CN103072354B - 用于具有改进的颜料分散性的光伏模块的背膜 - Google Patents
用于具有改进的颜料分散性的光伏模块的背膜 Download PDFInfo
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- CN103072354B CN103072354B CN201210520699.5A CN201210520699A CN103072354B CN 103072354 B CN103072354 B CN 103072354B CN 201210520699 A CN201210520699 A CN 201210520699A CN 103072354 B CN103072354 B CN 103072354B
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- layer
- moulding compound
- film
- weight
- polyamide
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Classifications
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Landscapes
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
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- Power Engineering (AREA)
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Abstract
本发明涉及用于具有改进的颜料分散性的光伏模块的背膜。在包括下述层的膜中：a)得自模塑料的第一外层，所述模塑料包含I.至少35重量％的聚酰胺比例以及II.1‑65重量％的反光填料比例，以及c)得自模塑料的第二外层，所述模塑料具有I.至少35重量％的聚酰胺比例和II.1‑65重量％的填料比例，其中，上述百分比数据在每种情况中基于所有模塑料计，将聚酰胺弹性体作为聚酰胺组分如此用于根据a)的层的模塑料中和/或用于根据c)的层的模塑料中，使得根据a)的层的模塑料和/或根据c)的层的模塑料包含1‑25重量％的聚酰胺弹性体。将这样的膜用作光伏模块的后盖，其中将根据a)的层与嵌入到密封层中的太阳能电池结合。
Description
技术领域
本发明涉及作为后盖用于含聚酰胺的太阳能模块的具有改进的颜料分散和填料分散的多层膜。
背景技术
太阳能模块，也常被称为光伏模块，起着由太阳光产生电能的作用，并且由层压件构成，所述层压件包含太阳能电池体系作为核心层。该核心层由封装材料包覆，该封装材料起保护作用以免受机械的和气候造成的影响。
在这种情况下，主动式太阳能电池位于前盖和后盖之间。前盖是透明的并且通常由玻璃构成；借助于助粘剂层将它与包含太阳能电池的层结合，所述助粘剂层通常由乙烯-醋酸乙烯酯共聚物构成。后盖确保电屏蔽并作为免受例如紫外光的气候影响的保护并作为潮气屏障起作用。
目前，按照标准将得自氟聚合物膜和聚酯的复合膜用作后盖。在这种情况中，位于外侧的氟聚合物膜确保耐候性，聚酯膜确保机械稳定性以及所需的电绝缘性能。位于内侧的另一层氟聚合物膜用于连接到太阳能电池系统的密封层。然而，这样的氟聚合物膜对密封层仅具有低附着力，该密封层被用作嵌入材料用于太阳能电池本身。另外，该氟聚合物膜仅对电绝缘有小的贡献，由此导致需要使用相当厚的聚酯膜。
因此，WO2008138022中提出，在这样的复合物中用得自聚酰胺12(PA12)的膜替代该两层氟聚合物膜。由此，在一个扩展方案中，在WO2011066595中提出，面向太阳能电池的热塑性塑料层包含反光填料如二氧化钛，而背向太阳能电池的热塑性塑料层包含第二填料如玻璃纤维、硅灰石或云母，其导致该层具有更高的热导率。示例性的热塑性塑料来自聚酰胺、聚酯或者聚酰胺与聚酯的共混物。明确提及PA11、PA12和PA1010及其与聚烯烃的共混物。
