CN103050560B - 具有氧气渗透阻隔的多层薄膜用于制造光伏模块的用途 - Google Patents

具有氧气渗透阻隔的多层薄膜用于制造光伏模块的用途 Download PDF

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CN103050560B
CN103050560B CN201210386025.0A CN201210386025A CN103050560B CN 103050560 B CN103050560 B CN 103050560B CN 201210386025 A CN201210386025 A CN 201210386025A CN 103050560 B CN103050560 B CN 103050560B
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A.帕夫利克
M.韦尔皮茨
H.赫格
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Abstract

本发明涉及具有氧气渗透阻隔的多层薄膜用于制造光伏模块的用途。具体地，本发明涉及其中氧化敏感的太阳能电池受保护以防止氧气进入的光伏模块，是使用多层薄膜作为后盖制造的，其中所述多层薄膜包括彼此直接相接的以下层：a)朝向太阳能电池的成型物料层，该成型物料的至少70重量%由EVOH组成，b)粘合促进剂层，c)热塑性成型物料中间层，d)任选的粘合促进剂层，和e)成型物料外层，该成型物料包括至少35重量%的聚酰胺含量。

Description

具有氧气渗透阻隔的多层薄膜用于制造光伏模块的用途
技术领域
本发明涉及具有由EVOH制成的氧气阻隔层的薄膜系统用于制造太阳能模块的用途。
背景技术
太阳能模块，经常也称为光伏模块，用于日光发电并且由包括太阳能电池系统作为核层(Kernschicht)的层压体组成。该核层用包封材料包覆，该包封材料用作对机械和由气候引起的影响的防护。
这里，活性（aktive）太阳能电池位于前盖和后盖之间。前盖是透明的并通常由玻璃组成；其借助于经常由乙烯-醋酸乙烯酯共聚物组成的粘合促进剂层与包括太阳能电池的层连接。后盖确保电屏蔽，用作对例如UV光的气候影响的防护和用作防潮层。
对于后盖，由氟聚合物薄膜和聚酯组成的薄膜复合体目前作为标准物使用。在外侧的氟聚合物薄膜确保耐气候性、聚酯薄膜确保机械稳定性和所需的电绝缘性。在内侧的另一个氟聚合物薄膜用于连接到太阳能电池系统的密封层。但是，这种氟聚合物薄膜对用作太阳能电池本身的包埋材料的密封层仅具有低粘合性。另外，氟聚合物薄膜仅提供较小程度的电绝缘，这导致需要使用较厚的聚酯薄膜。
WO2008138022因此建议用聚酰胺12(PA12)的薄膜替代这种复合体中的两个氟聚合物薄膜。在其改进中，WO2011066595建议朝向太阳能电池的热塑性塑料层包括例如二氧化钛的反光填料，而背向太阳能电池的热塑性塑料层包括例如玻璃纤维、硅灰石或云母的第二种填料，它为该层带来较高的导热率。示例性的热塑性塑料来自聚酰胺、聚酯，或聚酰胺和聚烯烃的共混物。明确提及PA11、PA12和PA1010，以及其与聚烯烃的共混物。
特别重要的是敏感(aktive)的活性太阳能电池的防护。这些电池主要由氧化敏感的硅组成。
发明内容
本发明的目的是将对活性太阳能电池的氧化侵蚀减到最少。
该目的通过使用多层薄膜作为光伏模块的后盖来实现，所述多层薄膜包括彼此直接相接的以下层：
a)朝向太阳能电池的成型物料层，该成型物料的至少70重量%，优选至少80重量%和更优选至少90重量%由乙烯-乙烯醇共聚物(EVOH)组成；
