CN101587848A - 封装光电组件的方法 - Google Patents
封装光电组件的方法 Download PDFInfo
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- CN101587848A CN101587848A CNA2009101389868A CN200910138986A CN101587848A CN 101587848 A CN101587848 A CN 101587848A CN A2009101389868 A CNA2009101389868 A CN A2009101389868A CN 200910138986 A CN200910138986 A CN 200910138986A CN 101587848 A CN101587848 A CN 101587848A
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- cap rock
- polymeric
- blowing agent
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Abstract
本发明涉及封装光电组件的方法,通过将待封装的组件嵌入第一透明聚合物层与填充有未活化的发泡剂的第二聚合物层之间,并随后活化该发泡剂,使得这两个聚合物层彼此连接、特别是彼此焊接,且将组件包裹在这两个聚合物层之间。
Description
技术领域
本发明涉及封装光电组件的方法。
背景技术
术语光电子学(有时也称作光导发光学(optronics或optotronics))产生于光学和微电子学的组合,且在最宽泛意义上包括所有容许电子上产生的数据和能量转化为光发射、和反过来的所有产品和工艺。背景是,例如,尝试将电子数据编辑和处理的优点,与光的快速且电磁上和静电上不可干扰的宽带传播能力的优点组合起来。同时,该术语也包括基于电子半导体技术电能转化为光,和反过来。
光电组件为起到电学和光学组件之间界面的作用的组件,或是包含这类组件的其它器件。该术语通常(但并非排他地)表示基于半导体发挥作用的微电子组件。光电组件依据它们的功能可以分为如下类别:
·激光二极管
·光电执行元件(optoelectronic actuator)
这些包括由电流产生光的所有半导体组件,即激光二极管和发光二极管。
·光电探测器
这些为执行元件的相反组装件,即光敏电阻器、光电二极管(包括太阳能电池)和光电晶体管。但是光电倍增管(photomultiplier)也包含在光电器件之内。
当执行元件和探测器作为系统操作时,结果为光学传感器,称作光传感器。
光电组件中的主要部分是处理所谓的光生伏打模块。
将光生伏打理解为利用太阳能电池将辐射能量(主要为太阳能)直接转化为电能。
存在太阳能电池的多种实施方式。最普遍的是厚层硅电池,其为单晶电池(c-Si)或是多晶电池(mc-Si)形式。变得越来越普遍的是无定形硅(a-Si)、GaAs、CdTe、CIS-、CIGS的薄膜电池,以及有机太阳能电池和染料电池。
出于能量回收目的,通常将太阳能电池连接起来以形成大的太阳能模块。为此,将电池采用导线(conductor)经前后侧串联。由此各个电池的电压累积地加起来。
太阳能模块的制作最普遍地通过使光活性侧向下来实现。首先将通常为低铁、钢化白玻璃(厚度为3-4mm,且在350-1150nm之间具有极低吸收)的相应玻璃进行清洁并布置就绪。在其之上随后存在切削到应有尺寸的(cut-to-size)EVA薄膜片。通过焊条的方式将太阳能电池连接以形成单股(称作串)并采用EVA薄膜在格网(screen)上定位。随后放置将单个串彼此相连且导致连接套节(connection socket)的位点的互联并焊接。随后将依次采用切削到应有尺寸的EVA薄膜和Tedlar(聚氟乙烯)薄膜将整体覆盖。制备中下一步骤是,在减压和约150℃下层压模块。层压阶段时,一直到已成乳白色的点的EVA薄膜变为不再可以熔融的透明、三维交联的塑料层,且随后将电池嵌入该层中并使该层牢固地连接于玻璃网格和后侧薄膜。层压之后,修整边缘且将连接套节附接。随后将模块加框,进行测量,依据其电值(electrical value)分类,并包装。
层压操作是非常耗时和耗能的,通常采用150℃温度进行10-20分钟。迄今显著加速层压的尝试并未成功实现其上市。
WO 94/22172A1提出用辊式层压机代替常规板式层压机。
JP 09312410A1描述了使用热塑性聚氨酯。
EP 1302988A1描述了通过脂族热塑性聚氨酯在具有低水蒸汽渗透性的两个基底之间封装和线连接太阳能电池的方法。
所述说明书中公开的所有方法的特征是,为了确保可靠封装,首先必须将一些情形下为200-400μm厚的线接太阳能电池在缓慢过程中包裹。
光电组件经常必须使其免受水蒸汽和氧气的渗入,还需要用机械进行保护,为了抑制或防止组件本身的退化或它们的接触。
发明内容
本发明目的是提供可靠的且快速的封装光电组件的方法,其可以采用确定的方法和原材料来实施,而不存在危险且高成本的投资。
该目的通过本说明书中更详细地表述的方法得以实现。本说明书描述了本发明的有利实施方式。
由此,本发明提供了封装光电组件的方法,通过将待封装的组件嵌入第一透明聚合物层与填充有未活化的发泡剂的第二聚合物层之间,并随后活化该发泡剂,使得这两个聚合物层彼此连接、特别是彼此焊接,且所述组件包裹在这两个聚合物层之间。
具体地,本发明涉及如下方面:
