CN101896342A - 酸性三元共聚物膜或片材以及包含此类膜或片材的制品 - Google Patents

酸性三元共聚物膜或片材以及包含此类膜或片材的制品 Download PDF

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Publication number
CN101896342A
CN101896342A CN200880120399XA CN200880120399A CN101896342A CN 101896342 A CN101896342 A CN 101896342A CN 200880120399X A CN200880120399X A CN 200880120399XA CN 200880120399 A CN200880120399 A CN 200880120399A CN 101896342 A CN101896342 A CN 101896342A
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China
Prior art keywords
film
sheet material
sheet
goods
solar cell
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Pending
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CN200880120399XA
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English (en)
Inventor
R·A·海斯
S·L·萨米尔斯
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication of CN101896342A publication Critical patent/CN101896342A/zh
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
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Abstract

本发明提供由包含酸性三元共聚物的膜或片材构成的安全层压板或太阳能电池模块，其中所述酸性三元共聚物包含衍生自α-烯烃、按所述酸性三元共聚物的总重量计约15至约30重量％的具有3至8个碳原子的α，β-烯键式不饱和羧酸、和约0.5至约40重量％的具有4至12个碳原子的α，β-烯键式不饱和羧酸酯的共聚单元。

Description

酸性三元共聚物膜或片材以及包含此类膜或片材的制品
本发明涉及含酸性三元共聚物的膜或片材以及包含此类膜或片材的制品。
发明背景
诸如安全玻璃的玻璃层压产品已在社会中应用了几乎一个世纪。还发现安全玻璃可用于结构应用、装饰应用或其他建筑应用中。
安全玻璃通常由用聚合物片材的聚合夹层粘合在一起的两块玻璃片材或板材的夹层体构成。这两块玻璃片材或其中之一均可被光学透明的刚性聚合物片材，例如由聚碳酸酯材料制成的片材来替换。安全玻璃已进一步演变，包括由夹层粘合在一起的多层玻璃和/或刚性聚合物片材。
夹层通常由相对较厚的聚合物片材制成，其表现出韧性和可粘结性以便在发生断裂或破碎的情况下提供对玻璃的粘附作用。被广泛使用的夹层材料包括基于聚(乙烯醇缩丁醛)(PVB)、聚氨酯(PU)、乙烯-乙酸乙烯酯共聚物(EVA)等的多组分复合组合物。
作为一种可持续能源，太阳能电池模块的应用范围正在迅速扩大。制造太阳能电池模块的一种优选方式涉及形成包括至少5个结构层的预层压组合件。太阳能电池预层压组合件按以下从顶层或入射层(即，与光最先接触的层)开始，并且延续到背衬层(离入射层最远的层)的顺序进行构造：(1)入射层(通常为玻璃板或聚合物膜(诸如含氟聚合物或聚酯膜)，但可以设想为能透射太阳光的任何材料)，(2)前包封层，(3)太阳能电池组件，(4)后包封层，和(5)背衬层。
包封层设计用于包封并保护易碎的太阳能电池组件。一般来讲，太阳能电池预层压组合件包括至少两个夹持太阳能电池组件的包封层。前包封层的光学特性可使得光能够被有效地透射至太阳能电池组件。此外，包封层一般具有与上述安全玻璃夹层类似的要求和组成。
该领域已知可使用α-烯烃与α，β-烯键式不饱和羧酸的酸性共聚物来形成安全玻璃夹层(参见例如美国专利3,762,988)。使用此类酸性共聚物形成太阳能电池包封层在例如美国专利5,508,205、6,187,448、6,320,116、6,414,236、6,586,271、6,693,237和6,777,610，美国专利申请2004/0191422和2006/0207645，欧洲专利1544921，日本专利JP2000186114、JP 2001089616、JP 2001119047、JP 2001119056、JP2001119057、JP 2001144313、JP 2001261904、JP 2001332751和JP2002335005、JP 2004031445、JP 2004058583、JP 2006032308、JP2006036875和JP 2006190867，以及PCT专利申请WO 03/041177中有所公开。
α-烯烃、α，β-烯键式不饱和羧酸和α，β-烯键式不饱和羧酸酯的酸性三元共聚物也已被用来形成安全玻璃夹层(参见例如美国专利申请2001/0008695)或太阳能电池包封层(参见例如美国专利3,957,537和6,414,236，和日本专利JP 2004031445和JP 2004058583)。
然而，由此类酸性共聚物形成的安全玻璃夹层和太阳能电池包封层缺乏足够的光透射特性以及对其他层压层的足够粘附强度，特别是在恶劣的环境条件下。此外，由此类酸性共聚物形成的太阳能电池包封层通常无法向太阳能电池组件提供足够的抗冲击保护。另一方面，由现有技术提出的酸性三元共聚物形成的安全玻璃夹层和太阳能电池包封层也不具有所需的光透射特性和对其他层压层的粘附强度。
需要透明的且可与其他层压层高度粘合的适于用作安全玻璃夹层或太阳能电池包封层的聚合物膜或片材。
发明概述
本发明涉及具有包含或由酸性三元共聚物组合物制成的膜或片材的制品，其中酸性三元共聚物包含衍生自α-烯烃、按酸性三元共聚物的总重量计约15至约30重量％的具有3至8个碳原子的α，β-烯键式不饱和羧酸、和约0.5至约40重量％的具有4至12个碳原子的α，β-烯键式不饱和羧酸酯的共聚单元；并且该制品为安全层压板或阳光控制预层压组合件。
