CN101932443B - 用于光伏电池的三层膜 - Google Patents
用于光伏电池的三层膜 Download PDFInfo
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- CN101932443B CN101932443B CN200980103684.5A CN200980103684A CN101932443B CN 101932443 B CN101932443 B CN 101932443B CN 200980103684 A CN200980103684 A CN 200980103684A CN 101932443 B CN101932443 B CN 101932443B
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Classifications
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
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Abstract
本发明涉及A/B/C结构的多层膜:包含含氟聚合物的组合物A的第一层;包含经填料的含氟聚合物的组合物B的第二层;和包含含氟聚合物的组合物C的第三层,其特征在于,该第一和第三层具有用DSC测得的大于150℃的熔点,和对于25微米的多层膜厚度,可见光透射比小于30%。本发明还涉及基于含氟聚合物的用于保护基材的用途,所述基材可以是:优选地光伏电池的后部板;工业用织物;金属。使用沉积在基材和膜之间的粘附层将该膜粘附在基材上。
Description
技术领域
本发明涉及基于偏二氟乙烯(VDF)聚合物的A/B/C结构的多层膜,这种膜特别可用于光伏电池的领域中。
技术问题
一般而言,含氟聚合物,特别是PVDF(聚偏二氟乙烯)因其极佳的抗恶劣气候性、耐辐射性和耐化学品性是用来保护物体和材料的聚合物。VDF聚合物也因它们的闪亮外观和抗涂写性得到重视。因此使得人们使用基于VDF的聚合膜来覆盖所有种类的物体。然而,必需的是,这种膜具有非常好的耐热性以用于经受严峻气候条件(雨、寒冷、酷热)的外部应用或用于在高温(>130℃)下进行的转化过程。还必需的是,这种膜具有良好挠性和抗断裂性以使得抵挡机械应力(当这种膜放置在欲覆盖的物体或材料上或一旦这种膜被沉积在物体或材料时),传统所用的应用试验在于将已在烤箱遭受老化的膜撕裂,然后察看该撕裂是否容易蔓延。
在光伏电池中,抗环境的保护是绝对需要的。基于此理由,电池后面部份必须受到保护以防止电池因紫外线(UV)和湿气渗透而降解。此降解作用可包括该保护电池后部板的保护膜的氧化作用。而且,该电池的后部板必须为电绝缘体。
此外,这种膜必须具有体积热稳定性以避免热膨胀,特别是电池装配期间的收缩。光伏电池的装配通过使用溶剂基的粘合剂粘合各层,然后再经由层压而进行。所述粘合剂中使用溶剂可使这些溶剂渗透到膜内。电池的装配是在高温(>130℃)下进行且任选地使用电晕类型(typeCorona)的表面氧化处理,特别地,其表现为含氟聚合物的黄化和机械性质的降低。
本申请人已开发呈基于含氟聚合物的膜形式的结构,其具有优异的耐热性(当其经历高温时体积收缩很低),以及对那些存在于用来构建光伏电池(更特别地电池的后部板)的胶和粘合剂中的溶剂具有优异抗性。所以,这种结构优选地适于保护光伏电池的后部板。
此膜具有A/B/C类型的特别结构。根据本发明的这种结构为不透明的(低的可见光和UV射线透射),同时对氧的渗透也具保护作用。此结构保证了膜的好的美学外观(随着时间也不黄化)。
现有技术
申请EP 1 382 640描述了一种具有二或三个基于VDF的均聚物或共聚物的层的膜。该VDF共聚物包含0至50质量%共聚单体。在这些实施例中,仅仅描述了使用PVDF均聚物。有机UV吸收剂也被详细描述在这些实施例中。
申请EP 1566 408描述一种具有二或三个基于VDF的均聚物或共聚物的层的膜。该VDF共聚物包含0至50重量%,有利地0至25重量%,优选地0至15重量%共聚单体。这种膜不含任何矿物填料。
国际申请WO 2005/081859描述一种基于含氟聚合物和丙烯酸聚合物的多层膜。
申请US 2005/0268961描述一种用膜保护的光伏电池,这种膜包含两个含氟聚合物层,其中一层具有大于135℃的熔点,另一层具有小于135℃的熔点。
申请US 2005/0172997和专利US 6369316描述一种用聚氟化乙烯(PVF)膜保护的光伏模块。
国际申请WO 2007/011580描述一种基于聚酯的膜,其是用于光伏电池的后部板。一层的聚氟化乙烯(PVF)可与聚酯膜结合。该后部板仅仅从湿气渗透的观点来评估。
