CN1316635C - 具有热塑性热熔融体粘合剂层的光电组件和其生产方法 - Google Patents
具有热塑性热熔融体粘合剂层的光电组件和其生产方法 Download PDFInfo
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- CN1316635C CN1316635C CNB021435820A CN02143582A CN1316635C CN 1316635 C CN1316635 C CN 1316635C CN B021435820 A CNB021435820 A CN B021435820A CN 02143582 A CN02143582 A CN 02143582A CN 1316635 C CN1316635 C CN 1316635C
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Abstract
本发明涉及具有特殊热塑性粘合剂层的光电组件,和它们的生产方法。所述光电组件包括:A)至少一层在面向能源的正面上的玻璃的或耐冲击、UV稳定、风化稳定、透明塑料的面层,该层的水蒸气渗透率低,B)至少一层在背向能源的背面上的玻璃的或风化稳定的塑料面层,该层的水蒸气渗透率低,C)至少一层在A)和B)之间的塑料粘合剂层,其中嵌入至少一个或多个互相电连接的太阳能电池。该光电组件是将包括盖片或盖膜与塑料粘合剂膜的复合材料、太阳能电池串列、和包括背面上的膜或片与塑料粘合剂膜的复合材料加到真空板式层压机或辊式层压机,经其压制和粘合而制成的。
Description
发明领域
本发明涉及具有特殊热塑性粘合剂层的光电组件和它们的生产方法。
发明背景
光电组件或太阳能组件(solar modules)被理解为系指从光,特别是从太阳光直接产生电流的光电结构元件。产生太阳能电流的关键性成本效率因素,是所用太阳能电池的效率、太阳能组件的生产成本、和寿命。
按照常规,太阳能组件包含玻璃复合材料、太阳能电池电路、嵌入材料、和背面结构。太阳能组件的各层必须具有下列功能:
采用前置玻璃(顶层)保护不受机械和风化的影响。为了保持在光谱350nm-1,150nm范围的吸收损失,必须具有非常高的透明度,因此,通常产生电流采用的硅太阳能电池的效率损失尽可能低。通常采用硬化的低铁燧石玻璃(3或4mm厚),它在上述光谱范围的透射率为90-92%。
采用嵌入材料(通常采用EVA(乙烯/乙酸乙烯酯)膜)粘合组件的复合材料。在约150℃的层压操作中,EVA熔融体因此也流入太阳能电池的间隙中,将太阳能电池焊接,或采用导电的粘合剂将太阳能电池相互连接,在此过程中,EVA发生热交联。在真空中和在机械压力下进行层压,能防止气泡的生成,气泡会产生折射损失。
组件的背面保护太阳能电池和嵌入材料不受潮湿和氧化。在组装太阳能组件的过程中,也利用背面作为防止划痕等的机械保护和起绝缘作用。虽然背面的结构也可以由玻璃制造,但通常采用复合膜。在复合膜中基本上采用PVF(聚氟乙烯)-PET(聚对苯二酸乙二酯)-PVF或PVF-铝-PVF方案。
在太阳能组件结构中(组件的正面和背面)采用的所谓封装材料,特别是对水蒸气和氧必须具有优良的阻挡性能。使太阳能电池本身不它们在层压过程中,直接落在太阳能电池相应的接点上。
9.根据权利要求8的光电组件,其中所述粘合剂以焊珠的形式施加。
10.根据权利要求1的光电组件,其中在A)中所述的面层和太阳能电池之间的C)中所述的塑料粘合剂层中,还存在一层厚度小于500μm的玻璃膜。
11.根据权利要求1的光电组件,其中所述聚氨酯的硬度为肖氏A级92-肖氏D级70。
12.一种生产光电组件的方法,其中将包括盖片或盖膜与塑料粘合剂膜的复合材料、太阳能电池串列、和包括背面上的膜或片与塑料粘合剂膜的复合材料加到真空板式层压机或辊式层压机,经其压制和粘合,制成光电组件,所述组件包括:
A)至少一层在面向能源的正面上的玻璃的或耐冲击、UV稳定、风化稳定、透明塑料的面层,该层的水蒸气渗透率低,
B)至少一层在背向能源的背面上的玻璃的或风化稳定的塑料面层,该层的水蒸气渗透率低,
C)至少一层在A)和B)之间的塑料粘合剂层,其中嵌入至少一个或多个互相电连接的太阳能电池,
其中C)中所述的塑料粘合剂层,包括脂肪族热塑性聚氨酯,硬度为肖氏A级75-肖氏D级70,在E’-模量2MPa下,根据DMS-方法测定的软化温度T软化为90-150℃,脂肪族热塑性聚氨酯是下列材料的反应产物:脂肪族二异氰酸酯;至少一种泽列维季诺夫-活性的多元醇,其中具有平均至少1.8-不大于3.0个泽列维季诺夫-活性的氢原子、数均分子量为600-10,000g/mol;和至少一种作为链增长剂的泽列维季诺夫-活性的多元醇,其中具有平均至少1.8-不大于3.0个泽列维季诺夫-活性的氢原子,数均分子量为60-500g/mol;脂肪族二异氰酸酯的NCO基团与链增长剂和多元醇的OH基团的摩尔比例为0.85-1.2。