在一个实施例中，制品为进一步包含至少一个包含或由刚性片材或聚合物膜形成的外部层压层的安全层压板，其中所述刚性片材选自由聚碳酸酯、丙烯酸类、聚丙烯酸酯、环状聚烯烃、聚苯乙烯、聚酰胺、聚酯、含氟聚合物、或它们中的两种或更多种的组合形成的玻璃或刚性聚合物片材；并且聚合物膜包含选自聚酯、聚碳酸酯、聚烯烃、降冰片烯聚合物、聚苯乙烯、苯乙烯-丙烯酸酯共聚物、丙烯腈-苯乙烯共聚物、聚砜、尼龙、聚氨酯、丙烯酸类、乙酸纤维素、玻璃纸、聚(氯乙烯)、含氟聚合物、以及它们中的两种或更多种的组合的聚合物材料。
在另一个实施方案中，制品为太阳能电池预层压组合件，其还包含太阳能电池元件，所述太阳能电池元件由一个或多个电互连的太阳能电池形成的、具有面向光源的受光面以及与光源相对的背面。
本发明还涉及包括以下步骤的方法：(i)提供如上所述的太阳能电池预层压组合件，以及(ii)层压该组合件以形成太阳能电池模块。
本发明还涉及由如上所述的太阳能电池预层压组合件制得的太阳能电池模块。
发明详述
术语“酸性共聚物”是指包含衍生自以下物质的共聚单元的聚合物：α-烯烃、α，β-烯键式不饱和羧酸、和任选的其他合适的共聚单体，例如α，β-烯键式不饱和羧酸酯。
术语“离聚物”是指通过将如上所公开的母体酸性共聚物部分地或完全地中和而衍生自所述母体酸性共聚物的聚合物。
酸性三元共聚物膜和片材
本发明提供包含酸性三元共聚物组合物的膜或片材(可以是单层或多层膜或片材)和包含此类膜或片材的层压制品，其中酸性三元共聚物包含衍生自具有2至10个碳原子的α-烯烃、按三元共聚物的总重量计约15至约30重量％的具有3至8个碳原子的α，β-烯键式不饱和羧酸、和约0.5至约40重量％的具有4至12个碳原子的α，β-烯键式不饱和羧酸酯的共聚单元。
优选地，酸性三元共聚物包含约18至约25重量％，或约18至约23重量％的α，β-烯键式不饱和羧酸共聚单元。优选地，酸性三元共聚物包含约0.5至约5重量％，或约15至约40重量％，或约15至约25重量％的α，β-烯键式不饱和羧酸酯共聚单元。
α-烯烃共聚单体可包括但不限于乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、3-甲基-1-丁烯、4-甲基-1-戊烯等等、以及它们中的两种或更多种的混合物。优选地，α-烯烃为乙烯。
α，β-烯键式不饱和羧酸共聚单体可包括但不限于丙烯酸、甲基丙烯酸、衣康酸、马来酸、马来酸酐、富马酸、一甲基马来酸、以及它们中的两种或更多种的混合物。优选地，α，β-烯键式不饱和羧酸选自丙烯酸、甲基丙烯酸、以及它们中的两种或更多种的混合物。
α，β-烯键式不饱和羧酸酯共聚单体可包括但不限于丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸异丙酯、甲基丙烯酸异丙酯、丙烯酸丁酯、甲基丙烯酸丁酯、以及它们中的两种或更多种的混合物。优选地，α，β-烯键式不饱和羧酸酯选自丙烯酸甲酯和丙烯酸丁酯。
酸性三元共聚物可按照美国专利3,404,134、5,028,674、6,500,888和6,518,365中所公开的方法进行聚合。
最优选的酸性三元共聚物是乙烯-丙烯酸丁酯-甲基丙烯酸共聚物。
酸性三元共聚物组合物还可包含本领域已知的任何合适的添加剂，包括增塑剂、加工助剂、润滑剂、阻燃剂、抗冲改性剂、成核剂、抗粘连剂(如二氧化硅)、热稳定剂、紫外线吸收剂、紫外线稳定剂、分散剂、表面活性剂、螯合剂、偶联剂、粘合剂、底漆等等、或者它们中的两种或更多种的混合物。酸性三元共聚物组合物中包含的添加剂的总量按组合物的总重量计可为约0.001至最多约5重量％。
酸性三元共聚物组合物任选地还包含一种或多种硅烷偶联剂以进一步增强包含这些成分的膜或片材的粘附强度。示例性偶联剂包括但不限于γ-氯丙基甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷、γ-乙烯基苄基丙基三甲氧基硅烷、N-β-(N-乙烯基苄基氨基乙基)-γ-氨基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三乙酰氧基硅烷、γ-环氧丙氧丙基三甲氧基硅烷、γ-环氧丙氧丙基三乙氧基硅烷、β-(3，4-环氧环己基)乙基三甲氧基硅烷、乙烯基三氯硅烷、γ-巯丙基甲氧基硅烷、γ-氨基丙基三乙氧基硅烷、N-β-(氨基乙基)-γ-氨基丙基三甲氧基硅烷等等、以及它们中的两种或更多种的混合物。硅烷偶联剂在酸性三元共聚物组合物中的含量按组合物的总重量计优选为约0.01至约5重量％，或约0.05至约1重量％。酸性三元共聚物组合物中也可不存在粘附促进剂，尤其是当组合物包含在膜或片材的表面亚层中时。
酸性三元共聚物组合物还任选地包含添加剂以将树脂的熔融流动性降低至在层压期间由该酸性三元共聚物组合物得到的膜或片材的热固性范围内，从而提供包含此类膜或片材的具有甚至更大热阻性和耐火性的层压产品。通过加入此类添加剂，可将最终使用温度升高约20℃至约70℃。有效降低熔融流动性的添加剂通常为有机过氧化物，例如如2，5-二甲基己烷-2，5-二氢过氧化物、2，5-二甲基-2，5-二(叔丁基过氧)己烷-3、二叔丁基过氧化物、过氧化叔丁基异丙苯、2，5-二甲基-2，5-二(叔丁基过氧)己烷、过氧化二异丙苯、α，α’-双(叔丁基过氧异丙基)苯、4，4-双(叔丁基过氧)戊酸正丁酯、2，2-双(叔丁基过氧)丁烷、1，1-双(叔丁基过氧)环己烷、1，1-双(叔丁基过氧)-3，3，5-三甲基环己烷、过氧苯甲酸叔丁酯、过氧化苯甲酰等、以及它们的混合物或组合。有机过氧化物在约100℃或更高的温度下可分解生成自由基，或具有分解温度，该分解温度在约70℃或更高的温度下提供10小时的半衰期以提高共混操作的稳定性。加入的有机过氧化物量按组合物的总重量计可为约0.01至约10重量％，或约0.5至约3.0重量％。酸性三元共聚物组合物中也可以不存在降低流动性的添加剂，以在层压期间提供足够的聚合物流动性并且对其他层压层提供足够的粘附性。
如果需要，酸性三元共聚物组合物中可包含引发剂，例如二月桂酸二丁基锡，所述引发剂的量按组合物的总重量计为约0.01至约0.05重量％。此外，如果需要，可将抑制剂诸如对苯二酚、对苯二酚一甲基醚、对苯醌和甲基氢醌加入到酸性三元共聚物组合物中，所述抑制剂的量按组合物的总重量计小于约5重量％。
包含酸性三元共聚物的膜或片材可为单层形式或多层形式。单层仅具有由酸性三元共聚物组合物制成的一层。优选地，酸性三元共聚物膜或片材为具有两个表面亚层和任选地一个或多个内亚层的多层膜或片材，其中至少一个亚层包含或由酸性三元共聚物组合物制成。术语“表面亚层”是指形成多层膜或片材的两个外表面的两个亚层，术语“内亚层”是指夹在两个表面亚层之间的亚层。更优选地，酸性三元共聚物膜或片材是具有包含或由酸性三元共聚物组合物制成的两个表面亚层中的至少一个的多层膜或片材。