这些文献中没有一个是提到具有和本发明的特征相同特征的多层结构,在这些文献中也没有一个能使技术人员获得这样的结构。
发明内容
本发明涉及A/B/C结构的多层膜,其包含:
●包含含氟聚合物的组合物A的第一层,
●包含经填料的含氟聚合物(polymère fluore chargé)的组合物B的第二层,
●包含含氟聚合物的组合物C的第三层,
其特征为,该第一和第三层具有用DSC测得的大于150℃的熔点,和对于厚度为25微米的多层膜的小于30%,优选地小于25%的可见光透射比(transmittance)。
本发明的另一目的是这种多层膜在光伏电池、工业用织物(textiletechnique)中的用途或用于覆盖金属。
更特别地,本发明涉及一种光伏电池,其后部板覆盖有如先前所述的多层膜。
详细描述
在说明书中,“介于x至y之间”表示边界值x和y也包括在内。
有利地,该第一、第二和第三层包含0.1至100重量%的一或多种含氟聚合物,优选地VDF的均聚物或共聚物。
更特别地,本发明涉及一种呈A/B/C类型多层膜形式的结构,其包括:
●包含100%VDF的均聚物或共聚物的组合物A的第一层;
●组合物B的第二层,组合物B包含30至75重量份VDF的均聚物或共聚物、5至45份MMA的均聚物或共聚物和10至30份的至少一种矿物填料,其中总共为100份;和
●包含100%VDF的均聚物或共聚物的组合物C的第三层。
在本发明的意义上“份”理解为重量份。
在第一层的组合物A和第三层的组合物C是相同的情况下,该结构以对称的A/B/A多层膜形式存在。
在实践中,组合物A和C的层的每一个的厚度可互相独立地,介于1至30微米之间,有利地介于2至20微米之间,优选地介于3至18微米之间,还更优选地介于5至15微米之间。
在本发明的一种变型中,组合物A和C的层的厚度是相同的。
在本发明的另一种变型中,第一和第三层的组合物A和C是相同的。
特别地,组合物B的层的厚度介于4至45微米之间,有利地介于5至40微米之间,优选地介于7至30微米之间,更优选地介于10至25微米之间。
关于含氟聚合物,其通过使一或多种式(I)的单体聚合进行制备:
其中:
●X1表示H或F;
●X2和X3表示H、F、Cl、式CnFmHp-的氟化烷基或氟化烷氧基CnFmHpO-,n为介于1至10之间的整数,m为介于1至(2n+1)之间的整数,p等于2n+1-m。
可用于本发明的单体的实例,可提及的有六氟丙烯(HFP)、四氟乙烯(TFE)、偏二氟乙烯(VDF,CH2=CF2)、氯代三氟乙烯(CTFE)、全氟代烷基乙烯基醚(如CF3-O-CF=CF2、CF3-CF2-O-CF=CF2或CF3-CF2CF2-O-CF=CF2)、1-氢五氟丙烯、2-氢-五氟丙烯、二氯二氟乙烯、三氟乙烯(VF3)、1,1-二氯代氟乙烯和它们的混合物。
聚合作用还可任选地包含其它不含氟的不饱和烯烃单体,如乙烯、丙烯、丁烯和高级同系物。含有氟的二烯烃类也可使用,例如全氟二烯丙基醚和全氟-1,3-丁二烯。
作为含氟聚合物的实例,可提及如下:
●TFE的均聚物或共聚物,特别是PTFE(聚四氟乙烯)、ETFE(乙烯/四氟乙烯共聚物)和下述共聚物:TFE/PMVE(四氟乙烯/全氟代(甲基乙烯基)醚共聚物)、TFE/PEVE(四氟乙烯/全氟代(乙基乙烯基)醚共聚物)、TFE/PPVE(四氟乙烯/全氟代(丙基乙烯基)醚共聚物)和E/TFE/HFP(乙烯/四氟乙烯/六氟丙烯三元共聚物);
●VDF的均聚物或共聚物,特别是PVDF和VDF/HFP共聚物;
●CTFE的均聚物或共聚物,特别是PCTFE(聚氯基三氟乙烯)和E-CTFE(乙烯/氯代三氟乙烯共聚物)。
优选地,该含氟聚合物为VDF的均聚物或共聚物。
有利地,可与VDF共聚合的含氟共聚单体例如选自氟乙烯;三氟乙烯(VF3);氯代三氟乙烯(CTFE);1,2-二氟乙烯;四氟乙烯(TFE);六氟丙烯(HFP);全氟代(烷基乙烯基)醚,如全氟代(甲基乙烯基)醚(PMVE)、全氟代(乙基乙烯基)醚(PEVE)和全氟代(丙基乙烯基)醚(PPVE);全氟代(1,3-二氧杂环戊烯);全氟代(2,2-二甲基-1,3-二氧杂环戊烯)(PDD);和它们的混合物。
优选地,该含氟共聚单体选自氯代三氟乙烯(CTFE)、六氟丙烯(HFP)、三氟乙烯(VF3)、四氟乙烯(TFE)、和它们的混合物。
共聚单体有利地为HFP,因其与VDF可很好地共聚合,并可以提供良好的热机械性质。优选地该共聚物只包含VDF和HFP。
