CN104220255A - 多层膜和包括该多层膜的光伏组件 - Google Patents

多层膜和包括该多层膜的光伏组件 Download PDF

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CN104220255A
CN104220255A CN201180063818.2A CN201180063818A CN104220255A CN 104220255 A CN104220255 A CN 104220255A CN 201180063818 A CN201180063818 A CN 201180063818A CN 104220255 A CN104220255 A CN 104220255A
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polymer
methyl
fluorine
multilayer film
oxazoline group
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CN104220255B (zh
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金贤哲
权润京
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LG Chem Ltd
LG Corp
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LG Chemical Co Ltd
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Abstract

本发明提供了一种多层膜，用于光伏组件的背板，制备该多层膜的方法和包括所述多层膜的光伏组件。可以设置所述多层膜，从而使包含基于氟的聚合物和含有噁唑啉基团的聚合物的树脂层形成在基板上。因此，包含基于氟的聚合物的树脂层可以具有优异的耐久性和耐候性，并且对基板显示高的界面粘结强度。在所述多层膜的制备过程中，在相对低的温度下还可以进行干燥步骤，从而可以降低制造成本并且可以防止由于热变形或热冲击导致的产品质量劣化。所述多层膜可以被有效地用作用于多种光伏组件的背板。

Description

多层膜和包括该多层膜的光伏组件
技术领域
本公开涉及一种多层膜，用于光伏组件的背板，制备该多层膜的方法和包括所述多层膜的光伏组件。
背景技术
近来，由于全球环境问题和化石燃料的枯竭，已经大量关注可再生能源和清洁能源。其中，作为能够解决环境污染和化石燃料枯竭的问题的无污染能源的代表，太阳能引起了人们的广泛重视。
光伏电池是应用光伏发电的原理将太阳光转换成电能而制造的装置。由于光伏电池需长期暴露在户外以利于吸收太阳光，通过一些封装工艺其可以被制造成单元从而保护光伏电池。所述单元被称作光伏组件。
一般而言，具有优异耐候性和耐久性的背板被用于光伏组件以稳定地保护长期暴露于外部环境中的光伏电池。这种背板通常包含层叠在基板上的其中包含基于氟的聚合物(例如聚氟乙烯(PVF))的树脂层。
然而，所述PVF树脂对通常用作背板的基板的聚对苯二甲酸乙二酯(PET)膜具有差的粘结力。因此，使用基于聚氨酯的粘合剂将通过挤出或铸塑得到的基于氟的聚合物膜层压在基板上。然而，这需要使用昂贵的制膜设备，粘合剂和额外的粘合剂涂布和层压工艺。此外，在制备膜的过程中应该使用具有比为便于处理所述膜的所需厚度更厚的膜，各种添加剂和填料的使用受到限制，且需要高处理温度。
另一方面，甚至当将被制成树脂悬浮液或溶液形式的基于氟的聚合物膜涂布在基板上并干燥时，通常使用具有高沸点的溶剂，而因此需要200℃以上的高的干燥温度。
使用大量的能源以给予PVF树脂溶液高温热量，其需要高的干燥温度。因此，这增加了用于光伏组件的背板的制造成本，还使基板承受热冲击或导致基板的热变形，因此降低了产品的质量(例如，机械特征等)以及在长期户外使用过程中使机械性能劣化。
因此，一直需求用于光伏电池的背板的材料，其具有优异的耐久性和耐候性，并且可以在低的干燥温度下干燥，从而可以降低制造成本，并且可以提高光伏组件的产率和质量。
发明内容
技术问题
本公开的实施方式涉及提供一种多层膜，用于光伏组件的背板，制备该多层膜的方法和包括所述多层膜的光伏组件。
技术方案
所述实施方式的一个方面提供了一种多层膜，其包括：基板；和树脂层，其在所述基板上形成并包含基于氟的聚合物和含有噁唑啉基团的聚合物。
所述实施方式的另一方面提供了一种制造多层膜的方法，包括：在基板上形成树脂层，该树脂层包含基于氟的聚合物和含有噁唑啉基团的聚合物。
所述实施方式的又一方面提供了用于光伏组件的背板，其包括根据本申请的一个说明性实施方式的多层膜。
所述实施方式的再一方面提供了包括用于根据本申请的光伏组件的背板的光伏组件。
参照所附的附图，下面将详细地描述本申请的说明性实施方式。为了帮助理解本发明，在附图的全部说明书中，相似的附图标记指的是相似的元件，并且将不再重复相同的元件的描述。
本申请的一个说明性实施方式涉及提供包括基板和在所述基板上形成的树脂层的多层膜。所述树脂层包含基于氟的聚合物和含有噁唑啉基团的聚合物。
图1为显示根据一个说明性实施方式的多层膜的剖视图。如在图1中所示，所述多层膜10包括基板12和在所述基板12上形成的树脂层11。在本文中，所述树脂层11包含基于氟的聚合物和含有噁唑啉基团的聚合物。
在所述多层膜10中包括的基板12的具体的类型不受特别限制，但是可以包括本领域内已知的多种材料。因此，根据所需的功能和用途可以适当地选择并使用这些材料。
根据一个说明性实施方式，例如，多种金属膜或聚合物膜可以被用作基板。这样，根据用途所述金属膜可以包括由金属成分(例如，铝或铁)形成的膜，以及所述聚合物膜可以包括单片，层叠的片或共挤出的产物，例如丙烯醛基膜、聚烯烃膜、聚酰胺膜、聚氨酯膜或聚酯膜。其中，通常使用聚酯膜，但是本申请并不特别限于此。聚酯膜的实例包括选自PET膜、聚萘二酸乙二酯(PEN)膜和聚对苯二甲酸乙二酯(PBT)膜中的至少一种，但是本申请并不特别限于此。
此外，具有优异的耐水解性的聚酯膜可以被用作聚酯膜。可以用于本申请中的具有优异的耐水解性的聚酯膜可以包括具有低含量的在缩聚过程中产生的低聚物的聚酯膜。此外，通过进一步使聚酯膜经历用于提高耐水解性的已知的热处理可以赋予所述聚酯膜更优异的耐水解性，从而可以降低在聚酯中的湿气的含量，并且可以减小收缩率。市售可得的产品也可以被用作具有优异的耐水解性的聚酯膜。