当包含酸性三元共聚物的膜或片材为多层形式时，其他包含非酸性三元共聚物的亚层可由任何其他合适的聚合物组合物形成，这些组合物包含选自以下的聚合物材料：酸性共聚物、离聚物、乙烯-乙酸乙烯酯共聚物、聚(乙烯醇缩醛)(如聚(乙烯醇缩丁醛))、热塑性聚氨酯、聚(氯乙烯)、聚乙烯(如茂金属催化的线性低密度聚乙烯)、聚烯烃嵌段弹性体、α-烯烃-α，β-烯键式不饱和羧酸酯共聚物(如乙烯-丙烯酸甲酯共聚物和乙烯-丙烯酸丁酯共聚物)、硅氧烷弹性体、环氧树脂和它们中的两种或更多种的混合物。优选地，其他亚层包含或由离聚物制成，该离聚物衍生自包含α-烯烃、α，β-烯键式不饱和羧酸、和任选地α，β-烯键式不饱和羧酸酯的共聚单元的酸性共聚物，并且约1％至约90％，或约10％至约40％的量用一种或多种金属离子来中和，例如锌、镁、锂以及它们中的两种或更多种的混合物。优选的金属离子为锌。更优选地，其他亚层由具有至少约80℃、或至少约90℃、或至少约95℃熔点的离聚物制成，以当将膜或片材用于层压制品时提供优异的蠕变阻力。此类离聚物组合物的具体实例包括那些得自E.I.du Pont de Nemours and Company(Wilmington，DE)(DuPont)的产品。最优选地，包含酸性三元共聚物的膜或片材为具有两个表面亚层和至少一个内亚层的多层膜或片材，其中每个表面亚层均包含或由本文所公开的酸性三元共聚物组合物制成，而内亚层则包含或由上文所述的具有高熔点的离聚物制成。
包含酸性三元共聚物的膜或片材可具有约2密耳(0.051mm)至约250密耳(6.35mm)的总厚度。当为多层形式时，包含酸性三元共聚物的各亚层可具有约0.5密耳(0.013mm)至约5密耳(0.13mm)，或约0.5密耳至约3密耳(0.076mm)的厚度，其他各亚层可具有约0.5密耳(0.013mm)至约120密耳(3mm)，或约10密耳(0.25mm)至约90密耳(2.28mm)，或约30密耳(0.76mm)至约60密耳(1.52mm)的厚度。
当酸性三元共聚物膜或片材被包含在安全层压板中作为夹层膜或片材时，其优选具有约10密耳(0.25mm)至约250密耳(6.35mm)，或约15密耳(0.38mm)至约90密耳(2.28mm)，或约30密耳(0.76mm)至约60密耳(1.52mm)的总厚度；并且当膜或片材被包含在太阳能电池模块中作为包封层时，其优选地具有约2密耳(0.051mm)至约20密耳(0.51mm)的总厚度。此外，对于挠性太阳能电池层压板而言，其优选具有至少一个由如上所公开的酸性三元共聚物薄膜形成的包封层，所述包封层具有约2密耳(0.051mm)至约10密耳(0.25mm)，或约2密耳(0.051mm)至约5密耳(0.13mm)的厚度。对于刚性太阳能电池层压板而言，其优选具有至少一个由如上所公开的酸性三元共聚物厚片材形成的包封层，所述包封层具有约10密耳(0.25mm)至约20密耳(0.51mm)的厚度。
酸性三元共聚物膜或片材可在一面或两面上具有光滑或粗糙的表面。优选地，这些膜或片材在两面上均具有粗糙的表面以有利于在层压过程中脱去层压板的空气。粗糙表面可通过以下方式得到：在膜或片材挤出期间进行机械压花或熔融破裂，然后骤冷，以便在处理期间保留粗糙度。可通过本领域的常用方法向酸性三元共聚物膜或片材施加表面图案。例如，可让刚挤出的膜或片材通过紧邻模具出口设置的模辊的特制表面，该表面向熔融聚合物的一面赋予所需的表面特性。因此，当该模辊的表面具有微小的峰和谷时，浇铸在其上的聚合物膜或片材在与辊接触的一面上将具有粗糙表面，该粗糙表面一般分别适形于辊表面的谷和峰。此类模辊在例如美国专利4,035,549、美国专利申请2003/0124296和2008/0286530中有所公开。
酸性三元共聚物膜或片材可通过任何适宜的方法制备。例如，膜或片材可以通过以下方法制得：浸涂、溶液浇铸、压塑、注塑、层压、熔融挤出、吹塑薄膜、挤压涂布、串联挤压涂布，或本领域技术人员已知的任何其他方法。优选地，膜或片材通过熔融共挤出、熔融挤压涂布或串联熔融挤压涂布制得。
按照ASTM D1003测得，酸性三元共聚物膜或片材具有约80％至约100％的透光百分率。优选地，酸性三元共聚物膜或片材具有约90％至约100％的透光百分率。此外，按照ASTM D1003测得，其适宜地提供约90％至100％，或约95％至100％，或约98％至100％的清晰度百分率。
制品
本发明还提供了包含至少一层本文所公开的含酸性三元共聚物膜或片材的预层压或层压制品(如安全层压板、太阳能电池预层压组合件或由其得到的太阳能电池模块)。
在安全层压板和太阳能电池模块中使用此类含酸性三元共聚物的膜或片材可提供比通过现有技术制得的其他聚合膜或片材更多的优势。首先，包含酸性三元共聚物的膜或片材具有对其他层压层增强的粘附强度，尤其是在苛刻的环境性老化之后。例如，层压板在85℃的温度和85％的相对湿度下经过1000小时的湿热试验，或经过根据国际电工委员会(IEC)实验方法16215第10-11和/或10-12节的热循环试验后可显示具有增强的粘附强度。具体地讲，包含酸性三元共聚物的膜或片材与其相邻的层压层之间的粘附强度可以按照修正的ASTM D903、通过采用夹头速度为100mm/min的
Figure GPA00001158383200081
1125型(1000lb(454kg)试验架)测试仪进行180°剥离强度试验来测得。根据本发明，层压制品在约85℃的温度和约85％的相对湿度条件下经过1000小时后，包含酸性三元共聚物的膜或片材与其相邻层之间的180°剥离强度保持至少约50％，或至少约60％，或至少约75％。其次，在酸性三元共聚物包含约0.5至约5重量％的α，β-烯键式不饱和羧酸酯共聚单元的实施方案中，包含酸性三元共聚物的膜或片材还表现出改善的抗冲击性，在那些酸性三元共聚物包含约15至约40重量％或约15至约25重量％的α，β-烯键式不饱和羧酸酯共聚单元的实施方案中，包含酸性三元共聚物的膜或片材还表现出改善的透明性。
在一个实施方案中，层压制品为包含聚合物夹层的安全层压板，其中夹层包含一层如上所公开的酸性三元共聚物膜或片材。
