CN101611079A - 高熔融流动离聚物组合物 - Google Patents
高熔融流动离聚物组合物 Download PDFInfo
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- CN101611079A CN101611079A CNA2008800050573A CN200880005057A CN101611079A CN 101611079 A CN101611079 A CN 101611079A CN A2008800050573 A CNA2008800050573 A CN A2008800050573A CN 200880005057 A CN200880005057 A CN 200880005057A CN 101611079 A CN101611079 A CN 101611079A
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- carboxylic acid
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- silane
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10697—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer being cross-linked
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
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Abstract
本发明公开了包含离聚物组合物的聚合物薄膜或片材,所述离聚物组合物包含α烯烃和具有3至8个碳原子的α,β-烯键式不饱和羧酸的离聚共聚物,所述α,β-烯键式不饱和羧酸的含量按所述离聚共聚物的总重量计为约1至约30重量%,其中使用一种或多种金属离子中和所述羧酸,按所述离聚共聚物中羧酸根的总摩尔数计,中和了1至100摩尔%含量的羧酸,并且其中所述离聚共聚物具有约20至约300g/10min的熔融指数。所述离聚物组合物优选地包含选自硅烷偶联剂、有机过氧化物以及它们的组合的添加剂。此外,还公开了一种包含夹层和附加层的制品,所述夹层由所述聚合物薄膜或片材形成,并且所述附加层选自玻璃、其它聚合物夹层片材、聚合物薄膜层、以及金属薄膜或片材。制品的实例包括安全窗和太阳能电池。
Description
发明领域
本发明涉及离聚物组合物、由其衍生的聚合物薄膜或片材,以及它们在安全层压体和太阳能电池模块中的使用。
发明背景
玻璃层压产品已服务社会近一个世纪。除了熟知的用于挡风玻璃的日常机动车安全玻璃以外,层压玻璃还应用于各种形式的交通运输行业。安全玻璃的特征在于其高度耐冲击和耐穿透性,并且在碎裂时不会散落出玻璃碎片和碎屑。
安全玻璃通常由通过聚合物片材夹层粘到一起的两块玻璃片材或板的夹心结构构成。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制成的片材替换。安全玻璃已进一步演变为包括多层玻璃和聚合物片材,它们通过聚合物片材夹层粘结到一起。
用于安全玻璃的夹层通常由相对厚的聚合物片材制成,在发生断裂或破碎的情况下,它们赋予玻璃韧性和可粘结性。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)、聚(乙烯乙酸乙烯酯)(EVA)、离聚物等的复合、多组分组合物。
作为一种可再生能源,太阳能电池组件的应用范围正迅速扩大。制造太阳能电池组件的一种优选方式涉及形成包含至少5个结构层的预层压组合件。太阳能电池预层压体按以下顺序从顶层或入射层(即,与光最先接触的层)开始,并延续到背衬(离入射层最远的层)进行构造:(1)入射层(通常为玻璃板或聚合物薄膜(例如含氟聚合物薄膜或聚酯薄膜),但能够想象到其可以为能透射太阳光的任何材料);(2)前包封层;(3)电压发生组件(或太阳能电池组件);(4)后包封层;以及(5)背衬层。
包封层被设计用于包封并保护易碎的电压发生组件。一般来讲,太阳能电池预层压体将结合至少两个包封层,它们夹住太阳能电池组件。前包封层的光学特性必须使得能够有效地将光传输到太阳能电池组件。另外,包封层一般具有与上述玻璃夹层类似的要求和组成。