根据说明性实施方式，如在下文中描述，为了提高对树脂层的粘结强度，可以使所述基板的一个或两个表面经历如下表面处理：例如，高频火花放电处理，如电晕或等离子体处理；热处理；火焰处理；锚固剂处理；偶联剂处理；底漆处理；或使用气态路易斯酸（如BF3）、硫酸或热的氢氧化钠的化学活化处理。表面处理可以使用本领域已知的所有的通用方法进行。
根据所述说明性实施方式，上述表面处理可以将羧基、芳族巯基和酚羟基引入到基板的表面上以提高与在树脂层中包含的噁唑啉基团的结合性，从而进一步提高基板与树脂层之间的亲合力。
此外，也可以在所述基板的一个或两个表面上形成无机氧化物沉积层以提高湿气阻隔性能。无机氧化物的种类不受特别限制，但是可以使用具有湿气阻隔性能的无机氧化物而不受限制。根据说明性实施方式，例如，氧化硅或氧化铝可以被用作无机氧化物，但是本申请不特别限于此。根据说明性实施方式，在所述基板的一个表面或两个表面上形成无机氧化物沉积层的方法不受特别限制，但是使用本领域已知的通用的沉积方法可以实现。
根据说明性实施方式，当在所述基板的一个表面或两个表面上形成无机氧化物沉积层时，在所述基板的表面上可以形成无机氧化物沉积层，以及然后可以使所述无机氧化物沉积层经历上述表面处理。
所述基板的厚度不受特别限制，但是可以为，例如，在50μm至500μm，或在100μm至300μm的范围内。当将基板的厚度控制在该厚度范围内时，所述多层膜可以显示优异的电绝缘性能、湿气阻隔性能、机械性能和处理性能。然而，所述基板的厚度并不限于该范围，可依需适当地调整。
根据说明性实施方式的多层膜包括在所述基板上形成的树脂层，以及所述树脂层包含基于氟的聚合物和含有噁唑啉基团的聚合物。当除了基于氟的聚合物之外，所述树脂层包含含有噁唑啉基团的聚合物时，可以提高所述基板与树脂层之间的粘结强度。也就是，可以选择具有与基于氟的聚合物的优异的相容性的含有噁唑啉基团的聚合物以促进在所述树脂层中与基于氟的聚合物的混合，并起到通过噁唑啉基团提高对基板的粘结强度的作用。
根据说明性实施方式，与含有噁唑啉的聚合物混合以形成所述多层膜的树脂层的基于氟的聚合物的种类可以为，例如，包含选自聚合形式的偏二氟乙烯(VDF)、氟化乙烯(VF)、四氟乙烯(TFE)、六氟丙烯(HFP)、氯三氟乙烯(CTFE)、三氟乙烯、六氟异丁烯、全氟丁基乙烯、全氟(甲基乙烯基醚)(PMVE)、全氟(乙基乙烯基醚)(PEVE)、全氟(丙基乙烯基醚)(PPVE)、全氟(己基乙烯基醚)(PHVE)、全氟-2,2-二甲基-1,3-二氧杂环戊烯(perfluoro-2,2-dimethyl-1,3-dioxol)(PDD)和全氟-2-亚甲基-4-甲基-1,3-二氧戊烷(PMD)中的至少一种单体的均聚物、共聚物或其混合物。
此外，基于氟的聚合物为包含VDF和共聚单体的共聚物或包含VF和共聚单体的共聚物。在基于氟的共聚物中可以以共聚形式包含的共聚单体的种类不受特别限制，但是可以包括选自例如，TFE、HFP、CTFE、三氟乙烯、六氟异丁烯、全氟丁基乙烯、PMVE、PEVE、PPVE、PHVE、PDD和PMD中的至少一种。作为一个实例，所述共聚单体可以为HFP和CTFE中的一种。
根据说明性实施方式，在基于氟的共聚物中的所述共聚单体的含量不受特别限制，但是可以为，例如，相对于基于氟的共聚物的总重量，在0.5wt%至50wt%，1wt%至40wt%，7wt%至40wt%，10wt%至30wt%，或10wt%至20wt%的范围内。根据说明性实施方式，当包含在基于氟的共聚物中的共聚单体的含量控制在该范围内时，可以确保所述多层膜的耐久性和耐候性，并且可以诱导有效的互扩散和低温干燥。
根据本申请的说明性实施方式，所述基于氟的聚合物可以具有50,000至1,000,000、100,000至700,000或300,000至500,000的重均分子量，但是本申请并不特别限于此。重均分子量为在使用凝胶渗透色谱法(GPC)测量时由聚苯乙烯标准转化得到的值。根据说明性实施方式，当将所述基于氟的聚合物的重均分子量控制在该范围内时，可以确保优异的溶解性和其它物理性能。
根据本申请的一些说明性实施方式，所述基于氟的共聚物包括：i)第一基于氟的共聚物，其具有155℃以下的熔点或100℃以下的软化点。由于这样的第一基于氟的聚合物特别地具有与含有噁唑啉基团的聚合物的良好的相容性，所述第一基于氟的聚合物可以起到提高所述多层膜的耐久性的作用。此外，除了所述第一基于氟的聚合物之外，所述基于氟的聚合物可以进一步包含ii)第二基于氟的聚合物，其具有155℃以上的熔点和100℃以上的软化点。然而，如有必要，可以任选地使用第二基于氟的聚合物。
所述第一和第二基于氟的聚合物对应于上述基于氟的聚合物，并且可以根据熔点和软化点分类，其为在基于氟的单体的聚合过程中的材料的固有特征。具有155℃以下的熔点和100℃以下的软化点的第一基于氟的聚合物可以占整个树脂层中基于氟的共聚物的20wt%以上，或50wt%以上。所述第一基于氟的聚合物的熔点的下限不受特别限制，但是可以为80℃以上。此外，所述第二基于氟的聚合物的熔点的上限不受特别限制，但是可以为175℃以下。根据本申请，可以控制基于氟的聚合物的熔点或软化点，从而可以提高与含有噁唑啉基团的聚合物的混合性，可以防止由使用多层膜引起的变形，也可以调节在溶剂中的溶解性，和可以提高涂布表面的光泽。在为水性分散组合物的情况下，也可以选择具有低熔点的并且在低温下熔融的基于氟的聚合物颗粒，从而在多层膜的制备过程中，可以得到均匀涂布的外观，可以防止在多层膜中包含的基板的劣化。
根据说明性实施方式，与基于氟的聚合物混合以形成多层膜的含有噁唑啉基团的聚合物的种类不受特别限制。然而，可以使用含有噁唑啉基团的聚合物而不受限制，只要它们具有与基于氟的聚合物的优异的相容性即可。根据说明性实施方式，例如，含有噁唑啉基团的单体的单一的聚合物；包含含有噁唑啉基团的单体和至少一种共聚单体的共聚物；或其混合物可以被用作含有噁唑啉基团的聚合物，但是本申请并不特别限于此。
可以在本文中使用的含有噁唑啉基团的单体可以为由下面通式1表示的化合物。
通式1
在通式1中，R1、R2、R3和R4各自独立地表示氢原子、烷基、卤素或取代或未取代的苯基，以及R5表示具有未取代键的无环烃基团。
用于取代的或未取代的苯基的取代基可以包括选自氨基、甲基、氯甲基和氯代基团中的至少一种。
此外，具有未取代键的无环烃基团可以包含可以与无环烃基团自由基聚合的链烯基、炔基或烯烃基团，但是本申请并不特别限于此。
所述链烯基可以为，例如，具有1至12个碳原子或1至5个碳原子的链烯基，所述炔基可以为，例如，具有1至12个碳原子或1至5个碳原子的炔基，以及所述烯烃基团可以为，例如，具有1至12个碳原子或1至5个碳原子的烯烃基团，但是本申请并不特别限于此。
