚氨酯树脂层的热塑性聚氨酯膜，其中两个聚氨酯树脂层之间的界面粘合强度为14MPa至18MPa，以及聚氨酯树脂层包含聚氨酯树脂组合物的固化产物，所述聚氨酯树脂组合物包含聚氨酯树脂、第一基于异氰酸酯的固化剂和有机溶剂。
根据本发明的一个示例性实施方案的热塑性聚氨酯膜可以通过上述用于制备热塑性聚氨酯膜的方法制备。
根据本发明的一个示例性实施方案的热塑性聚氨酯膜可以具有大的厚度和优异的耐久性。具体地，热塑性聚氨酯膜包括设置成彼此直接接触的两个聚氨酯树脂层，并因此与已有的聚氨酯膜相比可以具有大的厚度。
此外，两个聚氨酯树脂层之间的界面粘合强度可以为14MPa至18MPa、15MPa至17MPa、14MPa至16MPa、或16.5MPa至18MPa。包括满足上述范围内的界面粘合强度的两个聚氨酯树脂层的热塑性聚氨酯膜可以具有优异的耐久性和使用寿命特性。
根据本发明的一个示例性实施方案，基于100重量份的聚氨酯树脂，第一基于异氰酸酯的固化剂的含量可以大于5重量份且小于7.5重量份或者为5.5重量份至7.25重量份。通过将第一基于异氰酸酯的固化剂的含量调节在上述范围内，可以提供包括具有优异的界面粘合强度的两个聚氨酯树脂层的热塑性聚氨酯膜。
根据本发明的一个示例性实施方案，聚氨酯树脂可以是混合物的共聚物，所述混合物包含：数均分子量为1800g/mol至2200g/mol的多元醇；含有具有4至10个碳原子的二醇的扩链剂；和第二基于异氰酸酯的固化剂。
根据本发明的一个示例性实施方案，聚氨酯树脂的重均分子量可以为40000g/mol至70000g/mol。通过调节聚氨酯树脂的重均分子量，可以容易地控制热塑性聚氨酯膜的物理特性例如拉伸强度和耐久性。
热塑性聚氨酯膜中的多元醇、扩链剂、第一基于异氰酸酯的固化剂、第二基于异氰酸酯的固化剂、有机溶剂、催化剂等可以与上述用于制备热塑性聚氨酯膜的方法中使用的多元醇、扩链剂、第一基于异氰酸酯的固化剂、第二基于异氰酸酯的固化剂、有机溶剂、催化剂等相同。
根据本发明的一个示例性实施方案，基于混合物的重量，多元醇的含量可以为45重量％至55重量％，具体地，48重量％至54重量％、或50重量％至53重量％。通过将混合物中多元醇的含量调节在上述范围内，可以改善热塑性聚氨酯膜的可加工性。
根据本发明的一个示例性实施方案，基于混合物的重量，扩链剂的含量可以为10重量％至15重量％。具体地，基于混合物的重量，扩链剂的含量可以为10.5重量％至14重量％或12重量％至12.5重量％。通过将混合物中扩链剂的含量调节在上述范围内，扩链剂可以与第二基于异氰酸酯的固化剂反应以有效地形成聚氨酯树脂的硬链段，并且可以改善所制备的热塑性聚氨酯膜的机械特性。
根据本发明的一个示例性实施方案，基于混合物的重量，第二基于异氰酸酯的固化剂的含量可以为32.5重量％至40重量％，具体地，34重量％至38重量％、或35重量％至36.5重量％。通过将第二基于异氰酸酯的固化剂的含量调节在上述范围内，可以有效地聚合聚氨酯树脂，并且可以改善所制备的热塑性聚氨酯膜的可加工性和耐久性。
根据本发明的一个示例性实施方案，混合物还可以包含催化剂，并且基于100重量份的混合物，催化剂的含量可以为0.005重量份至0.02重量份或0.008重量份至0.015重量份。通过将催化剂的含量调节在上述范围内，可以有效地促进聚氨酯树脂的聚合反应，并且可以在相对低的温度下聚合聚氨酯树脂。
根据本发明的一个示例性实施方案，基于100重量份的聚氨酯树脂，有机溶剂的含量可以为30重量份至80重量份。通过将有机溶剂的含量调节在上述范围内，可以控制聚氨酯树脂组合物的固体内容物的含量，并且可以改善聚氨酯树脂组合物的可涂覆性。
根据本发明的一个示例性实施方案，聚氨酯树脂组合物的固体内容物的含量可以为20％至70％。具体地，聚氨酯树脂组合物的固体内容物的含量可以为30％至60％、或40％至55％。当聚氨酯树脂组合物的固体内容物的含量在上述范围内时，可以将聚氨酯树脂组合物厚厚地施加在基底膜上，并且可以在基底膜上形成具有大的厚度的聚氨酯树脂层。
