CN107163880B - 一种改性水滑石及太阳能电池背板 - Google Patents
一种改性水滑石及太阳能电池背板 Download PDFInfo
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- CN107163880B CN107163880B CN201710203514.0A CN201710203514A CN107163880B CN 107163880 B CN107163880 B CN 107163880B CN 201710203514 A CN201710203514 A CN 201710203514A CN 107163880 B CN107163880 B CN 107163880B
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- solar cell
- fluorine
- cell backboard
- modified hydrotalcite
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
- C09J127/22—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers modified by chemical after-treatment
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Abstract
本发明提供了一种有机改性水滑石的制备及其在太阳能电池背板上的应用，得到一种耐湿热老化、阻燃性及阻隔性能优异的太阳能电池背板，其包括耐候层、绝缘层和含氟粘结涂层，所述含氟粘接涂层是由氟碳树脂、有机改性水滑石、聚氨酯丙烯酸酯(PUA)、异氰酸酯制备的含氟涂料涂布而成。由于在含氟粘结涂层中使用了改性水滑石，本发明的太阳能电池背板与EVA初粘性能以及湿热老化后粘结性能良好，具有优异的阻燃性、耐侯性及水汽阻隔性。
Description
技术领域
本发明涉及一种水滑石的改性及其在太阳能电池背板上的应用，特别涉及一种与EVA高粘结性、高耐候性、高阻燃性的太阳能电池背板。
背景技术
水滑石作为一类酸碱双功能性的层状双金属氢氧化物，由于其层间阴离子的可交换性，可以对其进行无机或有机改性，广泛应用在阻燃材料、催化、医药及吸附等方面。通过无机阴离子的离子交换可制备出一系列高效阻燃、抑烟的新型阻燃剂，如硼酸根或磷酸根插层改性水滑石；通过有机阴离子改性，主要集中在药物载体应用方面，如水杨酸、氨基酸、卡托普利、布洛芬、烷基糖苷等药物分子插层水滑石，得到分子水平控制释放的药物。这些有机药物分子中含有取代苯甲酸、取代苯酚、或烷基多元醇结构，多数属于芳香族化合物，耐紫外性能差，不能满足在太阳能电池背板领域的应用。
近年来，太阳能作为绿色能源的代表，越来越受到人们的瞩目。目前，太阳能的应用主要是利用太阳能电池组件将太阳能转换成电能加以利用。太阳能电池组件主要由前板、封装材料、晶硅电池片、背板组成。背板位于太阳能电池板的背面，对晶硅电池片起保护和支撑作用，因此必须具有可靠的电气绝缘性、良好的力学性能、水气阻隔性能以及耐候性能。
目前，背板主要由三层结构组成，由外到内依次为耐候层，绝缘层，粘结层。由于组件厂商对太阳能电池组件的使用寿命要求越来越高，双面含氟背板成了顺应市场的主流产品。含氟粘结层一直是各大背板厂商的研究热点，含氟粘结膜层制备成本高，含氟粘结涂层在工艺及成本方面具有明显优势。然而含氟粘结涂层背板与EVA在层压过层中，高温会引发EVA中过氧化物裂解产生自由基，该自由基很难引发C-F键(键能486kJ/mol)产生自由基，发生后续链反应，同时含氟粘结涂层中的氟碳树脂的极性较弱，与EVA封装胶膜中的EVA分子间作用力小，因此，含氟粘结涂层与EVA的粘结力小，不能满足背板粘结层的要求。