离聚物组合物作为防威胁安全层压体夹层片材的用途在本领域内是已知的(参见,例如US 3,344,014、US 3,762,988、US 4,663,228、US4,668,574、US 4,799,346、US 5,759,698、US 5,763,062、US5,895,721、US 6,150,028、US 6,432,522、US 2002/0155302、US2002/0155302、WO 99/58334、以及WO 2006/057771)。例如,US5,759,698公开了衍生自离聚物树脂的玻璃层压体夹层,离聚物树脂预先用有机过氧化物和硅烷试剂进行过热固处理。
离聚物组合物作为太阳能电池包封薄膜或片材的用途在本领域内也是已知的(参见,例如US 5,476,553、US 5,478,402、US 5,733,382、US5,762,720、US 5,986,203、US 6,114,046、US 6,187,448、US6,660,930、US 2003/0000568、US 2005/0279401、JP 2000186114、以及JP 2006032308)。
然而,用于安全层压体或太阳能电池模块领域的离聚物树脂一般具有15g/10min或更低的低熔流指数(MI)(2160g,190℃,ISO 1133,ASTMD1238)。此类低熔融流动离聚物树脂的使用要求较高的层压温度(即,130℃-170℃),并因此可能使层压方法复杂化。
Chou等人在US 6,680,821中描述了使用包含某些被金属中和的酸共聚物的树脂粉末涂覆金属表面的方法,这些酸共聚物包含α-烯烃和α-β不饱和羧酸,并具有在约20至约1,000g/10min范围内的MI。该专利并未描述此类材料在安全玻璃或光电模块层压体或添加剂包装内增强共聚物在此类用途中的性能的应用。
在没有上述缺点的玻璃层压体最终用途应用中,例如在安全窗和太阳能电池中,存在着对适合用作夹层的聚合物薄膜或片材的需求,以及存在对可用于形成此类薄膜或片材的组合物的需求。比如,期望制备出具有降低的挤出复合温度的可用组合物。此外,还存在降低层压温度的需求,优选地降低到约100℃至约120℃,或存在减少层压循环时间的需求,或同时实现这两者,从而简化层压方法。另外,期望得到在宽范围的层压温度下(包括上述所期望的较低温度)具有提高的粘附强度的薄膜或片材,并期望改善层压体的抗冲击性。
发明概述
本发明涉及包含离聚物组合物的聚合物薄膜或片材,所述离聚物组合物包含α烯烃和具有3至8个碳原子的α,β-烯键式不饱和羧酸的离聚共聚物,按该离聚共聚物的总重量计,所述不饱和羧酸的含量为约1至约30重量%,其中使用一种或多种金属离子中和羧酸,按离聚共聚物中羧酸根的总摩尔数计,中和了1至100摩尔%含量的羧酸,并且其中离聚共聚物具有约20至约300g/10min的熔融指数。
本发明还涉及包括夹层和附加层的制品,所述夹层由上述聚合物薄膜或片材形成,所述附加层选自玻璃、其它聚合物夹层片材、聚合物薄膜层、以及金属薄膜或片材。在一个实施方案中,所述制品为安全玻璃层压体,其中附加层为玻璃片材,并且夹层被层压到该玻璃片材上。在另一个实施方案中,所述制品为太阳能电池预层压组合件并且含有包括一个或多个太阳能电池的太阳能电池组件。
本发明还涉及通过以下步骤制备的太阳能电池层压体,所述步骤包括:(a)提供由所述聚合物薄膜或片材形成的夹层,(b)提供包括一个或多个太阳能电池的太阳能电池组件;以及(c)将太阳能电池组件包封在包含离聚物组合物的基质中。
本发明还涉及制造制品的方法,其中制品是太阳能电池模块,该方法包括:(i)提供如上所述的太阳能电池预层压组合件,以及(ii)层压该预层压组合件以形成太阳能电池模块。
本发明还涉及包含离聚物组合物和添加剂的聚合物组合物,其中(i)离聚物组合物包含α烯烃和具有3至8个碳原子的α,β-烯键式不饱和羧酸的共聚物,按该离聚共聚物的总重量计,不饱和羧酸的含量为约1至约30重量%,其中使用一种或多种金属离子中和羧酸,按离聚共聚物中羧酸根的总摩尔数计,中和了1至100摩尔%含量的羧酸,(ii)离聚共聚物具有约20至约300g/10min的熔融指数,并且(iii)添加剂选自硅烷偶联剂、有机过氧化物以及它们的组合。
发明详述
本文提及的所有出版物、专利申请、专利和其它文档全文以引用方式并入。除非另行定义,否则本文所用的所有科技术语的含义与本发明所属领域的普通技术人员通常理解的一样。在发生矛盾的情况下,以本说明书所包括的定义为准。
尽管在本发明的实践或测试中可以使用与本文所述的那些方法和材料类似或等同的方法和材料,但合适的方法和材料是本文所描述的那些。
除非另行指出,否则所有百分数、份数、比率等均按重量计。
