CN103275570A - 含氟聚合物涂覆膜、用于形成所述涂覆膜的方法以及含氟聚合物液体组合物 - Google Patents

含氟聚合物涂覆膜、用于形成所述涂覆膜的方法以及含氟聚合物液体组合物 Download PDF

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CN103275570A
CN103275570A CN2013101371019A CN201310137101A CN103275570A CN 103275570 A CN103275570 A CN 103275570A CN 2013101371019 A CN2013101371019 A CN 2013101371019A CN 201310137101 A CN201310137101 A CN 201310137101A CN 103275570 A CN103275570 A CN 103275570A
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fluoropolymer
polymer
coating
polymkeric substance
binding agent
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CN103275570B (zh
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L.G.斯诺
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DuPont Electronics Inc
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EI Du Pont de Nemours and Co
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    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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Abstract

本发明公开了用于形成多层膜的方法，所述方法包括用液体含氟聚合物涂料来涂布聚合物基底膜。所述液体含氟聚合物涂料包含含氟聚合物、溶剂、相容的可交联粘合剂聚合物、和交联剂。所述方法还包括将相容的可交联粘合剂聚合物交联以在含氟聚合物涂层中形成交联聚合物网络，从含氟聚合物涂层中移除溶剂，并且使含氟聚合物涂层粘合到聚合物基底膜上。液体含氟聚合物涂料组合物包含含氟聚合物、溶剂、相容的可交联粘合剂聚合物、以及交联剂，所述含氟聚合物选自氟乙烯的均聚物和共聚物以及偏二氟乙烯的均聚物和共聚物。含氟聚合物涂覆膜包括聚合物基底膜和所述聚合物基底膜上的含氟聚合物涂层。所述含氟聚合物涂层包含含氟聚合物和相容的交联粘合剂聚合物。

Description

含氟聚合物涂覆膜、用于形成所述涂覆膜的方法以及含氟聚合物液体组合物
本申请是以下申请的分案申请：申请日2008年4月18日，申请号200880013042.1，发明名称“含氟聚合物涂覆膜、用于形成所述涂覆膜的方法以及含氟聚合物液体组合物”。 
技术领域
本公开涉及含氟聚合物涂覆膜、用于形成含氟聚合物涂覆膜的方法、以及含氟聚合物液体组合物。 
背景技术
光电(PV)电池可用于从阳光获得电能，从而提供可替代传统发电方法的更加环境友好的方法。这些太阳能电池由各种半导体系统构成，所述半导体系统必须被保护以隔绝环境影响，诸如水分、氧气和紫外光。所述电池的两面通常被玻璃和/或塑料薄膜包封层包封，从而形成被称为光电模块的多层结构。含氟聚合物薄膜由于它们极好的强度、耐候性、抗紫外性和防潮性而被认为是光电模块中的重要组件。在这些模块中，尤其可用的是由含氟聚合物薄膜和聚合物基底膜制成的薄膜复合材料，所述薄膜复合材料可用作所述模块的衬片。此类复合材料传统上由粘附在聚酯基底膜(具体地讲聚对苯二甲酸乙二醇酯)上的含氟聚合物预成形薄膜(具体地讲是聚氟乙烯(PVF))来制成。当含氟聚合物诸如PVF用作PV模块的衬片时，其特性显著改善模块的寿命，使模块能够保用最多25年。含氟聚合物衬片通常以与聚对苯二甲酸乙二醇酯(PET)薄膜的层压体形式使用，通常PET被夹在两个PVF薄膜之间。 
然而，难以制得在具有粘合力的聚合物基底上的、露天暴露若干年而不会分层的预成形含氟聚合物薄膜的层压体。现有技术体系诸如授予Simms 的美国专利3,133,854、授予Kim等人的美国专利5,139,878和授予Schmidt等人的美国6,632,518描述了用于预成形薄膜的可获得耐用层压体结构的底料和粘合剂。然而，这些方法需要在实际层压步骤之前施用至少一个粘合剂层，或者底料和粘合剂层两者。然后层压步骤需要施热和施压以形成层压体。因此，使用预成形含氟聚合物薄膜的现有技术层压体制备费用昂贵和/或需要耗资庞大的设备。由于预成形含氟聚合物薄膜必须具有足够的厚度来提供制造以及后续加工期间处理所需的强度，因此所得的层压体还可与含氟聚合物厚层合并，即，比有效保护层所需的厚度更厚。 
发明内容
本发明提供了涂布有含氟聚合物的聚合物基底膜，所述薄膜的总工序少于用预成形含氟聚合物薄膜制备层压体的总工序，同时还提供了对基底具有强粘附性和良好的耐久性的含氟聚合物涂覆膜。此外，提供涂料形式的含氟聚合物能够获得更薄、性价比更高的含氟聚合物涂层。使用含氟聚合物涂料还能够将添加剂掺入到为预期使用含氟聚合物涂覆膜而定制的含氟聚合物层中，例如可改善防护性能的填料。 