聚合物夹层还任选地包含一种或多种由其他合适的聚合材料制得的其他夹层膜或片材。此类任选的其他夹层片材可由聚合材料制得，聚合材料选自酸性共聚物、离聚物、乙烯-乙酸乙烯酯共聚物、聚(乙烯醇缩醛)(包括隔音级聚(乙烯醇缩醛))、聚氨酯、聚(氯乙烯)、聚乙烯(如茂金属催化的低密度聚乙烯)、聚烯烃嵌段弹性体、乙烯-丙烯酸酯共聚物(例如乙烯-丙烯酸甲酯共聚物和乙烯-丙烯酸丁酯共聚物)、硅氧烷弹性体、环氧树脂、以及它们中的两种或更多种的混合物。此类任选的其他夹层膜可由聚合材料制得，聚合材料选自聚酯(例如聚对苯二甲酸乙二醇酯和聚萘二甲酸乙二醇酯)、聚碳酸酯、聚烯烃(例如聚丙烯、聚乙烯和环状聚烯烃)、降冰片烯聚合物、聚苯乙烯(包括间同立构聚苯乙烯)、苯乙烯-丙烯酸酯共聚物、丙烯腈-苯乙烯共聚物、聚砜(例如聚醚砜、聚砜等)、尼龙、聚氨酯、丙烯酸类、乙酸纤维素类(例如乙酸纤维素、三乙酸纤维素等)、玻璃纸、氯乙烯聚合物(例如聚(偏二氯乙烯))、含氟聚合物(例如聚氟乙烯、聚偏氟乙烯、聚四氟乙烯、乙烯-四氟乙烯共聚物等)，以及它们中的两种或更多种的混合物。如果需要，任选地其他夹层膜还可被涂覆。例如，可向膜上涂覆有机红外吸收剂、金属镀层(例如银)、涂层等。涂覆金属的聚合物膜在例如美国专利3,718,535、3,816,201、4,465,736、4,450,201、4,799,745、4,846,949、4,954,383、4,973,511、5,071,206、5,306,547、6,049,419、6,104,530、6,204,480、6,255,031和6,565,982中有所公开。例如，涂层可以充当氧气和水分阻挡涂层，例如美国专利6,521,825和6,818,819以及欧洲专利EP1182710中所公开的金属氧化物涂层。
其他任选的夹层膜的厚度可在约0.1密耳(0.003mm)至约密耳10密耳(0.26mm)，或优选约1密耳(0.025mm)至约7密耳(0.18mm)的范围内，其他任选的夹层片材的厚度可为约10密耳(0.25mm)至约250密耳(6.35mm)，或约15密耳(0.38mm)至约90密耳(2.28mm)，或约30密耳(0.76mm)至约60密耳(1.52mm)，并且夹层中所有组件膜或片材的总厚度不超过250密耳(6.35mm)。
层压板还可包含一个与夹层的一面粘合的外层，或与夹层的各面粘合的两个外层，其中每个外层可以是刚性片材或聚合物膜。
刚性片材包括具有约10密耳(0.25mm)至约250密耳(6.35mm)厚度的玻璃片材和刚性聚合物片材，包括但不限于聚碳酸酯、丙烯酸类、聚丙烯酸酯、环状聚烯烃(例如乙烯降冰片烯聚合物)、聚苯乙烯(优选茂金属催化的聚苯乙烯)、聚酰胺、聚酯、含氟聚合物等、以及它们中的两种或更多种的组合。刚性聚合物片材优选由具有至少10,000psi(69MPa)模量的聚合材料制得。
玻璃不仅包括窗玻璃、平板玻璃、硅酸盐玻璃、玻璃片、低铁玻璃、钢化玻璃、钢化无氧化铈玻璃和浮法玻璃，而且还包括彩色玻璃、特种玻璃(诸如含有可控制例如太阳能加热的成分的那些)、镀膜玻璃(诸如为控制太阳能而用金属(例如银或氧化铟锡)喷镀的那些)、E-玻璃、Toroglass、
Figure GPA00001158383200101
玻璃(PPG Industries，Pittsburgh，PA)。此类特种玻璃在例如美国专利4,615,989、5,173,212、5,264,286、6,150,028、6,340,646、6,461,736和6,468,934中有所公开。具体层压板所选择的玻璃类型取决于预期用途。
聚合物膜优选由以下材料制得，这些材料选自聚酯(例如聚对苯二甲酸乙二醇酯和聚萘二甲酸乙二醇酯)、聚碳酸酯、聚烯烃(例如聚丙烯、聚乙烯和环状聚烯烃)、降冰片烯聚合物、聚苯乙烯(例如间同立构聚苯乙烯)、苯乙烯-丙烯酸酯共聚物、丙烯腈-苯乙烯共聚物、聚砜(例如聚醚砜、聚砜等)、尼龙、聚氨酯、丙烯酸类、乙酸纤维素类(例如乙酸纤维素、三乙酸纤维素等)、玻璃纸、聚(氯乙烯)(例如聚(偏二氯乙烯))、含氟聚合物(例如聚氟乙烯、聚偏氟乙烯、聚四氟乙烯、乙烯-四氟乙烯共聚物等)等等、以及它们中的两种或更多种的组合。聚合物膜更优选为聚酯膜，最优选为双轴取向的聚对苯二甲酸乙二醇酯膜。聚合物膜优选在外表面上进行硬涂覆。“硬涂覆”是指将透明的防刮伤和抗磨蚀硬涂层涂覆在聚合物膜的外表面上，其中外表面是远离安全层压板夹层的表面。硬涂层可包含或由聚硅氧烷或交联(热固性)聚氨酯制成。还适用于本文的是公开于美国专利申请2005/0077002中的基于低聚物的涂料，其组合物通过(A)含羟基低聚物与含异氰酸酯低聚物的反应或(B)含酸酐低聚物与含环氧化物化合物的反应制得。优选地，硬涂层由例如美国专利4,177,315、4,469,743、5,415,942和5,763,089中公开的那些聚硅氧烷耐磨涂料形成。
在施加硬涂层之前，聚合物膜的外表面可能需要经过如下所公开的粘附性强化处理。
聚合物膜还可具有在其一个或两个表面上涂覆的阳光控制材料。阳光控制材料可以是红外线吸收材料，诸如金属氧化物纳米颗粒(例如氧化锑锡纳米颗粒、氧化铟锡纳米颗粒、或它们的组合)、金属硼化物纳米颗粒(例如六硼化镧纳米颗粒)、或它们中的两种或更多种的组合。聚合物膜还可涂覆有红外能反射层，诸如金属层、Fabry-Perot型干涉滤光层、液晶层、或它们中的两种或更多种的组合。
如果需要，可处理层压层的一个或两个表面，例如本文所公开的酸性三元共聚物膜或片材、任选的其他夹层片材或膜层、刚性片材、或聚合物膜，以进一步增强对其他层压层的粘附性。此粘附性强化处理可以采用本领域中已知的任何形式，并且包括火焰处理(参见例如美国专利2,632,921、2,648,097、2,683,894和2,704,382)、等离子处理(参见例如US 4,732,814)、电子束处理、氧化处理、电晕放电处理、化学处理、铬酸处理、热空气处理、臭氧处理、紫外线处理、喷砂处理、溶剂处理等、以及它们中的两种或更多种的组合。还可通过将粘合剂或底漆涂层施用在层压层表面上来进一步改善粘附强度。例如，美国专利4,865,711公开了可粘结性得到改善的膜或片材，其具有沉积在一个或两个表面上的碳薄层。其他示例性粘合剂或底漆可以包括硅烷、聚(烯丙胺)基底漆(参见例如美国专利5,411,845、5,770,312、5,690,994和5,698,329)以及丙烯酸基底漆(参见例如美国专利5,415,942)。粘合剂或底漆涂层可采用该粘合剂或底漆的单层形式并具有约0.0004至约1密耳(约0.00001至约0.03mm)、或优选约0.004至约0.5密耳(约0.0001至约0.013mm)、或更优地约0.004至约0.1密耳(约0.0001至约0.003mm)的厚度。
粘合剂或底漆涂层的厚度可为约0.0004密耳(0.00001mm)至约1密耳(0.03mm)，或约0.004密耳(0.0001mm)至约0.5密耳(0.013mm)，或约0.004密耳(0.0001mm)至约0.1密耳(0.003mm)。
酸性三元共聚物膜或片材也可不经过任何粘附性强化处理并自粘附到其他层压层上。
安全层压板可采用本领域内已知的任何形式。优选的具体玻璃层压板构造包括：
·玻璃/ATR；
·玻璃/ATR/膜(例如硬涂覆的聚对苯二甲酸乙二醇酯膜)；
·玻璃/ATR/玻璃；
·膜/ATR/膜；
·玻璃/ATR/膜/ATR/玻璃；
·玻璃/ATR/膜/ATR/膜；
等等，其中“ATR”代表上文所公开的酸性三元共聚物膜或片材。
安全层压板可由下文详细描述的任何层压方法或本领域技术人员已知的任何其他方法制得。