1)封装光电组件的方法,通过将待封装的组件嵌入第一透明聚合物层与填充有未活化的发泡剂的第二聚合物层之间,并随后活化该发泡剂,使得这两个聚合物层彼此连接、特别是彼此焊接,且所述组件包裹在这两个聚合物层之间。
2)1)的方法,其特征在于,该发泡剂包括由包裹起泡剂的聚合物膜组成的微球体,称作微球。
3)1)或2)的方法,其特征在于,在第一聚合物层上自由侧之上在外部和/或在第二聚合物层上自由侧之上在外部,存在至少一个额外层,优选地该额外层的水蒸汽渗透性在37.8℃和90%相对湿度下小于200g/m2/24h,且氧气渗透性在23℃和50%相对湿度下小于20cm3/m2/24h。
4)1)-3)中至少一项的方法,其特征在于,该第一透明聚合物层对于350-1150nm波长的透射率大于60%,更特别地透射率大于90%。
5)前述各项中至少一项的方法,其特征在于,该第一透明聚合物层的厚度为10-500μm,更特别地为50-300μm。
6)前述各项中至少一项的方法,其特征在于,填充有发泡剂的第二聚合物层,在发泡之后其密度小于900kg/m3,更特别地小于700kg/m3。
7)前述各项中至少一项的方法,其特征在于,该第一透明聚合物层和/或第二聚合物层存在于抗粘连处理过的辅助载体之上。
8)前述各项中至少一项的方法,其特征在于,选择具有低水蒸汽渗透性的UV-稳定且风化-稳定的塑料或者玻璃的透明层作为第一聚合物层之上的额外层,和/或选择低水蒸汽渗透性的单层或多层、UV-稳定且风化-稳定聚合物薄膜或者玻璃的层作为第二聚合物层之下的额外层。
9)前述各项中至少一项的方法,其特征在于,使填充有未活化的发泡剂的第二聚合物层位于盖层5形式的额外层之上,
使待封装的产品配置在第二聚合物层4之上,
其上为第一透明聚合物层,又使所述第一透明聚合物层位于透明盖层形式的额外层之上或之下(which is located in turn on an additional layer in theform of a transparent cover),
且以这种排列,优选地在压力机中在减压下,诱发发泡剂发泡,且使得两个聚合物层彼此焊接且将所述组件包裹在两个聚合物层之间。
10)前述各项中至少一项的方法,其特征在于,使透明盖层之上的第一透明聚合物层、待封装的组件和在另一盖层之上或之下的(on a furthercover layer)填充有未活化的发泡剂的第二聚合物层,导入辊层压机的辊距中,透明盖层和另一盖层直接在辊上运转,且将待封装的组件导入两个聚合物层之间,在辊距中发生发泡剂的发泡,且使得两个聚合物层彼此焊接且使所述组件包裹在两个聚合物层之间。
11)前述各项中至少一项的方法,其特征在于,使透明盖层之上的第一透明聚合物层、置于透明聚合物层之上(且特别地在与透明盖层覆盖的侧相对的侧上)的待封装的组件、和在另一盖层之上或之下的填充有未活化的发泡剂的第二聚合物层,导入辊层压机的辊距中,透明盖层和另一盖层直接在辊上运转,且在辊距中发生发泡剂的发泡,且使得两个聚合物层彼此焊接且使所述组件包裹在两个聚合物层之间。
附图说明
图1显示密封前结构:1.透明盖层、2.透明聚合物层、3.待封装的产品、4.MB填充的聚合层、5.盖层
图2显示密封后结构:1.透明盖层、2.透明聚合物层、3.待封装的产品、4.在聚合物层中膨胀的MB、5.盖层
图3显示制备透明盖层与透明聚合物层的组装件:7.辅助载体、2.透明聚合物层、1.透明盖层
图4显示采用辊式层压机密封组件:4.MB填充的聚合物层、5.盖层、6.聚合物层中膨胀的MB、3.待封装的产品、8.图3中无辅助载体7的组装件
图5显示采用辊式层压机密封组件以获得柔性组装件:4.MB填充的聚合物层、5.盖层、6.聚合物层中膨胀的MB、3.待封装的产品、2.透明聚合物层、1.透明盖层
图6显示:1.3mm玻璃板、2.100g/m2透明聚合物层、3.待封装的产品(高度985μm)、4.500g/m2微球填充的聚合物层、5.盖层PET/PP/AI/PP/PET(厚度142μm)
图7显示:1.具有透明聚合物层的玻璃板、3.待封装的产品、8.两个聚合物层之间完全密封的区域、9.包含气体(air inclusion)、不完全密封。
发明详述
依据本发明,术语“焊接(weld)”应理解为表示聚合物层彼此不可分地连接,或者至少仅在将所获结构破坏时才可以将它们不可逆地分开。
本领域技术人员选择组件的位置,使得组件的光活性侧位于透明聚合物层之下。
该透明聚合物层优选对于350-1150nm波长的透射率大于60%,更特别地透射率大于90%。透射率,通常以%表示,是到达光透过的物体的相反侧的光输出与入射到前面上的光输出之比。反射率和吸收率降低了透射率。由此是如下情形:透射率=(1-折射率)×(1-吸收率)。
可替换地,聚合物层可以采取可热活化层、在施压下逐渐粘着的层、或者在压力和不加热(without temperature)下牢固粘着的层的形式。
适合于该第一、透明聚合物层的原材料与适合于第二聚合物层(特别地将其与未膨胀的但可膨胀的微球共混)的原材料是相同聚合物。
除了传统聚合物如EVA(例如DuPont的)、乙烯/甲基丙烯酸(例如DuPont的)、TPU(例如Bayer的)和PVB(例如DuPont的)之外,也能够使用丙烯酸酯(acrylates)、有机硅橡胶(silicone rubber)、PIB和苯乙烯嵌段共聚物。
本发明的另一实施方式中,该聚合物层组成基于聚乙烯-乙酸乙烯酯(EVA)的粘合剂,其乙酸乙烯酯含量为10-90wt%且依据ISO 1133(A/4)在190℃和2.16kg下熔体指数(melt index)MFI为0.5-25g/10min。