用于形成多层膜的方法包括用液体含氟聚合物涂料来涂布聚合物基底膜。所述液体含氟聚合物涂料包含含氟聚合物、溶剂、相容的可交联粘合剂聚合物以及交联剂，所述含氟聚合物选自氟乙烯的均聚物和共聚物以及偏二氟乙烯的均聚物和共聚物。所述方法还包括将相容的可交联粘合剂聚合物交联以在含氟聚合物涂层中形成交联聚合物网络，从所述含氟聚合物涂层中移除溶剂，并且将所述含氟聚合物涂层粘附到所述聚合物基底膜上。 
液体含氟聚合物涂料组合物包含含氟聚合物、溶剂、相容的可交联粘合剂聚合物以及交联剂，所述含氟聚合物选自氟乙烯的均聚物和共聚物以及偏二氟乙烯的均聚物和共聚物。 
含氟聚合物涂覆膜包括聚合物基底膜和所述聚合物基底膜上的含氟聚合物涂层。所述含氟聚合物涂层包含含氟聚合物和相容的交联粘合剂聚合物，所述含氟聚合物选自氟乙烯的均聚物和共聚物以及偏二氟乙烯的均聚物和共聚物。所述相容的交联粘合剂聚合物包含官能团，所述官能团选自羧酸、磺酸、氮丙啶、酸酐、胺、异氰酸酯、三聚氰胺、环氧、羟基、以及它 们的组合。所述聚合物基底膜包含与所述相容交联粘合剂聚合物相互作用以促进所述含氟聚合物涂层与所述聚合物基底膜粘合的官能团。 
以上综述以及以下发明详述仅出于示例性和说明性的目的，而不是对于本发明进行限制，本发明受所附权利要求的限定。 
具体实施方式
在第一方面，用于形成多层膜的方法包括用液体含氟聚合物涂料来涂布聚合物基底膜。所述液体含氟聚合物涂料包含含氟聚合物、溶剂、相容的可交联粘合剂聚合物以及交联剂，所述含氟聚合物选自氟乙烯的均聚物和共聚物以及偏二氟乙烯的均聚物和共聚物。所述方法还包括将相容的可交联粘合剂聚合物交联以在含氟聚合物涂层中形成交联聚合物网络，从所述含氟聚合物涂层中移除溶剂，并且将所述含氟聚合物涂层粘合到所述聚合物基底膜上。 
在第一方面的一个实施方案中，交联、移除和粘合可通过加热来进行。在更具体的实施方案中，所述含氟聚合物在分散体中为颗粒形式，并且加热还包括聚结所述含氟聚合物。在另一个更具体的实施方案中，加热为一次性加热。在更具体的实施方案中，加热还包括加热至约150℃至250℃范围内的温度。 
在第一方面的另一个实施方案中，所述相容的可交联粘合剂聚合物选自聚酯、聚碳酸酯、聚丙烯酸类、聚醚、乙烯乙烯醇共聚物、酰胺、丙烯酰胺、聚氨酯以及它们的组合。在更具体的实施方案中，所述相容的可交联粘合剂聚合物选自聚酯多元醇、聚碳酸酯多元醇、丙烯酸类多元醇、聚醚多元醇、乙烯乙烯醇共聚物、以及它们的组合。 
在第一方面的另一个实施方案中，交联所述相容的可交联粘合剂聚合物还包括形成聚氨酯网络。在第一方面的另一个实施方案中，所述交联剂包括异氰酸酯官能化化合物或封端异氰酸酯官能化化合物。 
在第一方面的另一个实施方案中，粘附包括在所述聚合物基底膜的官能团与所述相容的可交联粘合剂聚合物、所述交联剂或它们的组合之间形成粘结。 
在第一方面的另一个实施方案中，所述方法还包括在涂布之前将所述 聚合物基底膜改性，以提供能够与相容的可交联粘合剂聚合物、交联剂或它们的组合形成粘结的附加官能团。在更具体的实施方案中，改性包括使用表面活化方法。 
在第一方面的另一个实施方案中，涂布还包括用含氟聚合物涂料来涂布聚合物基底膜的两个表面。 
在第二方面，液体含氟聚合物涂料组合物包含含氟聚合物、溶剂、相容的可交联粘合剂聚合物、以及交联剂，所述含氟聚合物选自氟乙烯的均聚物和共聚物以及偏二氟乙烯的均聚物和共聚物。 
在第二方面的一个实施方案中，所述相容的可交联粘合剂聚合物包含官能团，所述官能团选自羧酸、磺酸、氮丙啶、酸酐、胺、异氰酸酯、三聚氰胺、环氧、羟基、以及它们的组合。在第二方面的另一个实施方案中，所述交联剂包含官能团，所述官能团选自羧酸、磺酸、氮丙啶、酸酐、胺、异氰酸酯、三聚氰胺、环氧、羟基、以及它们的组合。 
在第二方面的另一个实施方案中，所述交联剂还包括异氰酸酯官能化化合物或封端异氰酸酯官能化化合物。在第二方面的另一个实施方案中，所述含氟聚合物选自包含至少60摩尔％氟乙烯的氟乙烯的均聚物和共聚物以及包含至少60摩尔％偏二氟乙烯的偏二氟乙烯的均聚物和共聚物。 
在第二方面的另一个实施方案中，所述含氟聚合物涂料包含按含氟聚合物固体含量计约1至约40重量％的相容的可交联粘合剂聚合物。在第二方面的另一个实施方案中，所述含氟聚合物涂料还包含颜料。在具体的实施方案中，所述含氟聚合物涂料包含按含氟聚合物固体含量计约1至约35重量％的颜料。 
在第二方面的另一个实施方案中，所述含氟聚合物在溶剂中为分散体颗粒形式，并且所述溶剂包括二甲基乙酰胺、碳酸亚丙酯、丁内酯、N-甲基吡咯烷酮、二甲基亚砜、或它们的组合。 
在第三方面，含氟聚合物涂覆膜包括聚合物基底膜和所述聚合物基底膜上的含氟聚合物涂层。所述含氟聚合物涂层包含含氟聚合物和相容的交联粘合剂聚合物，所述含氟聚合物选自氟乙烯的均聚物和共聚物以及偏二氟乙烯的均聚物和共聚物。所述相容的交联粘合剂聚合物包含官能团，所述官能团选自羧酸、磺酸、氮丙啶、酸酐、胺、异氰酸酯、三聚氰胺、环氧、羟 基、以及它们的组合。所述聚合物基底膜包含与所述相容交联粘合剂聚合物相互作用以促进所述含氟聚合物涂层与所述聚合物基底膜粘合的官能团。 
在第三方面的一个实施方案中，所述相容的交联粘合剂聚合物选自聚酯、聚酯型聚氨酯、聚碳酸酯、聚碳酸酯型聚氨酯、聚丙烯酸类、丙烯酸型聚氨酯、聚醚、聚醚型聚氨酯、乙烯乙烯醇共聚物、乙烯乙烯醇共聚物型聚氨酯、聚酰胺、聚酰胺型聚氨酯、聚酰胺型脲、聚丙烯酰胺、聚丙烯酰胺型聚氨酯、以及它们的组合。在第三方面的另一个实施方案中，所述含氟聚合物涂层包括含氟聚合物与相容的交联粘合剂聚合物的互穿网络。 
在第三方面的另一个实施方案中，所述含氟聚合物选自包含至少60摩尔％氟乙烯的氟乙烯的均聚物和共聚物以及包含至少60摩尔％偏二氟乙烯的偏二氟乙烯的均聚物和共聚物。在第三方面的另一个实施方案中，所述含氟聚合物涂料包含按含氟聚合物固体含量计约1至约40重量％的相容的交联粘合剂聚合物。 