有利地,VDF的均聚物或共聚物具有从100Pa.s至3000Pa.s的粘度,该粘度是在230℃和100s-1剪切速率(gradient de cisaillement)下使用毛细管流变仪进行测量。这是因为这种聚合物很适于挤出。优选地,这种聚合物具有从500Pa.s至2900Pa.s的粘度,该粘度是在230℃和100s-1剪切速率下使用毛细管流变仪进行测量。
优选地,含氟聚合物为VDF的均聚物(PVDF)或VDF的共聚物,如VDF/HFP,其含有至少50重量%的VDF,有利地至少75重量%的VDF,和优选地至少90重量%的VDF。事实上这种含氟聚合物具有良好的耐化学性,特别是抗UV射线,并且其易于变形(比在PTFE或ETFE共聚物更容易)以形成膜。例如,更特别地可提及下述的VDF均聚物或含有大于75%VDF和其余为HFP的VDF共聚物:Arkema公司销售的
关于组合物A和/或组合物C的含氟聚合物,有利地是使用偏二氟乙烯的均聚物(VDF,CH2=CF2)(PVDF)和优选地含有至少90重量%VDF的VDF共聚物。
在本发明的另一种变型中,组合物A和C包含PVDF均聚物。
特别推荐Arkema公司的产品,如,例如系列的产品(VDF均聚物)或某些(VDF共聚物),如果所得的共聚物具有非均质或嵌段结构且熔点大于150℃,优选地大于160℃时,上述VDF共聚物含有小于5%无规分布的共聚单体,或小于10%的共聚单体。尤其,这些含氟聚合物具有从150℃至300℃的高熔点的优点。
关于组合物B的含氟聚合物,有利地是使用偏二氟乙烯的均聚物(VDF,CH2=CF2)(PVDF)和优选地含有至少85重量%VDF的VDF共聚物。
特别推荐Arkema公司的产品,如,例如700系列的产品(VDF均聚物)或某些(VDF共聚物),所述VDF共聚物含有小于15重量%(包括此数值)共聚单体,有利地小于13重量%(包括此数值)共聚单体,优选地至多等于11重量%,和还更优选地至多等于10重量%;并且具有高于140℃,优选地大于150℃,有利地大于160℃,优选地低于300℃的熔点。
共聚单体有利地为HFP,因其与VDF可充分共聚合,并可提供良好的热机械性质。优选地,该共聚物只包含VDF和HFP;共聚单体含量为0.5至15重量%,优选地3至13重量%,例如6至10重量%。
除了该含氟聚合物的外,根据本发明的组合物B的层还包含“填料”,其以附加聚合物的形式(可为甲基丙烯酸甲酯(MMA)的均聚物或共聚物)或无机颗粒形式存在。
组合物B的层(也称为功能层),对UV射线和可见光是不透明的。“不透明”是表示与B层的组合物中不含任何“填料”(尤其是矿物填料)的A/B/C类型的结构比较,对于给定厚度,UV射线和可见光的透射比低于某一数值或百分比。这种A/B/C结构与现有技术的结构比较在随温度的尺寸收缩方面有显著优势,且组合物A和C的层可以保护B层免于含氟聚合物的降解作用(因为填料(如矿物填料)、氧和温度的组合作用,或在矿物填料的存在时任何电晕形式的表面氧化处理的作用下所致)。
关于MMA聚合物,有利地使用甲基丙烯酸甲酯(MMA)的均聚物,和含有至少50重量%MMA和至少一种可与MMA共聚合的其它单体的共聚物。
作为可与MMA共聚合的单体的实例,可以提及例如(甲基)丙烯酸烷酯、丙烯腈、丁二烯、苯乙烯和异戊二烯。(甲基)丙烯酸烷酯的实例描述在Kirk-Othmer,Encyclopedia of Chemical Technology,第4版(1991)在第1卷中,第292-293页和在第16卷中,第475-478页。
有利地,MMA聚合物(均聚物或共聚物)包含0至20重量%(优选地5至15重量%)的甲基丙烯酸C1-C8烷酯,其优选地为丙烯酸甲酯和/或丙烯酸乙酯。MMA聚合物(均聚物或共聚物)可被官能化,也就是说其含有例如酸、酰基氯、醇或酐官能。这些官能可通过接枝或共聚合而被引入。有利地,该官能度特别地为由丙烯酸共聚单体所提供的酸官能。也可使用具有两个邻近的丙烯酸官能(其可经脱水而形成酐)的单体。官能度的比例可为0至15重量%,例如0至10重量%的MMA聚合物。
MMA聚合物有利地可含有至少一种抗冲击改性添加剂。已有被称为“抗冲击性”的商品级的MMA聚合物,其含有多层颗粒形式的丙烯酸抗冲击改性添加剂。因此抗冲击改性添加剂已存在于MMA聚合物中(如销售的MMA聚合物),(即,在制造期间已引入MMA树脂中),但也可在膜制造期间添加。对于70至100份MMA聚合物,抗冲击改性添加剂的数量为0至30份,总量是100份。
多层颗粒类型的抗冲击改性添加剂(通常也被称为核-外壳(noyau-écorce))包含至少一层弹性(或软的)层,即由具有低于-5℃的玻璃化转变温度(Tg)的聚合物所形成的层,和至少一个刚性(硬的)层,即由具有大于25℃的Tg的聚合物所形成。颗粒尺寸通常小于μm,有利地介于50至300nm之间。核-外壳类型的多层颗粒形式的抗冲击改性添加剂的实例可在下述文献中找到:EP 1061100A1、US 2004/0030046A1、FR-A-2446296或US 2005/0124761A1。优选具有至少80重量%的软弹性相的核-外壳类型颗粒。