除了基于EVA的体系之外,基于PIB和SBC的体系也显著适用,因为它们组合了极高的粘合剂粘结强度和极低的水蒸汽渗透性。
在一个具体的实施方式中,该粘合剂是基于作为基础聚合物的聚异丁烯。为了使该粘合剂具有必要的粘着性,将其与树脂混合。使用中分子量聚异丁烯与更高分子量聚异丁烯的混合物作为弹性体。作为迄今为止具有最高剪切强度的方式,已证实适宜地采用平均分子量Mw为40000的品种(grade)(其可自由地以名称“Oppanol B10”从BASF SE公司商购获得)作为中分子量的聚异丁烯组分,且采用平均分子量Mw为2600000的品种(其同样可自由地以名称“Oppanol B150”获得)作为高分子量的聚异丁烯组分。
另外,用于该聚合物层的粘合剂(优选压敏粘合剂)是基于含有由乙烯基芳烃(A嵌段)(例如苯乙烯)形成的聚合物嵌段,和由1,3-二烯(B嵌段)(例如丁二烯和异戊二烯或两者的共聚物)的聚合形成的那些聚合物嵌段的嵌段共聚物。也可以采用不同嵌段共聚物的混合物。也可以使用部分或者完全氢化的产物。
该嵌段共聚物可以具有线性A-B-A结构。同样能够使用辐射状设计(radial design)的嵌段共聚物,以及星形和线性多嵌段共聚物。作为另一组分,使用A-B双嵌段共聚物,双嵌段共聚物相对于整个弹性体的含量比例为至少50%。优选使用聚苯乙烯含量大于20wt%的那些嵌段共聚物。
嵌段共聚物的典型使用浓度范围为30-70wt%,更具体的范围为35-55wt%。
聚合物层的粘合剂可以进行化学交联,更具体地通过辐射,例如通过UV辐射、或者通过使用快速电子的辐射进行化学交联。
出于获得补充的期望性能的目的,可以将粘合剂与一种或多种添加剂如增粘剂树脂、增塑剂、老化抑制剂或填料混合。
用于提高粘合剂粘合性能的增粘剂树脂,例如为烃树脂(例如由不饱和C5和/或C9单体形成),双环戊二烯的氢化聚合物,萜烯-酚树脂,由诸如α-或β-蒎烯的原材料形成的萜烯树脂,芳族树脂如苯并呋喃-茚树脂或者由苯乙烯或α-甲基苯乙烯形成的树脂,优选基于松香及其衍生物如歧化、二聚或酯化(酯化能够使用二醇、甘油或季戊四醇)树脂(松香)的未氢化的、部分氢化的或完全氢化的树脂,以及Ullmann’sder technischenChemie,第12卷,第525-555页(第4版)Weinheim中列出的其它增粘剂树脂。特别适宜的是老化稳定的、不具有烯属双键的树脂,例如氢化树脂。特别优选使用基于α-蒎烯或β-蒎烯和/或δ-柠檬烯的聚萜烯树脂。前述增粘剂树脂可以单独地或者以混合物来使用。
任选使用的增塑剂,例如为脂肪族、脂环族和芳族矿物油,邻苯二甲酸、苯偏三酸或己二酸的二酯或多酯,聚醚和液体橡胶(例如腈橡胶或聚异戊二烯橡胶),丁烯和/或异丁烯的液体聚合物,丙烯酸酯,聚乙烯基醚,基于用于增粘剂树脂的原材料的液体树脂和增塑剂树脂,羊毛蜡和其它蜡,或者液体有机硅。
为了使粘合剂甚至更加抗UV的影响,能够加入光稳定剂。它们的功能主要在于防止粘合剂的分解。特别适用于粘合剂的是HALS光稳定剂,例如采用4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的二甲基琥珀酸酯聚合物(CAS No.65447-77-0)、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯(CAS No.52829-07-9)或者聚[[6-(1,1,3,3-四甲基丁基)氨基]-1,3,5-三嗪-2,4-二基][[(2,2,6,6-四甲基-4-哌啶基)亚胺基]六亚甲基[(2,2,6,6-四甲基-4-哌啶基)亚胺基]](CAS No.70624-18-9)。
典型地可以使用的其它添加剂如下:
·主抗氧化剂,例如空间受阻酚,
·次抗氧化剂,例如亚磷酸酯或硫醚,
·生产中的稳定剂,例如C-自由基去除剂,
·光稳定剂,例如UV吸收剂或空间受阻胺,
·加工助剂,
·端基封闭补强树脂(end block reinforcer resin),和
·如果期望的话,其它聚合物,优选性能上是弹性体的;由此可以利用的弹性体尤其包括基于纯烃的那些(实例为不饱和聚二烯如天然或合成聚异戊二烯或聚丁二烯),具有基本上化学饱和的弹性体(例如饱和乙烯-丙烯共聚物、α-烯烃共聚物、聚异丁烯、丁基橡胶、乙烯-丙烯橡胶),和化学官能化的烃(例如含卤素的、含丙烯酸酯的和含乙烯基醚的聚烯烃,仅举数例)。
在另一优选实施方式中,该聚合物层是由丙烯酸酯组成的,且具有高老化稳定性、极高粘结值和低吸收率的特性。优选地,该粘合剂基于丙烯酸酯聚合物和聚乙烯-乙酸乙烯酯聚合物。
丙烯酸酯分散体是公知的且大量用于胶带粘合剂和用于标签粘合剂二者。丙烯酸酯分散体包含分散分布于该分散体含水相中的丙烯酸酯聚合物颗粒。丙烯酸酯分散体通常在含水介质中通过适宜单体的聚合来制备。制备工艺可以包括分批操作或是聚合期间计量添加一种或多种组分。在分批工艺的情形下,初始进料中同时包含所有必要组分。
丙烯酸酯分散体和相应粘合剂的性质主要由单体的选择和所获分子量来决定。主要单体为丙烯酸正丁酯、丙烯酸2-乙基己酯和丙烯酸。适宜的单体单元描述于“Acrylic Adhesives”,Donatas Satas,于Handbook of PressureSensitive Adhesive Technology,第二版,Donatas Satas编,Van NostrandReinhold New York,第396-456页。
所用的丙烯酸酯分散体具体地含有[每种情形下以wt%计]