b)粘合促进剂层，
c)热塑性成型物料中间层，
d)任选的粘合促进剂层，和
e)成型物料外层，该组合物包括至少35重量%，优选至少40重量%，更优选至少45重量%，特别优选至少50重量%和最特别优选至少55重量%的聚酰胺含量，基于整个成型物料。
c)的层的成型物料可以包括例如聚酰胺、聚烯烃和/或聚酯作为热塑性塑料。另外，可存在常见的助剂和添加剂，特别地为光稳定剂和/或热稳定剂，反光填料，例如二氧化钛，以及补强填料，例如玻璃纤维、硅灰石或云母。
e)的层的成型物料可以包括下述聚酰胺之一或其多种的混合物。另外，可以存在至多40重量%的其它热塑性塑料，基于成型物料的整个聚合物含量，实例为抗冲改性橡胶。根据现有技术，存在的任何橡胶优选包括借助其获得与聚酰胺基质的相容性的官能团。此外，可以存在聚酰胺的常见助剂和添加剂，特别为光稳定剂和/或热稳定剂。对于填料，对c)的层的成型物料的论述也适用。另外，e)的层的成型物料可以是着色的和/或可以包括消光剂。
b)的层的粘合促进剂取决于c)的层的特性。当该层由基于聚酰胺、聚酯和/或聚烯烃的成型物料组成时，则粘合促进剂可以为包含至少35重量%，优选至少40重量%，更优选至少45重量%，更特别优选至少50重量%和极特别优选至少55重量%的聚烯烃的成型物料，所述聚烯烃带有0.1至5重量%，优选0.3至4重量%和更优选0.5至4重量%的酸酐基团。其它合适的粘合促进剂，特别是在其中c)的层基于聚酰胺或聚酯构成的那些情况下，包括多胺-聚酰胺接枝共聚物，任选和与EVOH相容的聚酰胺例如PA6结合，或并用第二种聚酰胺。合适的组合物例如在EP1065048A2以及EP1216826A1中公开。b)的层的成型物料可以进一步包括光稳定剂和/或热稳定剂以及反光填料，例如二氧化钛(WO2011066595)。
d)的层的粘合促进剂可以具有任何合适的组成。合适的例如为与针对上述b)的层的粘合促进剂的那些相同的体系。
EVOH是公知的。其为乙烯和乙烯醇的共聚物，以及有时也称为EVAL。共聚物中的乙烯含量通常为25至60mol%和特别为28至45mol%。许多类型是可商购的。可以参考例如公司手册“IntroductiontoKurarayEVALTMResins”，1.2/9810版，来自KurarayEVALEurope公司。
聚酰胺可以为部分结晶聚酰胺，例如PA6、PA66、PA610、PA612、PA10、PA810、PA106、PA1010、PA11、PA1011、PA1012、PA1210、PA1212、PA814、PA1014、PA618、PA512、PA613、PA813、PA914、PA1015、PA11、PA12，或部分芳香族聚酰胺，所谓的聚邻苯二甲酰胺(PPA)。(聚酰胺的命名符合国际标准，开头的一个或多个数字赋予起始二胺的碳原子数，结尾的一个或多个数字赋予二羧酸的碳原子数。如果仅提及一个数字，这意味着起始材料为α,ω-氨基羧酸或由其衍生的内酰胺；至于其他，参考H.Domininghaus，DieKunststoffeundihreEigenschaften[聚合物及其特性]，272页及其后，VDI-Verlag，1976。)合适的PPA为例如PA66/6T，PA6/6T，PA6T/MPMDT(其中MPMD表示2-甲基戊烷二胺)，PA9T，PA10T，PA11T，PA12T，PA14T，以及这些后几种类型与脂肪族二胺和与脂肪族二羧酸或与ω-氨基羧酸或内酰胺的共缩聚物。部分结晶的聚酰胺具有大于25J/g的熔融焓，按照ISO11357，由DSC法，在第二次加热中和熔融峰的积分测量。