综上，综合性能优异的含氟粘结涂层配方的开发需要兼顾与封装胶膜EVA的初粘性以及湿热老化后的粘结性、抗紫外线辐射性能、水汽阻隔性能和涂层阻燃性能等。
中国专利文献CN105505183A提供一种高性能氟碳涂料，是由含羟基的氟碳树脂与含-NCO基团的聚氨酯预聚物混合制得的氟碳涂料，该氟碳涂料耐黄变、耐紫外、耐风沙侵蚀。然而，由于聚氨酯易水解的特性，该涂料用于背板粘结层，湿热老化后，涂层交联密度受到破坏，与封装胶膜EVA的粘结性骤减，而且易出现涂层残留在EVA上；中国专利文献CN101792639A公开了一种耐磨抗划伤的聚氨酯涂料,由羟基丙烯酸、氟碳树脂、聚酯树脂为主体树脂，用纳米级无机填料填充，与异氰酸酯固化而成的表面装饰涂料，其聚酯树脂的引入，降低了涂料的耐老化性，纳米级填料与主体树脂分散困难造成了涂层龟裂等弊端。
发明内容
针对现有技术存在的不足之处，本发明提供一种改性水滑石，及使用该改性水滑石制备的具有含氟粘结涂层的太阳能电池背板，与EVA初粘性能以及湿热老化后粘结性能良好，具有优异的阻燃性、耐侯性及水汽阻隔性。
为解决上述技术问题，本发明采用如下技术方案：
一种改性水滑石，其化学式为：[Mg1-xAlx(OH)2]x+(A-)x·mH2O，Mg2+和Al3+位于水滑石主体层板上，A-为乙酰乙酸甲基丙烯酸乙二醇酯阴离子、双丙酮丙烯酰胺阴离子、N-羟甲基丙烯酰胺阴离子、N-羟乙基丙烯酰胺阴离子中的一种，0.2＜x≤0.5；m为层间水分子的个数，m＝0-6。
上述改性水滑石的层间距为1.2nm～4.0nm，平均粒径为0.4μm～3μm。
一种太阳能电池背板，包括耐候层、绝缘层和含氟粘结涂层，所述含氟粘接涂层是由氟碳树脂、上述改性水滑石、聚氨酯丙烯酸酯(PUA)、异氰酸酯制备的含氟涂料涂布而成，其中，所述改性水滑石的添加量为含氟涂料固含量的20wt％～50wt％。
上述太阳能电池背板，所述PUA为聚酯多元醇或聚醚多元醇与异氰酸酯反应，用丙烯酸封端的PUA中的一种或多种，所述PUA的Mn为2000～8000，所述PUA的添加量为氟碳树脂固含量的5wt％～30wt％。
上述太阳能电池背板，所述氟碳树脂选自含羟基或氨基改性的四氟乙烯-乙烯基醚共聚物、四氟乙烯-乙烯基酯共聚物、三氟氯乙烯-乙烯基醚共聚物、三氟氯乙烯-乙烯基酯共聚物、聚氟乙烯、聚偏氟乙烯、四氟乙烯-全氟烷基乙烯基醚共聚物中的一种或多种。
上述太阳能电池背板，所述异氰酸酯选自所述异氰酸酯选自甲苯二异氰酸酯(TDI)三聚体、异佛尔酮二异氰酸酯(IPDI)三聚体、六亚甲基二异氰酸酯(HDI)三聚体、二苯基甲烷二异氰酸酯(MDI)三聚体、甲苯二异氰酸酯(TDI)二聚体、异佛尔酮二异氰酸酯二聚体(IPDI)、六亚甲基二异氰酸酯(HDI)二聚体、二苯基甲烷二异氰酸酯(MDI)二聚体中的一种或多种。
上述太阳能电池背板，所述异氰酸酯中含有的异氰酸基团和氟碳树脂中羟基/氨基的摩尔比为0.6～1.5。
上述太阳能电池背板，所述含氟粘结涂层的干厚为3μm～20μm。
上述太阳能电池背板，所述绝缘层选自聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸丙二醇酯中的一种或多种。
上述太阳能电池背板，所述耐候层为氟碳树脂类涂层、聚氟乙烯膜、聚偏氟乙烯膜、聚四氟乙烯-乙烯共聚物膜中的一种。
与现有技术相比，本发明具有如下优点：