0-10%丙烯酸单元
0-100%丙烯酸正丁酯单元
0-100%丙烯酸2-乙基己酯单元。
在一种优选的实施方式中,使用具有0.5-3wt%丙烯酸单元的丙烯酸酯分散体。在另一优选的实施方式中,使用具有0.5-3wt%丙烯酸单元和99.5-90wt%、更优选99.5-96wt%丙烯酸正丁酯单元的丙烯酸酯分散体。本发明丙烯酸酯分散体的另外的实例为具有80-90wt%丙烯酸2-乙基己酯单元和8-20wt%丙烯酸正丁酯单元的丙烯酸酯分散体。
该丙烯酸酯分散体可以额外地包含其它单体单元,通过该单体单元能够例如控制玻璃化转变温度和交联性。实例为丙烯酸甲酯、丙烯酸乙酯、丙烯酸甲基乙酯、马来酸酐、丙烯酰胺、甲基丙烯酸缩水甘油酯、丙烯酸异丙酯、丙烯酸正丙酯、丙烯酸异丁酯、丙烯酸正辛酯、和对应于这些丙烯酸酯的甲基丙烯酸酯。该丙烯酸酯分散体通常含有0-10wt%这些额外单体单元,仅使用一种额外单体单元或者其混合物。
所获玻璃化转变温度取决于采用的单体。用于本发明粘合剂的丙烯酸酯分散体,在干燥状态下,其玻璃化转变温度更特别地为-80至-15℃,优选为-75至-25℃且更优选为-55至-35℃。
该丙烯酸酯分散体的固含量更特别地为30-70wt%,优选为45-60wt%。实例包括Rohm&Haas公司的丙烯酸酯分散体Primal PS 83d和Primal PS 90。
如果期望的话,该分散体可以包含其它添加剂。适宜的交联剂可以是环氧树脂,胺衍生物(例如六甲氧基甲基蜜胺)和/或胺(例如蜜胺或脲)与醛(例如甲醛)的缩合产物。为了获得非粘性聚丙烯酸酯分散体,已发现适当时有利地加入例如与聚合物的羧基反应的其它化合物。这种化合物的实例为氮丙啶,如乙撑亚胺(ethylenimine)和丙撑亚胺(propylenimine)。
该粘合剂可以包含其它组分。实例为树脂、增塑剂、染料、消泡剂和增稠剂,以及用于设定期望的流变学行为的其它佐剂。丙烯酸酯分散体的改性是公知的,且描述于例如“Modification of Acrylic Dispersions”,AlexanderZettl,于Handbook of Pressure Sensitive Adhesive Technology,第二版,Donatas Satas编,Van Nostrand Reinhold New York,第457-493页。
含水树脂分散体,即树脂在水中的分散体,是已知的。制备和性能描述于例如“Resin Dispersions”,Anne Z.Casey,于Handbook of PressureSensitive Adhesive Technology,第二版,Donatas Satas编,Van NostrandReinhold New York,第545-566页。
烃树脂和改性烃树脂的树脂分散体同样是已知的,且例如可从HerculesBV公司以商品名Tacolyn(实例:Tacolyn 4177)获得。
适宜的树脂分散体为基于烃树脂或改性烃树脂的那些,其软化点为50-100℃。该粘合剂可以包含,例如,5-28wt%树脂分散体。该树脂分散体的固含量通常为40-70wt%。
该粘合剂可以与基于不同烃树脂的混合物的、以及基于烃树脂与其它已知树脂的混合物的树脂分散体混合。例如,可以是烃树脂与少量基于松香或改性松香或酚醛树脂、其它天然树脂、树脂酯或树脂酸的树脂的混合物。
该粘合剂也可以与增塑组分如增塑剂树脂、液体树脂、油或其它已知组分(例如烷氧基化的烷基酚)混合。烷氧基化的烷基酚是已知的且描述于例如US 4,277,387A和EP 0006571A。烷氧基化的烷基酚用作增塑剂已在参考文献提到,其中包括“Modification of Acrylic Dispersions”,Alexander Zettl,于Handbook of Pressure Sensitive Adhesive Technology,第二版,Donatas Satas编,Van Nostrand Reinhold New York,第471页。
烷氧基化的烷基酚的性能由烷基基团且主要由聚二醇醚链的结构来决定。对于制备,能够使用环氧乙烷和环氧丙烷二者。在一个具体实施方式中,使用丙氧基化的烷基酚。优选不溶于水的烷氧基化的烷基酚。另外优选的是沸点高于100℃、优选高于130℃且更优选高于200℃的烷氧基化的烷基酚。
可以使用交联剂优化该粘合剂以获得更高剪切强度。交联剂的选择和比例是本领域技术人员公知的。用于丙烯酸酯分散体的交联剂原则上是已知的且描述于例如“Acrylic Adhesives”,Donatas Satas,于Handbook ofPressure Sensitive Adhesive Technology,第二版,Donatas Satas编,VanNostrand Reinhold New York,第411-419页。
基于异氰酸酯的交联剂原则上是适宜的,但是考虑到有限的贮存期以及与工作场所安全性相关的成本和复杂性的增加则不是优选的。基于异氰酸酯的交联剂的实例为Basonat F DS 3425X(BASF)。
优选无异氰酸酯的交联剂,实例为基于多官能金属的盐的交联剂。这些交联剂原则上是已知的且描述于例如US 3,740,366A、US 3,900,610A、US 3,770,780A和US 3,790,553A。特别适宜的交联剂为基于锌络合物的那些,其能够与羧基形成共价键和/或络合物型键合。
已证实适宜的另一粘合剂是基于K值为至少20、更特别地大于30的丙烯酸酯热熔体的粘合剂,其可通过将这种粘合剂的溶液浓缩以获得可以加工为热熔体的体系来获得。