聚酰胺也可以为部分结晶聚酰胺。部分结晶聚酰胺具有4至25J/g的熔融焓，按照ISO11357，由DSC法，在第二次加热中和熔融峰的积分测量。合适的部分结晶聚酰胺的实例为
-1,10-癸二酸或1,12-十二烷二酸和4,4'-二氨基二环己基甲烷的聚酰胺(PAPACM10和PAPACM12)，由具有35至65%的反式,反式异构体含量的4,4'-二氨基二环己基甲烷开始；
-基于上述部分结晶聚酰胺的共聚物；和
-上述部分结晶聚酰胺和与其相容的无定形聚酰胺的共混物。
聚酰胺也可以为无定形聚酰胺。无定形聚酰胺具有低于4J/g的熔融焓，按照ISO11357，由DSC法，在第二次加热中和熔融峰的积分测量。无定形聚酰胺的实例为：
-对苯二甲酸和/或间苯二甲酸与2,2,4-和2,4,4-三甲基六亚甲基二胺的异构体混合物的聚酰胺，
-间苯二甲酸与1,6-己二胺的聚酰胺，
-对苯二酸/间苯二甲酸的混合物与任选以与4,4'-二氨基二环己基甲烷的混合物形式的1,6-己二胺的共聚酰胺，
-对苯二甲酸和/或间苯二甲酸，3,3'-二甲基-4,4'-二氨基二环己基甲烷与月桂内酰胺或己内酰胺的共聚酰胺，
-1,12-十二烷二酸或癸二酸，3,3'-二甲基-4,4'-二氨基二环己基甲烷，与任选月桂内酰胺或己内酰胺的(共)聚酰胺，
-间苯二甲酸，4,4'-二氨基二环己基甲烷与月桂内酰胺或己内酰胺的共聚酰胺，
-1,12-十二烷二酸与4,4'-二氨基二环己基甲烷(在低反式,反式-异构体含量的情况下)的聚酰胺，
-对苯二甲酸和/或间苯二甲酸与任选以与己二胺的混合物形式的烷基取代的双(4-氨基环己基)甲烷同系物的(共)聚酰胺，
-双(4-氨基-3-甲基-5-乙基环己基)甲烷，任选与另一种二胺一起，与间苯二甲酸，任选与另一种二羧酸一起的共聚酰胺，
-间-苯二甲胺和另一种二胺，例如己二胺的混合物，与间苯二甲酸，任选与另一种二羧酸，例如对苯二甲酸和/或2,6-萘二羧酸一起的共聚酰胺，
-双(4-氨基环己基)甲烷和双(4-氨基-3-甲基环己基)甲烷的混合物，与具有8至14个碳原子的脂肪族二羧酸的共聚酰胺，和
-包含1,14-十四烷二酸和芳族、芳基脂族或脂环族二胺的混合物的聚酰胺或共聚酰胺。
这些实例可以通过添加另外的组分(例如己内酰胺，月桂内酰胺或二胺/二羧酸组合)或通过用其它组分部分或完全替代起始组分在极大的程度上变化。
聚醚酯酰胺例如由DE-A-2523991和DE-A-2712987已知；它们包含聚醚二醇作为共聚单体。聚醚酰胺例如由DE-A-3006961已知；它们包含聚醚二胺作为共聚单体。
在聚醚二醇或聚醚二胺中，聚醚单元可以例如基于1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇或1,3-丁二醇。聚醚单元也可以混合地构造，例如具有来源于二醇的单元的无规或嵌段分布。聚醚二醇或聚醚二胺的重均分子量为200至5000g/mol和优选为400至3000g/mol；其在聚醚酯酰胺或聚醚酰胺中的比例优选为4至60重量%和更优选为10至50重量%。合适的聚醚二胺可通过将相应的聚醚二醇通过还原胺化转变，或通过偶合至丙烯腈，随后氢化来获得；它们例如以JEFFAMINE?D或ED类型或ELASTAMINE?类型的形式由HuntsmanCorp.销售，或以PolyetheramineD系列的形式由BASFSE销售。如果将使用支化的聚醚酰胺，也可一并使用少量的聚醚三胺，例如JEFFAMINE?T类型。优选使用在链中每个醚氧原子包含平均至少2.3个碳原子的聚醚二胺或聚醚三胺。根据本发明，聚醚酰胺是优选的，因为抗水解性更好。