1.本发明中的改性水滑石，由于使用了特定的改性剂，具有更大的层间距，制备的含氟粘结涂层，易与EVA胶膜水解出的醋酸根阴离子发生吸附交换，抑制含氟粘结涂层中由于引入PUA所引起的脲基甲酸酯、缩二脲、氨基甲酸酯水解反应的发生，改善了含氟粘结涂层的耐水解性。
2.本发明中的太阳能电池背板，由于在含氟粘结涂层中使用了改性水滑石，与EVA初粘性能以及湿热老化后粘结性能良好，具有优异的阻燃性、耐侯性及水汽阻隔性。
具体实施方式
研究表明，通过使用双官或多官的PUA与氟碳树脂共混使用，由于PUA分子硬段存在极性基团，以及具有三维网状交联结构，能与EVA胶膜之间通过缠绕及分子间作用力实现良好粘结，同时由于分子结构中不饱和基团-C＝C的存在，在与EVA胶膜层压过程中，通过胶膜中过氧化物产生的自由基引发链反应，实现与EVA分子形成化学键，进一步加强与EVA的粘结力。
然而，太阳能电池组件长期处于户外，在湿热条件下，封装胶膜EVA会水解释放小分子醋酸。将PUA应用在背板含氟粘结涂层中，会受到EVA降解产物的影响，即PUA中的脲基甲酸酯、缩二脲、氨基甲酸酯等基团在酸性条件下会加速降解。破坏了PUA的三维网状交联结构，影响粘结层的交联密度。导致湿热老化后背板与EVA胶膜的剥离强度急剧降低，并且涂层易残留在EVA上。
同时，PUA引入背板含氟粘结涂层中，会降低背板含氟粘结涂层的阻燃性能。
通过有机改性剂对水滑石进行插层改性，能很好的改善含氟粘结涂层的耐水解性，提高了湿热老化后背板粘结涂层与EVA的剥离强度。由于水滑石具有特殊的层状晶体结构，主体层板由金属阳离子构成，层间为客体阴离子，主体与客体之间通过共价键、离子键、氢键、静电力等相互作用。本发明中所用水滑石中的客体阴离子由中性有机分子在强碱环境下夺H得到，该客体阴离子结构较大；与市售的水滑石相比，具有更大的层间距，易与EVA胶膜水解出的醋酸根阴离子发生吸附交换，抑制含氟粘结涂层中由于引入PUA所引起的脲基甲酸酯、缩二脲、氨基甲酸酯水解反应的发生；同时，随着醋酸的产生，缓慢置换出的有机改性剂由于具有两个反应活性位点，可以作为桥梁，起到提高湿热老化后含氟粘结涂层与EVA的剥离强度的作用，其一，与羰基相连的α碳(或羟基)具有亲核性，能与氨基甲酸酯降解片段含有的-NCO基团反应；其二，α-β不饱和羰基结构能够在碱性条件下与聚氨酯降解片段中的-OH，-NH2或-COOH等基团发生加成反应。
本发明中的一种改性水滑石，其化学式为：[Mg1-xAlx(OH)2]x+(A-)x·mH2O，Mg2+和Al3+位于水滑石主体层板上；A-为乙酰乙酸甲基丙烯酸乙二醇酯阴离子、双丙酮丙烯酰胺阴离子、N-羟甲基丙烯酰胺阴离子、N-羟乙基丙烯酰胺阴离子中的一种；0.2＜x≤0.5；m为层间水分子的个数，m＝0-6。
本发明制备改性水滑石时所用Mg(NO3)2、Al(NO3)3中[Mg2+]/[Al3+]的摩尔比为3/1～1/1，优选2/1或1/1；若[Mg2+]/[Al3+]的比值小于1/1，所得水滑石中含有Al2O3杂质；若[Mg2+]/[Al3+]的比值大于3/1，所得水滑石中含有MgO杂质，均会导致有机改性水滑石纯度降低,加入含氟粘结涂层不能有效解决含氟粘结涂层的抗水解能力。
本发明制备改性水滑石时控制溶液PH值为9-10，若PH值低于9，不能有效地将有机改性剂组装进水滑石的片层结构中；若PH值高于10，易发生有机单体的自聚反应。
本发明中所述改性剂为乙酰乙酸甲基丙烯酸乙二醇酯、双丙酮丙烯酰胺、N-羟甲基丙烯酰胺或N-羟乙基丙烯酰胺。
本发明的改性水滑石的平均粒径为0.3μm-4μm，优选0.3μm-1μm。若平均粒径低于0.3μm，改性水滑石纳米颗粒不易在含氟涂料中分散均匀；若粒径高于4μm，使含氟粘结涂层致密度降低，不能有效隔绝基材与氧气的接触，阻燃性能下降。