浓缩可以在适当装配的罐或挤出机中进行;特别是在伴随脱气的情形下,脱气挤出机是优选的。
DE 4313008A1中给出了一种这样的粘合剂,其内容通过参考引入以变为本公开内容和发明的一部分。在中间步骤中,将溶剂从这样制得的这些丙烯酸酯组合物中彻底除去。
另外,在这种工序的过程中,除去其它挥发性组分。从熔体中涂布之后,这些组合物仅具有小部分的挥发性组分。由此,能够采用上述专利中要求保护的所有单体/配方。了解所述组合物的另一优点是,它们具有高K值且由此具有高的分子量。本领域技术人员知道,可以使更高分子量的体系更有效地交联。相应地减少了挥发性组分的比例。该组合物的溶液可以含有5-80wt%、更特别地30-70wt%溶剂。
优选使用商业溶剂,尤其是低沸点烃、酮、醇和/或酯。
另外优选使用单螺杆、双螺杆或多螺杆挤出机,其具有一个或者特别是两个或更多个脱气单元。
该基于丙烯酸酯热熔体的粘合剂中也可以共聚安息香(benzoin)衍生物,实例为安息香丙烯酸酯或安息香甲基丙烯酸酯、丙烯酸酯或甲基丙烯酸酯。这种类型的安息香衍生物描述于EP 0578151A1。
可替换地,可以将该基于丙烯酸酯热熔体的粘合剂进行化学交联。
在一个特别优选的实施方式中,所用的自粘合组合物为(甲基)丙烯酸及其具有1-25个碳原子的酯,马来酸、富马酸和/或衣康酸和/或它们的酯,取代的(甲基)丙烯酰胺,马来酸酐,和其它乙烯基化合物(如乙烯基酯(特别是乙酸乙烯酯)、乙烯基醇和/或乙烯基醚)的共聚物。
残留溶剂含量应当低于1wt%。
对于涉及特别高温度负荷的封装组件的应用领域,具有突出性能的有机硅橡胶具有特别的适用性。除了高抗UV性和抗臭氧性之外,它们特别地显示高耐温性、弹性以及针对冲击和振动的显著缓冲的组合功能。另外,在-75至260℃范围内的长期温度负荷对有机硅橡胶的物理性能没有不利影响。
作为压敏有机硅粘合剂,能够特别有利地不仅使用由硅酸盐树脂和聚二甲基硅氧烷或聚二苯基硅氧烷组成的以下缩合-交联体系:Dow Corning的DC 280、DC 282、Q2-7735、DC 7358、Q2-7406,GE Bayer Silicones的PSA 750、PSA 518、PSA 910,ShinEtsu的KRT 001、KRT 002、KRT 003,Wacker Silicones的PSA 45559,和Rhodia的PSA 400,而且有利地使用由硅酸盐树脂、聚二甲基硅氧烷或聚二苯基硅氧烷和交联剂(交联剂物质,特别是官能化的氢硅烷)组成的以下加成-交联体系:Dow Corning的DC 7657、DC 2013,GE Bayer Silicones的PSA 6574,和ShinEtsu的KR 3700、KR 3701。
为了使聚合物层具有更大强度,经常也切合实际地在光伏模块所需的所有组件组装之后进行热交联。特别适于热交联的是过氧化物,例如Pennwalt Corp,Luccidol Divison的Lupersol。
透明聚合物层和第二聚合物层可以以光滑或拉毛片材形式存在。在可替换的实施方式中,二者聚合物层位于辅助载体之上,特别是下层厚度为10-500μm。辅助载体可以是双侧抗粘连涂布的材料,如隔离纸或隔离薄膜(也称作衬(liner)),并在施用之后除去。其不会形成所获层压体的一部分。
填充有发泡剂的第二聚合物层,优选地在发泡之后密度小于900kg/m3,更特别地小于700kg/m3。
在本发明的一个有利实施方式中,该发泡剂包括由包裹起泡剂的聚合物膜组成的微球体(microsphere),称作微球(microballoon)。
该第二聚合物层中,这些微球的比例更优选为0.5-20wt%,且进一步优选为2-12wt%。
微球为弹性中空球体,其具有热塑性聚合物壳。这些球体填充有低沸点液体或液化气体。作为壳材料,特别地使用聚丙烯腈、PVDC、PVC或聚丙烯酸酯。适宜的低沸点液体特别地为低级烷烃,例如异丁烯/异丁烷或异戊烷,其在加压下以液化气体形式包裹于聚合物壳中。
对于微球的作用,特别是热作用,一方面存在软化外层聚合物壳的影响。同时,位于壳中的液体推进剂气体发生向其气态的转化。这个过程中,微球不可逆地且在三维尺度上膨胀。当内压等于外压时膨胀结束。由于聚合物壳保持完好,这样获得闭孔(closed-cell)泡沫。
多种类型的微球是可商购获得的,例如Akzo Nobel的Expancel DU(干燥未膨胀的)类型,其基本上区别在于它们的尺寸(未膨胀状态下直径为6-45μm)和它们膨胀所需的初始温度(75-220℃)。使微球的类型和/或发泡温度与机器参数和配料该组合物所需的温度分布相匹配,该组合物的配料和发泡也可以在一个步骤中同时进行。
另外适宜的是未膨胀的微球类型,其为具有大约40-50wt%的固体比例或微球比例的含水分散体的形式,以及微球浓度为65wt%的聚合物-粘结微球(母料)形式(例如在乙烯-乙酸乙烯酯中)。不仅微球分散体而且母料(如DU产品)均适于使依据本发明方法的粘合剂发泡。
依据本发明的另一有利实施方式,在第一聚合物层上自由侧之上在外部和/或在第二聚合物层上自由侧之上在外部,存在至少一个额外层,优选地该额外层的水蒸汽渗透性在37.8℃和90%相对湿度下小于200g/m2/24h,且氧气渗透性在23℃和50%相对湿度下小于20cm3/m2/24h。这些层由此提供了对于封装组件的进一步保护。
适宜的透明层为玻璃,更特别是低铁、钢化白玻璃,以及具有低水蒸汽渗透性或水蒸汽渗透的UV-稳定且风化-稳定的聚合物薄膜。
渗透的含义是,物质(渗透)迁移通过或者穿透固体的过程。驱动力为浓度梯度。通过渗透测量来进行渗透性试验。