当一个数量、浓度或其它数值或参数以范围、优选范围或一系列优选上限数值和优选下限数值给出时,它应被理解为具体地公开由任何范围上限或优选数值和任何范围下限或优选数值的任何一对所构成的所有范围,而无论所述范围是否被单独地公开。凡在本文中给出某一数值范围之处,该范围都旨在包括其端点,以及位于该范围内的所有整数和分数,除非另行指出。当定义一个范围时,不希望将本发明的范围限定于所列举的具体数值。
当术语“约”用于描述数值或范围的端点时,所公开的内容应被理解为包括具体的数值或所涉及的端点。
如本文所用,术语“包含”、“含有”、“包括”、“涵盖”、“特征在于”、“具有”或它们的任何其它变形都旨在涵盖非排他性的包含物。例如,包括要素列表的工艺、方法、制品或设备不必仅限于那些要素,而是可以包括未明确列出的或该工艺、方法、制品或设备所固有的其它要素。此外,除非另外明确说明,否则“或”是指包含性的“或”,而不是指排他性的“或”。例如,以下任何一种情况均满足条件A或B:A是真实的(或存在的)且B是虚假的(或不存在的),A是虚假的(或不存在的)且B是真实的(或存在的),以及A和B都是真实的(或存在的)。
短语“由...组成”不包括未在权利要求中指定的任何要素、步骤或成分,从而将权利要求限定为只包括列出的那些,而不含通常与其相关的物项。当短语“由...组成”出现在权利要求项的条款中,而不是立即跟在前序后时,其只限制在该条款中阐述的要素;而其它要素作为整体未被排除在权利要求之外。
过渡短语“基本上由...组成”将权利要求的范围限制在指定的材料或步骤,以及不会对受权利要求书保护的发明所具有的基本特征和新型特征造成实质影响的那些材料或步骤。“‘基本上由...组成’的权利要求处于以‘由...组成’格式书写的封闭式权利要求和以‘包含/包括’格式起草的全开放式权利要求之间的中间地带。”
当申请人使用开放式术语(例如“包含”)来限定发明或其部分时,应当容易地理解到(除非另有指明),该说明应被解释为也使用了术语“基本上由...组成”或“由...组成”描述这一发明。
“一个”或“一种”被用于描述本发明的要素或组分。这仅仅是为了方便并且给出本发明的一般含义。这种描述应被理解为包括一个或至少一个,并且该单数也包括复数,除非很明显地另指他意。
在描述某些聚合物时,应当理解,有时申请人提及聚合物时使用的是用来制成它们的单体、用来制成它们的单体的量、或被包含在它们之内的单体残基。虽然此类描述可能不包括用于描述最终聚合物的具体命名或者可能不包含以方法限定产品的术语,但是对单体、单体残基、重复单元和量的任何此类提及应被解释为是指聚合物由那些单体或单体的那个量,和对应的聚合物以及它们的组合物制成。就此而言,提及包含单体残基的共聚物是指共聚物包含得自该单体的重复单元这一事实。当申请人提及包含一定百分比的单体的共聚物时,应当理解,该提及是指包含得自该单体的重复单元的共聚物。
在描述本发明和/或提出本发明的权利要求时,术语“共聚物”用来指包含两种或更多种单体的聚合物。
术语“有限量”和“有限值”用来指大于零的量。
术语“酸共聚物”用来指由α烯烃的共聚残基和具有3至8个碳原子的α,β-烯键式不饱和羧酸的共聚残基构成的树脂组合物。术语“离聚物”在本文中用来指衍生自被部分或全部中和的“酸共聚物”的树脂组合物。
高熔融流动离聚物组合物
本发明涉及某些高熔融流动离聚物组合物,它们可用于形成安全夹层片材或者太阳能电池包封薄膜或片材。具体地讲,该高熔融流动离聚物组合物由具有约20至约300g/10min(根据ASTM D1238在190℃的温度和2160g的负荷下测量)的MI的离聚共聚物构成。(类似的ISO测试为ISO1133。)
离聚共聚物:
所述高熔融流动离聚共聚物衍生自某种母体酸共聚物,该母体酸共聚物包含有限量的α烯烃和具有3至8个碳原子的α,β-烯键式不饱和羧酸,所述羧酸按该共聚物的总重量计占约1至约30重量%。优选地,按共聚物的总重量计,母体酸共聚物包含约10至约25重量%,或更优选约15至约23重量%,或更优选约18至约23重量%的α,β-烯键式不饱和羧酸。
α烯烃共聚单体通常包含2至10个碳原子。优选的α烯烃包括但不限于: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、以及它们的混合物。更优选地,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、以及它们的混合物。优选的α,β-烯键式不饱和羧酸共聚单体包括丙烯酸、甲基丙烯酸、以及它们的混合物。
母体酸共聚物可如US 3,404,134、US 5,028,674、US 6,500,888和US 6,518,365中所公开的方法进行共聚。