粘合剂层的挠性也不够。
专利申请JP-A 09-312410和JP-A 09-312408叙述了应用热塑性聚氨酯或弹性体作为太阳能组件的粘合剂层。设计太阳能汽车的太阳能组件,必须防止太阳能电池受机械振动。这是采用极其柔软的TPUs实现的,TPUs比EVA柔软得多。粘合是借助真空进行的。正如上面已经叙述的,粘合需要长的加工时间。此外,从组件尺寸2m2开始就不能再采用真空层压机了,因为气泡在边缘上的逸出路径太长,使它们在常规的加工时间内不能逸出,而被“冻结”在粘合剂中。这造成由于折射引起的损失。在JP-A 09-312410中所述的热塑性聚氨酯,在真空容器内的加热过程中确实变软,但它们还不足以成为充满太阳能电池之间间隙的液体。因而制成不能使用的太阳能电池。
专利申请WO 99/52153和WO 99/52154称,应用聚碳酸酯层和氟聚合物层的复合膜或复合体封装太阳能组件。这些申请采用只能缓慢加工的EVA热熔体粘合剂进行粘合。
专利申请DE-A 3 013 037叙述了在正面和背面上具有PC片材的对称结构的太阳能组件,该太阳能电池嵌入层(粘合剂层)的特征在于,最大E模量为1,000MPa,它太硬了使在热膨胀过程中会撕裂易碎的太阳能电池。
作为热熔融体粘合剂的EVA必须在约150℃熔融;然后EVA成为水一样的液体。如果现在组件的结构很重,在这种情况下,在层压过程中EVA被挤压到侧面,因此粘合剂层的有效厚度下降。在约150℃开始交联过程,需要15-30分钟。由于这个过程时间较长,EVA只能用真空层压机间断地加工。EVA的加工窗口(依赖时间的加压加温过程)非常窄。此外,在UV的辐射下EVA变黄,考虑到UV辐射,例如需在EVA上面的玻璃板中掺杂铈作为UV的吸收剂[F.J.Pern,S.H.Glick,太阳能材料和太阳能电池,
61(2000),153-188页]。
塑料具有比硅(2·10-6K-1)或玻璃(4·10-6K-1)明显较高的热膨胀系数(50-150·10-6K-1)。因此如果太阳能电池采用塑料而不用玻璃封装,就必须采用挠性适宜的粘合剂层,防止硅太阳能电池与塑料的机械分离。然而,为了使整个太阳能组件复合材料仍然具有足够的机械扭变稳定性,粘合剂层的挠性也不应该太大。EVA解决了硅和塑料扩散系数不同以及扭变稳定性不够的问题。
发明概述
本发明的目的是提供一些光电组件,这些组件的特征在于,能够采用又快又便宜的方法生产它们,而且重量轻。
可以采用根据本发明的光电组件实现这一目的。
本发明提供结构如下的光电组件:
A)至少一层在面向能源的正面上的玻璃的或耐冲击、UV稳定、风化稳定的透明塑料的面层,该层的水蒸气渗透率低,
B)至少一层在背向能源的背面上的玻璃的或风化稳定的塑料面层,该层的水蒸气渗透率低,
C)至少一层在A)和B)之间的塑料粘合剂层,其中嵌入至少一个或多个互相电连接的太阳能电池,
其中在C)中的塑料粘合剂层包括脂肪族热塑性聚氨酯,硬度为肖氏A级75-肖氏D级70,优选肖氏A级92-肖氏D级70,在E’-模量2MPa下,软化温度T软化为90-150℃(根据DMS-方法测定),脂肪族热塑性聚氨酯是下列材料的反应产物:脂肪族二异氰酸酯;至少一种泽列维季诺夫(Zerewitinoff)-活性的多元醇,其中具有平均至少1.8-不大于3.0个泽列维季诺夫-活性的氢原子、数均分子量为600-10,000g/mol;和至少一种作为链增长剂的泽列维季诺夫-活性的多元醇,其中具有平均至少1.8-不大于3个泽列维季诺夫-活性的氢原子、数均分子量为60-500g/mol;脂肪族二异氰酸酯的NCO基团与链增长剂和多元醇OH基团的摩尔比例为0.85-1.2。
附图简述
图1示出具有盖片和背面膜的根据本发明的太阳能组件。
图2示出具有盖膜和背面片的根据本发明的太阳能组件。
图3示出生产片材和粘合剂膜的复合材料的示意图。
图4示出采用辊式层压机生产太阳能组件的示意图。
图5示出采用辊式层压机生产连续组件的示意图。
图6示出将连续组件分割成标准组件的示意图。
图7示出具有膜折合处的可折叠太阳能组件的示意图。
图8示出以导电粘合剂电连接的太阳能组件的示意图。
发明详述
本发明提供具有如下结构的光电组件:
A)至少一层在面向能源的正面上的玻璃的或耐冲击、UV稳定、风化稳定的透明塑料的面层,该层的水蒸气渗透率低,
B)至少一层在背向能源的背面上的玻璃的或风化稳定的塑料面层,该层的水蒸气渗透率低,
C)至少一层在A)和B)之间的塑料粘合剂层,其中嵌入至少一个或多个互相电连接的太阳能电池,