改性水滑石的制备过程为：
将一定量的改性剂溶于乙醇中,倒入三口烧瓶中，再将Mg(NO3)2·6H2O溶于去离子水得到A溶液(2mol·L-1)，将Al(NO3)3·9H2O溶于去离子水,得到B溶液(3mol·L-1)。在磁力搅拌及N2保护下，将溶液A和溶液B分别缓慢滴加到三口烧瓶中,同时滴加2mol·L-1NaOH溶液，使反应体系的pH维持在10,常温下反应48h，产物经过滤,洗涤后在烘箱中干燥,得到改性水滑石。
制备水滑石的试剂均为公知的市售产品。
含氟涂料的制备过程：
在一广口容器中加入氟碳树脂，PUA树脂，乙酸乙酯，改性水滑石(自制)，分散20min后，倒入研磨机研磨1-2h，倒入广口容器中，加入异氰酸酯，在200rpm条件下搅拌30min，过滤，得到含氟涂料。
本发明采用的PUA的分子量为2000-8000，若分子量低于2000，PUA交联度偏低，层压过程中与EVA界面间分子缠绕作用弱，会导致含氟粘结涂层与EVA之间的剥离强度低，不能满足背板粘结层的要求；若分子量大于8000，PUA与氟树脂的相容性差，影响产品性能的均一性。
适用本发明的异氰酸酯选自所述异氰酸酯选自甲苯二异氰酸酯(TDI)三聚体、异佛尔酮二异氰酸酯(IPDI)三聚体、六亚甲基二异氰酸酯(HDI)三聚体、二苯基甲烷二异氰酸酯(MDI)三聚体、甲苯二异氰酸酯(TDI)二聚体、异佛尔酮二异氰酸酯二聚体(IPDI)、六亚甲基二异氰酸酯(HDI)二聚体、二苯基甲烷二异氰酸酯(MDI)二聚体中的一种或多种。
适用本发明的溶剂可以选择丁酮、乙酸乙酯、乙酸丁酯、甲基异丁酮中的一种或几种。
本发明选用的氟碳树脂与异氰酸酯的使用比例在适当的工艺条件下可调节，需满足异氰酸酯中含有的异氰酸基团和氟碳树脂中含有的羟基/氨基的摩尔比：0.6～1.5，优选：0.8～1.1。若异氰酸基团和羟基/氨基的比例低于0.8，则羟基/氨基反应不完全，并且交联密度较低，造成固化不彻底，从而降低含氟粘结涂层的耐湿热老化性能；若异氰酸基团和羟基/氨基的比例高于1.5，剩余的异氰酸酯基团会与空气中的水分发生反应，固化后交联密度较高，含氟粘结涂层较硬，导致含氟粘结涂层与PET附着力较低，含氟粘结涂层密封性能下降。
本发明中氟碳树脂、PUA树脂、乙酸乙酯均为市售的公知产品。
本发明中太阳能电池背板的结构为：耐候层/绝缘层/含氟粘结涂层。
本发明所述含氟粘结涂层在适当的工艺条件下厚度可调节，干厚在3μm～20μm。当涂层干厚小于3μm时，涂层对于PET的保护作用不足，不能起到足够的屏蔽紫外光的作用；当涂层干厚大于20μm时，成本增加较多，且涂层在干燥过程中容易出现表干现象，影响涂层表观甚至是性能。
太阳能电池背板的绝缘层可以是聚对苯二甲酸乙二醇酯(PET)树脂、聚对萘二甲酸乙二醇酯(PEN)树脂等构成的单层或多层薄膜。从热稳定性、电绝缘性、成本等评价，最佳选择为聚对苯二甲酸乙二醇酯(PET)薄膜。根据太阳能电池背板的用途不同，可选择不同厚度、不同颜色的基材。
适用于本发明的耐候层可以是氟碳树脂、丙烯酸树脂、聚氨酯和聚酯类涂层中的一种，或者为聚氟乙烯(PVF)膜、聚偏氟乙烯(PVDF)膜、聚四氟乙烯-乙烯共聚物(ETFE)膜中的一种。
本发明各涂层的涂布采用公知的涂布方式，这些涂布方法包括但不限于浸涂、辊涂、喷涂、微凹版等公知的涂布方式。
下面结合实施例对本发明做优选的说明，但本发明的保护范围并不限于此。
实施例1
取75.8mL乙酰乙酸甲基丙烯酸乙二醇酯溶于50mL乙醇中,至于三口烧瓶种，再将25.8g Mg(NO3)2·6H2O溶于40mL去离子水得到A溶液(2mol·L-1)，将66.17g Al(NO3)3·9H2O溶于30mL去离子水,得到B溶液(3mol·L-1)。在磁力搅拌及N2保护下，将37.5mL溶液A和12.5mL溶液B分别缓慢滴加到三口烧瓶中,同时滴加2mol·L-1NaOH溶液，使反应体系的pH维持在10,常温下反应48h，产物经过滤,洗涤后在烘箱中干燥,得到乙酰乙酸甲基丙烯酸乙二醇酯改性水滑石。