在第三方面的另一个实施方案中，所述含氟聚合物涂层包含颜料。在具体的实施方案中，所述含氟聚合物涂料包含按含氟聚合物固体含量计约1至约35重量％的颜料。 
在第三方面的另一个实施方案中，所述含氟聚合物涂层在所述聚合物基底膜的两面上。在第三方面的另一个实施方案中，所述聚合物基底膜还包括聚酯、聚酰胺、聚酰亚胺、或它们的任何组合。在具体的实施方案中，所述聚酯选自聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、以及它们的组合。 
在第三方面的另一个实施方案中，所述含氟聚合物涂层具有约0.1至约10.0密耳的厚度。在第三方面的另一个实施方案中，所述聚合物基底膜具有约0.5至约10密耳的厚度。 
在第三方面的另一个实施方案中，所述聚合物基底膜还包含填料。在第三方面的另一个实施方案中，光电模块的衬片包括所述含氟聚合物涂覆膜。 
许多方面和实施方案已在上文进行了描述，并且仅是示例性的而非限制性的。在读完本说明书后，技术人员应认识到，在不脱离本发明范围的情况下，其他方面和实施方案也是可能的。根据以下的发明详述和权利要求， 本发明的其他特点和优点将显而易见。 
含氟聚合物
根据本发明的一个方面，可用于所述含氟聚合物涂覆膜中的含氟聚合物选自氟乙烯(VF)的均聚物和共聚物以及偏二氟乙烯(VF2)的均聚物和共聚物。在一个实施方案中，所述含氟聚合物选自包含至少60摩尔％氟乙烯的氟乙烯的均聚物和共聚物以及包含至少60摩尔％偏二氟乙烯的偏二氟乙烯的均聚物和共聚物。在更具体的实施方案中，所述含氟聚合物选自包含至少80摩尔％氟乙烯的氟乙烯的均聚物和共聚物以及包含至少80摩尔％偏二氟乙烯的偏二氟乙烯的均聚物和共聚物。含氟聚合物与无氟聚合物例如丙烯酸类聚合物的共混物也适用于本发明某些方面的实践中。聚氟乙烯(PVF)均聚物和聚偏氟乙烯(PVDF)均聚物很好地适用于实施本发明的具体方面。选自聚氟乙烯均聚物和氟乙烯共聚物的含氟聚合物尤其有效地用于实施本发明。 
在一个实施方案中，共聚单体可用VF共聚物或VF2共聚物来氟化，或非氟化，或它们的组合。术语“共聚物”是指VF或VF2与任何数目的附加氟化单体单元的共聚物以形成二聚物、三聚物、四聚物等。如果使用非氟化单体，则应限制所用的量，以使所述共聚物保持所期望的含氟聚合物特性，即耐候性、耐溶剂性、防护性等。在一个实施方案中，所用的氟化共聚单体包括氟化的烯烃、氟化的乙烯基醚、或氟化的间二氧杂环戊烯。可用的氟化共聚单体的实例包括四氟乙烯(TFE)、六氟丙烯(HFP)、三氟氯乙烯(CTFE)、三氟乙烯、六氟异丁烯、全氟丁基乙烯、全氟(丙基乙烯基醚)(PPVE)、全氟(乙基乙烯基醚)(PEVE)、全氟(甲基乙烯基醚)(PMVE)、全氟-2，2-二甲基-1，3-二氧杂环戊烯(PDD)和全氟-2-亚甲基-4-甲基-1，3-氧杂环戊烷(PMD)等等。 
PVDF均聚物涂层可由高分子量PVDF形成。可使用PVDF与(甲基)丙烯酸烷基酯聚合物的共混物。聚甲基丙烯酸甲酯是尤其是理想的。通常，这些共混物可包含按重量计50-70％的PVDF和按重量计30-50％的(甲基)丙烯酸烷基酯聚合物，在具体的实施方案中为聚甲基丙烯酸甲酯。此类共混物可包含增容剂以及其它添加剂以稳定所述共混物。聚偏氟乙烯、或偏二氟乙烯共聚物、与作为主要组分的丙烯酸类树脂的此类共混物描述于美国专利 3,524,906、4,931,324和5,707,697中。 
PVF均聚物涂层可由高分子量PVF来形成。适宜的VF共聚物由授予Uschold的美国专利6,242,547和6,403,740提出。 
相容的可交联粘合剂聚合物和交联剂
根据本发明的一个方面，用于所述含氟聚合物涂覆膜中的相容的可交联粘合剂聚合物包含官能团，所述官能团选自羧酸、磺酸、氮丙啶、胺、异氰酸酯、三聚氰胺、环氧、羟基、酸酐、以及它们的组合。在一个实施方案中，所述相容的可交联粘合剂聚合物具有(1)与所述组合物中的含氟聚合物相容的主链组分，和(2)能够与基底膜表面上的互补官能团反应的侧链官能团。所述可交联粘合剂聚合物主链与所述含氟聚合物的相容性将有变化，但是足以使得所述相容的可交联粘合剂聚合物能够以所需的量被引入到所述含氟聚合物中，以将所述含氟聚合物涂层固定在所述聚合物基底膜上。然而一般而言，主要由氟乙烯和偏二氟乙烯衍生的均聚物和共聚物将显示出相容特性，所述相容特性将有利于丙烯酸类、聚氨酯、脂族聚酯、聚酯型聚氨酯、聚醚、乙烯乙烯醇共聚物、酰胺、丙烯酰胺、脲以及具有上述官能团的聚碳酸酯主链。 
衍生自丙烯酸类和丙烯酰胺单体的自由基加成聚合物非常适于使用大量可得的官能化单体来引入侧链官能团。某些代表性物质包括用于引入环氧基团的丙烯酸甘油醚酯和甲基丙烯酸甘油醚酯。然后通过环氧官能化丙烯酸类与氨或伯烷基胺的反应，可将这些转变成反应性氨基醇基团。分别使用丙烯酸类/甲基丙烯酸、甲基丙烯酸异氰酸基乙酯、甲基丙烯酸羟乙酯或马来酸酐可获得羧酸、异氰酸酯、羟基和酸酐官能团。如本领域所熟知，许多其它官能化单体可用于官能团的引入。 
在具体的实施方案中，其中聚合物基底膜为本身具有羟基和羧酸官能团的未改性聚酯，可在适宜交联剂(例如异氰酸酯官能化化合物或封端异氰酸酯官能化化合物)的存在下，使用反应性多元醇(例如聚酯多元醇、聚碳酸酯多元醇、丙烯酸类多元醇、聚醚多元醇等)作为相容的可交联粘合剂聚合物来将含氟聚合物涂层粘合到聚合物基底膜上。所述粘合可通过反应性多元醇、交联剂、或二者的官能团来产生。固化之后，在所述涂层中形成交联 聚氨酯网络作为与含氟聚合物的互穿网络。此外，据信所述交联聚氨酯网络还提供将所述含氟聚合物涂层粘合到所述聚酯基底膜上的官能团。 
本领域的技术人员将会明白，相容的可交联粘合剂聚合物和交联剂的选择可基于与含氟聚合物的相容性、与所选的含氟聚合物溶液或分散体的相容性、它们与用于在所选聚合物基底膜上形成含氟聚合物涂层的处理条件的相容性、它们在含氟聚合物涂层形成期间形成交联网络的能力、和/或在含氟聚合物涂层与聚合物基底膜之间形成提供强粘合性的粘附时它们的官能团与聚合物基底膜的那些官能团的相容性。 