层压板可以是太阳能电池预层压组合件，其包含由一个或多个太阳能电池形成的太阳能电池组件和至少一层上述酸性三元共聚物膜或片材。
太阳能电池旨在包括能将光转换成电能的任何制品。各种形式的太阳能电池的典型领域实例包括例如单晶硅太阳能电池、多晶硅太阳能电池、微晶硅太阳能电池、非晶硅太阳能电池、铜铟硒化物太阳能电池、化合物半导体太阳能电池、染料敏化太阳能电池等。最常见的太阳能电池类型包括多晶太阳能电池、薄膜太阳能电池、化合物半导体太阳能电池和非晶硅太阳能电池。
薄膜太阳能电池通常通过将若干薄膜层沉积到基底例如玻璃或柔性膜上来制备，并使各层图案化，从而形成多个单个电池，这些单个电池电互连在一起以提供合适的电压输出。根据多层沉积进行的顺序，基底可以充当太阳能电池模块的后表面或前窗口。作为举例，薄膜太阳能电池在美国专利5,512,107、5,948,176、5,994,163、6,040,521、6,137,048和6,258,620中有所公开。
太阳能电池预层压组合件通常包含至少一层酸性三元共聚物膜或片材，其靠近太阳能电池组件，并用作一个包封层，或者优选地，酸性三元共聚物膜或片材位于与太阳能电池组件相邻的受光面上并用作前包封层。
太阳能电池预层压组合件还可包含由其他聚合材料形成的包封层，所述聚合材料如酸性共聚物、离聚物、乙烯-乙酸乙烯酯、聚(乙烯醇缩醛)(包括隔音级聚(乙烯醇缩醛))、聚氨酯、聚氯乙烯、聚乙烯(如线性低密度聚乙烯)、聚烯烃嵌段弹性体、α-烯烃与α，β-烯键式不饱和羧酸酯的共聚物(如乙烯-丙烯酸甲酯共聚物和乙烯-丙烯酸丁酯共聚物)、硅氧烷弹性体、环氧树脂、以及它们中的两种或更多种的组合。优选地，太阳能电池预层压组合件包含两层酸性三元共聚物膜或片材，其中两层酸性三元共聚物膜或片材中的每一层分别层压到太阳能电池组件的两面中的每一面上，并用作前包封层和后包封层。
除酸性三元共聚物膜或片材外的各个包封层的厚度可独立地为约1密耳(0.026mm)至约120密耳(3mm)，或约1密耳至约40密耳(1.02mm)，或约1密耳至约20密耳(0.51mm)。包括在太阳能电池预层压组合件中的所有包封层可具有平滑或粗糙的表面。优选地，包封层具有粗糙的表面以有利于通过层压过程脱去层压板的空气。
太阳能电池预层压组合件还可以包含入射层和/或背衬层，它们分别用作受光面和背光面上的组合件的外层。
太阳能电池预层压组合件的外层即入射层和背衬层可得自任何适宜的片材或膜。适合的片材可以是玻璃或塑性片材，例如聚碳酸酯、丙烯酸类、聚丙烯酸酯、环状聚烯烃(例如乙烯降冰片烯聚合物)、聚苯乙烯(优选茂金属催化的聚苯乙烯)、聚酰胺、聚酯、含氟聚合物等等、以及它们中的两种或更多种的组合。此外，可以利用金属片材诸如铝、钢、镀锌钢或陶瓷板来形成背衬层。适合的膜可由聚合物制得，这些聚合物选自聚酯(例如聚对苯二甲酸乙二醇酯和聚萘二甲酸乙二醇酯)、聚碳酸酯、聚烯烃(例如聚丙烯、聚乙烯和环状聚烯烃)、降冰片烯聚合物、聚苯乙烯(例如间同立构聚苯乙烯)、苯乙烯-丙烯酸酯共聚物、丙烯腈-苯乙烯共聚物、聚砜(例如聚醚砜、聚砜等)、尼龙、聚氨酯、丙烯酸类、乙酸纤维素类(例如乙酸纤维素、三乙酸纤维素等)、玻璃纸、聚(氯乙烯)(例如聚(偏二氯乙烯))、含氟聚合物(例如聚氟乙烯、聚偏氟乙烯、聚四氟乙烯、乙烯-四氟乙烯共聚物等)等等、或它们中的两种或更多种的组合。聚合物膜可为双轴取向的聚酯膜(优选聚对苯二甲酸乙二醇酯膜)或含氟聚合物膜(例如得自DuPont的和
Figure GPA00001158383200132
膜)。TPT膜也是某些应用的优选材料。金属膜诸如铝箔也可用作背衬片材。
太阳能电池预层压组合件还可以包含嵌入在组合件中的其他功能性膜或片材层(例如介电层或阻挡层)。此类功能性层可得自任何上述聚合物膜，或涂覆有其他功能性涂层的那些。例如，涂覆有金属氧化物涂层的聚对苯二甲酸乙二醇酯膜，诸如美国专利6,521,825和6,818,819以及欧洲专利EP1182710中公开的那些，可作为层压板中的氧气和水分阻挡层。
如果需要，还可在太阳能电池层压板中包含一层非织造玻璃纤维(稀松布)以有利于在层压过程中排气或用作包封层的加固物。此类稀松布层在太阳能电池层压板中的用途在例如美国专利5,583,057、6,075,202、6,204,443、6,320,115和6,323416以及欧洲专利EP0769818中有所公开。
位于太阳能电池组件受光面的膜或片材层可由透明材料制成以使太阳光能够有效地透射到太阳能电池组件中。可包含特殊的膜或片材以同时起到包封层和外层的作用。还可设想到，包含在组合件中的任何膜或片材层可为预成形的单层或多层膜或片材的形式。
如果需要，可对太阳能电池预层压组合件的层压层(例如包含酸性三元共聚物的膜或片材)的一个或两个表面进行处理以增强粘附强度，如上所述。
酸性三元共聚物膜或片材也可不经过任何粘附性强化处理并自粘附到其他层压层上。
太阳能电池预层压组合件可采用本领域内已知的任何形式。优选的具体太阳能电池预层压构造(顶(受光)面至背面)包括：
·玻璃/ATR/太阳能电池/ATR/玻璃；
·玻璃/ATR/太阳能电池/ATR/含氟聚合物膜(例如膜)；
·含氟聚合物膜/ATR/太阳能电池/ATR/玻璃；
·含氟聚合物膜/ATR/太阳能电池/ATR/含氟聚合物膜；
·玻璃/ATR/太阳能电池/ATR/聚酯膜(如聚对苯二甲酸乙二醇酯膜)；
·含氟聚合物膜/ATR/太阳能电池/ATR/聚酯膜；
·玻璃/ATR/太阳能电池/ATR/阻挡涂覆膜/ATR/玻璃；
·含氟聚合物膜/ATR/阻挡物涂覆膜/ATR/太阳能电池/ATR/阻挡涂覆膜/ATR/含氟聚合物膜；
·玻璃/ATR/太阳能电池/ATR/铝板锭；
·含氟聚合物膜/ATR/太阳能电池/ATR/铝板锭；
·玻璃/ATR/太阳能电池/ATR/镀锌钢片；
·玻璃/ATR/太阳能电池/ATR/聚酯膜/ATR/铝板锭；
·含氟聚合物膜/ATR/太阳能电池/ATR/聚酯膜/ATR/铝板锭；
·玻璃/ATR/太阳能电池/ATR/聚酯膜/ATR/镀锌钢片；
·含氟聚合物膜/ATR/太阳能电池/ATR/聚酯膜/ATR/镀锌钢片；
·玻璃/ATR/太阳能电池/聚(乙烯醇缩丁醛)包封层/玻璃；
·玻璃/ATR/太阳能电池/聚(乙烯醇缩丁醛)包封层/含氟聚合物膜；
·含氟聚合物膜/ATR/太阳能电池/酸性共聚物包封层/含氟聚合物膜；
·玻璃/ATR/太阳能电池/乙烯-乙酸乙烯酯包封层/聚酯层；
·含氟聚合物膜/ATR/太阳能电池/乙烯-丙烯酸甲酯共聚物包封层/聚酯层；以及
·玻璃/乙烯-丙烯酸丁酯共聚物包封层/太阳能电池/ATR/阻挡涂覆膜/乙烯-丙烯酸丁酯共聚物包封层/玻璃，等等，其中“ATR”代表酸性三元共聚物膜或片材。此外，除了得自DuPont的
Figure GPA00001158383200151
膜以外，适宜的含氟聚合物膜还包括TPT三层膜。