MMA聚合物的MVI (熔体流动指数)在230℃和3.8千克负载下测定为介于2至15cm3/10分钟之间。
组合物B中的MMA聚合物含量为介于1至55重量%之间,有利地介于5至50重量%之间,优选地介于10至45重量%之间,更优选地介于20至40重量%之间。
关于矿物填料,可使用金属氧化物,例如二氧化钛(TiO2)、二氧化硅、石英、氧化铝、碳酸盐如碳酸钙、滑石、云母、白云石(CaCO3·MgCO3)、蒙脱石(铝硅酸盐)、BaSO4、ZrSiO4、Fe3O4和它们的混合物。
矿物填料在UV/可见光范围内具有遮光功能。填料的保护作用和UV吸收剂是互补的。从此观点来看TiO2填料最特别优选的。矿物填料,例如TiO2类型,主要通过UV射线的扩散/反射(对可见光也一样)起太阳光过滤作用以具有不透明膜。
矿物填料可以有另一功能。例如,其可具有阻燃功能,如,例如氧化锑(Sb2O3、Sb2O5)、Al(OH)3、Mg(OH)2、白云石(3MgCO3·CaCO3)、水菱镁矿(3MgCO3·Mg(OH)2·3H2O)。矿物填料也可为电导性填料(例如,碳黑或碳纳米管)。
以平均直径表示的填料的尺寸通常介于0.05微米至1毫米之间,有利地介于0.1微米至700微米之间,优选地介于0.2微米至500微米之间。矿物填料在组合物B中的含量介于0.1至30重量%之间,有利地介于5至28重量%之间,优选地介于10至27重量%之间,和更优选地15至25重量%之间。
关于基于含氟聚合物的膜
基于含氟聚合物,更特别地基于VDF的均聚物或共聚物的膜具有A/B/C类型的结构。例如,膜形式的结构包含组合物A的第一层,组合物A由100重量%VDF的均聚物或共聚物组成;组合物B的第二层,组合物B含有30至75份VDF均聚物或共聚物中的至少一种、10至45份MMA的均聚物或共聚物和10至25份至少一种矿物填料(总量为100份);和组合物C的第三层,组合物C由100重量%VDF的均聚物或共聚物组成。优选地,组合物A和/或C的VDF均聚物或共聚物为VDF均聚物。
保护基材的基于VDF均聚物和/或共聚物的膜因此以从基材开始按顺序包含,组合物A或C的层、组合物B的层、组合物A或C的层,且这种膜通过粘合层而粘附在基材上。
在第一层的组合物A和第三层的组合物C相同的情况下,这时结构呈对称的A/B/A多层膜形式。
组合物A和C的层的每个的厚度可互相独立,特别地为介于1至30微米之间,有利地介于2至20微米之间,优选地介于3至18微米之间,和更优选地介于5至15微米之间。
在本发明的一种变型中,组合物A和C的层的厚度是相同的。
在本发明的另一种变型中,第一和第三层的组合物A和C是相同的。
特别地,组合物B的层的厚度介于4至45微米之间,有利地介于5至40微米之间,优选地介于7至30微米之间,更优选地介于10至25微米之间。
在第一层的组合物A和第三层的组合物C是相同的情况下,该多层膜具有对称的A/B/A结构。在这种情况下,可保护基材的基于PVDF的膜从基材开始按顺序包含,组合物A的层、组合物B的层、组合物A的层,且这种膜通过粘合剂层而粘附在基材上。
A/B/A类型的结构完全不意味着,这两个A层有相同厚度。
制造基于含氟聚合物的膜
基于含氟聚合物,更特别地基于VDF的均聚物或共聚物的膜优选地是通过共挤出技术(如吹塑法(soufflage))进行制造,但也可使用挤出铸形(extrusion cast)技术或另外通过溶剂途径实施技术或通过使用涂覆技术。
膜的用途
现将更加详细地说明基于含氟聚合物的膜,更特别地基于VDF的均聚物或共聚物的膜的用途。
作为用于光伏电池后部的保护膜
光伏电池可通过基于含氟聚合物的,更特别地基于VDF的均聚物或共聚物的膜在其后部进行保护。光伏电池可将光能转换为电流。通常,光伏电池包含多个以串联方式安装并通过电连接手段彼此联结的光伏电池。一般来说,这种光伏电池通常为由基于在硅的熔融期间用硼进行P-掺杂的和在其被照亮的表面上用磷进行N-掺杂的多晶硅进行制造的单结电池。这些电池放置在层压叠层中。层压叠层可由覆盖光伏电池的EVA(乙烯-乙酸乙烯酯共聚物)构成,以保护硅不受氧化作用和湿气。该叠层(empilage)被涂覆在在一侧作为支撑体的玻璃板之间,并且通过另一侧的膜进行保护。因此光伏模块可受到抗老化(UV、盐雾等)、刮痕、湿气或水蒸气的保护。
一般而言,该电池通过以商标或销售的多层结构来保护,其是为(聚氟化乙烯或PVF)膜与PET(聚对苯二甲酸乙二酯)片的组合。