在一广口容器中加入200g氟碳树脂GK 570(大金氟化工制，OH值为60mgKOH/g,固含量60％)，36g PUA树脂UV-2032(东莞井上化工科技有限公司)，195g乙酸乙酯，89g乙酰乙酸甲基丙烯酸乙二醇酯改性水滑石(自制)，25g HDI三聚体N 3300(德国BayerMaterialscience制，NCO含量为21.8％，固含量90％)，在200rpm条件下搅拌30min，过滤，得到含氟粘结层涂料。
在已清洁并电晕处理的基材PET膜的一面经凹版涂布法涂布上述含氟粘结层涂布液，在90℃干燥3.0分钟，得到20μm的含氟粘结层；再在基材另一侧通过涂布或者复合的方法形成耐候层，将制得产品经过50℃，3天的熟化期过后，得到太阳能电池背板。
实施例2
取75.8mL双丙酮丙烯酰胺溶于50mL乙醇中,至于三口烧瓶种，再将25.8g Mg(NO3)2·6H2O溶于40mL去离子水得到A溶液(2mol·L-1)，将66.17g Al(NO3)3·9H2O溶于30mL去离子水,得到B溶液(3mol·L-1)。在磁力搅拌及N2保护下，将35mL溶液A和23mL溶液B分别缓慢滴加到三口烧瓶中,同时滴加2mol·L-1NaOH溶液，使反应体系的pH维持在10,常温下反应48h，产物经过滤,洗涤后在烘箱中干燥,得到双丙酮丙烯酰胺改性水滑石。
在一广口容器中加入200g氟碳树脂ETERFLON4101(长兴化学工业股份有限公司制，OH值为56mgKOH/g，固含量60％)，24g PUA树脂JZ-302(南京嘉中化工科技有限公司)，156g乙酸丁酯，67g双丙酮丙烯酰胺改性水滑石(自制)，34g IPDI三聚体Z4470BA(德国Bayer Materialscience制，NCO含量为11.9％，固含量70％)，在200rpm条件下搅拌30min，过滤，得到含氟粘结层涂料。
在已清洁并电晕处理的基材PET膜的一面经凹版涂布法涂布上述含氟粘结层涂布液，在140℃干燥3.0分钟，得到15μm的含氟粘结层；再在基材另一侧通过涂布或者复合的方法形成耐候层，将制得产品经过50℃，3天的熟化期过后，得到太阳能电池背板。
实施例3
取50mL N-羟甲基丙烯酰胺溶于33mL乙醇中,至于三口烧瓶中，再将25.8g Mg(NO3)2·6H2O溶于40mL去离子水得到A溶液(2mol·L-1)，将66.17g Al(NO3)3·9H2O溶于30mL去离子水,得到B溶液(3mol·L-1)。在磁力搅拌及N2保护下，将37.5mL溶液A和12.5mL溶液B分别缓慢滴加到三口烧瓶中,同时滴加2mol·L-1NaOH溶液，使反应体系的pH维持在10,常温下反应48h，产物经过滤,洗涤后在烘箱中干燥,得到N-羟甲基丙烯酰胺改性水滑石。
在一广口容器中加入200g氟碳树脂ETERFLON41011(长兴化学工业股份有限公司制，OH值为56mgKOH/g，固含量60％)，30g PUA树脂JZ-304(南京嘉中化工科技有限公司)，145g乙酸乙酯，54g N-羟甲基丙烯酰胺改性水滑石(自制)，30g HDI二聚体N100(德国BayerMaterialscience制，NCO含量为22.0％，固含量100％)，在200rpm条件下搅拌30min，过滤，得到含氟粘结层涂料。
在已清洁并电晕处理的基材PET膜的一面经凹版涂布法涂布上述含氟粘结层涂布液，在90℃干燥2.5分钟，得到10μm的含氟粘结层；再在基材另一侧通过涂布或者复合的方法形成耐候层，将制得产品经过50℃，3天的熟化期过后，得到太阳能电池背板。