本发明还提供由上文所公开的太阳能电池预层压组合件制得的太阳能电池层压板。具体地讲，太阳能电池层压板通过下文详细提供的使太阳能电池预层压组合件经受进一步层压处理形成。
层压方法
可使用本领域已知的任何层压方法来制备安全玻璃层压板或太阳能电池层压板。层压方法可为高压釜法或非高压釜法。
在示例性方法中，将安全玻璃层压板或太阳能电池预层压组合件以所需顺序堆叠，以形成预层压组合件。然后将组合件放入能够承受真空的袋(“真空袋”)中，通过真空管线或其他装置排出袋中的空气，将袋密封同时保持真空(例如约27至约28inHg(约689至约711mmHg))，并且将密封袋在压力为约150至约250psi(约11.3至约18.8巴)，温度为约130℃至约180℃，或约120℃至约160℃，或约135℃至约160℃，或约145℃至约155℃的高压釜中放置约10至约50分钟，或约20至约45分钟，或约20至约40分钟，或约25至约35分钟。可以用真空环来代替真空袋。美国专利3,311,517公开了一种类型的合适真空袋。加热和加压循环后，使高压釜中的空气冷却，但不加入额外的气体以保持高压釜内的压力。冷却约20分钟之后，释放掉多余的空气压力，并从高压釜中取出层压板。
作为另外一种选择，可将预层压组合件在约80℃至约120℃，或约90℃至约100℃的烘箱中加热约20至约40分钟，之后使热组合件通过一组咬送辊以使各层之间的空隙空间中的空气被挤出，并将组合件的边缘密封。本阶段的组合件称为预压件。
然后将预压件放入到空气高压釜中，在约100至约300psi(约6.9至约20.7巴)，或约200psi(13.8巴)的压力下，将高压釜中的温度升至约120℃至约160℃，或约135℃至约160℃。将这些条件保持约15至约60分钟，或约20至约50分钟，然后使空气冷却，而不将额外的空气加入到高压釜中。冷却约20至约40分钟之后，释放掉多余的空气压力，并从高压釜中取出层压产品。
也可通过非高压釜法制备层压板。此类非高压釜法在以下专利中有所公开：例如美国专利3,234,062、3,852,136、4,341,576、4,385,951、4,398,979、5,536,347、5,853,516、6,342,116和5,415,909；美国专利申请2004/0182493；欧洲专利EP1235683B1；以及PCT专利申请WO91/01880和WO03/057478A1。一般来讲，非高压釜法包括加热预压组合件并且施加真空、压力或它们二者。例如可使组合件依次通过加热烘箱和咬送辊。
可使用基本上任何的层压方法。
实施例
下列实施例旨在举例说明本发明，并不旨在以任何方式限制本发明的范围。
熔融指数
使用2160g的负荷在190℃下按照ASTM D1238测量熔融指数(MI)。
熔点
按照差示扫描量热法(DSC)测定熔点。
层压方法1
将层压板的组件层堆叠以形成预层压组合件。就包含聚合物膜层作为外表面层的组合件而言，将玻璃覆盖片材放置在膜层上方。然后将预层压组合件放入Meier
Figure GPA00001158383200171
10/08层压机(Meier层压机；MeierVakuumtechnik GmbH，Bocholt，Germany)中。层压循环包括5.5分钟的排空步骤(3inHg(76mmHg)真空)和145℃温度下5.5分钟的加压步骤(1000毫巴压力)。然后将所得层压板从层压机中取出。
层压方法2
将层压板的组件层堆叠以形成预层压组合件。就包含聚合物膜层作为外表面层的组合件而言，将玻璃覆盖片材放置在膜层上方。然后将该预层压组合件放入真空袋内，将真空袋密封，并通过施加真空来除去真空袋内的空气。将该真空袋置于烘箱中并加热到约90℃至约100℃维持30分钟，以除去包含在组合件之间的任何空气。然后在加压至200psig(14.3巴)的空气高压釜中，使组合件在140℃下热压处理30分钟。将空气冷却，并且不将额外的空气加入到高压釜中。冷却20分钟之后，并且当空气温度低于约50℃时，释放多余压力，并将所得的层压板从高压釜中取出。
材料
下列膜和片材用于实施例中：
·AL为3.2mm厚的铝片材，其为与2.5重量％镁铸合的5052铝片材，并且符合美国联邦规范QQ-A-250/8和ASTM B209；
·ATR 1为由酸性三元共聚物A制成的30密耳(0.76mm)厚的压花片材，其中酸性三元共聚物A为乙烯-丙烯酸正丁酯-甲基丙烯酸共聚物，其具有2.5g/10min的MI并包含按三元共聚物的总重量计2重量％的丙烯酸正丁酯共聚单元和19重量％的甲基丙烯酸共聚单元；
·ATR 2为60密耳(1.52mm)厚的压花三层片材，其具有两个1密耳(0.03mm)厚的表面亚层和由离聚物A制成的内亚层，其中所述表面亚层由包含以下组分的组合物制得：按组合物的总重量计99.85重量％的酸性三元共聚物B和0.15重量％的TINUVIN 328(Ciba Specialty Chemicals，Tarrytown，NY)，其中酸性三元共聚物B为乙烯-丙烯酸正丁酯-甲基丙烯酸共聚物，其具有10g/10min的MI并包含按三元共聚物的总重量计4重量％的丙烯酸正丁酯共聚单元和15重量％的甲基丙烯酸共聚单元；并且离聚物A衍生自乙烯-甲基丙烯酸共聚物，后者具有5g/10min的MI，包含按酸性共聚物的总重量计15重量％的甲基丙烯酸共聚单元，并且按酸性共聚物的总羧酸含量计，其中70％被钠中和；
·ATR 3为15密耳(0.38mm)厚的压花三层片材，其具有两个由酸性三元共聚物C制成的1密耳(0.03mm)厚的表面亚层和由乙烯-丙烯酸正丁酯共聚物制成的内亚层，乙烯-丙烯酸正丁酯共聚物具有3g/10min的MI并包含按聚合物的总重量计35重量％的丙烯酸正丁酯共聚单元，其中酸性三元共聚物C为乙烯-丙烯酸正丁酯-甲基丙烯酸共聚物，其具有25g/10min的MI并包含按三元共聚物的总重量计15重量％的丙烯酸正丁酯共聚单元和22重量％的甲基丙烯酸共聚单元；
·ATR 4为90密耳(2.25mm)厚的压花三层片材，具有两个由酸性三元共聚物D制成的2密耳(0.06mm)厚的表面亚层和由乙烯-甲基丙烯酸共聚物制成的内亚层，乙烯-甲基丙烯酸共聚物具有1.5g/10min的MI，包含按酸性共聚物的总重量计22重量％的甲基丙烯酸共聚单元，并且按酸性共聚物的总羧酸含量计其中35％被钠中和，其中酸性三元共聚物D为乙烯-丙烯酸正丁酯-甲基丙烯酸共聚物，其具有1g/10min的MI并包含按酸性三元共聚物的总重量计20重量％的丙烯酸正丁酯共聚单元和18重量％的甲基丙烯酸共聚单元；
·ATR 5为20密耳(0.51mm)厚的压花双层片材，其具有由酸性三元共聚物E制成的1密耳(0.03mm)厚的第一亚层和由乙烯-丙烯酸甲酯共聚物制成的第二亚层，乙烯-丙烯酸甲酯共聚物具有5g/10min的MI并包含按聚合物的总重量计25重量％的丙烯酸甲酯共聚单元，其中酸性三元共聚物E为乙烯-丙烯酸正丁酯-甲基丙烯酸共聚物，其具有1g/10min的MI并包含按三元共聚物的总重量计1重量％的丙烯酸正丁酯共聚单元和23重量％的甲基丙烯酸共聚单元；