本申请人发现,对这种应用而言,可有利地使用以基于含氟聚合物,更特别地基于如前面所定义的VDF均聚物或共聚物的膜或对称膜的结构,来替代膜。这种A/B/C或A/B/A结构的膜在随温度的尺寸收缩方面具有重要优势,且组合物A和C的层可保护功能层B免于含氟聚合物的降解作用(在例如TiO2类型的矿物填料、氧和温度的组合作用下);或在矿物填料(如TiO2类型)的存在时任何电晕形式的处理。
事实上,尺寸收缩在层压在基材(如PET片)上期间应是尽可能低的。同时,尺寸收缩在于高温(140至155℃)和真空下进行的面板组装期间也应尽可能地低,这是为了要保护该基于含氟聚合物,更特别地基于VDF的均聚物或共聚物的膜的结构;特别是各层的厚度和因此的机械、光学和抗老化性质的完整性。这种性质是由A/B/C结构或对称的A/B/A结构(其保证膜平面度)和组成所述膜的各个层的温度稳定性所提供。
在例如挤出的薄膜的情况下,尺寸收缩尤其通过在挤出方向上和在与挤出相横交的方向的线性收缩进行估计。特别地,这种膜在150℃下的体积或尺寸收缩小于2%,有利地小于1.5%,优选地小于1%,和更优选地小于0.5%。
在温度、氧和UV辐射的组合作用下,存在高含量的矿物填料(如TiO2类型)可导致含氟聚合物(如VDF均聚物或共聚物)的降解。这种氧化作用特别地表现为黄化和机械性质的降低。所以,所述两个组合物A和C的含氟聚合物层是必要的,以为了不仅在基材上层压(经由粘合层)以形成后部板的期间,而且在高温下进行的板组装(任选地在电晕类型的表面氧化处理后)的期间保护由组合物B制得的功能层。
相对于B层,位于该组装的光伏电池后部的由组合物A或C制成的层而且提供提高的耐化学性,和更佳的抗UV老化性质。
根据本发明的A/B/C结构的多层膜包括,例如:
●组合物A的第一层,组合物A包含100重量%VDF的均聚物或共聚物;
●组合物B的第二层,组合物B包含30至75份VDF均聚物或共聚物的至少一种、5至45份MMA均聚物或共聚物的至少一种、和10至30份矿物填料的至少一种,其中总量为100份;和
●组合物C的第三层,组合物C包含100重量%VDF的均聚物或共聚物。
优选地,组合物B的第二层包含30至75份VDF均聚物或共聚物的至少一种、10至45份MMA均聚物或共聚物的至少一种、和10至25份矿物填料的至少一种,其中总量为100份;
然后,使用任何类型的粘合剂和本领域的技术人员已知的层压技术将前述的膜(缩写为PVDF膜)层压到PET类型基材的每一侧。因此,光伏模件的后部板的最终结构如下:
PVDF膜/粘合剂/PET/粘合剂/PVDF膜
例如,所用的粘合剂为含有甲基乙基酮(MEC)或甲苯的聚酯或聚氨酯的配制剂。
作为柔性基材的保护膜
基于含氟聚合物,更特别地基于VDF的均聚物或共聚物的膜也可用来保护柔性基材,如工业用织物(由PVC、玻璃织物、玻璃垫、芳族聚酰胺、Kevlar等所制成)。PVC制成的防水油布可成为PVC制成的柔性基材的实例。基于含氟聚合物,更特别地基于VDF的均聚物或共聚物的膜可利用层压技术经由粘合剂层进行施用。
存在两个含氟聚合物的组合物A的层(更特别地基于VDF的均聚物或共聚物的组合物A的层)可以保护组合物B的层在层压期间抗降解,同时提供最终结构的增高的耐化学性和抗UV老化性质。
作为金属片的保护膜
基于含氟聚合物,更特别地基于VDF的均聚物或共聚物的膜也可用来保护金属基材,如钢、铜或铝。基于含氟聚合物,更特别地基于VDF的均聚物或共聚物的膜可利用层压技术经由粘合剂层进行施用。
试验:
UV不透明性:UV不透明性利用分光光度计并通过在UV谱范围中的透射吸收的测量进行评估。
根据ASTM D 1003标准的透射比:可见光范围中的透射比的测量利用分光比色计根据ASTM D1003标准使用D65光源和2°角度而进行。透射比的值对应于400至740nm的光谱范围的平均值。
抗MEC的化学耐性试验根据EN 438-2:2000标准而进行。该方法在于在环境温度下将2至3滴甲基乙基酮沉积在这种膜上,并使用表玻璃覆盖达16小时。随后移除表玻璃,再以含有肥皂的水洗清污点,然后以去离子水冲洗。清洁1小时后检测该污点。
这种膜根据下列评估尺度进行评分:
5级:没有可看见的变化。
4级:只有在某些角度下可见的光泽和/或颜色的弱变化。
3级:光泽和/或颜色有中等的变化。
2级:光泽和/或颜色有很大的变化。
1级:表面降解和/或起泡。
差示扫描量热法(DSC)根据ISO 11357-3标准而进行。所得的差示热分析图的峰表示该结构中的每个层的组合物的熔点Tf。其被当作为耐热性的指示。
收缩根据ISO 11501标准进行测定。在12×12平方厘米的正方形膜片上画出10×10平方厘米的正方形,并将其放在150℃的通风烤箱内10分钟。随后,再次测量该框的尺寸。然后,通过每个尺寸相对于最初尺寸的变化来评估收缩。被保持的数值是最大的数值。