其中在C)中的塑料粘合剂层包括脂肪族热塑性聚氨酯,硬度为肖氏A级75-肖氏D级70,优选肖氏A级92-肖氏D级70,在E’-模量2MPa下,软化温度T软化为90-150℃(根据DMS-方法测定),脂肪族热塑性聚氨酯是下列材料的反应产物:脂肪族二异氰酸酯;至少一种泽列维季诺夫-活性的多元醇,其中具有平均至少1.8-不大于3.0个泽列维季诺夫-活性的氢原子、数均分子量为600-10,000g/mol;和至少一种作为链增长剂的泽列维季诺夫-活性的多元醇,其中具有平均至少1.8-不大于3个泽列维季诺夫-活性的氢原子、数均分子量为60-500g/mol;脂肪族二异氰酸酯的NCO基团与链增长剂和多元醇OH基团的摩尔比例为0.85-1.2,优选0.9-1.1。
动态-机械分析(DMS-方法)
从注塑成型的片材上冲压一些矩形的片材(30mm×10mm×1mm)。使这些试片在不变的预加载荷下(任选取决于储存的组件),定期地经受非常小的变形并以温度和激励频率为函数,测定作用在夹具上的力。
外加的预加载荷用来保持在变形幅度为负值的时间点上,试样仍被适当地拉紧。
测定软化点温度T软化,作为在E′=2MPa下的耐热特征温度。
在1Hz下,在温度-150-200℃的范围内,采用Seiko生产的SeikoDMS 210型仪器进行DMS测定,加热速度为2℃/min。
面层A)优选包括片或一层或多层膜。
层B)优选包括片或一层或多层膜。
面层A)优选是以条存在的膜或片材,这些条配置在所谓的太阳能电池串列上。
优选将嵌入在C)中所述的塑料粘合剂层中的太阳能电池排列成太阳能电池串列。
为了使太阳能电池产生最高可能的电压,优选将太阳能电池串列串联焊接,或借助导电的粘合剂层将其相互串联连接。
当采用导电的粘合剂时,以所谓粘合剂焊珠(20)的形式,优选将这些粘合剂直接放在塑料粘合剂层的里面(102,111)[“Kleben,Grundlagen-Technologie-Anwendungen(粘合剂,基础-工艺-应用),Handbuch Münchener Ausbildungsseminar”(慕尼黑教育讲座手册),Axel Springer出版社,柏林,海得堡1997],采用这种方法,它们在层压过程中能直接落在太阳能电池(24)的相应接点上,并具有重叠区(21),使太阳能电池串联(参见图8)。因此,可以省去层压之前的焊接,使电连接和封装在一个步骤中完成。
优选在面层A)和C)中所述的塑料粘合剂层中的太阳能电池之间,还存在一层厚度小于500μm的玻璃膜。
根据本发明的太阳能组件,优选包括在正面上的透明盖层(1,5),封闭太阳能电池(4)的粘合剂层(2),和背面(3,6),背面可以是不透明的或透明的(见图1和图2)。盖层应具有下列性能:在350nm-1,150nm内透明度高、冲击强度高、对UV和风化稳定、以及水蒸气渗透率低。盖层(1,5)可由下列材料制造:玻璃、聚碳酸酯、聚酯、聚氯乙烯、含氟的聚合物、热塑性聚氨酯、或任何所需的这些材料的组合。盖层(1,5)可以制成片、膜、或复合膜。背面(3,6)应对风化稳定,而且水蒸汽渗透率低和电阻高。除了对用于正面所提到的材料以外,后面还可以由对风化稳定的聚酰胺、ABS、或其它塑料制造,或由在里面提供电绝缘层的金属片或金属箔制造。背面(3,6)可以制成片、膜、或复合膜。
粘合剂层(2)应具有下列性质:在350nm-1,150nm内透射率高,对太阳能电池背面的硅、铝接点、镀锡的前面接点、太阳能电池的防折射层、盖层材料和背面材料具有优良的粘合作用。粘合剂层可以包括一层或多层粘合剂膜,可以将粘合剂膜层压在盖层和/或背面上。
粘合剂膜(2)应是挠性的,以便补偿由于塑料和硅热膨胀系数不同产生的应力。粘合剂膜(2)的E模量应为大于1MPa至小于200MPa,优选大于10MPa至小于140MPa,熔点低于连接太阳能电池的焊剂的熔融温度,焊剂的熔融温度一般为180-220℃,或低于导电粘合剂的Vicat软化点(热稳定性),Vicat软化点一般高于220℃。此外,粘合剂膜还应该电阻高,吸水率低、耐UV辐射和热氧化的性能好、在化学上是惰性的、和在未交联的情况下容易处理。
在本发明优选的实施方案中,盖层和背面包括塑料膜或塑料片。盖层和背面的总厚度为至少2mm,优选至少3mm。因此太阳能电池足以免受机械影响。粘合包括至少一层热塑性聚氨酯粘合剂膜,其总厚度为300-1,000μm。
本发明另一个优选的实施方案是一种太阳能组件,其中盖层和背面包含一些厚度小于1mm的上述材料,复合材料被固定在适宜的金属或塑料支持物上,该支持物使整个系统具有必要的刚性。塑料的支持物优选玻璃纤维加强的塑料。
本发明另一个优选的实施方案是一个太阳能组件,其中覆盖层包括一层厚度小于1mm的上述材料,后侧包括多层的塑料片材,以增加刚性并明显地减轻重量。