众多交联剂与相容的可交联粘合剂聚合物的组合是可行的。实例包括胺官能化交联剂与环氧、酸酐或羧酸相容的可交联粘合剂聚合物、环氧官能化交联剂与羧酸或胺官能团相容的可交联粘合剂聚合物、氮丙啶官能化交联剂与羧酸、或胺官能团相容的可交联粘合剂聚合物、以及三聚氰胺交联剂与羟基官能团相容的可交联粘合剂聚合物。本领域的技术人员将能够根据处理时所用的聚合物体系的性质和最终多层膜所需的特性来选择相容的粘合剂聚合物与交联剂。 
颜料和填料
如果需要，可通过在制备期间将颜料和填料掺入到所述含氟聚合物涂料组合物分散体中来达到多种着色效果、不透明效果和/或其它特性效果。在一个实施方案中，按含氟聚合物固体的重量计约1至约35重量％的量来使用颜料。可使用的典型颜料包括透明颜料诸如无机硅质颜料(例如二氧化硅颜料)和常规颜料。可使用的常规颜料包括金属氧化物诸如二氧化钛、和氧化铁；金属氢氧化物；金属薄片诸如铝薄片；铬酸盐诸如铬酸铅；硫化物；硫酸盐；碳酸盐；炭黑；二氧化硅；滑石；陶土；酞菁蓝和酞菁绿、有机红色；有机栗色以及其它有机颜料和染料。在一个实施方案中，选择颜料的类型和用量，以防止对所期望的含氟聚合物涂层特性例如耐侯性产生任何显著的不利影响，并且选择在加工高温下稳定的颜料以在成膜期间使用。 
通过将颜料与分散树脂混合可将颜料配制成颜料浆，所述分散树脂可与待将颜料掺入到其中的含氟聚合物组合物相同或相容。颜料分散体可通过常规方法形成，诸如砂磨、球磨、磨碎机粉碎或双辊研磨。虽然通常不需要或不使用，但仍可掺入其它添加剂，诸如玻璃纤维和矿物填料、防滑剂、增 塑剂、成核剂等。 
抗紫外添加剂和热稳定剂
所述含氟聚合物涂料组合物可包含一种或多种光稳定剂作为添加剂。光稳定剂添加剂包括吸收紫外线辐射的化合物，诸如羟基二苯甲酮和羟基苯并三唑。其它可能的光稳定剂添加剂包括受阻胺光稳定剂(HALS)和抗氧化剂。如果需要，还可使用热稳定剂。 
阻挡颗粒
在一个实施方案中，所述含氟聚合物涂料组合物包含阻挡颗粒。在具体的实施方案中，所述颗粒为板形颗粒。此类颗粒在涂料施用期间趋于排列，并且由于水、溶剂和气体诸如氧气不易穿过颗粒自身，因此在所得的涂层中形成了机械屏障，所述屏障可降低水、溶剂和气体的渗透性。例如在光电模块中，所述阻挡颗粒可显著增加所述含氟聚合物的防潮特性，并且增强向太阳能电池提供的保护。在一些实施方案中，阻挡颗粒的含量按所述涂料中含氟聚合物组合物的总干重计为约0.5至约10重量％。 
典型的板形填料颗粒的实例包括云母、玻璃片和不锈钢薄片、以及铝薄片。在一个实施方案中，所述板形颗粒为云母颗粒，包括涂布有氧化物层诸如氧化铁或氧化钛的云母颗粒。在一些实施方案中，这些颗粒具有约10至200μm的平均粒度，在更具体的实施方案中，具有20至100μm的平均粒度，同时不超过50％的所述薄片的颗粒具有大于约300μm的平均粒度。涂布有氧化物层的云母颗粒在以下文献中有所描述：美国专利3,087,827(Klenke和Stratton)；3,087,828(Linton)；和3,087,829(Linton)。描述于这些专利中的云母涂布有下列金属的氧化物或水合氧化物：钛、锆、铝、锌、锑、锡、铁、铜、镍、钴、铬、或钒。也可使用涂布有云母的混合物。 
含氟聚合物液体涂料组合物制剂
所述含氟聚合物液体涂料组合物可包含含氟聚合物溶液或分散体形式的含氟聚合物。使用沸点足够高以避免在成膜/干燥处理期间形成气泡的溶剂来制备含氟聚合物的典型溶液或分散体。对于分散体形式的聚合物，有助于含氟聚合物聚结的溶剂是可取的。可调节所述聚合物在这些溶液或分散体中的浓度以获得所述溶液的适用粘度，并且所述浓度将随具体聚合物、所述 组合物中的其它组分、以及所用的加工设备和条件而变化。在一个实施方案中，对于溶液而言，所述含氟聚合物的含量按所述组合物的总重量计为约10重量％至约25重量％。在另一个实施方案中，对于分散体而言，所述含氟聚合物的含量按所述液体组合物的总重量计为约25重量％至约50重量％。 
所述聚合物在所述液体涂料组合物中的形式取决于所用含氟聚合物和溶剂的类型。PVF均聚物通常为分散体形式。根据所选的溶剂，PVDF均聚物可为分散体或溶液形式。例如在室温下，PVDF均聚物可在许多极性有机溶剂诸如酮、酯和某些醚中形成稳定的溶液。适宜的实例包括丙酮、甲基乙基酮(MEK)和四氢呋喃(THF)。根据共聚单体含量和所选的溶剂，VF和VF2的共聚物可以分散体或溶液形式使用。 
在使用聚氟乙烯(PVF)均聚物的一个实施方案中，使用含氟聚合物分散体来制备适宜的涂料制剂。分散体的性质和制备更详细地描述于美国专利2,419,008、2,510,783、和2,599,300中。在具体的实施方案中，在二甲基乙酰胺、碳酸亚丙酯、γ-丁内酯、N-甲基吡咯烷酮、或二甲基亚砜中形成PVF分散体。 
为了制备分散体形式的含氟聚合物液体涂料组合物，一般首先在适宜的溶剂中将含氟聚合物和相容的可交联粘合剂聚合物、交联剂、以及任选地一种或多种分散剂和/或颜料一起研磨。作为另外一种选择，可分别研磨或适当混合各种组分。可溶于所述溶剂中的组分不需要研磨。 
可使用多种研磨来制备所述分散体。通常，所述研磨在诸如球磨机、得自Union Process(Akron，Ohio)的
Figure BDA00003073058300101
或旋转媒介研磨机诸如得自Netzsch，Inc.(Exton，Pennsylvania)的“Netzsch”研磨机中，使用致密搅拌研磨剂诸如砂、钢丸、玻璃珠、陶瓷球、氧化锆、或卵石来进行。将所述分散体研磨足够的时间以将PVF解聚集。所述分散体在Netzsch研磨机中的典型保留时间在三十秒至最多十分钟的范围内。 