根据说明性实施方式，由通式1表示的化合物的具体的实例可以包括2-乙烯基-2-噁唑啉、2-乙烯基-4-甲基-2-噁唑啉、2-乙烯基-5-甲基-2-噁唑啉、2-异丙烯基-2-噁唑啉、2-异丙烯基-4-甲基-2-噁唑啉和2-异丙烯基-5-乙基-2-噁唑啉中的至少一种，但是本申请并不特别限于此。
在根据所述说明性实施方式的包含含有噁唑啉基团的单体和至少一种共聚单体的共聚物中，基于所述共聚物的总重量，可以包含1wt%以上，5wt%至95wt%或10wt%至90wt%量的含有噁唑啉基团的单体。当所述含有噁唑啉基团的单体以小于1wt%的量存在于根据本申请的包含含有噁唑啉基团的单体和至少一种共聚单体的聚合物中时，难以赋予所述基板与底漆层之间足够的粘结强度。
在本申请的说明性实施方式中，在包含含有噁唑啉基团的单体和至少一种共聚单体的共聚物中以聚合形式包含的共聚单体的种类不受特别限制，可以使用不与噁唑啉基团反应但是可与含有噁唑啉基团的单体共聚合的共聚单体而不受限制。根据说明性实施方式，所述共聚单体可以包括选自，例如，(甲基)丙烯酸烷基酯、含酰胺基团的单体、基于不饱和腈的单体、基于乙烯基酯的单体、基于乙烯基醚的单体、含卤素的α,β-不饱和单体和α,β-不饱和芳族单体中的至少一种，但是本申请并不限于此。
所述(甲基)丙烯酸烷基酯可以包含具有1至14个碳原子的烷基以平衡与基于氟的聚合物的相容性，并赋予优异的压敏粘合性能。例如，所述（甲基）丙烯酸烷基酯可以包括选自（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸仲丁酯、（甲基）丙烯酸叔丁酯、（甲基）丙烯酸异丁酯、（甲基）丙烯酸己酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸正辛酯、（甲基）丙烯酸异辛酯、（甲基）丙烯酸正壬酯、（甲基）丙烯酸异壬酯、（甲基）丙烯酸正癸酯、（甲基）丙烯酸异癸酯、（甲基）丙烯酸正十二烷基酯、（甲基）丙烯酸正十三烷基酯和（甲基）丙烯酸正十四烷基酯中的至少一种。
在本申请的说明性实施方式中，含酰胺基基团的单体的实例还可以包括(甲基)丙烯酰胺、二乙基丙烯酰胺、N-乙烯基吡咯烷酮、N,N-二甲基(甲基)丙烯酰胺、N,N-二乙基(甲基)丙烯酰胺、N,N'-亚甲基双丙烯酰胺、N,N-二甲基氨基丙基丙烯酰胺、N,N-二甲基氨基丙基甲基丙烯酰胺、二丙酮(甲基)丙烯酰胺或羟甲基(甲基)丙烯酰胺，不饱和腈单体的实例可以包括(甲基)丙烯腈、乙基丙烯腈(ethacrylonitrile)、苯基丙烯腈或α-氯丙烯腈，乙烯基酯的实例可以包括醋酸乙烯酯或丙酸乙烯酯，乙烯基醚的实例可以包括甲基乙烯基醚或乙基乙烯基醚，含卤素的α,β-不饱和的单体的实例可以包括氯乙烯、偏二氯乙烯或不饱和的乙烯基，所述α,β-不饱和芳族单体的实例可以包括苯乙烯或α-甲基苯乙烯，但是本申请不特别限于此。
根据本申请的说明性实施方式，所述含有噁唑啉基团的聚合物可以具有5,000至500,000、10,000至250,000或20,000至150,000的重均分子量，但是本申请并不特别限于此。根据说明性实施方式，当所述含有噁唑啉基团的聚合物的重均分子量控制在该范围内时，可以确保与所述基于氟的聚合物的合适的相容性和流动性以赋予粘结强度。
在本申请中可以使用的聚合含有噁唑啉基团的聚合物的方法并不受到特别限制，但是使用已知的方法，如溶液聚合法、乳液聚合法、本体聚合法或悬浮聚合法可以聚合所述含有噁唑啉基团的聚合物。此外所得的共聚物可以是无规共聚物、嵌段共聚物、交替共聚物和接枝共聚物中的任何一种。在本领域内已知制备含有噁唑啉基团的聚合物的多种方法，以及所有的这些方法可应用于本申请。
根据说明性实施方式，基于100重量份的基于氟的聚合物，所述树脂层可以包括0.1重量份至50重量份，0.5重量份至25重量份，或1重量份至10重量份的含有噁唑啉基团的聚合物。根据说明性实施方式，所述含有噁唑啉基团的聚合物的含量可以控制至该含量范围内从而可以确保优异的粘合稳定性、耐光性和耐候性。根据说明性实施方式，所述树脂层的厚度不受特别限制，但是可以为，例如，在3μm至50μm，或在10μm至30μm的范围内。当树脂层的厚度小于3μm时，所述树脂层太薄而不能用足够量的填料填充，其导致光屏蔽性能的劣化。另一方面，当所述树脂层的厚度超过50μm时，制造成本可能会增加。
除了基于氟的聚合物和含有噁唑啉基团的聚合物之外，根据说明性实施方式的树脂层可以进一步包含颜料或填料中的至少一种，从而调整树脂层的颜色或不透明性或实现其它目的。在此情况下，可以在本申请中使用的颜料或填料的实例可以包括金属氧化物，例如，二氧化钛（TiO2）、二氧化硅或氧化铝；黑色颜料，例如，碳酸钙（CaCO3）、硫酸钡（BaSO4）或碳黑；或显示其它颜色的颜料组分，但本申请并不限于此。这种颜料或填料可以起到提高控制树脂层的颜色和不透明性的内在效果的作用，并且由于存在各组分中包含的内在官能团，还进一步增强树脂层的粘结强度。
相对于基于氟的聚合物和含有噁唑啉基团的聚合物的固含量，其它添加剂，如颜料或填料的含量可以为60wt%以下，但是本申请并不特别限于此。
此外，根据说明性实施方式的树脂层可进一步包括至少一种常规组分，如UV稳定剂、热稳定剂或阻隔颗粒(barrier particle)。
包含基于氟的聚合物和含有噁唑啉基团的聚合物的树脂层可以为涂层。可以在本申请中使用的术语“涂层”指的是使用涂布方法形成的树脂层。更具体地，术语“涂层”表示：代替使用粘合剂以层叠例如铸塑或挤出至基板上制备的片的方法，通过用通过将组成树脂层的组分溶解在溶剂（例如，具有低沸点的溶剂）中而制备的树脂组合物，或通过将组成树脂层的组分分散在水中制备的涂料溶液涂布在基板上而形成的包含上述基于氟的聚合物和含有噁唑啉基团的聚合物的混合物的树脂层。
图1显示根据本申请的一个说明性实施方式的多层膜10，其包括基板12和仅在所述基板12的一个表面上形成的树脂层11。然而，树脂层可以在所述基板的另一表面上形成，从而根据本申请的另一说明性实施方式的多层膜(未示出)可以包括在所述基板的两个表面上形成的树脂层。
此外，根据需要，根据本申请的说明性实施方式的多层膜可进一步包括本领域已知的多种功能层。功能层的实例可以包括粘合剂层或绝缘层。对于根据所述说明性实施方式的多层膜，例如，上述树脂层可以在基板的一个表面上形成，以及粘合剂层和绝缘层可以依次形成在所述基板的另一表面上。所述粘合层或绝缘层可使用本领域公知的多种方法形成。例如，所述绝缘层可以为由醋酸乙烯酯(EVA)或低密度线性聚乙烯(LDPE)组成的层。由EVA或LDPE组成的层可以起到绝缘层的作用，并且还起到提高粘结强度的作用以密封光伏组件、降低制造成本并且还保持优异的再加工(re-workability)的作用。