在本发明的另一个优选的实施方案中,盖层(103)和/或背面(113)包括一些条状的膜和片材,它们具有太阳能电池串列的准确尺寸。按几毫米-几厘米的间隔,将这些条固定在粘合剂膜(102或111)上,使在各电池串(见图7)之间,存在只有粘合剂膜,而没有覆盖层或背面的区域,该区可以用作例如膜的折合处(131)。这种太阳能组件可以是折叠的和/或卷起来的,例如使其容易输送。这种太阳能组件,更优选由重量轻的塑料构成,使其能在宿营区域、户外区域、或在如移动电话、膝上计算机等其它可移动的应用中得到应用。
本发明还提供一种生产根据本发明的光电组件的方法,其特征在于采用板式真空层压机(真空热扎机)或辊式层压机生产光电组件。
层压过程的温度优选至少20℃,至多比所采用的热塑性聚氨酯的软化温度T软化高40℃。
优选将包括盖片或盖膜与塑料粘合剂膜的复合材料、太阳能电池串列、包括背面上的膜或片与塑料粘合剂膜的复合材料,加到辊式层压机上,经其压制和粘合制成太阳能组件。
辊式层压机包括至少二个按相反方向运行的辊,这二个辊以规定的速度旋转,在规定的温度下以规定的压力相对地压制各种材料的复合物。
在这种方法的优选实施方案中,覆盖层(101)与粘合剂膜(102)的层压是在第一步中采用辊式层压机(12)进行的。这种辊式层压机可以直接设在挤出膜的挤出机的下游。随后将下列复合材料/层以一个放在另一个的上面地加到第二步中的辊式层压机(12)中:覆盖层(101)与粘合剂膜(102)的复合材料;太阳能电池串列(4);背面(112)与粘合剂膜(111)的复合材料(见图4)。在每一种情况下,都将本发明的粘合剂膜层压或共挤压到盖层或背面的里面。就盖层或背面而言,在厚度大于1mm时,就不能再利用辊式层压机的辊将其加热,因为导热性差。在这种情况下,为了将片预热到相应的温度,则需要采用辐射加热或其它形式的预热。辊式层压机的温度应该足够高,以使粘合剂膜充满各个太阳能电池/太阳能电池串列之间的所有间隙,将它们互相焊接在一起,而没有太阳能电池破裂。
采用这种方法,可以在成品组件中不出现气泡的情况下生产任何所需尺寸的太阳能组件,气泡会对组件的质量产生不利的影响。
采用辊式层压机加工膜的加料速度,优选0.1m/min-3m/min,更优选0.2m/min-1m/min。
在这种方法的另一个优选的实施方案中,以连续太阳能组件的形式生产太阳能组件,即在连续的过程中(见图5),采用辊式层压机(12),将盖层(10)、背面(11)、和太阳能电池串列(14)互相粘合在一起。在这种方法中,将焊接或用粘合剂连接的太阳能电池串列以与层压方向成直角地放在背面膜上。随后在这些电池串列到达辊之前,它们在左、右两侧分别与前、后的电池串列焊上,或采用专家熟知的方法使用导电的粘合剂层将它们相互连接(15)。可以这样生产任何所需长度的组件。在组件层压以后,可将其分割成各种长度,宽度总是相应于电池串列的长度(17),长度则相应于多倍电池串列的宽度(18)。采用切割装置沿线(16)切割组件(见图6)。
可以采用的脂肪族二异氰酸酯(A)是脂肪族和脂环族的二异氰酸酯或这些二异氰酸酯的混合物(参见HOUBEN-WEYL的“有机化学方法”卷20E“大分子物质”,Georg Thieme出版社,斯图加特,纽约,1987,1587-1593页,或Justus Liebigs Annalen der Chemie,562,75-136页)。
通过实例可具体列举的是:脂肪族二异氰酸酯,例如二异氰酸亚乙酯、1,4-四亚甲基二异氰酸酯、1,6-六亚甲基二异氰酸酯、和1,12-十二烷二异氰酸酯;脂环族二异氰酸酯,例如异佛尔酮二异氰酸酯、1,4-环己烷二异氰酸酯、1-甲基-2,4-环己烷-二异氰酸酯、和1-甲基-2,6-环己烷-二异氰酸酯、和相应的异构体混合物、4,4′-二环己基甲烷-二异氰酸酯、2,4′-二环己基甲烷-二异氰酸酯、2,2′-二环己基甲烷-二异氰酸酯、和相应的异构体混合物。优选采用1,6-六亚甲基-二异氰酸酯、1,4-环己烷-二异氰酸酯、异佛尔酮-二异氰酸酯、和二环己基甲烷-二异氰酸酯、和它们的异构体混合物。所列举的二异氰酸酯可以单独使用,或以相互混合物的形式使用。它们也可以与高达15mol%(以对总二异氰酸酯计算)的聚异氰酸酯一起使用,但聚异氰酸酯的最大加入量也应使形成的产品仍能以热塑性塑料形式加工。
根据本发明采用的泽列维季诺夫-活性的多元醇(B),是具有平均至少1.8-不大于3.0个泽列维季诺夫-活性的氢原子的多元醇,其数均分子量Mn为600-10,000,优选600-6,000。
除了包含氨基、硫醇基或羧基的化合物以外,这些多元醇还包括,特别是含2-3个,优选2个羟基的化合物,特别是具有数均分子量Mn为600-10,000,更优选数均分子量Mn为600-6,000的化合物;例如包含羟基的聚酯、聚醚、聚碳酸酯、和聚酯-酰胺。