相容的可交联粘合剂聚合物在所述液体涂料组合物中的用量足以提供所需的对聚合物基底膜的粘结，但是低于将显著不利地影响含氟聚合物所期望特性的含量。在一个实施方案中，所述液体涂料组合物包含按所述含氟聚合物的重量计约1至约40重量％的相容的可交联粘合剂聚合物，在更具体 的实施方案中，包含约1至约25重量％的相容的可交联粘合剂聚合物，并且在更具体的实施方案中，包含1至约20重量％的相容的可交联粘合剂聚合物。 
所述交联剂在所述液体涂料组合物中的用量足以提供所需的对相容的可交联粘合剂聚合物的交联。在一个实施方案中，所述液体涂料组合物包含约50至约400摩尔％的交联剂每摩尔当量可交联粘合剂聚合物。在更具体的实施方案中，所述液体涂料组合物包含约75至约150摩尔％的交联剂每摩尔当量可交联粘合剂聚合物。在另一个更具体的实施方案中，所述液体涂料组合物包含约90至约125摩尔％的交联剂每摩尔当量可交联粘合剂聚合物。 
聚合物基底膜
用于本发明的聚合物基底膜可选自多种聚合物，所述聚合物具有的热塑性适于使得它们能够经受更高的加工温度。所述聚合物基底膜在其表面上包含与相容的可交联粘合剂聚合物、交联剂、或两者相互作用以促进含氟聚合物涂层与基底膜粘合的官能团。在一个实施方案中，所述聚合物基底膜为聚酯、聚酰胺或聚酰亚胺。在具体的实施方案中，用于聚合物基底膜的聚酯选自聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯以及聚对苯二甲酸乙二醇酯/聚萘二甲酸乙二醇酯的共挤出物。 
填料也可包含在基底膜中，其中它们的存在可改善所述基底的物理特性，例如更高的模量和拉伸强度。它们还可改善含氟聚合物与基底膜的粘合。一种示例性的填料是硫酸钡，然而也可使用其它的填料。 
待涂布的聚合物基底膜的表面可自然具有适于粘合的官能团，诸如聚酯薄膜中的羟基和/或羧酸基，或聚酰胺薄膜中的胺和/或酸官能团。聚合物基底膜的表面上存在的这些固有官能团通过简化将涂层结合到聚合物基底膜上以形成多层膜的过程而明确地提供了商业利益。本发明在可利用所述聚合物基底膜固有官能团的所述涂料组合物中使用相容的可交联粘合剂聚合物和/或交联剂。这样，未改性的聚合物基底膜可与含氟聚合物涂料化学粘合(即不使用单独的底漆层或粘合剂或单独的表面活化处理)，以形成具有极好粘附性的多层膜。如本专利申请中所用，术语“未改性聚合物基底膜”是指不包括底漆层或粘合剂并且不包括那些诸如下段所述的表面处理或表面活 化的那些聚合物基底。此外，未涂底漆的聚合物基底膜可与含氟聚合物涂料进行化学粘合以形成具有极好粘附性的多层膜。如本专利申请中所用，术语“未涂底漆的聚合物基底膜”是指不包括底漆层但是可包括诸如下段所述的那些表面处理或表面活化的聚合物基底。 
然而许多聚合物基底膜需要或将进一步受益于改性以提供适于粘合含氟聚合物涂层的附加官能团，并且这可通过表面处理或表面活化来实现。即，通过在表面上形成羧酸、磺酸、氮丙啶、胺、异氰酸酯、三聚氰胺、环氧、羟基、酸酐和/或它们的组合的官能团可使所述表面更具活性。在一个实施方案中，可通过化学接触诸如气态路易斯酸(诸如BF3)或硫酸或热氢氧化钠来实现表面的活化。作为另外一种选择，可通过使一个或两个表面接触明火同时冷却相反面来活化所述表面。还可通过使薄膜经历高频、火花放电诸如电晕处理、或氮气氛等离子体处理来实现表面活化。此外，还可通过在成膜时将相容的共聚单体掺入到聚合物基底中来实现表面活化。本领域的技术人员将会知道，有多种不同方法可用于在聚合物基底膜表面上形成相容的官能团。 
此外，可通过向聚合物基底膜的表面上施加底漆层以增加其表面官能度来进行改性以提供适于粘合含氟聚合物涂层的附加官能团，如2007年7月5日公布的DeBergalis等人的美国专利申请公布美国2007/0154704A1“FLUOROPOLYMER COATED FILMS USEFUL FOR PHOTOVOLTAIC MODULES”中所述。 
涂料施用
根据本发明的一个方面，可通过常规涂布方法将用于制备含氟聚合物涂覆膜的含氟聚合物组合物作为液体直接涂布在适宜的聚合物基底膜上而无需形成预成形薄膜。制备此类涂层的技术包括常规的浇铸、浸渍、喷雾和涂覆方法。当所述含氟聚合物涂料包含分散体形式的含氟聚合物时，通常通过使用常规装置诸如喷雾式、辊式、刮刀式、幕帘式、凹版印刷式涂布装置，或能够施用均匀涂层而无条痕或其它缺陷的任何其它方法，将所述分散体浇铸在基底膜上来施用。在一个实施方案中，压铸分散体的干燥涂层厚度介于约2.5μm(0.1密耳)至约250μm(10密耳)之间，在更具体的实施方案中，介于约13μm(0.5密耳)至约130μm(5密耳)之间。 
施用后，使相容的可交联粘合剂聚合物交联，去除溶剂，并且使含氟聚合物涂层粘附到聚合物基底膜上。对于其中所述含氟聚合物为溶液形式的一些组合物，所述液体含氟聚合物涂料组合物可被涂布在聚合物基底膜上，并且使其在环境温度下风干。虽然不需要制成聚结薄膜，但一般需要加热来交联相容的可交联粘合剂聚合物，并且使含氟聚合物涂层更快干燥。可在一次性加热中或通过多次加热来实施相容的可交联粘合剂聚合物的交联、溶剂的去除、以及含氟聚合物涂层与聚合物基底的粘合。干燥温度在约25℃(环境条件)至约200℃(烘箱温度-薄膜温度将较低)的范围内。所用温度还应足以促使相容的可交联粘合剂聚合物和/或交联剂中的官能团与聚合物基底膜的官能团交互作用，以提供含氟聚合物涂层与聚合物基底膜的牢固粘合。该温度随所用相容的可交联粘合剂聚合物和交联剂以及基底膜的官能团而广泛变化。干燥温度可在室温至烘箱温度范围内，所述烘箱温度超出如下所述的以分散体形式的含氟聚合物聚结所需的温度。 