有用的热塑性聚酯包括线型(linear)构造的热塑性聚酯。这些通过二醇与二羧酸或其可形成聚酯的衍生物，例如二甲酯进行缩聚来制备。合适的二醇具有式HO-R-OH，其中R为具有2至40个和优选2至12个碳原子的二价支化或未支化的脂肪族和/或脂环族基团。合适的二羧酸具有式HOOC-R'-COOH，其中R'为具有6至20个和优选6至12个碳原子的二价芳族基团。
二醇的实例包括乙二醇，丙二醇，丁二醇，己二醇，新戊二醇，环己烷二甲醇，和C36二醇二聚物二醇。二醇可以单独使用或以二醇混合物的形式使用。至多25mol%的所述二醇可以由具有以下通式的聚亚烷基二醇替代
其中R''为具有2至4个碳原子的二价基团，x可以取2至50的值。
有用的芳族二羧酸的实例包括对苯二甲酸，间苯二甲酸，1,4-、1,5-、2,6-或2,7-萘二甲酸，联苯甲酸和二苯醚4,4'-二羧酸。至多30mol%的这些二羧酸可以由脂族或脂环族二羧酸，例如琥珀酸，己二酸，癸二酸，十二烷二酸或环己烷-1,4-二羧酸替代。
合适聚酯的实例为聚对苯二甲酸乙二醇酯，聚对苯二甲酸丙二醇酯，聚对苯二甲酸丁二醇酯，聚2,6-萘二甲酸乙二醇酯，聚2,6-萘二甲酸丙二醇酯和聚2,6-萘二甲酸丁二醇酯。
这些聚酯的制备属于现有技术(DE-OSS2407155，2407156；UllmannsEncyclop?diedertechnischenChemie，第4版，19卷，65页及其后，VerlagChemie，Weinheim，1980)。
聚烯烃可以为例如聚乙烯或优选为聚丙烯。聚丙烯原则上可以为任何商业上常见的聚丙烯类型，实例为全同立构或间同立构均聚丙烯，丙烯与乙烯和/或丁-1-烯的无规共聚物，丙烯-乙烯嵌段共聚物等。聚丙烯可以由任何已知的方法，例如由齐格勒-纳塔(Ziegler-Natta)法或借助于茂金属催化制备。其中可以存在抗冲改性组分，例如EPM橡胶或EPDM橡胶或SEBS。
对于多胺-聚酰胺接枝共聚物，可参考EP1065048A2的公开内容。
单独的薄膜层通常具有以下厚度：
·a)的层：50至250μm和优选100至200μm；
·b)的层：15至100μm和优选25至50μm；
·c)的层：100至500μm和优选150至400μm；
·d)的层：3至40μm和优选5至25μm；
·e)的层：15至100μm和优选25至50μm。
本发明使用的多层薄膜在通常良好的粘合性情况下就尽可能低的层数方面优化。其可以由所有现有技术方法，例如由共挤出或层压制造。其例如通过层压或粘合与其中包埋太阳能电池的密封层连接。由于a)的层中的EVOH含量，在层压的情况下获得对密封层的良好粘合性。使用的密封层可以为现有技术通常使用的任何材料。
本发明还提供一种使用根据权利要求的多层薄膜制造的光伏模块。
具体实施方式
本发明通过以下来示例性说明。为了该目的，制造以下成型物料；“份”始终为重量份。
层A(O 2 阻隔)的配混料：
借助于双螺杆挤出机(Zweiwellenextruder)(CoperionWerner&PfleidererZSK25WLE，36L/D)，在220℃的机筒温度下，混合95份的来自Kuraray的EVALTMF101B和5份的二氧化钛SachtlebenR420。股线(Strang)通过水浴冷却并切断；颗粒随后在80℃在循环空气烘箱中干燥12小时。
层B(粘合促进剂)的配混料：