实施例
所用产品
PVDF-1:颗粒形式的PVDF均聚物,其MFI(熔体流动指数或熔融态主体流动性指数)为10克/10分钟(230℃,12.5千克)、粘度在230℃,100s-1下为1900mPa.s和熔点为165℃。
PVDF-2:颗粒形式的VDF/HFP共聚物(11重量%HFP),其MFI为5克/10分钟(230℃,12.5千克)、粘度在230℃,100s-1下为2500mPa.s、和熔点为142℃。
PVDF-3:颗粒形式的VDF/HFP非均质共聚物(10重量%HFP),其MFI为5克/10分钟(230℃,12.5千克)、粘度在230℃,100s-1下为2300mPa.s、和熔点为163℃。
PVDF-4:颗粒形式的VDF/HFP共聚物(17重量%HFP),其MFI为10克/10分钟(230℃,12.5千克)、粘度在230℃、100s-1下为2200mPa.s、和熔点为135℃。
PMMA:来自Altuglas International公司的珍珠形态的含有共聚单体(为6重量%含量的丙烯酸甲酯)的其MFI为4.5克/10分钟(230℃,3.8千克)。这种PMMA不含抗冲击添加剂。
TiO2:使用来自DuPont公司的二氧化钛。根据供货商,粒子平均直径为0.5微米。
实施例1(根据本发明)
具有A/B/A三层的膜由下述组成:
●5微米厚的含有100%PVDF-1的层;和
●20微米厚的含有60重量%PVDF-2、24重量%PMMA和16重量%TiO2的层;和
●5微米厚的含有100%PVDF-1的层。实施例2(根据本发明)
具有A/B/A三层的膜由下述组成:
●5微米厚的含有100%PVDF-1的层;和
●20微米厚的含有60重量%PVDF-1、24重量%PMMA和16重量%TiO2的层;和
●5微米厚的含有100%PVDF-1的层。
实施例3(根据本发明)
具有A/B/A三层的膜由下述组成:
●5微米厚的含有100%PVDF-1的层;和
●20微米厚的含有60重量%PVDF-3、24重量%PMMA和16重量%TiO2的层;和
●5微米厚的含有100%PVDF-1的层。
实施例4(根据本发明)
具有A/B/A三层的膜由下述组成:
●5微米厚的含有100%PVDF-1的层;和
●15微米厚的含有50重量%PVDF-3、30重量%PMMA和20重量%TiO2的层;和
●5微米厚的含有100%PVDF-1的层。
实施例5(根据本发明)
具有A/B/A三层的膜由下述组成:
●5微米厚的含有100%PVDF-1的层;和
●15微米厚的含有40重量%PVDF-3、36重量%PMMA和24重量%TiO2的层;和
●5微米厚的含有100%PVDF-1的层。
实施例6(根据本发明)
具有A/B/A三层的膜由下述组成:
●5微米厚的含有100%PVDF-1的层;和
●20微米厚的含有40重量%PVDF-3、36重量%PMMA和24重量%TiO2的层;和
●5微米厚的含有100%PVDF-1的层。
实施例7(根据本发明)
具有A/B/A三层的膜由下述组成:
●8微米厚的含有100%PVDF-1的层;和
●20微米厚的含有60重量%PVDF-3、24重量%PMMA和16重量%TiO2的层;和
●8微米厚的含有100%PVDF-1的层。
实施例8(对比实施例)
具有两层的膜由下述组成:
●10微米厚的含有100%PVDF-1的层;和
●20微米厚的含有60重量%PVDF-2、24重量%PMMA和16重量%TiO2的层。
实施例9(对比实施例)
具有A/B/C三层的膜由下述组成:
●10微米厚的含有100%PVDF-1的层;和
●20微米厚的含有60重量%PVDF-2、24重量%PMMA和16重量%TiO2的层;和
●5微米厚的含有30重量%PVDF-2和70重量%PMMA的层。
实施例10(对比实施例)
具有A/B/C三层的膜由下述组成:
●5微米厚的含有100%PVDF-1的层;和
●20微米厚的含有60重量%PVDF-2、24重量%PMMA和16重量%TiO2的层;和
●5微米厚的含有100%PVDF-4的层。
实施例11(根据本发明)
具有A/B/A三层的膜由下述组成:
●5微米厚的含有100%PVDF-1的层;和
●30微米厚的含有60重量%PVDF-1、24重量%PMMA和16重量%TiO2的层;和
●5微米厚的含有100%PVDF-1的层。
实施例12(根据本发明)
具有A/B/A三层的膜由下述组成:
●5微米厚的含有100%PVDF-1的层;和
●10微米厚的含有60重量%PVDF-1、24重量%PMMA和16重量%TiO2的层;和