可以使亚烷基中具有2-4个碳原子的一种或多种烯化氧与包含结合了二个键合的活性氢原子的引发剂分子反应来制备适宜的聚醚多元醇。可以列举的烯化氧是,例如:环氧乙烷、1,2-环氧丙烷、表氯醇、1,2-环氧丁烷、和2,3-环氧丁烷。优选采用环氧乙烷、环氧丙烷、和1,2-环氧丙烷与环氧乙烷的混合物。烯化氧可以单独使用,也可以依次交替使用,或以混合物的形式使用。可以采用的引发剂分子的实例是:水,N-烷基-二乙醇胺等氨基醇类如N-甲基-二乙醇胺,和二醇如乙二醇、1,3-丙二醇、1,4-丁二醇、和1,6-己二醇。也可以任选采用引发剂分子的混合物。此外,适宜的聚醚-醇是包含羟基的四氢呋喃的聚合产物。也可以采用三官能的聚醚,以二官能聚醚计,其量为0-30重量%,但其最大量也要使形成的产品仍能以热塑性塑料形式加工。基本上是直链的聚醚二醇,优选数均分子量Mn为600-10,000,更优选600-6,000。它们可以单独使用,也可以以相互混合物的形式使用。
适宜的聚酯二醇可以由例如具有2-12个碳原子,优选4-6个碳原子的二羧酸和多元醇制备。可以采用的二羧酸的实例是:脂肪族二羧酸、例如丁二酸、戊二酸、己二酸、辛二酸、壬二酸、和癸二酸,或芳香族二羧酸,例如邻苯二酸、间苯二酸、和对苯二酸。二羧酸可以单独使用,或以混合物的形式使用,例如以丁二酸、戊二酸、和己二酸混合物的形式使用。为了制备聚酯二元醇,任选使用相应的二羧酸衍生物如在醇基上具有1-4个碳原子的羧酸二酯、羧酸酐、或羧酸氯化物代替二羧酸是有利的。多元醇的实例是具有2-10个碳原子,优选2-6个碳原子的二醇,例如乙二醇、二甘醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,10-癸二醇、2,2-二甲基-1,3-丙二醇、1,3-丙二醇、或二丙甘醇。多元醇可以以其本身的形式使用,或以相互混合物的形式使用,视所需的性质而定。此外,碳酸与所述二醇的酯类,特别是与具有4-6个碳原子的二醇如1,4-丁二醇或1,6-己二醇的酯类,如ω-羟基己酸等ω-羟基羧酸的缩合产物,或内酯的聚合产物如任选取代的ω-己内酯的聚合产物也均是适宜的。优选采用乙二醇聚己二酸酯、1,4-丁二醇聚己二酸酯、乙二醇-1,4-丁二醇聚己二酸酯、和聚己内酯作为聚酯二醇。聚酯二醇的平均分子量Mn为600-10,000,优选600-6,000,聚酯二醇可以单独使用,或以相互混合物的形式使用。
泽列维季诺夫-活性的多元醇(C)是所谓的链增长剂,具有平均1.8-3.0个泽列维季诺夫-活性的氢原子,数均分子量为60-500。除了含氨基、硫羟基、或羧基的化合物以外,应将这些多元醇理解为系指具有2-3个,优选2个羟基的多元醇。
优选采用的链增长剂,是具有2-14个碳原子的脂肪族二醇如乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊二醇、1,6-己二醇、二甘醇、和二丙甘醇等。然而,对苯二酸与具有2-4个碳原子的二醇如对苯二酸双乙二醇、或对苯二酸双-1,4-丁二醇的二酯、氢醌如1,4-二(β-羟乙基)-氢醌的羟基亚烷醚、乙氧基化的双酚如1,4-二(β-羟乙基)-双酚A,脂(环)族二胺如异佛尔酮二胺、乙二胺、1,2-丙二胺、1,3-丙二胺、N-甲基-丙-1,3-二胺、或N,N′-二甲基乙二胺,和芳香族二胺如2,4-甲代苯二胺、2,6-甲代苯二胺、3,5-二乙基-2,4-甲代苯二胺、或3,5-二乙基-2,6-甲代苯二胺、或主要是一-、二-、三-、或四烷基-取代的4,4′-二氨基二苯基甲烷也是适宜的。更优选采用乙二醇、1,4-丁二醇、1,6-己二醇、1,4-二(β-羟乙基)-氢醌,或1,4-二(β-羟乙基)-双酚A作为链增长剂。此外,也可以加入少量的三醇。
可以采用对异氰酸酯是单官能的化合物作为所谓的链终止剂,以脂肪族热塑性聚氨酯计,其用量达2重量%。适宜的化合物是如一元胺和一元醇,前者例如丁胺和二丁胺、辛胺、硬脂胺、N-甲基硬脂胺、吡咯烷、呱啶或环己胺,后者例如丁醇、2-乙基己醇、辛醇、十二烷醇、硬脂醇、各种戊醇、环己醇、和乙二醇一甲基醚。
优选化合物(C)和(B)的相对量,使(A)中异氰酸酯基团的总量与(C)和(B)中泽列维季诺夫活性的氢原子总量的比例为0.85∶1-1.2∶1,优选0.95∶1-1.1∶1。
根据本发明采用的热塑性聚氨酯弹性体(TPU),可以包含常规辅助材料和添加剂作为辅助材料和添加剂(D),其最大量以TPU总量计为20重量%。典型的辅助材料和添加剂是催化剂、颜料、染料、耐火剂、防止老化和风化影响的稳定剂、增塑剂、润滑剂和脱模剂、抑制霉菌和抑制细菌的活性材料、填料、和它们的混合物。