根据本发明的一个示例性实施方案，热塑性聚氨酯膜的厚度可以为20μm至500μm。具体地，由两个聚氨酯树脂层组成的热塑性聚氨酯膜的厚度可以为40μm至450μm、100μm至300μm或200μm至450μm。即，与现有的聚氨酯膜相比，热塑性聚氨酯膜可以具有大的厚度。
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100：层合体
10、10'：基底膜
20、20'：聚氨酯树脂层
200：热塑性聚氨酯膜
300：用于测量界面粘合强度的实验装置发明实施方式
在下文中，将参照用于具体地描述本发明的实施例详细地对本发明进行描述。然而，根据本发明的实施例可以以各种形式进行修改，并且不应理解为本发明的范围受限于下面描述的实施例。本说明书的实施例是为了向本领域普通技术人员更完整地解释本发明而提供。
实施例1
聚氨酯树脂组合物的制备
准备作为多元醇的数均分子量为2050g/mol的聚碳酸酯二醇(PCDL，Asahi KaseiChemicals Corporation)、作为扩链剂的1,4-丁二醇(1,4BD，由BASF SE制造)、作为第一基于异氰酸酯的固化剂的含有两个异氰酸酯官能团的H12MDI(由Evonik Industries制造)、作为第二基于异氰酸酯的固化剂的异佛尔酮二异氰酸酯(IPDI，由Evonik Industries制造)、作为催化剂的二月桂酸二丁基锡(DBTDL)、和作为有机物溶剂的甲基乙基酮。此后，制备其中多元醇的含量为约52.6重量％，扩链剂的含量为约12.3重量％，以及第二基于异氰酸酯的固化剂的含量为约35.1重量％的混合物，并通过将100重量份的混合物与约50重量份的有机溶剂混合来制备混合溶液。
将制备的混合溶液装入反应器中并加热至55℃，并在保持该温度的同时向100重量份的混合物中添加0.005重量份的催化剂。通过使所得混合物在57℃下反应25小时来制备包含重均分子量为约51000g/mol的聚氨酯树脂的组合物。此后，通过向组合物中添加基于100重量份的所制备的聚氨酯树脂的约7重量份的第一基于异氰酸酯的固化剂，制备聚氨酯树脂组合物。制备的聚氨酯树脂组合物的固体内容物的含量为约45％。
热塑性聚氨酯膜的制备
将制备的聚氨酯树脂组合物施加在作为基底膜的聚对苯二甲酸乙二醇酯(PET)膜上至约200μm的厚度。此后，通过在100℃下对聚氨酯树脂组合物进行热处理，制备其中在基底膜上形成有厚度为95μm的聚氨酯树脂层的层合体。通过相同的方法制备另一个层合体，并布置层合体使得两个层合体的各自的聚氨酯树脂层彼此面对。此后，通过使两个层合体通过加热至100℃的一对压辊之间以使层合体接合来使两个聚氨酯树脂层彼此粘附。此后，使接合的层合体在25℃的温度下老化24小时，然后从层合体上除去PET膜，从而制备厚度为约190μm的热塑性聚氨酯膜。
实施例2至5
以与实施例1中相同的方式制备热塑性聚氨酯膜，不同之处在于，如下表1中调节用于使层合体接合的温度和用于使接合的层合体老化的温度。
比较例1至5
以与实施例1中相同的方式制备热塑性聚氨酯膜，不同之处在于，如下表1中调节用于使层合体接合的温度和用于使接合的层合体老化的温度。
测量聚氨酯树脂层之间的界面粘合强度的实验
以与实施例1中相同的方式制备根据实施例1的热塑性聚氨酯膜的样品，不同之处在于制备各自的尺寸为15cm宽度和2.5cm长度的两个层合体，仅使两个层合体的宽度7.5cm和长度2.5cm的部分接合，并且其他部分未接合。此外，以与上述方法中相同的方式制备根据实施例2至5和比较例1至5的各样品。
通过使用极限拉伸机(UTM，型号3343，由INSTRON Inc.制造)测量根据实施例1至5和比较例1至5的样品的聚氨酯树脂层之间的界面粘合强度。
图2是示意性地示出根据本发明的一个示例性实施方案的测量聚氨酯树脂层之间的界面粘合强度的实验的视图。
如图2所示，在将根据实施例1的样品中的两个聚氨酯树脂层20和20′的彼此未粘附的端部固定至UTM 30，并拉伸端部的同时，在两个聚氨酯树脂层彼此剥离的时间点测量施加在样品上的拉伸强度。以与上述方法中相同的方式测量根据实施例2至5和比较例1至5的样品的聚氨酯树脂层之间的界面粘合强度，并且结果示于下表1中。
[表1]