实施例4
取50mLN-羟乙基丙烯酰胺溶于33mL乙醇中,至于三口烧瓶中，再将25.8g Mg(NO3)2·6H2O溶于40mL去离子水得到A溶液(2mol·L-1)，将66.17g Al(NO3)3·9H2O溶于30mL去离子水,得到B溶液(3mol·L-1)。在磁力搅拌及N2保护下，将35mL溶液A和23mL溶液B分别缓慢滴加到三口烧瓶中,同时滴加2mol·L-1NaOH溶液，使反应体系的pH维持在10,常温下反应48h，产物经过滤,洗涤后在烘箱中干燥,得到N-羟乙基丙烯酰胺改性水滑石。
在一广口容器中加入200g氟碳树脂ETERFLON4102(长兴化学工业股份有限公司制，OH值为56mgKOH/g，固含量50％)，15g PUA树脂JZ-302(南京嘉中化工科技有限公司)，68g乙酸丁酯，29g N-羟乙基丙烯酰胺改性水滑石(自制)，30g HDI三聚体D-170N(日本三井化学株式会社制，NCO含量为20.7％，固含量100％)，在200rpm条件下搅拌30min，过滤，得到含氟粘结层涂料。
在已清洁并电晕处理的基材PET膜的一面经凹版涂布法涂布上述含氟粘结层涂布液，在140℃干燥2.0分钟，得到6μm的含氟粘结层；再在基材另一侧通过涂布或者复合的方法形成耐候层，将制得产品经过50℃，3天的熟化期过后，得到太阳能电池背板。
实施例5
在一广口容器中加入200g氟碳树脂ETERFLON4101(长兴化学工业股份有限公司制，OH值为56mgKOH/g，固含量60％)，6g PUA树脂UV-2032(东莞井上化工科技有限公司)，74g乙酸乙酯，14g乙酰乙酸甲基丙烯酸乙二醇酯改性水滑石(自制)，15.5g HDI三聚体N3390(德国Bayer Materialscience制，NCO含量为19.6％，固含量90％)，在200rpm条件下搅拌30min，过滤，得到含氟粘结层涂料。
在已清洁并电晕处理的基材PET膜的一面经凹版涂布法涂布上述含氟粘结层涂布液，在90℃干燥1.5分钟，得到3μm的含氟粘结层；再在基材另一侧通过涂布或者复合的方法形成耐候层，将制得产品经过50℃，3天的熟化期过后，得到太阳能电池背板。
对比例1
在一广口容器中加入200g氟碳树脂ETERFLON4101(长兴化学工业股份有限公司制，OH值为56mgKOH/g，固含量60％)，24g PUA树脂JZ-302(南京嘉中化工科技有限公司)，140g乙酸丁酯，65g水滑石FM300(康高特塑料科技有限公司制)，18.5g HDI三聚体N 3300(德国Bayer Materialscience制，NCO含量为21.8％，固含量100％)，在200rpm条件下搅拌30min，过滤，得到含氟粘结层涂料。
在已清洁并电晕处理的基材PET膜的一面经凹版涂布法涂布上述含氟粘结层涂布液，在140℃干燥3.0分钟，得到15μm的含氟粘结层；再在基材另一侧通过涂布或者复合的方法形成耐候层，将制得产品经过50℃，3天的熟化期过后，得到太阳能电池背板。
对比例2
在一广口容器中加入200g氟碳树脂ETERFLON4101(长兴化学工业股份有限公司制，OH值为56mgKOH/g，固含量60％)，59g乙酸丁酯，18.5g HDI三聚体N 3300(德国BayerMaterialscience制，NCO含量为21.8％，固含量100％)，在200rpm条件下搅拌30min，过滤，得到含氟粘结层涂料。
在已清洁并电晕处理的基材PET膜的一面经凹版涂布法涂布上述含氟粘结层涂布液，在140℃干燥2.5分钟，得到15μm的含氟粘结层；再在基材另一侧通过涂布或者复合的方法形成耐候层，将制得产品经过50℃，3天的熟化期过后，得到太阳能电池背板。