此外，本申请的另一说明性实施方式涉及提供一种制造多层膜的方法，包括：在基板上形成树脂层，该树脂层包含基于氟的聚合物和含有噁唑啉基团的聚合物。
根据说明性实施方式，在基板上形成树脂层的方法不受特别限制。例如，基于本领域已知的多种方法通过应用用于在基板上形成底漆层的树脂组合物或涂料溶液可以形成底漆层，以及在预定的条件下干燥所述树脂组合物或涂料溶液。在此，所述树脂组合物或涂料溶液可以通过将上述基于氟的聚合物和含有噁唑啉基团的聚合物溶解或分散在合适的有机溶剂或水性溶剂中而制备。在这种情况下，涂布方法不受特别限制，但是可应用形成均一的涂层的任意方法，其包括已知的印刷方法，例如，胶版印刷法或凹版印刷法或已知的涂布方法，例如，辊涂法、刀口涂布法或凹版涂布法。根据说明性实施方式，除了上述方法之外，可应用多种本领域已知的方法，以及按照需要，所述树脂组合物或涂料溶液可以进一步包含其它多种添加剂。
可以在根据说明性实施方式的制备方法中使用的基板的具体种类如上所述。在形成所述树脂层之前，在所述基板的一个或两个表面上可以进行选自沉积、等离子体处理、电晕处理、锚固剂处理、偶联剂处理、底漆处理和热处理中的至少一种合适的表面处理，以及在此可以使用其表面已经预先经过表面处理以形成至少一个表面处理层的基板。
根据说明性实施方式，用于形成树脂层的涂料溶液，也就是，树脂组合物，可以通过将用于形成底漆层的上述组分溶解在具有相对低沸点的溶剂中，更特别地，具有小于200℃沸点的溶剂中或将上述组分分散在水中而制备。也就是，根据本申请，当将所述基于氟的聚合物与含有噁唑啉的聚合物混合时，所述基于氟的聚合物可以有效地溶解在具有相对低沸点的溶剂中，或有效地分散在水中。因此，根据本申请的制备步骤不需要高温干燥步骤，从而可以降低制造成本，并且还可以防止在高温干燥步骤中可能引起的热变形或基板的热冲击，因此提高了产品质量。
可以在此使用的上述溶剂的实例可以包括选自水（例如，蒸馏水）、丙酮、甲基乙基酮(MEK)、二甲基甲酰胺(DMF)和二甲基丙酰胺(DMAC)中的至少一种，但是本申请并不特别限于此。
所述溶剂（例如，MEK、DMF或DMAC）可以在200℃以下的温度下蒸发。在这种情况下，所述溶剂可以起到容易地溶解用于涂布包含上述基于氟的聚合物和含有噁唑啉基团的聚合物的树脂层材料的作用，并且在与用于涂布树脂层的材料一起涂布至基板上之后，还可以在相对低的温度下干燥。具体地，在树脂组合物中的溶剂还可以起到在涂布步骤的过程中溶胀基板的表面或表面处理层（例如，底漆层）的作用，从而可以在基板与涂布至基板的树脂层之间的接触界面上发生树脂层基于氟的聚合物和含有噁唑啉的聚合物与基板之间的互扩散。所述含有噁唑啉基团的聚合物通过噁唑啉基团中的双键可以与多种官能团（例如，羧基、芳族巯基或酚羟基，其存在于基板的表面上）形成键。因此，所述多层膜具有分布在与树脂层相临的基板中的基于氟的聚合物和含有噁唑啉基团的聚合物，由于提高的树脂层与基板之间的物理和化学亲和力，可以进一步提高所述基板与树脂层之间的粘结强度。
只有当用所述树脂组合物涂布基板形成多层膜时才会发生。在这种情况下，当使用粘合剂层压或粘附基于氟的膜和基板时，元素氟没有扩散至基板上。也就是，根据说明性实施方式，分布在与树脂层相邻的基板的内部的所述基于氟的聚合物和含有噁唑啉基团的聚合物可以互扩散至基板的表面上，当将所述树脂组合物涂布至基板上时，所述基板的表面与树脂组合物的组分接触。因此，所述氟原子和含有噁唑啉基团的聚合物可以分布在与所述树脂层相邻的基板的内部。
根据说明性实施方式，除了基于氟的聚合物和含有噁唑啉的聚合物之外，用于形成树脂层的所述树脂组合物可以进一步包含多种添加剂，例如，颜料、填料、UV稳定剂或热稳定剂。各添加剂与基于氟的聚合物可以一起溶解在溶剂中，或者可以制备成漆浆的形式，而无需考虑组分，然后与包含基于氟的聚合物和含有噁唑啉基团的聚合物的溶剂混合。通过在添加剂（例如填料或颜料分散剂）中包含的官能团可以发生化学反应，例如，范德华力连接、氢连接、离子连接或共价连接，所述添加剂可以包含在上述树脂层中。因此，可以进一步提高树脂层与基板之间的粘结强度。
根据说明性实施方式，制备树脂组合物的方法，或在树脂组合物中包含的各组分的比例不受特别限制，但是在此可以适当地选择和使用本领域内已知的多种方法。
根据说明性实施方式，在用树脂组合物涂布基板的步骤之后，可以进一步进行干燥涂布的树脂组合物的步骤。所述干燥条件不受特别限制，但是可以，例如，在200℃以下或100℃至180℃的温度下进行干燥步骤30秒至30分钟或1分钟至10分钟。根据本申请，在上述干燥条件下可以进行所述干燥步骤，从而可以防止由在200℃以上高温下引起的制造成本的增加，并且可以防止由热变形或热冲击导致的产品质量的劣化。
此外，本申请的又一方面涉及提供用于光伏组件的背板，所述光伏组件包括根据说明性实施方式的上述多层膜。
如上所述，该用于光伏组件的背板可以包括包含基于氟的聚合物和含有噁唑啉基团的聚合物的树脂层。在此，在所述含有噁唑啉基团的聚合物中包含的噁唑啉基团可以与在基板表面上存在的多种官能团形成化学共价键，从而获得基板与树脂层之间优异的粘结强度。
更具体地，在制备用于光伏组件的背板的过程中，在所述树脂层中包含的基于氟的聚合物和含有噁唑啉基团的聚合物可以从树脂层与基板之间的界面或树脂层与基板的表面处理层之间的界面互扩散至基板或基板的表面处理层。由此，可在基板和树脂层之间形成化学共价键，且可由于链缠结以及范德华力而可提高粘结强度。
此外，根据本申请的说明性实施方式的光伏组件的背板具有例如绝缘和湿气阻隔性能的性能，并且甚至长期暴露于外部环境时，还显示耐久性和耐候性以稳定地保护光伏电池。
此外，本申请的又一说明性实施方式涉及提供用于光伏组件，所述光伏组件包括根据本申请的上述背板。
只要所述光伏组件包括作为用于光伏组件的背板的多层膜，根据本申请的光伏组件的结构不受任何特别的限制。可以选择并使用在本领域广为人知的光伏组件的多种结构。
根据说明性实施方式，例如，所述光伏组件可以被设置为包括背板、光伏电池或在背板上形成的光伏阵列，在光伏电池或光伏电池阵列上形成的光接收板，用于密封背板与光接收板之间的光伏电池或光伏电池阵列的密封层。
根据本申请的上述多层膜可以被用作背板。在此，所述背板的厚度不受特别限制，但是可以为，例如，在30μm至2,000μm，50μm至1,000μm，或100μm至600μm的范围内。所述背板的厚度可以控制在30μm至2,000μm，从而可以以更薄的形式制备光伏组件，并且还可以保持光伏组件的优异物理性能，例如耐候性。