在这样的光伏模块中，反光填料的分布具有特殊的意义。这样，反射度和由此太阳能电池的电流产率随着增加的分散度而增加。另外，分布品质同时影响背膜的表面质量。这在后盖通常完全基于聚酰胺的层中是异常重要的，所述层面向实际的太阳能电池并且在外侧是可以看得见的，因为这里由于小的层厚度，颜料附聚体变得特别显而易见。
发明内容
因此，本发明的目的在于在光伏模块的背膜的两个外层中获得改进的颜料分散和填料分散。
出乎意料地，已经发现该目的可以通过使用聚醚酯酰胺或聚醚酰胺类型的聚酰胺弹性体来实现。
因此，本发明提供包括下述层的膜：
a)得自模塑料的第一外层，所述模塑料包括：
I.至少35重量％，优选至少40重量％，特别优选至少45重量％，尤其优选至少50重量％，并且最优选至少55重量％的聚酰胺比例，以及
II.1-65重量％，优选2-60重量％，特别优选3-55重量％，尤其优选4-50重量％，并且最优选5-45重量％的反光填料比例，
b)任选地，热塑性模塑料的中间层，以及
c)得自模塑料的第二外层，所述模塑料具有
I.至少35重量％，优选至少40重量％，特别优选至少45重量％，尤其优选至少50重量％，并且最优选至少55重量％的聚酰胺比例，以及
II.1-65重量％，优选地2-60重量％，特别优选3-55重量％，尤其优选4-50重量％，并且最优选5-45重量％的反光填料比例，
其中，上述百分比数据在每种情况中基于所有模塑料计，并且其中通过将选自聚醚酯酰胺和聚醚酰胺的聚酰胺弹性体作为聚酰胺组分用于根据a)的层的模塑料中和/或用于根据c)的层的模塑料中进行复合膜的改性，以至于根据a)的层的模塑料和/或根据c)的层的模塑料包含1-25重量％，优选2-20重量％和特别优选4-20重量％的聚酰胺弹性体。
在这种情况下，优选根据a)、b)和c)的层彼此直接相随。此外优选的是，根据a)的层和根据c)的层都包含聚酰胺弹性体。此外，在一些情况下可以插入助粘剂层用于改进在根据a)和b)的层之间的和/或在根据b)和c)的层之间的层粘附力。
所述聚酰胺可以是部分结晶的聚酰胺，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，或者半芳族聚酰胺，所谓的聚邻苯二甲酰胺(PPA)。(聚酰胺的命名按照国际标准，其中第一个数字给出的是起始二元胺中的碳原子数目且最后一个数字给出的是二元羧酸中的碳原子数目。如果仅提及一个数字，那么这意味着从α，ω-氨基羧酸或者从由其衍生出的内酰胺开始；此外可参考H.Domininghaus，Die Kunststoffe undihre Eigenschaften 272页及以后几页，VDI-Verlag，1976。)适合的PPA是，例如，PA66/6T、PA6/6T、PA6T/MPMDT(MPMD代表2-甲基戊亚甲基二胺)、PA9T、PA10T、PA11T、PA12T、PA14T以及这些后面的类型与脂族二元胺和脂族二元羧酸或者与ω-氨基羧酸或内酯的共缩聚物。部分结晶的聚酰胺具有大于25J/g的熔化焓，根据ISO 11357用DSC方法在第二加热步骤时及用熔融峰的积分测量。
但是，聚酰胺也可以是半结晶的聚酰胺。半结晶的聚酰胺具有4到25J/g的熔化焓，根据ISO 11357用DSC方法在第二加热步骤时及用熔融峰的积分测量。适合的半结晶聚酰胺的例子是
-得自1，10-癸二酸或1，12-十二烷二酸以及4，4’-二氨基二环己基甲烷(PAPACM10和PAPACM12)的聚酰胺，从具有35-65％的反式，反式异构体比例的4，4’-二氨基二环己基甲烷开始；
-基于上面提到的部分结晶的聚酰胺的共聚物；以及
-得自上面提到的部分结晶的聚酰胺和与之相容的非晶形的聚酰胺的共混物。
所述聚酰胺也可以是非晶形的聚酰胺。非晶形聚酰胺具有小于4J/g的熔化焓，根据ISO 11357用DSC方法在第二加热步骤时及用熔融峰的积分测量。非晶形聚酰胺的例子是：
-得自对苯二甲酸和/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，
-得自间苯二甲酸和1，6-六亚甲基二胺的聚酰胺，
-得自对苯二甲酸/间苯二甲酸和1，6-六亚甲基二胺的混合物的共聚酰胺，任选在与4，4’-二氨二环己基甲烷的混合物中，
-得自对苯二甲酸和/或间苯二甲酸、3，3’-二甲基-4，4’-二氨基二环己基甲烷和十二内酰胺或己内酰胺的共聚酰胺，
-得自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和任选的十二内酰胺或己内酰胺的(共)聚酰胺，