当所述组合物中的含氟聚合物为分散体形式时，需要将溶剂去除，需要使相容的粘合剂聚合物发生交联，并且还需要将含氟聚合物加热至足够高的温度以使所述含氟聚合物颗粒聚结成连续的薄膜。此外，期望与聚合物基底膜粘合。在一个实施方案中，将涂料中的含氟聚合物的温度加热至约150℃至约250℃。期望所用溶剂可有助于聚结，即，能够采用比无溶剂存在情况下所需的温度更低的温度来使所述含氟聚合物涂层聚结。因此，用于聚结所述含氟聚合物的条件将随所用的含氟聚合物、压铸分散体和基底膜的厚度、以及其它操作条件而变化。对于PVF均聚物涂层和约1至约3分钟的停留时间，可使用340°F(171℃)至约480°F(249℃)的炉温来聚结所述薄膜，并且已发现，约380°F(193℃)至约450°F(232℃)的温度是尤其合适的。当然，烤炉空气温度不代表含氟聚合物涂层所达到的温度，其温度将低于所述烤炉空气温度。 
在聚结含氟聚合物的存在下形成相容的粘合剂聚合物的交联网络可导致形成相容的可交联粘合剂聚合物与含氟聚合物的互穿网络，从而产生互锁的网络结构。因此，即使在含氟聚合物涂层中存在两种聚合物网络的离析或相分离，并且在两种网络之间缺乏化学粘合，但是仍可形成坚固的耐久涂层。只要在相容的交联粘合剂聚合物与聚合物基底膜之间存在足够的粘合 力，就可在多层膜的各层之间获得极好的粘附性。 
将含氟聚合物涂料组合物施用到聚合物基底膜上。在一个实施方案中，所述聚合物基底膜为聚酯、聚酰胺、或聚酰亚胺。在具体的实施方案中，所述聚合物基底膜为聚酯诸如聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、或聚对苯二甲酸乙二醇酯/聚萘二甲酸乙二醇酯的共挤出物。在另一个实施方案中，将所述含氟聚合物涂料施用到所述基底膜的两面上。这可在所述聚合物基底膜的两面上同时实施，或作为另外一种选择，可使涂布的基底膜干燥，转至未涂布的面，并且再经受相同涂布头涂布，以将涂料施用到薄膜的相对面上，以在薄膜两面上获得涂层。 
光电模块
含氟聚合物涂覆膜尤其可用于光电模块中。光电模块的典型构造包括厚玻璃层作为覆盖材料。玻璃保护太阳能电池，所述太阳能电池包括结晶硅片和嵌入到防潮塑料密封化合物诸如交联乙烯乙酸乙烯酯中的电线。作为另外一种选择，薄膜太阳能电池可采用各种半导体材料进行包封，诸如CIGS(铜-铟-镓-硒化物)、CTS(镉-碲-硫化物)、a-Si(无定形硅)以及载体片上的其它材料，所述载体片的两面同样被包封材料包封。将衬片粘附到包封材料上。含氟聚合物涂覆膜可用于此类衬片中。所述含氟聚合物涂层包含含氟聚合物，所述含氟聚合物选自氟乙烯的均聚物和共聚物、以及与包含官能团的相容的可交联粘合剂聚合物共混的偏二氟乙烯聚合物的均聚物和共聚物，所述官能团选自羧酸、磺酸、氮丙啶、酸酐、胺、异氰酸酯、三聚氰胺、环氧、羟基、以及它们的组合。所述聚合物基底膜在其表面上包含与所述相容的可交联粘合剂聚合物相互作用以促进所述含氟聚合物涂层与所述基底膜粘合的官能团。在一个实施方案中，所述聚合物基底膜为聚酯，并且在更具体的实施方案中，聚酯选自聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯以及聚对苯二甲酸乙二醇酯/聚萘二甲酸乙二醇酯的共挤出物。聚酯提供电绝缘特性和防潮特性，并且是经济型衬片组件。在一些实施方案中，所述聚合物基底膜的两个表面均用含氟聚合物涂布，形成聚酯夹在两层含氟聚合物涂层之间的夹层结构。含氟聚合物薄膜向所述衬片提供极好的强度、耐候性、抗紫外性和防潮性。 
实施例
本文所描述的概念将在下列实施例中进一步描述，所述实施例不限制权利要求中描述的本发明的范围。 
测试方法
180度剥离强度
使用4201型Instron材料试验机，以2”/min的速率来测定剥离强度，记录峰值并且取3个样本的平均值(ASTM D1876-01T-剥离测试)。如果在剥离起始步骤期间样本易于用手剥离，则将值记为0。 
湿度箱剥离测试
在从湿度箱取出后，用剃刀和直尺切划样本，以获得1/4”宽的条痕。使用1”突出部作为柄部，并且使用缓慢均匀的张力，以大约180度角拉伸该突出部，直至薄膜破裂或剥离。薄膜在EVA/玻璃或EVA/含氟聚合物涂层界面处破裂和剥离被认为是结果合格。在含氟聚合物涂层与基底之间剥离被认为是不合格。 
十字切口粘附性
在从湿度箱取出后，借助不锈钢模板，用剃刀切划样本，以获得从薄膜至玻璃表面的间隔约3/32英寸(2.4mm)的11条平行切口。在与第一条切口成直角的方向重复此步骤，以获得由100个正方形构成的网格。将一条0.75英寸乘2.16英寸(1.9cm乘5.5cm)的透明胶带(3M牌No.467 PSA胶带)牢固地压贴在切划区域上，使透明带取向与切划线方向平行。然后以90°角将胶带快速拉离，但不是猛地拉离。含氟聚合物涂层与基底之间的任何失效被认为是不合格。 
聚酯型聚氨酯/PVF共混组合物
实施例1
实施例1显示了含氟聚合物涂层对未改性聚合物基底膜的粘附性。使用六亚甲基二异氰酸酯的异氰脲酸酯三聚体(N-3300，Bayer MaterialScience)，交联到PVF基含氟聚合物涂层中的多种聚酯二醇和三醇(
Figure BDA00003073058300162
Bayer MaterialScience)显示出对未改性PET的粘附性。表1中示出的聚酯是代表性的。 
表1：聚酯二醇和三醇。 
Figure BDA00003073058300163
EG＝乙二醇 
BD＝1，4-丁二醇 
HD＝1，6-己二醇 
NPG＝新戊二醇 
PG＝丙二醇 
TMP＝三羟甲基丙烷 
AA＝己二酸 
PA＝邻苯二甲酸 
步骤： 
1.使表1中示出的每一种聚酯与含42％固体的PVF在碳酸亚丙酯中的分散体(30份聚酯每100份PVF，使用含50％固体的聚酯在碳酸亚丙酯中的溶液)、相对于聚酯羟基含量而言一当量的
Figure BDA00003073058300164
N-3300(多异氰酸酯交联剂)、以及0.02份二月桂酸二丁基锡每100份PVF进行混合。 
2.在涂料摇动器上将所得的混合物摇动15分钟。 
3.使用12密耳涂布刀，将所述混合物涂布在未改性的3密耳 