在所述背板上形成的光伏电池的具体种类不受特别限制，只要它们可以起到引起光电动势的作用即可。因此，可以通常用于本领域中的光伏元件可以用于光伏电池。根据本申请，例如，由单晶硅或多晶硅制成的晶体硅光伏电池，非晶硅光伏电池，例如，单结合型或堆叠(tandem structure)式，由锗-砷(GaAs)或铟-磷(InP)制成的元素周期表第III-V族化合物半导体光伏电池，和由镉-碲(CdTe)或铜-铟-硒化物(CuInSe2)制成的元素周期表第II-VI族的化合物半导体光伏电池可以被用作光伏电池。此外，薄膜多晶硅光伏电池，薄膜微晶硅光伏电池和由薄膜晶体硅和非晶硅制成的复合光伏电池可以被用作光伏电池。
通过用于连接光伏电池的电线，所述光伏电池可以形成光伏电池阵列(光伏电池组)。当太阳光照耀根据本申请的光伏电池组件时，在光伏电池中产生了电子(-)和空洞(+)，从而电流可以流动经过连接所述光伏电池的电线。
当光伏电池长期暴露于户外环境时，在所述光伏电池或光伏电池阵列上形成的光接收板可以起到保护光伏组件内部免受风、雨、外部冲击或火的作用，并且确保长期可靠性。根据本申请的光接收板的具体种类不受特别限制，只要所述光接收板具有优异的光透过性，电绝缘性和机械、物理或化学强度即可。在此可以使用，例如，玻璃板、基于氟的树脂板、基于环聚烯烃的树脂板、基于聚碳酸酯的树脂板、基于聚(甲基)丙烯酸系的树脂板、基于聚酰胺的树脂板或基于聚酯的树脂板。根据本申请的一个说明性实施方式，可以使用具有优异的耐热性玻璃板，但是本申请并不特别限于此。
可以在此使用的光接收基板的厚度不受特别限制，但是可以为，例如，在0.5mm至10mm，1mm至8mm，或2mm至5mm的范围内。所述光接收基板的厚度控制在0.5mm至10mm，从而所述光伏组件可以被制的更薄，并且可以具有优异的物理性能，例如，长期可靠性。
根据本申请，还可以使用在本领域公知的密封剂而没有限制，其可以用于密封层以将光伏电池或光伏电池阵列密封在光伏组件的内部，更具体地，密封在背板与光接收板之间。
图2和3为显示根据本申请的多个说明性实施方式的光伏组件的剖面图。
图2显示包括用于根据本申请的光伏组件的背板的基于晶片的光伏组件20的一个实例。如在图2中所示，根据本申请的一个说明性实施方式的光伏组件可以通常包括由铁电材料（例如，玻璃）制成的光接收板21、用于根据本申请的光电组件的背板23、光电元件24(例如基于硅的晶片)和用于密封所述光电元件24的密封层22。在这种情况下，所述密封层22可以包括：当密封所述光伏元件24时粘附至光接收板21上的第一层22a，和当密封所述光伏元件24时粘附至背板23上的第二层22b。根据本申请，如上所述，组成密封层22的第一层和第二层可以由本领域公知的材料形成。
图2为显示根据本申请的另一说明性实施方式的薄膜光伏组件30的剖视图。如图3所示，在薄膜光伏组件30的情况下，光伏元件34可以通常形成在可以由铁电材料形成的光接收板31上。通常可以使用例如化学气相沉积法(CVD)沉积这样的薄膜光伏元件34。与如在图2中显示的光伏组件20相似，如在图3中显示的光伏组件30包括密封层32和背光板33，以及所述密封层32可以以单层的形式形成。上述已经描述了密封层32和背板33的详细描述。
根据本申请，制备这样的光伏组件的方法不受特别限制，但是所述光伏组件可以使用本领域已知的多种方法制备，而不受限制。
在图1和2中显示的光伏组件仅仅为根据本申请的光伏组件的多个说明性实施方式中的一种。只要光伏组件包括用于根据本申请的光伏组件的背板，所述光伏组件的结构和组成光伏组件的材料的种类和尺寸不受特别限制。因此，可以选择并使用在本领域公知的光伏组件。
有益效果
本申请的说明性实施方式可以提供在高温度/湿度条件下具有优异的可靠性的多层膜，并且所述多层膜还显示优异的耐候性和耐久性，因为所述多层膜包含含有基于氟的聚合物和含有噁唑啉基团的聚合物的树脂层。此外，根据本申请的多层膜的树脂层可以使用具有低沸点的溶剂在低干燥温度下以低成本制备，从而可以降低制备成本。甚至当长期暴露于外部环境中时，所述多层膜可以有效地用于光伏组件的背板从而所述光伏组件可以显示优异的耐久性。
附图说明
参照附图，通过详细地描述其说明性实施方式，本申请的上述和其它目的，特征和优点对于本领域的技术人员而言变得更加显而易见，其中：
图1为显示根据一个说明性实施方式的多层膜的剖视图。
图2为显示根据一个说明性实施方式的光伏组件的剖视图。
图3为显示根据另一说明性实施方式的光伏组件的剖视图。
附图标记
10： 多层膜
11： 树脂层
12： 基板
20： 光伏组件
30： 薄膜光伏组件
21，31： 光接收板
22，32： 密封层
22a： 第一层
22b： 第二层
23，33： 背板
24，34： 光电元件
具体实施方式
以下，将参考实施例进一步详述本申请的说明性实施方式。然而，下述实施例仅用于说明的目的，而不偏离本发明的范围。
在实施例和对比实施例中制备的各种膜的物理性能使用以下方法测量。
1、180度剥离强度
基于ASTM D1897标准，将样品切割成约10mm宽度的片，并在约4.2mm/s的速率以及约180°的剥离角度剥离测试样品，测量其剥离强度。
2、交叉影线粘结强度（Cross-hatch adhesion）
基于十字切口测试标准ASTM D3002/D3359进行十字切口测试。具体而言，用刀以1mm的间隔在样品上纵向地和垂直地划出11行和11列以形成100个方格阵，每个方格为1mm的宽度和长度。接着，将可以从Nichiban有限公司购得的CT-24胶带粘附到测试样品的切割表面并从切割表面撕下，并基于以下标准测量与胶带一起剥离的样品的表面状态。
<交叉影线粘结强度的评价标准>
5B：没有表面剥离
4B：剥离的表面为小于样品的整个表面积的5%
3B：剥离的表面为样品的整个表面积的5%至15%
2B：剥离的表面为样品的整个表面积的15%至35%
1B：剥离的表面为样品的整个表面积的35%至65%
0B：几乎整个表面剥离
3、湿热测试
将在实施例和对比实施例中制备的多层膜（其中涂布基板的两个表面以形成底漆层和包含基于氟的聚合物和含有噁唑啉基团的聚合物的树脂层）在约85℃的温度和85%R.H.的条件下在烘箱中保持1000小时、2000小时和3000小时，然后测量其粘结强度的变化。在本申请中，单位“R.H.”是指相对湿度。
4、压力锅测试（PCT）
将在实施例和对比实施例中制备的多层膜（其中涂布基板的两个表面以形成底漆层和包含基于氟的聚合物和含有噁唑啉基团的聚合物的树脂层）在2个大气压、121℃的温度和100%R.H.的条件下在烘箱中保持25小时、50小时或75小时，然后测量其粘结强度的变化。
制备实施例1
基板层的制备