·ATR 6为由包含以下成分的组合物制成的20密耳(0.51mm)厚的压花片材：按组合物的总重量计，99.5重量％的酸性三元共聚物F和0.5重量％的CYASORB UV-1164(Cytec Industries Inc.，West Paterson，NJ)，其中酸性三元共聚物F为乙烯-丙烯酸甲酯-甲基丙烯酸共聚物，其具有5g/10min的MI并包含按三元共聚物的总重量计25重量％的丙烯酸甲酯共聚单元和15重量％的甲基丙烯酸共聚单元；
·ATR 7为由酸性三元共聚物G制成的1密耳(0.03mm)厚的膜，其中酸性三元共聚物G为乙烯-丙烯酸甲酯-甲基丙烯酸共聚物，其具有15g/10min的MI并包含按三元共聚物的总重量计5重量％的丙烯酸甲酯共聚单元和18重量％的甲基丙烯酸共聚单元；
·ATR 8为由酸性三元共聚物H制成的1密耳(0.03mm)厚的膜，其中酸性三元共聚物H为乙烯-丙烯酸正丁酯-甲基丙烯酸共聚物，其具有2.5g/10min的MI并包含按三元共聚物的总重量计18重量％的丙烯酸正丁酯共聚单元和20重量％的甲基丙烯酸共聚单元；
·ATR 9为由包含以下成分的组合物制成的1密耳(0.03mm)厚的膜：按组合物的总重量计99.4重量％的酸性三元共聚物C、0.3重量％的TINUVIN 1577和0.3重量％的CHIMASSORB 944(CibaSpecialty Chemicals)；
·ATR 10为20密耳(0.51mm)厚的压花三层片材，具有两个由酸性三元共聚物G制成的1密耳(0.03mm)厚的表面亚层和由离聚物A制成的内亚层；
·ATR 11为20密耳(0.51mm)厚的压花三层片材，具有两个由酸性三元共聚物H制成的1密耳(0.03mm)厚的表面亚层和由离聚物B制成的内亚层；
·ATR 12为20密耳(0.51mm)厚的压花三层片材，具有两个由酸性三元共聚物C制成的1密耳(0.03mm)厚的表面亚层和由离聚物A制成的内亚层；
·EBA为30密耳(0.76mm)厚的由乙烯-丙烯酸正丁酯共聚物制成的片材，该乙烯-丙烯酸正丁酯共聚物包含按聚合物的总重量计30重量％的丙烯酸正丁酯共聚单元，并具有2g/10min的MI；
·EVA为SC50B，据信其为基于乙烯-乙酸乙烯酯共聚物的配制组合物，其形式为20密耳(0.51mm)厚的片材(Hi-Sheet Industries，Japan)；
·FPF为1.5密耳(0.038mm)厚、经过电晕表面处理的
Figure GPA00001158383200201
膜(DuPont)；
·玻璃1为2.5mm厚的浮法玻璃；
·玻璃2为3.0mm厚的透明的退火浮法玻璃板层；
·玻璃3为3.0mm厚的
Figure GPA00001158383200202
阳光控制玻璃；
·玻璃4为得自PPG Industries(Pittsburgh，PA)的
Figure GPA00001158383200203
玻璃；
·ION 1是由离聚物A制成的60密耳(1.52mm)厚的压花片材，其中离聚物A衍生自乙烯-甲基丙烯酸共聚物，该共聚物具有大约2g/10min的MI，包含按酸性共聚物的总重量计22重量％的甲基丙烯酸共聚单元，并且按酸性共聚物的总羧酸含量计大约27％被钠中和；
·ION 2为20密耳(0.51mm)厚的离聚物B的压花片材，其中离聚物B衍生自乙烯-甲基丙烯酸共聚物，该共聚物具有2g/10min的MI，包含按酸性共聚物的总重量计19重量％的甲基丙烯酸共聚单元，并且按酸性共聚物的总羧酸含量计有37％被锌中和；
·PET 1为7密耳(0.18mm)厚、涂有聚(烯丙胺)底漆的双轴取向的聚对苯二甲酸乙二醇酯膜层；
·PET 2为
Figure GPA00001158383200211
HP Auto膜(Southwall Company，Palo Alto，CA)；
·PET 3为Auto Blue V-1膜(Southwall)；
·PET 4为SoftUV/IR 25阳光控制膜(Tomoegawa PaperCompany，Ltd.，Tokyo，Japan)；
·PET 5为Green膜(Southwall)；
·PET 6为
Figure GPA00001158383200215
TFK-2583阳光控制膜(Sumitomo OsakaCement，Japan)；
·PVB-A为20密耳(0.51mm)厚的由隔音级聚(乙烯醇缩丁醛)制成的压花片材；
·PVB-B为B51V，据信其为基于聚(乙烯醇缩丁醛)的配制组合物，其形式为20密耳(0.51mm)厚的片材(DuPont)；
·太阳能电池1为10×10英寸(254×254mm)的非晶硅光伏器件，所述器件包括具有非晶硅半导体层的不锈钢基底(125μm厚)(参见例如美国专利6,093,581实施例1)；
·太阳能电池2为10×10英寸(254×254mm)二硒铜铟(CIS)光伏器件(参见例如美国专利6,353,042第6栏第19行)；
·太阳能电池3为10×10英寸(254×254mm)碲化镉(CdTe)光伏器件(参见例如美国专利6,353,042第6栏第49行)；
·太阳能电池4为由10×10英寸(254×254mm)的EFG法生成的多晶硅片制成的硅太阳能电池(参见例如美国专利6,660,930第7栏第61行)。
·TPT为
Figure GPA00001158383200216
PTL 3-38/75膜层(
Figure GPA00001158383200217
膜层；AugustKrempel Soehne GmbH & Co.，Germany)，其被描述为7密耳厚的具有底漆的聚(偏二氟乙烯)/聚对苯二甲酸乙二醇酯/聚(偏二氟乙烯)白色三层膜。
实施例1-12
按照层压方法1组装和层压下表1中所述的一系列12×12英寸(305×305mm)层压板结构。对于所有实施例，夹层的酸性三元共聚物表面都接触玻璃片材的锡面。对于实施例7和11，聚对苯二甲酸乙二醇酯膜的涂覆表面接触酸性三元共聚物膜或片材。
实施例13-24
按照层压方法2组装和层压下表1中所述的一系列12×12英寸(305×305mm)层压板结构。对于所有实施例，夹层的酸性三元共聚物表面均接触玻璃片材的锡面。对于实施例19和23，聚对苯二甲酸乙二醇酯膜的涂覆表面接触酸性三元共聚物膜或片材。
表1
Figure GPA00001158383200221
实施例25-38
按照层压方法1组装和层压下表2中所述的一系列12×12英寸(305×305mm)太阳能电池层压板结构。层1和层2分别构成入射层和前包封层，并且层4和层5分别构成后包封层和背衬层。
实施例39-52