实施例和对比例中改性水滑石在含氟涂料中的添加量、PUA在含氟涂料中的添加量、异氰酸酯中含有的异氰酸基团和氟碳树脂中羟基/氨基的摩尔比见表1。
表1改性水滑石在含氟涂料中的添加量、PUA在含氟涂料中的添加量、羟基/氨基的摩尔比
| PUA含量 | 改性水滑石 | NCO/OH | |
| 实施例1 | 30％ | 50％ | 1/1 |
| 实施例2 | 20％ | 40％ | 0.8/1 |
| 实施例3 | 25％ | 30％ | 1.3/1 |
| 实施例4 | 15％ | 20％ | 1.5/1 |
| 实施例5 | 5％ | 10％ | 0.6/1 |
| 对比例1 | 20％ | 未改性(40％) | 0.8/1 |
| 对比例2 | 0 | 0 | 0.8/1 |
背板的性能测试：
1、背板与EVA间剥离强度测试
依据标准GB/T2790-1995进行测试；
2、阻燃性测试
依据标准UL94-2010，水平燃烧测试。
3、阻隔性测试(WVTR)
依据标准GB/T26253-2010，38℃，90％RH条件下进行测试。
测试结果见表2。
表2实施例和对比例的背板的性能测试结果
Claims (9)
1.一种改性水滑石，其特征在于，所述改性水滑石的化学式为：
[Mg1-xAlx(OH)2]x+(A-)x·mH2O,Mg2+和Al3+位于水滑石主体层板上，A-为乙酰乙酸甲基丙烯酸乙二醇酯阴离子、双丙酮丙烯酰胺阴离子、N-羟甲基丙烯酰胺阴离子、N-羟乙基丙烯酰胺阴离子中的一种，0.2＜x≤0.5，m为层间水分子的个数，m＝0-6。
2.根据权利要求1所述的改性水滑石，其特征在于，所述改性水滑石的层间距为1.2～4.0nm，平均粒径为0.4μm～3μm。
3.一种太阳能电池背板，包括耐候层、绝缘层和含氟粘结涂层，其特征在于，所述含氟粘结涂层是由氟碳树脂、权利要求1或2所述的改性水滑石、聚氨酯丙烯酸酯(PUA)、异氰酸酯制备的含氟涂料涂布而成，所述改性水滑石的添加量为含氟涂料固含量的20wt％～50wt％。
4.根据权利要求3所述的太阳能电池背板，其特征在于，所述PUA为聚酯多元醇或聚醚多元醇与异氰酸酯反应，用丙烯酸封端的PUA中的一种或多种，所述PUA的Mn为2000～8000，所述PUA为氟碳树脂固含量的5wt％～30wt％。
5.根据权利要求4所述的太阳能电池背板，其特征在于，所述氟碳树脂选自含羟基或氨基改性的四氟乙烯-乙烯基醚共聚物、四氟乙烯-乙烯基酯共聚物、三氟氯乙烯-乙烯基醚共聚物、三氟氯乙烯-乙烯基酯共聚物、聚氟乙烯、聚偏氟乙烯、四氟乙烯-全氟烷基乙烯基醚共聚物中的一种或多种。
6.根据权利要求5所述的太阳能电池背板，其特征在于，所述异氰酸酯选自甲苯二异氰酸酯三聚体、异佛尔酮二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体、二苯基甲烷二异氰酸酯三聚体、甲苯二异氰酸酯二聚体、异佛尔酮二异氰酸酯二聚体、六亚甲基二异氰酸酯二聚体或二苯基甲烷二异氰酸酯二聚体中的一种或多种。
7.根据权利要求6所述的太阳能电池背板，其特征在于，所述异氰酸酯中含有的异氰酸基团和氟碳树脂中羟基/氨基的摩尔比为0.6～1.5。
8.根据权利要7所述的太阳能电池背板，其特征在于，所述含氟粘结涂层的干厚为3μm～20μm。
9.根据权利要8所述的太阳能电池背板，其特征在于，所述耐候层为氟碳树脂类涂层、聚氟乙烯膜、聚偏氟乙烯膜或聚四氟乙烯-乙烯共聚物膜中的一种。
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