为生产该高熔融流动离聚共聚物,使用金属离子中和母体酸共聚物,按羧酸的总含量计,中和程度为约1%至约100%,或优选约1%至约50%,或更优选约2%至约40%,或还要优选约2%至约20%。金属离子可以是一价的、二价的、三价的、多价的、或它们的混合形式。可用的一价金属离子包括但不限于:钠、钾、锂、银、汞、铜等,以及它们的混合物。可用的二价金属离子包括但不限于:铍、镁、钙、锶、钡、铜、镉、汞、锡、铅、铁、钴、镍、锌等,以及它们的混合物。可用的三价金属离子包括但不限于:铝、钪、铁、钇等、以及它们的混合物。可周的多价金属离子包括但不限于:钛、锆、铪、钒、钽、钨、铬、铈、铁等、以及它们的混合物。需要注意的是,当金属离子为多价时,可包含络合剂,例如硬脂酸盐、油酸盐、水杨酸盐和苯酚盐基团,如US 3,404,134中所公开。金属离子优选为一价的或二价的金属离子。更优选地,金属离子选自钠、锂、镁、锌、以及它们的混合物。更优选地,金属离子选自钠、锌、以及它们的混合物。本发明的母体酸共聚物可以如US 3,404,134中所公开的方法进行中和。
高熔融流动离聚共聚物具有约20至约300g/10min的MI。优选地,离聚共聚物具有约30至约200g/10min的MI。一般来讲,要实现离聚共聚物所期望的高熔融流动速率,母体酸共聚物应具有约50至约600g/10min,或优选约50至约400g/10min,或更优选约50至约200g/10min的MI。
当它们用于安全层压体或太阳能电池层压体时,此高熔融流动速率为由其衍生的离聚物薄膜或片材提供降低的层压温度、或更短的循环时间、或这两者。此外,当在层压温度以下进行层压时,由此类高熔融流动离聚物组合物衍生的薄膜或片材比由具有相对低熔融流动速率的离聚物组合物衍生的那些薄膜或片材具有更高的粘附强度。
高熔融流动离聚共聚物可任选地包含其它不饱和的共聚单体。优选的其它不饱和共聚单体的具体实例包括但不限于: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、以及它们的混合物。一般来讲,按共聚物的总重量计,离聚共聚物可包含0至约50重量%,或优选0至约30重量%,或更优选0至约20重量%的其它不饱和共聚单体。
添加剂:
高熔融流动离聚物组合物还可包含一种或多种添加剂。
在一个特定实施方案中,离聚物组合物还包含一种或多种硅烷偶联剂以进一步增大由其衍生的薄膜或片材的粘附强度。
在本发明中可用的示例性硅烷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-环氧基环己基)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,以及它们的混合物。优选地在离聚物组合物中掺入硅烷偶联剂。所述掺入量按组合物的总重量计为约0.01至约5重量%,或更优选约0.05至约1重量%。
需要注意的是,硅烷偶联剂能够降低掺入有硅烷偶联剂的离聚物组合物的熔融流动速率。因此,通过一定含量的硅烷,高熔融流动离聚物组合物与现有技术的较低熔融流动离聚物组合物相比能够保持一定水平的粘度。
在本发明的另一个实施方案中,离聚物组合物还可以包含添加剂。添加剂在层压期间将树脂的熔融流动有效降低至使薄膜或片材热固化的极限值。此类添加剂的使用将增大由此衍生的层压体夹层片材或者太阳能电池包封薄膜或片材的最终用途上限温度和减小它们的蠕变。通常,最终用途温度可被增高最多约20至约70℃。此外,由此类材料制备的安全层压体和太阳能电池层压体将具有防火性。具体地讲,通过在层压期间使离聚物树脂热固化,树脂发生熔融和流出层压体的趋势将降低,反之其可能起到添加燃料的作用。
通常,有效降低熔融流动的添加剂为有机过氧化物,例如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、正丁基-4,4-双(叔丁基过氧)戊酸酯、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、叔丁基过氧苯甲酸酯、过氧化苯甲酰等以及它们的混合物。优选地,有机过氧化物在约100℃或更高的温度下分解生成自由基。更优选地,有机过氧化物具有的分解温度在约70℃或更高的温度下提供达10小时的半衰期,从而为共混操作提供改善的稳定性。
此外,介于离聚物组合物复合温度和有机过氧化物分解温度之间的温度差对避免在复合期间和薄膜与片材形成过程中发生过早交联至关重要。在挤出方法(制造高熔融流动离聚物薄膜或片材的优选方法)中,与其它低熔融流动离聚物组合物相比,高熔融流动离聚物组合物需要所期望的降低的挤出温度,并因此在挤出复合、薄膜或片材形成期间能够有效地防止过早交联。