适宜的催化剂是根据现有技术已知的常规叔胺,例如三乙胺、二甲基环己胺、N-甲基吗啉、N,N′-二甲基呱嗪、2-(二甲氨基-乙氧基)乙醇、二氮杂二环[2,2,2]辛烷等,特别是有机金属化合物,例如钛酸酯、铁化合物或锡化合物如二乙酸锡、二辛酸锡、二月桂酸锡、或脂肪族羧酸的二烷基锡盐如二乙酸二丁基锡或二月桂酸二丁基锡等。优选的催化剂是有机金属化合物,特别是钛酸酯、和铁和锡的化合物。以TPU的总量计,在TPU中催化剂的总量一般为约0-5重量%,优选0-2重量%。
另一种添加剂的实例是润滑剂如脂肪酸酯、它们的金属皂类、脂肪酸酰胺、脂肪酸酯-酰胺和硅氧烷化合物,防结块剂,阻聚剂,防水解、防光、防热、和防脱色的稳定剂,耐火剂,染料,颜料,无机和/或有机填料、以及加强剂。加强剂特别是纤维加强材料,例如根据现有技术制备的无机纤维等,也可以加入胶料。关于所述辅助材料和添加剂更详细的资料,可以在技术文献中找到,例如J.H.Saunders和K.C.Frisch的专著“高聚物”,卷XVI,Polyurethane[聚氨酯],部分1和2,交叉科学出版社发行,1962和1964;R.G_chter和H.Müller所著Taschenbuch für Kunststoff-Additive[塑料添加剂手册](Hanser出版社,慕尼黑,1990);或DE-A 29 01 774。
可以在TPU中加入的另一些添加剂是热塑性塑料,例如聚碳酸酯和丙烯腈/丁二烯/苯乙烯三聚物,特别是ABS。也可以采用其它弹性体,例如橡胶、乙烯/乙酸乙烯酯共聚物、苯乙烯/丁二烯共聚物、和其它TPU。
此外,在市场上可以买到的适合加入的增塑剂是例如磷酸酯、苯二酸酯、己二酸酯、癸二酸酯、和烷基磺酸酯。
TPU的制备可以间歇或连续地进行。例如可以采用混合头/混合带的方法,或采用所谓的挤出机方法连续地制备TPU。在挤出机方法中,例如在多轴挤出机中,可同时计量加入成分(A)、(B)、和(C),即采用一步法,或逐次加入,即采用预聚合物方法。本发明可以采用一开始就分批加入预聚合物的方法,或采用挤出机的一部分或在预聚合物单元前采用一个单独的挤出机连续制备预聚合物的方法。
下面利用实施例更详细地说明本发明。
实施例1
以下列方法将Texin_ DP7-3007膜(Bayer公司的工业产品,硬度:萧氏D级58)挤压到Makrofol_膜上:将竖直排列的模具固定在具有辊单元(冷却辊)的挤出机上,该设备是Reifenh_user生产的。表面覆盖橡胶的承压辊位于该设备的浇铸辊之前。模具位于浇铸辊和承压辊之间。为了达到这个“冷却辊”单元非常缓慢的卷紧速度,只用一个卷紧机卷走膜的复合材料,为了改善Texin_熔融体对所采用的Makrofol_膜DE 1-1(厚度为375μm(Bayer股份公司的工业产品))的粘合,在加入熔融体中之前,采用IR灯将Makrofol_膜预热。Texin_熔融体在60℃下于干燥空气的干燥器中预干燥6小时。
给定下列加工参数:
模具温度 180℃
Texin_的材料温度 186℃
在模具前的压力 75bar
挤出机的旋转速度 80rpm
浇铸辊的温度 20℃
冷却辊的温度 10℃
卷紧速度 3m/min
然后在160℃下采用热辊方法,在辊式层压机中,将采用这种方法生产的复合膜层压到放置在其中间的太阳能电池串列上,作为盖层利用底下的Texin_面,作为背面利用顶上的Texin_面。为了使粘合作用最佳,采用IR灯预热复合膜。辊式层压机的进料速度为0.3m/min。在30秒内可以生产尺寸为15×15cm2的组件。
在无裂缝和破裂的情况下制成一些嵌入有将太阳能电池的太阳能组件(组件4和5)。
采用这种生产方法,太阳能电池的效率仍保持不变。
采用二个不同的实验,使太阳能组件风化。在表中示出风化前后的效率。
实施例2
使用Desmopan_88382(Bayer股份公司的工业产品,硬度:肖氏A级80)来挤出膜的方法如下:
将水平排列的模具固定在具有辊单元(冷却辊)的挤出机上,该辊是Somatec生产的。冷却辊位于模具以下约5cm。
为了达到这个“冷却辊”单元非常缓慢的卷紧速度,只采用一个卷紧机卷走膜。Desmopan_在75℃下在干燥空气的干燥器中预干燥6小时。
给定下列加工参数:
模具温度 170℃
Texin_的材料温度 177℃
在模具前的压力 27bar
挤出机的旋转速度 40rpm
冷却辊的温度 10℃
卷紧速度 1.7m/min
然后采用以这种方法生产的膜作为图1所述太阳能组件的粘合剂层。组件(15×15cm2)的顶面是由硬化的白色玻璃制造的,背面是由复合膜(Tedlar-PET-Tedlar)制造的。这些太阳能组件是在150℃下,采用真空层压机在10分钟内生产的。
在无裂缝和破裂的情况下制成一些嵌入有太阳能电池的太阳能组件(组件4和5)。
采用这种生产方法,太阳能电池的效率仍保持不变。