借助于双螺杆挤出机(CoperionWerner&PfleidererZSK25WLE，36L/D)，在240℃的机筒温度下，混合59.3份的PA612，18份的PA6，2份的多胺-聚酰胺接枝共聚物(根据EP1065236A2，由87.063重量%的月桂内酰胺，0.164重量%的十二烷二酸，8.205重量%的50%Lupasol?G100，0.010重量%的50%次磷酸和4.558重量%的去离子水制备)，0.5份的IRGANOX?1098(位阻酚抗氧剂)，0.2份的TINUVIN?312(UV吸收剂)和20份的二氧化钛SachtlebenR420。股线(Strang)通过水浴冷却并切断；颗粒随后在80℃在循环空气烘箱中干燥12小时。
层C(中间层)的配混料：
通过双螺杆挤出机(CoperionWerner&PfleidererZSK25WLE，36L/D)，在200℃的机筒温度下，混合75.6份的Hostalen?EPD60R(丙烯-乙烯嵌段共聚物)，4份的LOTADER?AX8900(乙烯、丙烯酸甲酯和甲基丙烯酸缩水甘油酯的三聚物)，20份的TEC110高岭土和0.4份的IRGANOX?1010(位阻酚抗氧剂)。股线(Strang)通过水浴冷却并切断；颗粒随后在80℃在循环空气烘箱中干燥12小时。
层D(粘合促进剂)的配混料：
通过双螺杆挤出机(CoperionWerner&PfleidererZSK25WLE，36L/D)，在200℃的机筒温度下，混合55.6份的Hostalen?EPD60R，40份的VESTAMID?L1901(PA12)，4份的LOTADER?AX8900和0.4份的IRGANOX?1010。股线(Strang)通过水浴冷却并切断；颗粒随后在80℃在循环空气烘箱中干燥12小时。
层E(外层，模块背面)的配混料：
通过双螺杆挤出机(CoperionWerner&PfleidererZSK25WLE，36L/D)，在220℃的机筒温度下，混合79.3份的VESTAMID?L1901nf，0.5份的IRGANOX?1098，0.2份的TINUVIN?312和20份的二氧化钛SachtlebenR420。股线(Strang)通过水浴冷却并切断；颗粒随后在80℃在循环空气烘箱中干燥12小时。
多层薄膜的挤出：
使用来自Collin的多层薄膜系统(5-层薄膜的共挤出供料区块(Co-Extrusionsfeedblock))来制造四-层和五-层薄膜(加工温度大约230℃)。层厚分布如下设定：
A/B/C/D/E：100μm/50μm/150μm/20μm/50μm
B/C/D/E：50μm/150μm/20μm/50μm(对比，没有层A)
结果示于表1。
表1：实施例；按照ISO15105-2在23℃和50%相对湿度下的O2渗透，以cm3/(m2·d·bar)计
层分布 O2渗透
实施例 A/B/C/D/E 0.4
对比例1 B/C/D/E 74。

Claims (3)

1.多层薄膜作为光伏模块的后盖的用途，所述多层薄膜包括彼此直接相接的以下层：
a)朝向太阳能电池的成型物料层，其中的成型物料的至少70重量％由乙烯-乙烯醇共聚物(EVOH)组成，
b)粘合促进剂层，
c)热塑性成型物料中间层，
d)任选的粘合促进剂层，和
e)成型物料外层，其中的成型物料包含基于在所述外层中的成型物料至少35重量％的聚酰胺含量。
2.根据权利要求1的用途，特征在于
·a)的层具有50至250μm的厚度，
·b)的层具有15至100μm的厚度，
·c)的层具有100至500μm的厚度，
·d)的层具有3至40μm的厚度，和
·e)的层具有15至100μm的厚度。
3.使用根据在前权利要求之一的多层薄膜获得的光伏模块。
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