按组合物的总重量计,有机过氧化物添加的量可为约0.01至约10重量%,或优选约0.5至约3重量%。
如果需要,引发剂(例如二月桂酸二丁锡)也可被包含在离聚物组合物中。按组合物的总重量计,其含量为约0.01至约0.05重量%。此外,为了增强对反应和稳定性的控制,如果需要,可添加抑制剂,例如对苯二酚、对苯二酚单甲醚、对苯醌以及甲基氢醌。通常,按组合物的总重量计,抑制剂可以小于约5重量%的含量进行添加。
在另一个实施方案中,高熔融流动离聚物组合物还可以包含本领域中已知的任何其它合适的添加剂。此类添加剂可以包括但不限于:增塑剂、加工助剂、流动增强剂、润滑剂、颜料、染料、阻燃剂、冲击改性剂、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、增强剂(如玻璃纤维)、填充剂等。一般来讲,当用在太阳能电池包封薄膜或片材中时,将可降低组合物光学透明度的添加剂(例如增强剂和填充剂)加入到那些用作后包封层的薄膜或片材中。
可使用热稳定剂,其已在本领域中广泛公开。任何已知的热稳定剂都可在本发明中使用。优选的一般类型的热稳定剂包括但不限于:酚类抗氧化剂、烷基化一元酚、烷硫基甲基苯酚、对苯二酚、烷基化对苯二酚、生育酚、羟基化硫代二苯醚、亚烷基双酚、O-、N-和S-苄基化合物、羟基苄基化丙二酸酯、芳族羟基苄基化合物、三嗪化合物、氨基酸类抗氧化剂、芳基胺、二芳基胺、聚芳基胺、酰氨基酚、草酰胺、金属减活化剂、亚磷酸盐、亚膦酸盐、苯基膦酸盐、抗坏血酸(维生素C)、破坏过氧化物的化合物、羟胺、硝酮、硫代增效剂、苯并呋喃酮、吲哚酮等,以及它们的混合物。高熔融流动离聚物组合物可包含任意有效量的热稳定剂。热稳定剂的使用是任选的,在某些情况下并非优选。使用时,按组合物的总重量计,高熔融流动离聚物组合物包含至少约0.05重量%,并且最多约10重量%,更优选最多约5重量%,并且最优选最多约1重量%的热稳定剂。
可使用紫外线吸收剂,其也在本领域中广泛公开。任何已知的紫外线吸收剂均可在本发明中使用。优选的一般类别的紫外线吸收剂包括但不限于苯并三唑、羟基苯甲酮、羟基苯基三嗪、取代和未取代的苯甲酸的酯等,以及它们的混合物。高熔融流动离聚物组合物可包含任意有效量的紫外线吸收剂。紫外吸收剂的使用是任选的,在某些情况下并非是优选的。使用时,按组合物的总重量计,高熔融流动离聚物组合物包含至少约0.05重量%,并且最多约10重量%,更优选最多约5重量%,并且最优选最多约1重量%的紫外线吸收剂。
可使用受阻胺光稳定剂(HALS),其也在本领域中广泛公开。一般来讲,所公开的位阻胺光稳定剂为仲、叔、乙酰化的、N-烃氧基取代的、羟基取代的并且N-烃氧基取代的、或其它取代的环胺,其还具有空间位阻,一般由邻近胺官能团的碳原子上的脂族取代产生。高熔融流动离聚物组合物可包含任意有效量的受阻胺光稳定剂。受阻胺光稳定剂的使用是任选的,在某些情况下并非是优选的。使用时,按组合物的总重量计,高熔融流动离聚物组合物包含至少约0.05重量%,并且最多约10重量%,更优选最多约5重量%,并且最优选最多约1重量%的受阻胺光稳定剂。
高熔融流动离聚物薄膜或片材
本发明还提供成型制品,例如包含高熔融流动离聚物组合物的薄膜或片材。这些高熔融流动离聚物薄膜和片材可采用任何合适的方法制备。例如,薄膜和片材可通过以下方法形成:浸涂、溶液浇铸、压模、注模、熔融挤出、熔喷或本领域技术人员已知的任何其它方法。优选地,高熔融流动离聚物薄膜和片材通过熔融挤出形成,这是形成“无限多个”产品尤其优选的方法。
如上所述,高熔融流动离聚物薄膜或片材可用于形成安全层压体中的夹层片材或者太阳能电池层压体中的包封薄膜或片材。此外,高熔融流动离聚物薄膜或片材可采用单层或多层薄膜或片材的形式。所谓单层是指,薄膜或片材只有一个单层并且这个单层由高熔融流动离聚物组合物制成。所谓多层是指,高熔融流动离聚物薄膜或片材具有两个或更多个亚层,并且至少一个亚层由高熔融流动离聚物组合物制成。多层薄膜或片材的其它亚层可由任何合适的聚合物组合物制成。然而优选的是,其它亚层由选自以下的聚合物组合物制成:酸共聚物及其衍生的离聚物、聚(乙烯乙酸乙烯酯)、聚(乙烯醇缩醛)(例如,聚(乙烯醇缩丁醛))、聚氨酯、聚氯乙烯、聚乙烯(例如,茂金属催化的线性低密度聚乙烯)、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)、硅氧烷弹性体和环氧树脂。更优选地,其它亚层由选自下列的聚合物组合物形成:酸共聚物及其衍生的离聚物、聚(乙烯乙酸乙烯酯)、茂金属催化的线性低密度聚乙烯、聚烯烃嵌段弹性体和乙烯丙烯酸酯共聚物。此外,为了提供足够的粘附强度,多层薄膜或片材的表面亚层中的至少一者,或优选地,两者均由高熔融流动离聚物组合物形成。在一个优选的实施方案中,具有高流动离聚共聚物表面和低流动芯层的多层薄膜和片材提供了本发明所期望的低层压温度和高粘附度。