例如,通过冲洗气体方法来测量渗透。
由此可以采用任意期望的气体和采用所有类型液体二者来试验薄膜和膜的渗透性。用于气体的测量技术都包括被试验中的膜分开的中心模块:在进料侧上使测量元件充满试验气体,并取出剩余的渗余物。通过冲洗气体使到达另一侧之上(渗透)的气体量通到检测器,在检测器中测量浓度。元件的顶部和底部部件围绕着居中的膜。位于样品上的O-环密封界面。这些类型的元件通常是由金属例如不锈钢制成的。
适用于非透明层,适当的时候在第二聚合物层上也存在具有低水蒸汽渗透性的UV-稳定且风化-稳定的薄膜(如DuPont的)或者玻璃。
同样合适的是薄膜,其包含由特别是聚酯的至少一种聚合物薄膜形成的薄膜部分,还包含施用到该薄膜部分的且由特别是铝的金属层形成的金属部分,且将粘合剂施用于金属层的暴露侧。
此时该金属层作为阻隔层,且由此使促进腐蚀的物质如水、水蒸汽、氧气、二氧化硫和二氧化碳远离待保护的产品(特别是片状功能层)。
在本发明的第一种有利实施方式中,该金属层的厚度为10nm-50μm,更特别地为12-25μm。
例如,通过蒸汽沉积的方式将金属层施用于薄膜部分,换句话说,通过在减压下由热蒸发使其涂布在聚合物薄膜上(电学上通过电子束,通过阴极溅射或线爆炸,适当的时候借助于激光束)。
作为聚合物膜,优选使用聚酯。
除了聚酯之外,由例如PU、PP、PE、PVC、PVDC、PEN、PAN、EVOH和PA、具有纳米复合物的PA制得的膜,也显示突出性质。
具有纳米复合物的PA包括填充有层状硅酸盐的PA。这些颗粒具有类似于滑石的片状(platelet-shaped)结构。与滑石不同的是,粒径显著更小(纳米范围)。将这些颗粒在挤出时排列并形成层结构。颗粒本身,如玻璃,完全不可渗透气体。阻碍气体渗透该薄膜,由此产生增强的阻隔效果。层结构形成了气体和气味必须从中通过的一类曲径(labyrinth)。考虑到小粒径,并未影响薄膜的光学性能。
对于该聚合物薄膜,优选膜厚为10-160μm。
本发明的另一有利实施方式中,该薄膜部分由聚合物薄膜、且优选聚酯薄膜和聚烯烃薄膜的层压体组成,另外优选地,所述聚烯烃膜设置有金属层。
采用粘合剂(层压树脂)如环氧树脂、蜜胺树脂、热塑性塑料等将聚合物薄膜粘结。
优选聚酯薄膜厚度为10-40μm且聚烯烃膜厚度为20-120μm。
另外,也能够采用三层或多层层压体,而不偏离本发明的范围。
另外,在Al箔核周围对称的层压体结构可以特别是在施用领域中是有利的。
另外,如果在金属层和粘合剂之间存在第二薄膜部分,其是有利的。
此时,两个薄膜部分优选地由相同聚合物薄膜组成,且进一步优选地第二箔部分同样是聚酯薄膜和聚烯烃薄膜的层压体,同样,特别地,该聚烯烃薄膜靠在(bear against)金属层上。
图1显示了一种有利实施方式中密封体系的结构。填充有未活化的发泡剂(此时为未膨胀微球)的第二聚合物层4,位于盖层5形式的额外层(聚合物薄膜)上。该第二聚合物层4之上布置的是待封装的产品3(太阳能电池)。通过第一透明聚合物层2完成该密封体系,该第一透明聚合物层2又位于透明盖层1形式的额外层之上或之下(该第一透明聚合物层2又挨着透明盖层1形式的额外层)。由此仅通过透明层覆盖了太阳能电池的光活性侧。
图2显示了已进行密封之后的密封体系。两个聚合物层2和6彼此焊接,且第二聚合物层6中的微球发生了膨胀。这样该聚合物层快速且安全地完全流到待封装产品的周围,使得太阳能电池之间的所有间隙被填充。
该两个聚合物层用于固定光电组件,并形成提供了对水蒸汽和氧气的阻隔的两个基底。
由此,将待封装的组件嵌入第一透明聚合物层和填充的聚合物层之间,并随后使发泡剂活化,使得两个聚合物层彼此焊接且所述组件包裹在两个聚合物层之间。
本领域技术人员预料不到的事实是,发泡和未发泡聚合物层之间的连接如此稳定,使得确保了组件的可靠封装。该封装步骤非常快速,使得封装期间不存在待封装产品的移动,通过辅助胶带的方式固定不再是必要的。
另外,层压之后修整边缘的操作步骤是不必要的,因为几乎没有任何聚合物出现在边缘之外。
微球形成的聚合物层和(自)粘合剂对于具有均匀尺寸的泡沫单元分布的规定元件结构是值得注意的。它们是不存在空腔的闭孔微泡沫,由此使得能够相对于开孔形式使敏感物件针具有对灰尘和液体介质的更好密封。
由于它们柔韧的热塑性聚合物壳,这种类型的泡沫比填充有不可膨胀的、非聚合物中空微球(中空玻璃珠)的那些具有更高顺应性(conformability)。它们比通常情形下(例如采用注塑时)更加适用于补偿制造公差,且考虑到它们的泡沫特性也能够更好地补偿热应力。
另外,通过聚合物壳的热塑性树脂的选择,可以进一步影响泡沫的机械性能。由此,例如,即使在该泡沫具有比基质更低的密度时,也能够制得比仅采用聚合物基质具有更高内聚强度(cohesive strength)的泡沫。由此,对于PSA泡沫,可以将典型泡沫性质如对于粗糙基底的顺应性与高内聚强度组合起来。
相反,常规化学或物理发泡的材料,更易受压力和温度下不可逆坍塌的影响。另外,内聚强度更低。
由此,该方法的优选实施方式提供了迄今本领域技术人员不能推断到的显著优点。
在该方法的一种可能实施方式中,将图1中所示的层在彼此之上进行排列。将这种排列在压力机中压制,优选地在160℃和/或不采用加压。压制可以任选地在减压下进行。压制中,促进发泡剂发泡,且由此两个聚合物层彼此焊接并使组件包裹在两个聚合物层之间。
图3-5显示了本发明方法的工序,使用了辊式层压机。
第一步骤(图3)中,将该第一透明聚合物层2置于透明盖层1之上或之下,层2又与辅助载体7相邻。在辊距(roll nip)中进行层压。