按照层压方法2组装和层压下表2中所述的一系列12×12英寸(305×305mm)太阳能电池层压板结构。层1和层2分别构成入射层和前包封层，并且层4和层5分别构成后包封层和背衬层。
表2
Figure GPA00001158383200231

Claims (15)

1.包含膜或片材的制品，其中
所述制品为安全层压板或阳光控制预层压组合件；
所述膜或片材包含或由酸性三元共聚物组合物制成；并且
所述酸性三元共聚物包含衍生自α-烯烃、按所述酸性三元共聚物总重量计约15至约30重量％的具有3至8个碳原子的α，β-烯键式不饱和羧酸、和约0.5至约40重量％的具有4至12个碳原子的α，β-烯键式不饱和羧酸酯的共聚单元。
2.权利要求1的制品，其中
所述酸性三元共聚物包含按所述三元共聚物的总重量计18至25重量％、优选18至23重量％的α，β-烯键式不饱和羧酸的共聚单元和0.5至5重量％、优选15至40重量％的α，β-烯键式不饱和羧酸酯的共聚单元；
所述膜或片材为包含第一表面亚层、第二表面亚层、和任选地一个或多个内亚层的多层结构；
所述第一表面亚层包含或由所述膜或片材制成，并且其他各亚层包含或由酸性共聚物、离聚物、乙烯-乙酸乙烯酯、聚(乙烯醇缩醛)、聚氨酯、聚氯乙烯、聚乙烯、聚烯烃嵌段弹性体、α-烯烃与α，β-烯键式不饱和羧酸酯的共聚物、硅氧烷弹性体、环氧树脂、或它们中的两种或更多种的组合制成。
3.权利要求2的制品，其中
所述膜或片材包含第二表面亚层、至少一个任选的内亚层、或它们两者，包含或由具有至少约80℃熔点的离聚物形成；
所述第二表面亚层包含或由所述膜或片材制成；并且
所述内亚层包含或由具有至少约90℃熔点的离聚物制成。
4.权利要求2或3的制品，其中所述膜或片材具有0.051mm至6.35mm的总厚度；所述第一表面亚层、所述第二表面亚层、或它们两者具有约0.013mm至0.13mm的厚度；各所述内亚层具有0.013mm至3mm的厚度。
5.权利要求1、2、3或4的制品，其中
所述制品为安全层压板；
所述安全层压板进一步包含至少一个外层压层；
所述外层压层包含或由刚性片材或聚合物膜形成；
所述刚性片材为玻璃或刚性聚合物片材；
所述刚性聚合物片材由聚碳酸酯、丙烯酸类、聚丙烯酸酯、环状聚烯烃、聚苯乙烯、聚酰胺、聚酯、含氟聚合物、或它们中的两种或更多种的组合制成；并且
所述聚合物膜包含聚酯、聚碳酸酯、聚烯烃、降冰片烯聚合物、聚苯乙烯、苯乙烯-丙烯酸酯共聚物、丙烯腈-苯乙烯共聚物、聚砜、尼龙、聚氨酯、丙烯酸类、乙酸纤维素、玻璃纸、聚(氯乙烯)、含氟聚合物、或它们中的两种或更多种的组合。
6.权利要求5的制品，其中
所述安全层压板包含两个外层压层和一个夹在所述两个外层压层之间的夹层；
所述两个外层压层中的每一个独立地包含或由所述刚性片材或聚合物膜形成；
所述夹层包含如权利要求1、2、3或4所表征的膜或片材，以及任选地其他聚合物膜或片材；
所述膜或片材具有0.38mm至2.28mm，优选0.38mm至2.28mm的厚度；并且
所述膜或片材夹在两个玻璃片材之间或玻璃片材与聚酯膜之间，可任选地在所述膜或片材的外表面上硬涂覆。
7.权利要求1、2、3或4的制品，其中
所述制品为太阳能电池预层压组合件；
所述组合件还包含太阳能电池组件，所述太阳能电池组件由一个或多个电互连的太阳能电池形成并具有面向光源的受光面和与所述光源相对的背面；并且
所述太阳能电池为多晶太阳能电池、薄膜太阳能电池、化合物半导体太阳能电池、非晶硅太阳能电池、或它们中的两种或更多种的组合。
8.权利要求7的制品，其中
所述组合件包含邻近所述太阳能电池组件的受光面设置的前包封层和邻近所述太阳能电池组件的背面设置的后包封层；
所述前包封层由具有0.051mm至0.51mm厚度的膜或片材形成；并且
所述后包封层包含或由酸性共聚物、离聚物、乙烯-乙酸乙烯酯、聚(乙烯醇缩醛)、聚氨酯、聚氯乙烯、聚乙烯、聚烯烃嵌段弹性体、α-烯烃与α，β-烯键式不饱和羧酸酯的共聚物、硅氧烷弹性体、环氧树脂、或它们中的两种或更多种的组合形成。
9.权利要求7或8的制品，所述制品还包含邻近所述前包封层设置的入射层和邻近所述后包封层设置的背衬层，其中
所述入射层为(i)玻璃片材，(ii)聚合物片材，或(iii)聚合物膜；
所述聚合物片材包含或由聚碳酸酯、丙烯酸类、聚丙烯酸酯、环状聚烯烃、聚苯乙烯、聚酰胺、聚酯、含氟聚合物、或它们中的两种或更多种的组合形成；并且
所述聚合物膜包含或由聚酯、聚碳酸酯、聚烯烃、降冰片烯聚合物、聚苯乙烯、苯乙烯-丙烯酸酯共聚物、丙烯腈-苯乙烯共聚物、聚砜、尼龙、聚氨酯、丙烯酸类、乙酸纤维素、玻璃纸、聚(氯乙烯)、含氟聚合物、或它们中的两种或更多种的组合形成。
10.权利要求8或9的制品，其中所述前包封层和所述后包封层均包含或由所述膜或片材形成。
11.权利要求8、9或10的制品，其中
所述背衬层为(i)玻璃片材，(ii)聚合物片材，(iii)聚合物膜，(iv)金属片材，或(v)陶瓷板；
所述聚合物片材包含或由聚碳酸酯、丙烯酸类、聚丙烯酸酯、环状聚烯烃、聚苯乙烯、聚酰胺、聚酯、含氟聚合物、或它们中的两种或更多种的组合形成；并且
所述聚合物膜包含或由聚酯、聚碳酸酯、聚烯烃、降冰片烯聚合物、聚苯乙烯、苯乙烯-丙烯酸酯共聚物、丙烯腈-苯乙烯共聚物、聚砜、尼龙、聚氨酯、丙烯酸类、乙酸纤维素、玻璃纸、聚(氯乙烯)、含氟聚合物、或它们中的两种或更多种的组合形成。
12.权利要求8、9、10或11的制品，所述制品从面向光源的顶面到与所述光源相对的底面基本上由以下组件组成：(i)邻近(ii)设置的入射层，(ii)邻近(iii)设置的前包封层，(iii)邻近(iv)设置的太阳能电池组件，(iv)邻近(v)设置的后包封层，(v)背衬层，其中所述前包封层或所述后包封层或它们两者由所述膜或片材形成。
13.方法，所述方法包括：(i)提供太阳能电池预层压组合件以及(ii)层压所述组合件以形成太阳能电池模块，其中所述组合件为权利要求7至12中任一项所表征的制品，并且所述层压优选地通过对所述组合件加热来进行。
14.权利要求13的方法，其中所述层压还包括对所述组合件施加真空或压力。
15.包括或由太阳能电池预层压组合件制备的太阳能电池模块，其中所述组合件为权利要求7至12中任一项所表征的制品，并且优选地，在所述模块于约85℃的温度和约85％的相对湿度下调理1000小时后，所述三元离聚物多层膜或片材与其相邻层之间的180°剥离强度的至少约75％得以保持。
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EP2219863B1 (en) 2013-03-20
WO2009079321A1 (en) 2009-06-25
US20110297233A1 (en) 2011-12-08
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