本发明的薄膜或片材优选地具有约0.1mil(0.003mm)至约250mil(6.35mm)的总厚度。当用作安全层压体夹层片材时,高熔融流动离聚物片材优选地具有约10mil(0.25mm)至约250mil(6.35mm),或更优选约15mil(0.38mm)至约90mil(2.28mm),或更优选约30mil(0.76mm)至约60mil(1.52mm)的总厚度。同样根据本发明,当用作太阳能电池包封材料时,片材或薄膜优选地具有约0.1mil(0.003mm)至约20mil(0.51mm)的厚度。也就是说,当作为太阳能电池包封薄膜在柔性的太阳能电池层压体中使用时,高熔融流动离聚物薄膜优选地具有约0.1mil(0.003mm)至约10mil(0.25mm),或更优选约1mil(0.03mm)至约5mil(0.13mm)的总厚度,而当作为太阳能电池包封片材在刚性的太阳能电池层压体中使用时,高熔融流动离聚物片材优选地具有约10mil(0.25mm)至约20mil(0.51mm)的总厚度。构成整个多层离聚物薄膜或片材的各个亚层的厚度不是关键性的,并且可根据具体的应用而独立地变化。然而优选地,多层薄膜或片材的表面层应具有约1mil(0.03mm)至约5mil(0.13mm)的厚度。
高熔融流动离聚物薄膜或片材在一侧或两侧上可具有平滑或粗糙的表面。优选地,高熔融流动薄膜或片材具有粗糙的表面,以有利于在层压过程中脱去层压体的空气。提供空气逸出通道并在层压期间除去空气是获得具有可接受外观的层压体的已知方法。粗糙表面可通过以下方式实现:在挤出夹层片材或者包封薄膜或片材时进行机械压花或熔融破裂,然后骤冷,以便粗糙度在处理期间保留下来。可通过本领域的常用方法向高熔融流动离聚物薄膜或片材施加表面图案。例如,可让挤出的薄膜或片材从模辊的特制表面上通过,模辊紧邻模具的出口布置,该特制表面向熔融聚合物的一侧赋予所需的表面特性。因此,当该辊的表面具有微小的峰和谷时,由浇铸在其上的聚合物形成的薄膜或片材在与辊接触的一侧上将具有粗糙表面,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US 4,035,549中有所公开。
如果需要,可对高熔融流动离聚物薄膜或片材的一个或两个表面进行处理,以增大对其它层压体层的粘附度。该处理可采用本领域中已知的任何形式,包括粘合剂、底漆(例如硅烷)、火焰处理(参见,例如US2,632,921、US 2,648,097、US 2,683,894、以及US 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、以及它们的组合。例如,如US 4,865,711中所公开,可通过真空溅射在薄膜或片材的一个或两个表面上沉积薄的碳层。在另一方面,US 5,415,942公开了羟基丙烯酸水溶胶底漆涂层,该涂层可用作聚(对苯二甲酸乙二醇酯)薄膜的促粘附性底漆。
粘合剂层可优选地采用单层粘合剂底漆或单层涂层的形式。粘合剂/底漆涂层可小于约1mil(0.03mm),或优选小于约0.5mil(0.013mm),或更优选小于约0.1mil(0.003mm)厚。粘合剂可以是本领域中已知的任何粘合剂或底漆。优选地,粘合剂或底漆为硅烷偶联剂或者聚(乙烯胺)或聚(烯丙胺)。基于聚(烯丙胺)的底漆和它们针对聚(对苯二甲酸乙二醇酯)聚合物薄膜的应用在US 5,411,845、US 5,770,312、US 5,690,994、以及US5,698,329中有所公开。
安全层压体
本发明还提供包含聚合物夹层片材的安全层压体,所述聚合物夹层片材由高熔融流动离聚物组合物形成。具体地讲,安全层压体包含至少一个刚性片材层和作为夹层片材的至少一层高熔融流动离聚物片材。
如上所述,在本文所使用的层压温度下,高熔融流动离聚物夹层片材通常比由其它低熔融流动离聚物衍生的那些片材拥有更高的粘附强度,并因此为安全层压体结构提供改善的抗冲击性。
刚性片材可以是玻璃或刚性塑料片材,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)、茂金属催化的聚苯乙烯、聚酰胺、聚酯、含氟聚合物等、以及它们的组合。金属片材(例如,铝、钢或镀锌钢)或陶瓷板可替代刚性聚合物片材或玻璃。