●5微米厚的含有100%PVDF-1的层。
这些实施例的膜具有下列性质:
在第一层的组合物A和第三层的组合物C是相同的情况下,仅对于组合物A存在耐热性。
(a)在B层侧上测量耐化学性
(b)在C层侧上测量耐化学性
(c)没有熔化焓,玻璃化转变在50℃下测量(根据ISO 11357-2)。
根据本发明的实施例中的A/B/A膜形式的结构具有非常好的耐化学性和在150℃的弱收缩(模的尺寸稳定性)。
Claims (23)
1.A/B/C结构的多层膜,其包含:
●组合物A的第一层,该组合物A包含100重量%VDF的均聚物或共聚物;
●组合物B的第二层,该组合物B包含30至75重量份VDF的均聚物或共聚物,5至45重量份MMA的均聚物或共聚物,和10至30重量份的至少一种矿物填料,总量为100重量份;和
●组合物C的第三层,该组合物C包含100重量%VDF的均聚物或共聚物,
其特征在于,该第一和第三层具有用DSC测得的大于150℃的熔点,和对于25微米的多层膜厚度可见光透射比小于30%,并且这种膜在150℃的体积或尺寸收缩小于1%。
2.如权利要求1的多层膜,特征在于该第一和/或第三层的含氟聚合物为VDF均聚物。
3.如权利要求1至2任一项的多层膜,特征在于该第二层的含氟聚合物含有小于或等于15重量%的共聚单体。
4.如权利要求3的多层膜,特征在于该第二层的含氟聚合物含有小于或等于13重量%的共聚单体。
5.如权利要求3的多层膜,特征在于该第二层的含氟聚合物含有至多等于11重量%的共聚单体。
6.如权利要求3的多层膜,特征在于该第二层的含氟聚合物含有至多等于10重量%的共聚单体。
7.如权利要求1-2任一项的多层膜,特征在于该第二层的含氟聚合物具有用DSC测得的大于140℃的熔点。
8.如权利要求1-2任一项的多层膜,特征在于该第二层的经填料的聚合物含有至少一种选自TiO2、碳酸钙、二氧化硅、石英、氧化铝、滑石和云母的填料。
9.如权利要求1-2任一项的多层膜,特征在于该组合物B中的填料含量介于10至27重量%之间。
10.如权利要求9的多层膜,特征在于该组合物B中的填料含量介于15至25重量%之间。
11.如权利要求1-2任一项的多层膜,特征在于填料尺寸介于0.05微米至1毫米之间。
12.如权利要求1-2任一项的多层膜,特征在于该第一和第三层的含氟聚合物为VDF均聚物。
13.如权利要求1-2任一项的多层膜,特征在于该第二层的含氟聚合物为VDF共聚物。
14.如权利要求1-2任一项的多层膜,特征在于组合物A和C的层的每个的厚度彼此互相独立地介于1至30微米之间。
15.如权利要求14的多层膜,特征在于组合物A和C的层的每个的厚度彼此互相独立地介于2至20微米之间。
16.如权利要求14的多层膜,特征在于组合物A和C的层的每个的厚度彼此互相独立地介于3至18微米之间。
17.如权利要求14的多层膜,特征在于组合物A和C的层的每个的厚度彼此互相独立地5至15微米之间。
18.如权利要求1-2任一项的多层膜,特征在于组合物B的层的厚度介于4至45微米之间。
19.如权利要求18的多层膜,特征在于组合物B的层的厚度介于5至40微米之间。
20.如权利要求18的多层膜,特征在于组合物B的层的厚度介于7至30微米之间。
21.如权利要求18的多层膜,特征在于组合物B的层的厚度介于10至25微米之间。
22.前述权利要求任一项的多层膜在光伏电池、工业用织物中的用途或在金属上的用途。
23.光伏电池,其在所述光伏电池的后部板中包含根据权利要求1-21任一项的膜。
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US4322908P | 2008-04-08 | 2008-04-08 | |
US61/043229 | 2008-04-08 | ||
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CN (1) | CN101932443B (zh) |
AT (1) | ATE525205T1 (zh) |
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WO2010092942A1 (ja) * | 2009-02-13 | 2010-08-19 | 電気化学工業株式会社 | フッ化ビニリデン系樹脂フィルム |
WO2010101811A1 (en) * | 2009-03-03 | 2010-09-10 | Arkema France | Acrylic photovoltaic module backsheet |