用于老化的温度(℃) 用于接合的温度(℃) 界面粘合强度(Mpa)
实施例1 25 100 14.1
实施例2 25 120 15.8
实施例3 50 80 15.6
实施例4 50 100 15.9
实施例5 50 120 16.5
比较例1 -20 60 5.2
比较例2 -20 80 9.2
比较例3 -20 100 10.1
比较例4 -20 120 12.5
比较例5 25 60 11.1
参照表1，确定在其中层合体在80℃至140℃的温度下接合，并且接合的层合体在20℃至60℃的温度下老化的实施例1至5中，两个聚氨酯树脂层之间的界面粘合强度为14MPa至18MPa。
相比之下，确定在其中层合体在60℃的温度下接合的比较例1和5中，两个聚氨酯树脂层之间的界面粘合强度较差。另外，确定在其中接合的层合体在-20℃的温度下老化的比较例2至4中，即使在将使层合体接合的温度调节为80℃至140℃的情况下，两个聚氨酯树脂层之间的界面粘合强度也较差。
因此，可以看出，根据本发明的一个示例性实施方案的用于制备热塑性聚氨酯膜的方法通过包括具有优异的界面粘合强度的两个聚氨酯树脂层而可以容易地制备具有优异的使用寿命特性和耐久性以及大的厚度的热塑性聚氨酯膜。

Claims (16)

1.一种用于制备热塑性聚氨酯膜的方法，所述方法包括：
制备包含聚氨酯树脂、第一基于异氰酸酯的固化剂和有机溶剂的聚氨酯树脂组合物；
通过将所述聚氨酯树脂组合物施加在基底膜上以及对所述聚氨酯树脂组合物进行热处理来制备包括聚氨酯树脂层的层合体；
提供两个层合体以使其接合，使得所述层合体的各自的聚氨酯树脂层彼此面对；以及
通过使接合的层合体老化来形成包括彼此直接接触的两个聚氨酯树脂层的热塑性聚氨酯膜，
其中所述两个聚氨酯树脂层之间的界面粘合强度为14MPa至18MPa。
2.根据权利要求1所述的方法，其中所述热处理在100℃至150℃的温度下进行。
3.根据权利要求1所述的方法，其中在80℃至140℃的温度下使所述层合体接合。
4.根据权利要求1所述的方法，其中在20℃至60℃的温度下使所述接合的层合体老化12小时至24小时。
5.根据权利要求1所述的方法，其中基于100重量份的所述聚氨酯树脂，所述第一基于异氰酸酯的固化剂的含量大于5重量份且小于7.5重量份。
6.根据权利要求1所述的方法，其中所述第一基于异氰酸酯的固化剂包含二至六个异氰酸酯官能团。
7.根据权利要求1所述的方法，其中所述聚氨酯树脂通过在有机溶剂中进行混合物的共聚反应来制备，所述混合物包含：数均分子量为1800g/mol至2200g/mol的多元醇；含有具有4至10个碳原子的二醇的扩链剂；和第二基于异氰酸酯的固化剂。
8.根据权利要求7所述的方法，其中所述共聚反应在50℃至70℃的温度下进行。
9.根据权利要求7所述的方法，其中基于所述混合物的重量，所述多元醇的含量为45重量％至55重量％。
10.根据权利要求7所述的方法，其中基于所述混合物的重量，所述扩链剂的含量为10重量％至15重量％。
11.根据权利要求7所述的方法，其中基于所述混合物的重量，所述第二基于异氰酸酯的固化剂的含量为32.5重量％至40重量％。
12.根据权利要求1所述的方法，其中所述聚氨酯树脂组合物的固体内容物的含量为20％至70％。
13.根据权利要求1所述的方法，其中所述热塑性聚氨酯膜的厚度为20μm至500μm。
14.一种热塑性聚氨酯膜，包括彼此直接接触的两个聚氨酯树脂层，
其中所述两个聚氨酯树脂层之间的界面粘合强度为14MPa至18MPa，以及
所述聚氨酯树脂层包含聚氨酯树脂组合物的固化产物，所述聚氨酯树脂组合物包含聚氨酯树脂、第一基于异氰酸酯的固化剂和有机溶剂。
15.根据权利要求14所述的热塑性聚氨酯膜，其中所述聚氨酯树脂是混合物的共聚物，所述混合物包含：数均分子量为1800g/mol至2200g/mol的多元醇；含有具有4至10个碳原子的二醇的扩链剂；和第二基于异氰酸酯的固化剂。
16.根据权利要求14所述的热塑性聚氨酯膜，其中所述热塑性聚氨酯膜的厚度为20μm至500μm。
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