术语“玻璃”不仅旨在包括窗玻璃、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(例如,那些含有控制例如太阳能加热的成分的玻璃)、镀膜玻璃(例如,那些为日照控制目的而溅射金属(例如,银或铟氧化锡)的玻璃)、E-玻璃、Toroglass、玻璃(Solutia)。此类特种玻璃在例如US 4,615,989、US 5,173,212、US 5,264,286、US 6,150,028、US6,340,646、US 6,461,736、以及US 6,468,934中有所公开。然而应当理解,应根据预期用途为具体的层压体选择玻璃类型。
本发明的一个优选实施方案为包括至少一层玻璃和至少一层高熔融流动离聚物片材的安全层压体。优选地,高熔融流动离聚物片材自粘附到玻璃上。如本文所用,当描述聚合物片材“自粘附”到玻璃上时,是指玻璃和聚合物层之间不存在中间层(例如底漆层或薄粘合剂层),而且玻璃或聚合物层的表面没有经过专门处理。本发明更优选的实施方案为下述层压体,其包含两层玻璃和粘结到其间的至少一层高熔融流动离聚物片材。优选地,高熔融流动离聚物片材自粘附到玻璃层中的一者或两者。
本发明的安全层压体可进一步包含其它任选的夹层片材和/或薄膜层。其它任选的夹层片材可由任何合适的材料形成,例如酸共聚物及其衍生的离聚物、聚(乙烯乙酸乙烯酯)、聚(乙烯醇缩醛)(例如,聚(乙烯醇缩丁醛))、聚氨酯、聚氯乙烯、聚乙烯(例如,茂金属催化的线性低密度聚乙烯)、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)、硅氧烷弹性体和环氧树脂。在一个优选的实施方案中,其它夹层为包含离聚物组合物的第二聚合物薄膜或片材。其它任选的夹层片材的厚度不是关键性的,并可以根据具体应用而独立地变化。在许多情况下,上文就酸共聚物层提供的值是优选的。
在安全层压体中使用的薄膜层可以为金属(例如铝箔)或聚合物。优选的聚合物薄膜材料包括但不限于:聚酯(例如,聚(对苯二甲酸乙二醇酯)(PET))、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(包括间规聚苯乙烯)、苯乙烯-丙烯酸酯共聚物、丙烯腈-苯乙烯共聚物、聚砜类(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、偏二氯乙烯共聚物等)、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。更优选地,聚合物薄膜为双轴取向的聚(对苯二甲酸乙二醇酯)薄膜。
聚合物薄膜的厚度不是关键性的,并可以根据具体应用而变化。然而一般来讲,聚合物薄膜的厚度范围可为约0.1mil(0.003mm)至约10mil(0.26mm),或优选约1mil(0.025mm)至约7mil(0.18mm)。
此外,聚合物薄膜可在涂布和层压处理下是充分消除应力并且收缩稳定的。优选地,聚合物薄膜受到高温时是热稳定的以提供低收缩特性(即,在150℃下30分钟后,在两个方向上的收缩都小于2%)。
如果需要,也可对薄膜进行涂覆。例如,可向薄膜上涂覆有机红外吸收剂、溅射金属层(例如银)、涂层等。涂布金属的聚合物薄膜在例如US3,718,535、US 3,816,201、US 4,465,736、US 4,450,201、US4,799,745、US 4,846,949、US 4,954,383、US 4,973,511、US5,071,206、US 5,306,547、US 6,049,419、US 6,104,530、US6,204,480、US 6,255,031、以及US 6,565,982中有所公开。例如,涂层可用作氧气或水分阻挡涂层,例如在US 6,521,825、US 6,818,819、以及EP1 182 710中所公开的金属氧化物涂层。
如果需要,可对层压体层(例如离聚物夹层片材、任选的其它夹层片材或薄膜层、或者刚性片材)的一个或两个表面进行处理,以增大它们的粘附强度,如上所述。
本发明的安全层压体可采用本领域内已知的任何形式。优选的具体玻璃层压体构造包括例如如下所述的构造,其中“ION”是指如上所述的、由优选的高熔融流动离聚物组成的夹层片材:
●玻璃/ION;
●玻璃/ION/薄膜;
●玻璃/ION/玻璃;
●玻璃/ION/薄膜/ION/玻璃;
●玻璃/ION/薄膜/ION/薄膜;
等等。
本发明的安全层压体可以采用如下详述的任何一种层压方法制备,或采用其它方法制备。
太阳能电池预层压组合件和太阳能电池层压体
本发明还提供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,以及至少一层上述高熔融流动离聚物薄膜或片材。