Figure BDA00003073058300165
442PET薄膜(DuPont Teijin薄膜)上。 
4.沿着湿测试薄膜的一个边缘施加纯PVF分散体的浓珠，以便为烘焙之后的起始剥离提供帮助。 
5.使用框架来支撑涂覆膜，将所述涂覆膜在220C烘箱中烘焙5分钟。 
6.冷却后，纯PVF珠用于起始剥离，将样本切割成1英寸宽的条，并且用仪器测定剥离强度。 
所得的剥离强度示于表2中。 
表2：未改性PET上的粘附性结果。 
Figure BDA00003073058300171
实施例2
实施例2显示了相容的交联粘合剂聚合物组合物对未改性聚合物基底膜上的含氟聚合物涂层粘附性强度的影响。某些相容的交联粘合剂聚合物功效好于其它的，并且可在更低的浓度下促进粘合。表3示出了浓度在10和30份聚酯每100份PVF之间变化的F-2060B和S-101P-55聚酯的结果。表4示出了浓度为1至10份聚酯每100份PVF的
Figure BDA00003073058300173
F-2060B的结果。使用更厚重的PET纤维网、5密耳A(DuPont Teijin薄膜)来分别制备样本10至25。 
表3：粘附性对聚酯类型和浓度的敏感性。 
Figure BDA00003073058300181
表4：低浓度
Figure BDA00003073058300182
F-2060B聚酯制剂的粘附性结果。 
实施例3
实施例3显示了交联剂组合物对未改性聚合物基底膜上的含氟聚合物涂层粘附性强度的影响。表5示出了以
Figure BDA00003073058300184
N-3300交联剂用量为因变量的多种聚酯粘附性结果。使用等量或过量的交联剂获得最好的结果。 
表5：以交联剂浓度为因变量的粘附性 
Figure BDA00003073058300191
实施例4
实施例4进一步显示了交联剂组合物对未改性聚合物基底膜上的含氟聚合物涂层粘附性强度的影响。此外，该实施例显示了颜料对聚合物基底膜上的含氟聚合物涂层粘附性强度的影响。表6显示了与HMDI异氰脲酸酯三聚体(
Figure BDA00003073058300192
N-3300)或与HMDI缩二脲三聚体(
Figure BDA00003073058300193
N-75)交联的聚酯
Figure BDA00003073058300194
F-2060B的粘附性结果对比。结果表明，在该体系中，
Figure BDA00003073058300195
N-75同样可有效地促进粘附。样本46至55在3密耳 442纤维网上采用上文实施例1中描述的步骤，但是此外还包含45份白色颜料每100份PVF。 
表6：可供选择的交联剂。 
Figure BDA00003073058300201
聚碳酸酯型聚氨酯/PVF共混组合物
实施例5
实施例5进一步显示了以相容的交联粘合剂聚合物在所述含氟聚合物涂层中的组成为因变量的含氟聚合物涂层对未改性聚合物基底膜的粘附性。表7示出了当在未改性PET表面上形成时，聚碳酸酯型聚氨酯网络在PV基质上的粘附性结果。所述聚碳酸酯型聚氨酯衍生自聚碳酸酯二醇 
Figure BDA00003073058300202
C-2200(Bayer MaterialScience)与
Figure BDA00003073058300203
N-3300异氰酸酯官能化交联剂的反应。所用步骤与上文对聚酯型聚氨酯所述的那些相同。所有样本使用相对于聚碳酸酯二醇而言一当量的异氰酸酯交联剂，并且使用0.02份二月桂酸二丁基锡每100份PVF。C-2200为形式上衍生自1，6-己二醇与碳酸的分子量为2000的聚碳酸酯。结果表明，在低浓度聚碳酸酯型聚氨酯并且无颜料下具有强粘附性。 
表7：使用聚碳酸酯型聚氨酯共混物制剂的粘合性 
Figure BDA00003073058300205
实施例6
表8示出了在1份聚碳酸酯每100份PVF和相对于聚碳酸酯二醇而言一当量的交联剂下，将白色颜料加入到实施例5的聚碳酸酯型聚氨酯共混物制剂中的粘附性结果。结果清楚地表明，颜料可破坏与该制剂的粘合性粘结的形成。 
表8：与白色颜料的粘附性结果。 
Figure BDA00003073058300211
实施例7
表9显示了在允许存在颜料的情况下描述于实施例5和6中的制剂类型的粘附性结果。增加与大于一当量的异氰酸酯官能化交联剂组合的聚碳酸酯二醇的量，可制得耐颜料并且还在聚碳酸酯型聚氨酯/PVF共混物与未改性PET纤维网之间提供强粘附性粘结的制剂。在10份聚碳酸酯二醇和30份白色颜料下，在相对于聚碳酸酯二醇具有150至200摩尔％交联剂的范围内可获得最佳的粘结。 
表9：与颜料的粘附性结果。 
Figure BDA00003073058300212
实施例8
实施例8显示了在商业应用条件下的涂布方法。此外，该实施例显示了充分加热对形成持久粘结的重要性，所述粘结在光电衬片测试常用的伤害性加热和湿度条件下将继续存在。所有这些样本含有相对于PVF10份聚碳酸酯二醇(
Figure BDA00003073058300221
C-2200)与150或200摩尔％多异氰酸酯交联剂(
Figure BDA00003073058300222
N-3300)的组合。此外，每种样本使用0.02份二月桂酸二丁基锡催化剂和30份白色颜料每100份PVF。使用反转凹印方法将涂料混合物施用到未改性的3密耳PET纤维网(
Figure BDA00003073058300223
377)上，然后在3区域浮选烘箱中烘焙。在涂布前，将分别长5英尺的烘箱区域调节至300/350/430。线速度从5英尺每分钟变化至30英尺每分钟。 
然后使用手持式电火花处理机，在外表面上对所得的涂层进行电晕处理以与EVA粘结。通过使用光电产业常用的EVA包封树脂15295P/UF(Specialized Technology Resources，Inc.)与玻璃面板真空压合(10分钟真空+150℃下加压5分钟)来形成仿真光电模块。所得的面板具有下列构造： 