采用二个不同的实验,使太阳能组件风化。在表中示出风化前后的效率。
对比例
生产对比的组件。采用EVA(乙烯/乙酸乙烯酯)代替Texin_DP7-3007。尺寸为15×15cm2的组件的生产时间为20分钟,采用真空层压机进行生产。对比组件也经风化作用(见表)。
表1
组件 | 风化前的效率 | 在热周期实验中风化之后的效率*(IEC 61215) | 在湿热实验中风化之后的效率**(IEC 61215) |
1 | 13.8% | 13.7% | - |
2 | 13.3% | 13.5% | - |
3 | 13.5% | - | 13.5% |
4 | 15.2% | 15.1% | - |
5 | 14.7% | - | 14.8% |
对比组件1 | 13.2% | 13.3% | - |
对比组件1 | 13.9% | - | 14.1% |
*50个-40℃-+85℃的循环,一个循环的时间约6小时
**在80℃和空气的相对湿度为85%下放置500小时
在测定效率时,测量绝对误差为±0.3%。
按照IEC 61215测定效率。
根据本发明的太阳能组件与对比组件(现有技术)具有相同的效率、相同的机械稳定性和对风化的稳定性。甚至在风化以后,效率仍保持不变。
然而,生产根据本发明的太阳能组件的生产速度可显著比对比组件快(是辊式层压机的40倍,是真空层压机的2倍)。
虽然前面为了说明的目的详细叙述了本发明,但应当理解,本发明只受权利要求的限制,这些细节只是为了说明的目的,本领域的技术人员可在本发明的内容和范围内,对本发明进行更动。
Claims (12)
1.一种光电组件,其中包括:
A)至少一层在面向能源的正面上的玻璃的或耐冲击、UV稳定、风化稳定、透明塑料的面层,该层的水蒸气渗透率低,
B)至少一层在背向能源的背面上的玻璃的或风化稳定的塑料面层,该层的水蒸气渗透率低,
C)至少一层在A)和B)之间的塑料粘合剂层,其中嵌入至少一个或多个互相电连接的太阳能电池,
其中C)中所述的塑料粘合剂层,包括脂肪族热塑性聚氨酯,硬度为肖氏A级75-肖氏D级70,在E’-模量2MPa下,根据DMS-方法测定的软化温度T软化为90-150℃,脂肪族热塑性聚氨酯是下列材料的反应产物:脂肪族二异氰酸酯;至少一种泽列维季诺夫-活性的多元醇,其中具有平均至少1.8-不大于3.0个泽列维季诺夫-活性的氢原子、数均分子量为600-10,000g/mol;和至少一种作为链增长剂的泽列维季诺夫-活性的多元醇,其中具有平均至少1.8-不大于3.0个泽列维季诺夫-活性的氢原子,数均分子量为60-500g/mol;脂肪族二异氰酸酯的NCO基团与链增长剂和多元醇的OH基团的摩尔比例为0.85-1.2。
2.根据权利要求1的光电组件,其中脂肪族二异氰酸酯的NCO基团与链增长剂和多元醇的OH基团的摩尔比例为0.9-1.1。
3.根据权利要求1的光电组件,其中A)中所述的面层包括片或一层或多层膜。
4.根据权利要求1的光电组件,其中B)中所述的层包括片或一层或多层膜。
5.根据权利要求1的光电组件,其中A)中所述的面层是以条存在的膜或片,这些条排列在所谓的太阳能电池串列上。
6.根据权利要求1的光电组件,其中嵌入C)中所述的塑料粘合剂层中的太阳能电池排列成太阳能电池串列。
7.根据权利要求6的光电组件,其中采用导电的粘合剂,将太阳能电池串列依次串联焊接或连接。
8.根据权利要求7的光电组件,其中太阳能电池之间的电连接由导电的粘合剂组成,直接施加在C)中所述的塑料粘合剂层的里面,使它们在层压过程中,直接落在太阳能电池相应的接点上。
9.根据权利要求8的光电组件,其中所述粘合剂以焊珠的形式施加。
10.根据权利要求1的光电组件,其中在A)中所述的面层和太阳能电池之间的C)中所述的塑料粘合剂层中,还存在一层厚度小于500μm的玻璃膜。
11.根据权利要求1的光电组件,其中所述聚氨酯的硬度为肖氏A级92-肖氏D级70。
12.一种生产光电组件的方法,其中将包括盖片或盖膜与塑料粘合剂膜的复合材料、太阳能电池串列、和包括背面上的膜或片与塑料粘合剂膜的复合材料加到真空板式层压机或辊式层压机,经其压制和粘合,制成光电组件,所述组件包括:
A)至少一层在面向能源的正面上的玻璃的或耐冲击、UV稳定、风化稳定、透明塑料的面层,该层的水蒸气渗透率低,
B)至少一层在背向能源的背面上的玻璃的或风化稳定的塑料面层,该层的水蒸气渗透率低,
C)至少一层在A)和B)之间的塑料粘合剂层,其中嵌入至少一个或多个互相电连接的太阳能电池,