-得自间苯二甲酸、4，4’-二氨基二环己基甲烷以及十二内酰胺或己内酰胺的共聚酰胺，
-得自1，12-十二烷二酸和4，4’-二氨基二环己基甲烷(在反式，反式异构体比例低的情况下)的聚酰胺，
-得自对苯二甲酸和/或间苯二甲酸以及烷基取代的双(4-氨基环己基)甲烷同系物的(共)聚酰胺，任选在与六亚甲基二胺的混合物中，
-得自双(4-氨基-3-甲基-5-乙基环己基)甲烷以及间苯二甲酸的共聚酰胺，其中双(4-氨基-3-甲基-5-乙基环己基)甲烷任选与另一种二胺一起，间苯二甲酸任选与另一种二元羧酸一起，
-得自间-苯二甲胺与另一种二胺例如六亚甲基二胺的混合物以及间苯二甲酸的共聚酰胺，间苯二甲酸任选与另一种二元羧酸例如对苯二甲酸和/或2，6-萘二甲酸一起，
-得自双(4-氨基环己基)甲烷与双(4-氨基-3-甲基环己基)甲烷的混合物，以及具有8-14个碳原子的脂族二元羧酸的共聚酰胺，以及
-得自包含1，14-十四烷二酸和芳族、脂族、芳脂族或脂环族二胺的混合物的聚酰胺或共聚酰胺。
这些例子可以通过另外添加其它成分(例如己内酰胺、十二内酰胺或二胺/二元羧酸组合)或通过用另外的成分部分地或完全地替换起始成分而使其在很大程度上加以改变。
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。聚醚酰胺从例如DE-A-3006961已知；它们包含聚醚二胺作为共聚单体。
在聚醚二元醇或聚醚二胺中，聚醚单元例如可以基于1，2-乙二醇、1，2-丙二醇、1，3-丙二醇、1，4-丁二醇或者1，3-丁二醇。该聚醚单元也可以混合构建，例如具有无规的或者嵌段分布的源于二元醇的单元。聚醚二元醇或聚醚二胺的重均摩尔质量是200到5000g/mol并且优选地为400到3000g/mol；其在聚醚酯酰胺或聚醚酰胺中的比例优选为4-60重量％并且特别优选为10-50重量％。适合的聚醚二胺可以通过相应的聚醚二元醇通过还原胺化或者通过耦合到丙烯腈上伴随随后的氢化作用而转化获得；它们是例如以Huntsman Corp.的D-或ED-型、或型的形式，或者以BASF SE的PolyetheramineD-系列的形式商购可得的。如果应使用支化的聚醚酰胺，也可以以更小的量一起使用聚醚三胺，例如T型。优选使用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，由于更好的水解稳定性优选聚醚酰胺。
根据a)的层的模塑料可以包含上述提及的聚酰胺之一或者可以包含作为混合物的上述提及的聚酰胺的多种。另外，基于模塑料的总的聚合物比例计，可以包含最高40重量％的其它热塑性塑料，例如冲击力改性的橡胶。根据现有技术，可能包含的橡胶优选包含官能团，用该官能团获得与聚酰胺基质的相容性。此外，可以包含惯用于聚酰胺的助剂和添加剂，尤其是光-和/或热稳定剂。所述反光填料可以是具有比根据a)的层的热塑性塑料组分的反射能力更高的反射能力的任何填料；其尤其是二氧化钛(WO2011066595)。
根据b)的层的模塑料可以包含例如聚酰胺、聚烯烃和/或聚酯作为热塑性塑料。此外，可以包含助剂和添加剂，尤其是光-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。
适合于根据c)的层的模塑料与用于根据a)的层的模塑料相同，以及对于填料，与用于根据b)的层的模塑料相同。另外，根据c)的层的模塑料可以是着色的和/或具有消光剂。
在三层的实施例中，各膜层通常具有以下厚度：
·根据a)和c)的层：15到100μm并且优选25到50μm；
·根据b)的层：100到500μm并且优选150到400μm。
在两层的实施例中，层的厚度通常如下：
·根据a)的层：15到100μm并且优选25到50μm；
·根据c)的层：100到500μm并且优选150到400μm。
可能存在于根据a)和b)的层和/或根据b)和c)的层之间的助粘剂层通常为3到40μm并且优选5到25μm厚。
根据本发明使用的多层膜可以根据所有现有技术的方法例如通过共挤出或层压来生产。
本发明的主题也是要求保护的膜作为光伏模块的后盖的用途。为此，将根据a)的层通过例如层压或粘附而与密封层结合，太阳能电池被嵌入在该密封层中。由于在根据a)的层中的聚酰胺或聚酰胺弹性体的比例，在层压时获得良好的对密封层的粘附力。作为密封层可以使用根据现有技术惯用的任何材料。