3密耳PET/1密耳涂层/26密耳EVA/125密耳玻璃面板。 
然后将以此方式制得的样本在85℃/85％湿度下暴露6周。在暴露0、2、4和6周时，进行剥离和十字切口测试。涂层与EVA之间的粘结过强，以致无法用手剥离。将止血钳夹在突出部上，然后扭曲以强制剥离。剥离测试结果示于表10中，十字切口测试结果示于表11中。 
表10：在湿度箱中暴露后的剥离测试。 
Figure BDA00003073058300224
表11：在湿度箱中暴露后的十字切口测试。 
应注意到的是，并不是所有的上文一般性描述或实施例中所描述的行为都是必须的，一部分具体行为不是必需的，并且除了所描述的那些以外，还可实施一个或多个其他行为。此外，所列行为的顺序不必是实施它们的顺序。在阅读本说明书后，技术人员将能确定其特定需要或需求所用的行为。 
在上述说明书中，已参考具体的实施方案描述了本发明。然而，本领域的普通技术人员认识到，在不脱离所附权利要求中所述的本发明范围的情况下，可进行一种或多种修改或一种或多种其他变化。因此，说明书和数字被认为是例证性的而非限制性的，并且所有此类修改和其他变化均旨在被包括在本发明的范围内。 
上文已结合一个或多个具体实施方案描述了任何一种或多种有益效果、一种或多种其他优点、一种或多种问题的一种或多种解决方案或它们的任何组合。然而，有益效果、优点、问题的解决方案、以及可致使任何有益效果、优点或解决方案产生或变得更显著的任何因素不可解释为是任何或所有权利要求的关键、必需或基本的特征或因素。 
应当理解，为清楚起见在参照不同实施方案的上文和下文中所描述的本发明的某些特点可在单个实施方案中以组合方式给出。反之，为简化起见而参照单个实施方案中描述的本发明的多个特点也可分别给出，或以任何子组合给出。此外，范围内描述的相关数值包括所述范围内的每个值。 

Claims (24)

1.用于形成多层膜的方法，所述方法包括：
用液体含氟聚合物涂料来涂布聚合物基底膜，其中所述液体含氟聚合物涂料包含：
含氟聚合物，所述含氟聚合物选自氟乙烯的均聚物和共聚物以及偏二氟乙烯的均聚物和共聚物；
溶剂；
相容的可交联粘合剂聚合物；和
交联剂；
将所述相容的可交联粘合剂聚合物交联以在所述含氟聚合物涂层中形成交联聚合物网络；
从所述含氟聚合物涂层中移除所述溶剂；并且
将所述含氟聚合物涂层粘附到所述聚合物基底膜上。
2.权利要求1的方法，其中交联、移除和粘附通过加热来进行。
3.权利要求2的方法，其中：
所述含氟聚合物为在分散体中的颗粒的形式；并且
加热还包括使所述含氟聚合物聚结。
4.权利要求2的方法，其中加热为一次性加热。
5.权利要求4的方法，其中加热包括加热至约150℃至250℃范围内的温度。
6.权利要求1的方法，其中所述相容的可交联粘合剂聚合物选自聚酯、聚碳酸酯、聚丙烯酸类、聚醚、乙烯乙烯醇共聚物、酰胺、丙烯酰胺、聚氨酯以及它们的组合。
7.权利要求6的方法，其中所述相容的可交联粘合剂聚合物选自聚酯多元醇、聚碳酸酯多元醇、丙烯酸类多元醇、聚醚多元醇、乙烯乙烯醇共聚物、以及它们的组合。
8.权利要求1的方法，其中交联所述相容的可交联粘合剂聚合物包括形成聚氨酯网络。
9.权利要求1的方法，其中所述交联剂包括异氰酸酯官能化化合物或封端异氰酸酯官能化化合物。
10.权利要求1的方法，其中粘附包括在所述聚合物基底膜的官能团与所述相容的可交联粘合剂聚合物、所述交联剂、或它们的组合之间形成粘结。
11.权利要求10的方法，其中所述聚合物基底膜是未涂底漆的聚合物基底膜。
12.权利要求10的方法，其中所述聚合物基底膜是未改性的聚合物基底膜。
13.权利要求10的方法，所述方法还包括在涂布之前将所述聚合物基底膜改性以提供能够与所述相容的可交联粘合剂聚合物、所述交联剂、或它们的组合形成粘结的附加官能团。
14.权利要求13的方法，其中改性包括使用表面活化方法。
15.权利要求1的方法，其中涂布包括用所述含氟聚合物涂料来涂布所述聚合物基底膜的两个表面。
16.液体含氟聚合物涂料组合物，所述组合物包含：
含氟聚合物，所述含氟聚合物选自氟乙烯的均聚物和共聚物以及偏二氟乙烯的均聚物和共聚物；
溶剂；
相容的可交联粘合剂聚合物；和
交联剂。
17.权利要求16的液体含氟聚合物涂料组合物，其中所述相容的可交联粘合剂聚合物包含官能团，所述官能团选自羧酸、磺酸、氮丙啶、酸酐、胺、异氰酸酯、三聚氰胺、环氧、羟基、以及它们的组合。
18.权利要求16的液体含氟聚合物涂料组合物，其中所述交联剂包含官能团，所述官能团选自羧酸、磺酸、氮丙啶、酸酐、胺、异氰酸酯、三聚氰胺、环氧、羟基、以及它们的组合。
19.权利要求16的液体含氟聚合物涂料组合物，其中所述交联剂包括异氰酸酯官能化化合物或封端异氰酸酯官能化化合物。
20.权利要求16的液体含氟聚合物涂料组合物，其中所述含氟聚合物选自包含至少60摩尔％氟乙烯的氟乙烯的均聚物和共聚物以及包含至少60摩尔％偏二氟乙烯的偏二氟乙烯的均聚物和共聚物。
21.权利要求16的液体含氟聚合物涂料组合物，其中所述含氟聚合物涂料包含按含氟聚合物固体含量计约1至约40重量％的所述相容的可交联粘合剂聚合物。
22.权利要求16的液体含氟聚合物涂料组合物，其中所述含氟聚合物涂料还包含颜料。
23.权利要求22的液体含氟聚合物涂料组合物，其中所述含氟聚合物涂料包含按含氟聚合物固体含量计约1至约35重量％的颜料。
24.权利要求16的液体含氟聚合物涂料组合物，其中所述含氟聚合物在所述溶剂中为分散体颗粒形式，并且所述溶剂包括二甲基乙酰胺、碳酸亚丙酯、丁内酯、N-甲基吡咯烷酮、二甲基亚砜、或它们的组合。
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