将没有进行表面处理的PET薄膜（厚度：250μm，购自Kolon）的表面进行电晕处理。
基于氟的聚合物的制备
为了制备基于氟的聚合物和含有噁唑啉基团的聚合物的混合物，制备如表1所列的多种基于氟的聚合物。在实施例和对比实施例中制备的基于氟的聚合物的单体组分、重均分子量、熔点和软化点列于下面的表1中。
表1
实施例1
用于形成树脂层的树脂组合物的制备
通过预先将70g的在制备实施例1中制备的基于氟的聚合物A(包含以重量比85:15(VDF:CTFE)的聚合形式的VDF和CTFE的共聚物),30g的在制备实施例1中基于氟的聚合物D(VDF的聚合物(PVDF))和1g的具有70,000的重均分子量的含有噁唑啉基团的基于丙烯醛基的共聚物(WS-500(固含量：40%)，购自Nippon Catalyst有限公司)溶解在400g的DMF中制备第一涂料溶液。
不管上述的步骤，将0.9g的颜料分散剂、BYK111(购自BYK)，以及将90g的颜料、二氧化钛(TiPure TS6200，购自DuPont)也溶解在90g的DMF中，并进一步加入50g的具有0.3mm的氧化锆珠子。然后，以1,000rpm的速率搅拌所得到的混合物1小时，然后完全地除去氧化锆珠子以制备180.9克的漆浆分散液。
将120.0g的制备的漆浆分散液（包含60g的二氧化钛）加入至预先制备的第一涂料溶液中，并再次搅拌以制备用于形成树脂层的树脂组合物。
涂布及干燥
使用逗点反向涂覆法（reverse comma method）在预先制备的基板上涂布用于形成树脂层的树脂组合物。具体而言，以干燥后的厚度可以调整至大约20μm的间距将所述涂料溶液涂布在基板上，以及使涂布的基板以1m/min的速度依次通过三个烘箱，每一个烘箱的长度为2m，三个烘箱的温度分别为80℃、180℃和180℃以形成树脂层。接着，以相同的方式，用树脂组合物涂布基板的另一表面以制备多层膜，其中，用基于氟的聚合物和含有噁唑啉基团的聚合物的混合物涂布该PET膜（基板）的两个表面。
实施例2～5
除了具有70,000的重均分子量的含有噁唑啉基团的基于丙烯醛基的共聚物(WS-500(固含量：40%)，购自Nippon Catalyst Co.Ltd.)的含量改变至下表2中所列的之外，以与在实施例1中相同的方式制备多层膜。
实施例6
除了使用5g的具有40,000的重均分子量的含有噁唑啉基团的基于丙烯醛基的共聚物(WS-700(固含量：25%)，购自Nippon Catalyst Co.Ltd.)代替1g的具有70,000重均分子量的含有噁唑啉基团的基于丙烯醛基的共聚物(WS-500(固含量：40%),购自Nippon Catalyst Co.Ltd.)之外，以与实施例1相同的方式制备多层膜。
实施例7
除了使用在制备实施例1中制备的基于氟的聚合物B(包含以重量比85:15(VDF:HFP)的聚合形式的VDF和HFP的共聚物)代替基于氟的聚合物A之外，以与实施例3的相同的方式制备多层膜。
实施例8
除了使用100g的在制备实施例1中制备的基于氟的聚合物C(VDF的聚合物(PVDF))代替70g的基于氟的聚合物A之外，以与实施例3相同的方式制备多层膜。
实施例9
除了在实施例1的树脂组合物的制备过程中使用搅拌器，通过分散250g在制备实施例1中制备的基于氟的聚合物A的乳液(包含以重量比85:15(VDF:CTFE)的聚合形式的VDF和CTFE的共聚物乳液，并且该分散体以20%的固含量被分散在水中)；250g在制备实施例1中制备的基于氟的聚合物D的乳液(PVDF乳液，并且该分散体以20%的固含量被分散在水中)；10g的具有70,000的重均分子量的含有噁唑啉基团的基于丙烯醛基的共聚物(WS-500(固含量：40%)，购自Nippon Catalyst Co.Ltd.)；和30g的颜料，二氧化钛(TiPure TS6200，购自DuPont)而制备水性分散组合物之外，以与实施例1相同的方式制备多层膜。
对比实施例1
将购买的Tedlar膜/粘合剂/PET膜/粘合剂/Tedlar膜的层叠结构用作多层膜。所述层叠结构为使用粘合剂通过将以挤出方法制备的Tedlar膜(PVF膜(厚度：38μm)，购自DuPont)层压在PET膜的两个表面上得到的产品。
对比实施例2
将购买的Tedlar膜/粘合剂/PET膜/粘合剂/Tedlar膜的层叠结构用作多层膜。所述层叠结构为使用粘合剂通过将以铸塑制备的Tedlar膜(PVF膜(厚度：25μm)，购自DuPont)层压在PET膜的两个表面上得到的产品。
对比实施例3
除了使用2g的具有40,000的重均分子量的含有环氧基团的基于丙烯醛基的共聚物(包含重量比49.5:35.5:10:5的甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸丁酯和苯乙烯的基于丙烯醛基的共聚物)代替1g的具有70,000重均分子量的含有噁唑啉基团的基于丙烯醛基的共聚物(WS-500(固含量：40%),购自Nippon Catalyst Co.Ltd.)之外，以与实施例1相同的方式制备多层膜。
对比实施例4
除了在此不使用具有70,000的重均分子量的含有噁唑啉基团的基于丙烯醛基的共聚物(WS-500(固含量：40%)，购自Nippon Catalyst Co.Ltd.)之外，以与在实施例1中相同的方式制备多层膜。
对比实施例5
除了使用100g的在制备实施例1中制备的基于氟的聚合物D(PVDF)代替基于氟的聚合物C之外，以与实施例8相同的方式制备多层膜。
对比实施例6
除了使用100g的在制备实施例1中制备的基于氟的聚合物E(包含以重量比90:10(VDF:HFP)的聚合形式的VDF和HFP的共聚物)代替基于氟的聚合物C之外，以与实施例8相同的方式制备多层膜。
表2
实验实施例1
对在实施例1至9和在对比实施例1至6中制备的各多层膜进行压力锅测试(PCT)，接着进行180度剥离强度和交叉影线粘结强度测试。更具体而言，将各多层膜保持在2个大气压、121℃和100%的R.H.的条件下25小时、50小时和75小时，然后进行180度剥离强度测试和交叉影线粘结强度测试以测定粘结强度的变化。评估结果示于下面的表3中。
表3