此外，本发明的主题是光伏模块，其包括根据权利要求的作为后盖的多层膜，其中将根据a)的层与密封层粘合，太阳能电池被嵌入在该密封层中。
具体实施方式
在下文中，示例性地说明本发明。为此生产以下的模塑料；“份”始终是重量份：
用于外层的配混物1：
借助于双螺杆挤出机(Coperion Werner&Pfleiderer ZSK 25 WLE，36L/D)在220℃的料筒温度下将79.25份的L1901 nf(PA12)、0.5份的1098(一种位阻酚抗氧化剂)、0.2份的312(紫外线吸收剂)以及20份的二氧化钛Sachtleben R 420混合。借助于水浴使挤出物冷却，并被切碎；随后，在循环空气烘箱内，在80℃下，将粒料干燥12个小时。
用于外层的配混物2：
借助于双螺杆挤出机(Coperion Werner&Pfleiderer ZSK 25WLE，36L/D)在220℃的料筒温度下将71.75份的L1901nf、7.5份的聚醚酯酰胺(由63.796重量％的十二内酰胺、6.645重量％的十二烷二酸、29.492重量％的PTHF 1000以及0.067重量％的50％次磷酸制备)、0.5份的1098、0.2份的312以及20份的二氧化钛Sachtleben R 420混合。借助于水浴使挤出物冷却，并被切碎；随后，在循环空气烘箱内，在80℃下，将粒料干燥12个小时。
用于外层的配混物3：
借助于双螺杆挤出机(Coperion Werner&Pfleiderer ZSK 25WLE，36L/D)在220℃的料筒温度下将64.25份的L1901 nf、15份的与配混物2中相同的聚醚酯酰胺、0.5份的1098、0.2份的312以及20份的二氧化钛Sachtleben R420混合。借助于水浴使挤出物冷却，并被切碎；随后，在循环空气烘箱内，在80℃下，将粒料干燥12个小时。
用于中间层的配混物4：
借助于双螺杆挤出机(Coperion Werner&Pfleiderer ZSK 25WLE，36L/D)在200℃的料筒温度下将50.6份的L1901、26份的MOPLEN HP552L(挤出型均聚聚丙烯)、20份的高岭土TEC 110、3份的FG1901(一种用马来酸酐改性的苯乙烯-乙烯/丁烯-嵌段共聚物)以及0.4份的1098混合。借助于水浴使挤出物冷却，并被切碎；随后，在循环空气烘箱内，在80℃下，将粒料干燥12个小时。
三层膜的挤出：
在约230℃的加工温度下，用Collin的多层膜设备(宽缝喷嘴300mm、缝隙0-6mm、用于3层或5层膜的共挤出喂料块)生产三层膜。中间层被设定为250μm，外层分别被设定为50μm。结果如表1所示。
表1：实施例
改进的颜料分散以根据本发明改进的反射性表现出来。
Claims (12)
1.光伏模块的背膜，其包含以下层：
a)得自模塑料的第一外层，所述模塑料包含
I．至少35重量％的聚酰胺比例以及
II.1-65重量％的反光填料比例，以及
c)得自模塑料的第二外层，所述模塑料具有
I．至少35重量％的聚酰胺比例和
II.1-65重量％的填料比例，
其中，上述百分比数据在每种情况中基于所有模塑料计，
其特征在于，
将选自聚醚酯酰胺和聚醚酰胺的聚酰胺弹性体作为聚酰胺组分用于根据a)的层的模塑料中和/或用于根据c)的层的模塑料中，使得根据a)的层的模塑料和/或根据c)的层的模塑料包含1-25重量％的聚酰胺弹性体。
2.根据权利要求1所述的膜，
其特征在于，
所述根据a)的层的模塑料和/或所述根据c)的层的模塑料包含2-20重量％的聚酰胺弹性体。
3.根据权利要求1或2所述的膜，
其特征在于，
所述聚酰胺弹性体是聚醚酰胺。
4.根据权利要求1或2所述的膜，
其特征在于，
如下的层存在于根据a)和c)的层之间：
b)得自热塑性模塑料的中间层。
5.根据权利要求4所述的膜，
其特征在于，
在根据a)和b)的层之间和/或在根据b)和c)的层之间存在助粘剂层。
6.根据权利要求1或2所述的膜，
其特征在于，
根据a)和c)的层直接彼此相随。
7.根据权利要求4所述的膜，
其特征在于，
- 所述根据a)和c)的层具有15到100μm的厚度并且
- 所述根据b)的层具有100到500μm的厚度。
8.根据权利要求5所述的膜，
其特征在于，
所述一层或多层助粘剂层分别为3-40μm厚。