可以将制得的三层产品缠绕或储存,或者可以可替换地直接供给随后进一步加工。
密封之前除去辅助载体7,其并不成为所获密封体系的一部分。
图4显示了如何将在透明盖层1之上的第一透明聚合物层2(依据图3在除去辅助载体7之后制得,所述透明聚合物层2具体地在与覆盖有透明盖层1的侧相对的侧上带有待封装组件3),和在另一盖层5之上或之下填充有未活化发泡剂(微球)的第二聚合物层4,导入辊式层压机的辊距之中。透明盖层1和另一盖层5直接在辊上运转。
在辊式层压机的辊距中使微球发泡,且由此两个聚合物层2和6彼此焊接并将组件3包裹在两个聚合物层2和6之间。
在辊式层压机中处理层时的前进速率优选为0.1m/min-3m/min,更优选为0.2m/min-1m/min。辊温度为160℃,将上端可运动的辊压在下端固定辊上的圆柱体中的压力为2巴。辊为软橡胶辊。
图5显示了如何将在透明盖层1之上的第一透明聚合物层2(依据图3制得,除去辅助载体7之后),待封装组件3,和在另一盖层5之上或之下填充有未活化发泡剂的第二聚合物层4,独立地导入辊式层压机的辊距之中,透明盖层1和另一盖层5直接在辊上运转,且将待封装组件3导入两个聚合物层2和4之间。在辊式层压机的辊距中使微球发泡,且由此两个聚合物层2和6彼此焊接并将组件3包裹在两个聚合物层2和6之间。
在辊式层压机中处理层时的前进速率优选为0.1m/min-3m/min,更优选为0.2m/min-1m/min。辊温度为160℃,将上端可运动的辊压在下端固定辊上的圆柱体中的压力为2巴。辊为软橡胶辊。
下面参照实施例更详细地阐述本发明,但并非意欲以任何形式对其进行限定。
实施例
实施例1
聚合物基础乙烯-乙酸乙烯酯:
乙烯-乙酸乙烯酯橡胶“Levamelt 456(Lanxess)”,乙酸乙烯酯含量为45wt%。
图6中显示了实验工序和实验结构。
该密封体系由如下层组成:
·3mm玻璃板
·100g/m2第一透明聚合物层
·待封装的产品,高度985μm
·550g/m2第二填充微球的聚合物层
·盖层PET/PP/AI/PP/PET,厚度142μm。
利用常规搅拌装置,在实验室制备由Levamelt 456(甲苯中固含量40wt%)组成的第一透明聚合物层2,并随后采用刮刀将其涂布到抗粘衬上,涂层重量为100g/m2。随后将此聚合物层2转移到3mm厚的玻璃板1上。
随后将待封装的产品3(高度985μm)固定到这种温和粘着的聚合物层2上,并将第二填充微球的聚合物层4层压于其上。
同样在搅拌装置中在实验室制备由98wt%Levamelt 456和2wt%Expancel 051DU 40(Akzo Nobel的微球)组成的这种填充微球的聚合物层4,并以550g/m2的涂层重量涂布到具有PET/PP/Alu/PP/PET(Nordenia)顺序的5层膜层压体(其水蒸汽渗透性在37.8℃和90%相对湿度下小于0.005g/m2/24h,且氧气渗透性在23℃和50%相对湿度下小于0.005cm3/m2/24h,其同时作为盖层5)上。
随后通过传统压力机(施加的压力趋向(toward)0巴)的方式加热这样制得的实验样品,从而引发微球的发泡和由此包裹和密封待封装的产品。
预备试验中发现1.5min的停留时间或压制时间和160℃的温度是最佳温度参数和发泡参数,换句话说,实现了最大发泡速率以及由此实现完全而可靠的封装,不存在气泡(参见表1:最佳发泡/封装参数的确定)。
表1:最佳发泡/封装参数的确定
密封比率可以通过密封仍不完全时在待封装产品周围的包含空气的面积部分与总面积的比例来表示。这表示,如果透明聚合物层A仍未连接于聚合物层B,那么密封比例为0%;反之如果待封装产品周围包含空气的面积部分为0,那么密封比例为100%。
在160℃温度下,发现最佳的是,在仅90s的压制时间之后是最快速和最稳定的。
作为对比,图7显示了大约50%的密封比率。
实施例2-对比实施例
聚合物基础乙烯-乙酸乙烯酯:
乙烯-乙酸乙烯酯橡胶“Levamelt 456(Lanxess)”,乙酸乙烯酯含量为45wt%。
该对比实施例的目的是研究和对比采用相同Levamelt 456聚合物基础的未填充或未发泡的组合物相对于微球发泡的组合物的密封性能。
由此,微球发泡对于封装的品质和性质的影响成为可清楚识别的,且可以确定相对于采用未发泡组合物体系密封的优点。
实验工序和实验结构类似于实施例1中那些。但是,此时第二聚合物层并未填充2wt%微球,而是代之以1wt%二氧化钛,这是为了确保待封装产品相对于透明盖层和密封比率的更好可视性。此时同样利用传统压力机(施加的压力趋向0巴)在160℃下加热这样制得的实验样品,并在多个规律时间间隔之后核查密封性能的完整性。
仅在160℃下10min之后获得了最佳和完全的封装(参见表2)。另外,发现了实验样品中额外不期望的变化,这点并不与本发明观念一致。
在仅5min的压制时间之后,未发泡的聚合物基质以这样的方式膨胀,该膨胀使得基质变形和使待封装的产品的排列和位置在透明聚合物层A之上以及在作为整体的系统中移动。由此,采用未发泡的聚合物层,并不能够实现待封装产品的可靠密封和同时永久定位。
表2:对照样品的密封比率
这点在图7中是显然的。考虑到加热的第二聚合物层的不足流动性能,并不能够完全包围在组件周围。虽然两个聚合物层在边缘区域完全(8)密封,然而在组件周围仍包含空气,且由此密封不彻底(9)(大约50%的密封比率)。
本发明通过使微球填充的组合物体系发泡的密封,由此缩短了完成封装所需的时间,且由此代表了温和的密封操作且对品质是有利的。