如在表3中所列出，对于根据本申请的说明性实施方式的多层膜，包含基于氟的聚合物和含有噁唑啉基团的基于丙烯醛基的共聚物的混合物的树脂层显示对基板（PET）高的起始粘结强度，并且甚至在进行PCT75小时之后还具有优异的粘结强度。甚至在进行PCT75小时之后，在树脂层中没有观察到如界面剥离和小孔产生的外观变化。同时，可以确认购买的多层膜，Tedlar膜/粘合剂/PET/粘合剂/Tedlar膜（对比实施例1和2），当对多层膜进行PCT时，其显示对基板的显著降低的粘结强度。在其中使用含有环氧基团的聚合物代替含有噁唑啉基团的聚合物作为与基于氟的聚合物混合的反应性聚合物的对比实施例3的情况下或在其中根本没有加入含有噁唑啉基团的聚合物的对比实施例4的情况下，与根据本申请的实施例相比，所述多层膜还显示差的粘结可靠性。在其中没有加入具有155℃以下的熔点或100℃以下的软化点的基于氟的聚合物的对比实施例5和6的情况下，可以确认所述多层膜还显示良好的起始粘结强度，但是在进行PCT之后具有显著下降的粘结强度。
实验实施例2
对在实施例1和9和在对比实施例1至6中制备的各多层膜进行湿热测试，接着进行180度剥离强度和交叉影线粘结强度测试。更具体而言，将各多层膜保持在85℃和85%的R.H.的条件下的烘箱中1,000小时，2,000小时和3,000小时，然后进行180度剥离强度测试和交叉影线粘结强度测试以测定粘结强度的变化。评估结果示于下面的表4中。
表4
如在表4中所列出，对于根据本申请的说明性实施方式的多层膜，包含基于氟的聚合物和含有噁唑啉基团的基于丙烯醛基的共聚物的混合物的树脂层显示对基板（PET）高的起始粘结强度，并且甚至在进行湿热测试3,000小时之后还具有优异的粘结强度。甚至在进行湿热测试3,000小时之后，在树脂层中没有观察到界面剥离和小孔产生的外观变化。同时，可以确认购买的多层膜，Tedlar膜/粘合剂/PET/粘合剂/Tedlar膜（对比实施例1和2），当对多层膜进行湿热测试时，其显示对基板显著降低的粘结强度。在其中使用含有环氧基团的聚合物代替含有噁唑啉基团的聚合物作为与基于氟的聚合物混合的反应性聚合物的对比实施例3的情况下或在其中根本没有加入含有噁唑啉基团的聚合物的对比实施例4的情况下，与根据本申请的实施例相比，所述多层膜还显示差的粘结可靠性。在其中没有加入具有155℃以下的熔点或100℃以下的软化点的基于氟的聚合物的对比实施例5和6的情况下，可以确认所述多层膜还显示良好的起始粘结强度，但是在进行湿热测试之后具有显著下降的粘结强度。
实施例10～15
除了将具有70,000的重均分子量的含噁唑啉基团的基于丙烯醛基的共聚物(WS-500(固含量：40%)，购自Nippon Catalyst Co.Ltd.)的含量按照在下表5中所列出的变化，以及使用按照下表5中列出的其它颜料和含量代替二氧化钛(TiPure TS6200，购自DuPont)作为在制备漆浆分散液的过程中的颜料之外，以在实施例1中相同的方式制备多层膜。
对比实施例7
除了使用5g的具有40,000的重均分子量的含有环氧基团的基于丙烯醛基的共聚物(包含重量比49.5:35.5:10:5的甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸丁酯和苯乙烯的基于丙烯醛基的共聚物)代替1g的具有70,000重均分子量的含有噁唑啉基团的基于丙烯醛基的共聚物(WS-500(固含量：40%),购自Nippon Catalyst Co.Ltd.)，以及在此不使用颜料，二氧化钛(TiPure TS6200，购自DuPont)之外，以与实施例1相同的方式制备多层膜。
对比实施例8
除了使用5g的具有40,000的重均分子量的含有环氧基团的基于丙烯醛基的共聚物(包含重量比49.5:35.5:10:5的甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸丁酯和苯乙烯的基于丙烯醛基的共聚物)代替1g的具有70,000重均分子量的含有噁唑啉基团的基于丙烯醛基的共聚物(WS-500(固含量：40%),购自Nippon Catalyst Co.Ltd.)，以及使用如在下表5中列出的其它颜料和含量代替二氧化钛(TiPure TS6200，购自DuPont)作为在制备漆浆分散液中的颜料之外，以与实施例1相同的方式制备多层膜。
表5
实验实施例3
对实施例10至15和对比实施例7和8中制备的各多层膜进行PCT，接着进行180度剥离强度和交叉影线粘结强度测试。更具体而言，将各多层膜保持在2个大气压、121℃和100%的R.H.的条件下25小时、50小时和75小时，然后进行180度剥离强度测试和交叉影线粘结强度测试以测定粘结强度的变化。评估结果示于下面的表6中。
表6
如在表6中所列出，对于根据本申请的说明性实施方式的多层膜，由于树脂层包含基于氟的聚合物和含有噁唑啉基团的基于丙烯醛基的共聚物的混合物，甚至当没有使用颜料或黑色颜料被用作颜料时，也就是，不管颜料的种类和是否存在，所述树脂层显示对基板（PET）高的起始粘结强度，并且甚至在进行PCT75小时之后还具有优异的粘结强度。甚至在进行PCT75小时之后，在树脂层中没有观察到界面剥离和小孔产生的外观变化。同时，在其中使用含有环氧基团的聚合物代替含有噁唑啉基团的聚合物作为与基于氟的聚合物混合的反应性聚合物的对比实施例7和8的情况下，与根据本申请的实施例的相比，所述多层膜还显示差的粘结可靠性。
实验实施例4
对在实施例10至15和在对比实施例7和8中制备的各多层膜进行湿热测试，接着进行180度剥离强度和交叉影线粘结强度测试。更具体而言，将各多层膜保持在85℃和85%的R.H.的条件下的烘箱中1,000小时，2,000小时和3,000小时，然后进行180度剥离强度测试和交叉影线粘结强度测试以测定粘结强度的变化。评估结果示于下面的表7中。
表7
如在表7中所列出，对于根据本申请的说明性实施方式的多层膜，由于树脂层包含基于氟的聚合物和含有噁唑啉基团的基于丙烯醛基的共聚物的混合物，甚至当没有使用颜料或黑色颜料被用作颜料时，也就是，不管颜料的种类和是否存在，所述树脂层显示对基板（PET）高的起始粘结强度，并且甚至在进行湿热测试3,000小时之后还具有优异的粘结强度。甚至在进行湿热测试3,000小时之后，在树脂层中没有观察到界面剥离和小孔产生的外观变化。同时，在其中使用含有环氧基团的聚合物代替含有噁唑啉基团的聚合物作为与基于氟的聚合物混合的反应性聚合物的对比实施例7和8的情况下，与根据本申请的实施例的相比，所述多层膜还显示差的粘结可靠性。
尽管参照一些说明性实施方式展示和描述了本发明的说明性实施方式，本领域的技术人员可以理解，在不偏离如所附权利要求中定义的本发明的范围的情况下，可对本发明进行多种形式和细节的变化。

Claims (32)

1.一种多层膜，其包括：
基板；和
树脂层，其在所述基板上形成并且包含基于氟的聚合物和含有噁唑啉基团的聚合物。
2.根据权利要求1所述的多层膜，其中，所述基板为金属膜或聚合物膜。