9.根据权利要求6所述的膜，
其特征在于，
- 所述根据a)的层具有15-100μm的厚度并且
- 所述根据c)的层具有100-500μm的厚度。
10.根据权利要求1或2所述的膜，
其特征在于，
所述反光填料是二氧化钛。
11.根据权利要求1-10的任意一项所述的膜用作光伏模块的后盖的用途，其中将根据a)的层与在其中嵌入太阳能电池的密封层结合。
12.光伏模块，其包含根据权利要求1-10的任意一项所述的膜作为后盖，其中将根据a)的层与在其中嵌入太阳能电池的密封层结合。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE201110084520 DE102011084520A1 (de) | 2011-10-14 | 2011-10-14 | Rückfolie für Photovoltaikmodule mit verbesserter Pigmentdispergierung |
| DE102011084520.8 | 2011-10-14 |
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| Publication Number | Publication Date |
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| CN103072354A CN103072354A (zh) | 2013-05-01 |
| CN103072354B true CN103072354B (zh) | 2016-12-28 |
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| US (1) | US10661541B2 (zh) |
| EP (1) | EP2581225B1 (zh) |
| JP (1) | JP6180096B2 (zh) |
| KR (1) | KR101998412B1 (zh) |
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| CA2782097A1 (en) * | 2009-12-01 | 2011-06-09 | Isovoltaic Ag | Solar module and coextrudate element |
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| JP2011042774A (ja) * | 2008-10-16 | 2011-03-03 | Ube Industries Ltd | ゴム組成物及びその製造方法 |
| CA2782097A1 (en) * | 2009-12-01 | 2011-06-09 | Isovoltaic Ag | Solar module and coextrudate element |
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| TW201332766A (zh) | 2013-08-16 |
| KR101998412B1 (ko) | 2019-07-09 |
| US20130092227A1 (en) | 2013-04-18 |
| ES2606373T3 (es) | 2017-03-23 |
| DE102011084520A1 (de) | 2013-04-18 |
| EP2581225A1 (de) | 2013-04-17 |
| EP2581225B1 (de) | 2016-09-14 |
| KR20130040722A (ko) | 2013-04-24 |
| JP2013086511A (ja) | 2013-05-13 |
| TWI558562B (zh) | 2016-11-21 |
| JP6180096B2 (ja) | 2017-08-16 |
| US10661541B2 (en) | 2020-05-26 |
| CN103072354A (zh) | 2013-05-01 |
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