其中C)中所述的塑料粘合剂层,包括脂肪族热塑性聚氨酯,硬度为肖氏A级75-肖氏D级70,在E’-模量2MPa下,根据DMS-方法测定的软化温度T软化为90-150℃,脂肪族热塑性聚氨酯是下列材料的反应产物:脂肪族二异氰酸酯;至少一种泽列维季诺夫-活性的多元醇,其中具有平均至少1.8-不大于3.0个泽列维季诺夫-活性的氢原子、数均分子量为600-10,000g/mol;和至少一种作为链增长剂的泽列维季诺夫-活性的多元醇,其中具有平均至少1.8-不大于3.0个泽列维季诺夫-活性的氢原子,数均分子量为60-500g/mol;脂肪族二异氰酸酯的NCO基团与链增长剂和多元醇的OH基团的摩尔比例为0.85-1.2。
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DE19814652A1 (de) * | 1998-04-01 | 1999-10-07 | Bayer Ag | Photovoltaik-Module mit Verbundfolien |
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DE19924092A1 (de) * | 1999-05-26 | 2000-11-30 | Bayer Ag | Adhäsionsstabiles Verbundmaterial aus Polyurethan und einem weiteren thermoplastischen Material, ein Verfahren zu dessen Herstellung sowie dessen Verwendung in Kraftfahrzeugen |
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2002
- 2002-09-30 EP EP02021860A patent/EP1302988A3/de not_active Withdrawn
- 2002-09-30 AU AU2002301252A patent/AU2002301252B2/en not_active Ceased
- 2002-10-08 US US10/266,212 patent/US20030075210A1/en not_active Abandoned
- 2002-10-08 CA CA002406966A patent/CA2406966A1/en not_active Abandoned
- 2002-10-11 MX MXPA02010070A patent/MXPA02010070A/es active IP Right Grant
- 2002-10-11 CN CNB021435820A patent/CN1316635C/zh not_active Expired - Fee Related
- 2002-10-11 JP JP2002298998A patent/JP2003188402A/ja active Pending
- 2002-10-11 KR KR1020020062000A patent/KR100902975B1/ko not_active IP Right Cessation
-
2003
- 2003-08-01 HK HK03105555A patent/HK1053389A1/xx not_active IP Right Cessation
-
2007
- 2007-01-23 US US11/656,668 patent/US20070131274A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
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KR20030030967A (ko) | 2003-04-18 |
KR100902975B1 (ko) | 2009-06-15 |
EP1302988A3 (de) | 2007-01-24 |
CN1412861A (zh) | 2003-04-23 |
MXPA02010070A (es) | 2003-04-25 |
US20070131274A1 (en) | 2007-06-14 |
EP1302988A2 (de) | 2003-04-16 |
CA2406966A1 (en) | 2003-04-12 |
HK1053389A1 (en) | 2003-10-17 |
JP2003188402A (ja) | 2003-07-04 |
US20030075210A1 (en) | 2003-04-24 |
AU2002301252B2 (en) | 2007-12-20 |
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