3.根据权利要求2所述的多层膜，其中，所述聚合物膜为选自丙烯醛基膜、聚烯烃膜、聚酰胺膜、聚氨酯膜、聚对苯二甲酸乙二酯(PET)膜、聚萘二酸乙二酯(PEN)膜和聚对苯二甲酸丁二酯(PBT)膜中的至少一种。
4.根据权利要求1所述的多层膜，其中，对所述基板的一个表面或两个表面进行选自等离子体处理、电晕处理、底漆处理、锚固剂处理和偶联剂处理和热处理中的至少一种表面处理。
5.根据权利要求1所述的多层膜，其中，在所述基板的一个表面或两个表面上形成无机氧化物沉积层。
6.根据权利要求1所述的多层膜，其中，所述基板具有50μm至500μm的厚度。
7.根据权利要求1所述的多层膜，其中，所述基于氟的聚合物为包含聚合形式的选自偏二氟乙烯（VDF）、氟乙烯（VF）、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（甲基乙烯基醚）（PMVE）、全氟（乙基乙烯基醚）（PEVE）、全氟丙基乙烯基醚（PPVE）、全氟（己基乙烯基醚）（PHVE）、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-1,3-二氧戊环（PMD）中的至少一种单体的均聚物、共聚物或其混合物。
8.根据权利要求1所述的多层膜，其中，所述基于氟的聚合物为包含偏二氯乙烯（VDF）或氯乙烯（VF）和选自四氟乙烯（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（甲基乙烯基醚）（PMVE）、全氟（乙基乙烯基醚）（PEVE）、全氟(丙基乙烯基醚)（PPVE）、全氟（己基乙烯基醚）（PHVE）、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-1,3-二氧戊环（PMD）中的至少一种共聚单体的共聚物或其混合物。
9.根据权利要求8所述的多层膜，其中，相对于基于氟的共聚物的总重量，在所述基于氟的共聚物中包含的共聚单体的量为0.5wt%至50wt%。
10.根据权利要求1所述的多层膜，其中，所述基于氟的聚合物具有50,000至1,000,000的重均分子量。
11.根据权利要求1所述的多层膜，其中，所述基于氟的聚合物包含：i)具有155℃以下的熔点或100℃以下的软化点的第一基于氟的聚合物；和ii)任选的具有155℃以上的熔点或100℃以上的软化点的第二基于氟的聚合物。
12.根据权利要求11所述的多层膜，其中，相对于基于氟的聚合物的总重量，所述具有155℃以下的熔点和100℃以下的软化点的第一基于氟的聚合物以20wt%的重量比存在。
13.根据权利要求1所述的多层膜，其中，所述含有噁唑啉基团的聚合物为含有噁唑啉基团的单体的均聚物，包含含有噁唑啉基团的单体和至少一种共聚单体的共聚物，或其混合物。
14.根据权利要求13所述的多层膜，其中，所述含有噁唑啉基团的单体为由下面的通式1表示的化合物：
通式1
其中，R1、R2、R3和R4各自独立地表示氢原子、烷基、卤素或取代或未取代的苯基，以及R5表示具有未取代键的无环烃基团。
15.根据权利要求13所述的多层膜，其中，所述含有噁唑啉基团的单体为选自2-乙烯基-2-噁唑啉、2-乙烯基-4-甲基-2-噁唑啉、2-乙烯基-5-甲基-2-噁唑啉、2-异丙烯基-2-噁唑啉、2-异丙烯基-4-甲基-2-噁唑啉和2-异丙烯基-5-乙基-2-噁唑啉中的至少一种。
16.根据权利要求13所述的多层膜，其中，基于包含含有噁唑啉基团的单体和至少一种共聚单体的共聚物的总重量，所述共聚物包含1wt%以上含量的所述含有噁唑啉基团的单体。
17.根据权利要求16所述的多层膜，其中，基于包含含有噁唑啉基团的单体和至少一种共聚单体的共聚物的总重量，所述含有噁唑啉基团的单体以5wt%至95wt%的含量被包含在所述共聚物中。
18.根据权利要求13所述的多层膜，其中，在所述共聚物中包含的共聚单体为选自(甲基)丙烯酸烷基酯、含酰胺基团的单体、基于不饱和腈的单体、基于乙烯基酯的单体、基于乙烯基醚的单体、含卤素的α,β-不饱和单体和α,β-不饱和芳族单体中的至少一种。
19.根据权利要求18所述的多层膜，其中，所述（甲基）丙烯酸烷基酯包括选自（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸仲丁酯、（甲基）丙烯酸叔丁酯、（甲基）丙烯酸异丁酯、（甲基）丙烯酸己酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸正辛酯、（甲基）丙烯酸异辛酯、（甲基）丙烯酸正壬酯、（甲基）丙烯酸异壬酯、（甲基）丙烯酸正癸酯、（甲基）丙烯酸异癸酯、（甲基）丙烯酸正十二烷基酯、（甲基）丙烯酸正十三烷基酯和（甲基）丙烯酸正十四烷基酯中的至少一种。
20.根据权利要求1所述的多层膜，其中，所述含有噁唑啉基团的聚合物具有5,000至500,000的重均分子量。
21.根据权利要求1所述的多层膜，其中，基于100重量份的基于氟的聚合物，所述树脂层包含0.1重量份至50重量份的含有噁唑啉基团的聚合物。
22.根据权利要求1所述的多层膜，其中，所述树脂层具有3μm至50μm的厚度。
23.根据权利要求1所述的多层膜，其中，所述树脂层进一步包含选自颜料、填料、UV稳定剂、热稳定剂和阻隔颗粒中的至少一种添加剂。
24.根据权利要求1所述的多层膜，其中，所述氟原子分布在与树脂层相邻的基板的内部。
25.一种制备多层膜的方法，其包括：
在基板上形成包含基于氟的聚合物和含有噁唑啉基团的聚合物的树脂层。
26.根据权利要求25所述的方法，其中，通过用包含基于氟的聚合物、含有噁唑啉基团的聚合物和具有200℃以下沸点的溶剂的树脂组合物，或包含基于氟的聚合物、含有噁唑啉基团的聚合物和水的水分散液组合物涂布基板进行包含基于氟的聚合物和含有噁唑啉基团的聚合物树脂层的形成。
27.根据权利要求26所述的方法，其中，所述具有200℃以下沸点的溶剂为选自丙酮、甲基乙基酮、二甲基甲酰胺和二甲基乙酰胺中的至少一种。
28.根据权利要求25所述的方法，在形成所述树脂层之前，其进一步包括：
对所述基板的一个表面或两个表面进行选自等离子体处理、电晕处理、底漆处理、锚固剂处理、偶联剂处理、沉积处理和热处理中至少一种表面处理。
29.根据权利要求26所述的方法，在用所述树脂组合物涂布基板之后，其进一步包括：
干燥所述树脂组合物。
30.根据权利要求29所述的方法，其中，在200℃以下的温度下进行干燥30秒至30分钟。
31.一种用于光伏组件的背板，其包括在权利要求1至24中任一项所定义的多层膜。
32.一种光伏组件，其包括在权利要求31中定义的用于光伏组件的背板。
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