DE102009001629A1 (de) * | 2009-03-18 | 2010-09-23 | Kuraray Europe Gmbh | Photovoltaikmodule enthaltend plastifizierte Zwischenschicht-Folien mit hoher Strahlungstransmission |
KR101114919B1 (ko) * | 2009-03-19 | 2012-02-14 | 주식회사 엘지화학 | 불소계 공중합체를 포함하는 태양전지 백시트 및 그 제조방법 |
FR2948943B1 (fr) | 2009-08-05 | 2012-03-16 | Arkema France | Film a base de polymere fluore et d'oxyde de zinc sans odeur acrylique pour application photovoltaique |
FR2955117B1 (fr) | 2010-01-14 | 2012-06-01 | Arkema France | Film a base de polymere fluore sans odeur acrylique pour application photovoltaique |
FR2955051B1 (fr) | 2010-01-14 | 2013-03-08 | Arkema France | Film resistant a l'humidite a base de polymere fluore et d'oxyde inorganique pour application photovoltaique |
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FR2966158B1 (fr) | 2010-10-13 | 2012-10-19 | Arkema France | Film a base de polymere fluore pour application photovoltaique |
WO2012049242A1 (en) | 2010-10-15 | 2012-04-19 | Solvay Specialty Polymers Italy S.P.A. | Fluoropolymer composition |
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JP5975032B2 (ja) * | 2011-06-30 | 2016-08-23 | Jnc株式会社 | 耐候性積層フィルム |
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EP2856016B1 (en) * | 2012-06-05 | 2022-06-01 | Trinseo Europe GmbH | Optical reflection films |
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EP2237950B2 (fr) | 2016-01-13 |
KR20100095622A (ko) | 2010-08-31 |
US20110232735A1 (en) | 2011-09-29 |
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TW200950966A (en) | 2009-12-16 |
FR2927016A1 (fr) | 2009-08-07 |
KR101196687B1 (ko) | 2012-11-06 |
ES2373423T5 (es) | 2016-04-21 |
WO2009101343A1 (fr) | 2009-08-20 |
JP2011510849A (ja) | 2011-04-07 |
EP2237950A1 (fr) | 2010-10-13 |
US8878054B2 (en) | 2014-11-04 |
FR2927016B1 (fr) | 2012-10-19 |
ES2373423T3 (es) | 2012-02-03 |
TWI566936B (zh) | 2017-01-21 |
JP5571582B2 (ja) | 2014-08-13 |
EP2237950B1 (fr) | 2011-09-21 |
ATE525205T1 (de) | 2011-10-15 |
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