Claims (11)
1、封装光电组件的方法,通过将待封装的组件嵌入第一透明聚合物层与填充有未活化的发泡剂的第二聚合物层之间,并随后活化该发泡剂,使得这两个聚合物层彼此连接、特别是彼此焊接,且所述组件包裹在这两个聚合物层之间。
2、权利要求1的方法,其特征在于,该发泡剂包括由包裹起泡剂的聚合物膜组成的微球体,称作微球。
3、权利要求1或2的方法,其特征在于,在第一聚合物层上自由侧之上在外部和/或在第二聚合物层上自由侧之上在外部,存在至少一个额外层,优选地该额外层的水蒸汽渗透性在37.8℃和90%相对湿度下小于200g/m2/24h,且氧气渗透性在23℃和50%相对湿度下小于20cm3/m2/24h。
4、权利要求1-3中至少一项的方法,其特征在于,该第一透明聚合物层对于350-1150nm波长的透射率大于60%,更特别地透射率大于90%。
5、前述权利要求中至少一项的方法,其特征在于,该第一透明聚合物层的厚度为10-500μm,更特别地为50-300μm。
6、前述权利要求中至少一项的方法,其特征在于,填充有发泡剂的第二聚合物层,在发泡之后其密度小于900kg/m3,更特别地小于700kg/m3。
7、前述权利要求中至少一项的方法,其特征在于,该第一透明聚合物层和/或第二聚合物层存在于抗粘连处理过的辅助载体之上。
8、前述权利要求中至少一项的方法,其特征在于,选择具有低水蒸汽渗透性的UV-稳定且风化-稳定的塑料或者玻璃的透明层作为第一聚合物层之上的额外层,和/或选择低水蒸汽渗透性的单层或多层、UV-稳定且风化-稳定聚合物薄膜或者玻璃的层作为第二聚合物层之下的额外层。
9、前述权利要求中至少一项的方法,其特征在于,使填充有未活化的发泡剂的第二聚合物层位于盖层5形式的额外层之上,
使待封装的产品配置在第二聚合物层4之上,
其上为第一透明聚合物层,又使所述第一透明聚合物层位于透明盖层形式的额外层之上或之下,
且以这种排列,优选地在压力机中在减压下,诱发发泡剂发泡,且使得两个聚合物层彼此焊接且将所述组件包裹在两个聚合物层之间。
10、前述权利要求中至少一项的方法,其特征在于,使透明盖层之上的第一透明聚合物层、待封装的组件和在另一盖层之上或之下的填充有未活化的发泡剂的第二聚合物层,导入辊层压机的辊距中,透明盖层和另一盖层直接在辊上运转,且将待封装的组件导入两个聚合物层之间,在辊距中发生发泡剂的发泡,且使得两个聚合物层彼此焊接且使所述组件包裹在两个聚合物层之间。
11、前述权利要求中至少一项的方法,其特征在于,使透明盖层之上的第一透明聚合物层、置于透明聚合物层之上(且特别地在与透明盖层覆盖的侧相对的侧上)的待封装的组件、和在另一盖层之上或之下的填充有未活化的发泡剂的第二聚合物层,导入辊层压机的辊距中,透明盖层和另一盖层直接在辊上运转,且在辊距中发生发泡剂的发泡,且使得两个聚合物层彼此焊接且使所述组件包裹在两个聚合物层之间。
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DE102008024551A DE102008024551A1 (de) | 2008-05-21 | 2008-05-21 | Verfahren zur Verkapselung von optoelektronischen Bauteilen |
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EP (1) | EP2123420B1 (zh) |
JP (1) | JP2009283939A (zh) |
KR (1) | KR20090121214A (zh) |
CN (1) | CN101587848A (zh) |
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CN108140962A (zh) * | 2015-10-09 | 2018-06-08 | 泰连德国有限公司 | 包括发泡的密封材料的端子组件,包括可发泡的密封材料的电端子和电线,以及用于密封电导体和电端子之间的连接的方法 |
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CN111718665A (zh) * | 2017-08-11 | 2020-09-29 | 杭州福斯特应用材料股份有限公司 | 一种多层结构光伏组件封装用胶膜及其制备方法 |
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EP2123420A3 (de) | 2012-07-11 |
JP2009283939A (ja) | 2009-12-03 |
US20090289381A1 (en) | 2009-11-26 |
CA2663183A1 (en) | 2009-11-21 |
TWI462321B (zh) | 2014-11-21 |
DE102008024551A1 (de) | 2009-11-26 |
EP2123420A2 (de) | 2009-11-25 |
EP2123420B1 (de) | 2019-05-01 |
US7976750B2 (en) | 2011-07-12 |
KR20090121214A (ko) | 2009-11-25 |
TW201005981A (en) | 2010-02-01 |
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