随着技术的进步和优化,常用的太阳能电池种类不断增加。在本发明的范围内,“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,这是由于它们的制造成本相对较低从而可制造大型太阳能电池。
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薄膜上来制备,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。例如,薄膜太阳能电池在US5,512,107、US 5,948,176、US 5,994,163、US 6,040,521、US6,137,048、以及US 6,258,620中有所公开。薄膜太阳能电池模块的实例是那些包含碲化镉或CIGS(Cu(In-Ga)(SeS)2)的薄膜电池。
在一个特定实施方案中,太阳能电池预层压组合件包含一层高熔融流动离聚物薄膜或片材,其相邻太阳能电池组件布置并充当一个包封层,或者优选地,高熔融流动离聚物薄膜或片材布置在受光面上与太阳能电池组件相邻并充当前包封层。
根据本发明,除至少一个高熔融流动离聚物薄膜或片材之外,太阳能电池预层压组合件可任选地进一步包含由其它聚合物材料形成的包封层,所述聚合物材料例如酸共聚物及其衍生的离聚物、聚(乙烯乙酸乙烯酯)、聚(乙烯醇缩醛)(例如,聚(乙烯醇缩丁醛),包括隔音级的聚(乙烯醇缩丁醛))、聚氨酯、聚氯乙烯、聚乙烯(例如,茂金属催化的线性低密度聚乙烯)、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)、硅氧烷弹性体和环氧树脂。
在另一个实施方案中,太阳能电池预层压组合件包含两层高熔融流动离聚物薄膜或片材,其中这两个高熔融流动离聚物薄膜或片材的每一个被分别层压到太阳能电池组件的两侧,并充当前后包封层。
除了高熔融流动离聚物薄膜或片材以外的各个包封层的厚度不是关键性的,并可以根据具体应用独立地变化。优选地,这些包封层每一个的厚度可以在以下范围内独立地变化:约1mil(0.026mm)至约120mil(3.00mm),或更优选约1mil至约40mil(1.02mm),或最优选约1mil至约20mil(0.51mm)。此外,包含在太阳能电池预层压组合件中的所有包封层均可具有平滑的或粗糙的表面。然而优选的是,包封层具有粗糙的表面以有利于在层压过程中脱去层压体的空气。
在另一个实施方案中,太阳能电池预层压组合件可进一步包含入射层和/或背衬层,它们分别在受光面和背面充当组合件的外层。
太阳能电池预层压组合件的外层,即入射层和背衬层,可衍生自任何合适的片材或薄膜。合适的片材可以是玻璃或塑料片材,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)、茂金属催化的聚苯乙烯、聚酰胺、聚酯、含氟聚合物等、以及它们的组合。此外,可以利用金属片材(例如铝、钢、镀锌钢)或陶瓷板来形成背板。
合适的薄膜层可以是聚合物。用来形成聚合物薄膜的优选聚合物包括但不限于:聚酯(例如,聚(对苯二甲酸乙二醇酯))、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(包括间规聚苯乙烯)、苯乙烯-丙烯酸酯共聚物、丙烯腈-苯乙烯共聚物、聚砜类(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、偏二氯乙烯共聚物等)、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。最优选地,聚合物薄膜为双轴取向的聚酯薄膜(优选聚(对苯二甲酸乙二醇酯)薄膜)或含氟聚合物薄膜(例如,和薄膜,得自E.I.du Pont de Nemours and Company,Wilmington,DE)。对某些应用而言,含氟聚合物-聚酯-含氟聚合物(“TPT”)薄膜也是优选的。金属薄膜,例如铝箔,也可在本文中用作背板。
本发明的太阳能电池预层压组合件可任选地进一步包含嵌入到组合件内的其它功能性薄膜或片材层(例如介电层或阻挡层)。此类功能性层可衍生自任何上述聚合物薄膜或涂覆有其它功能性涂层的那些。例如,涂覆有金属氧化物涂层的聚(对苯二甲酸乙二醇酯)薄膜,诸如在US 6,521,825、US6,818,819和EP 1 182 710中所公开的那些,可充当层压体中的氧气和水分阻挡层。
如果需要,还可以在太阳能电池层压体内包含一层非织造玻璃纤维(稀松布),以利于在层压过程中排气,或起到加强包封层的作用。在例如US 5,583,057、US 6,075,202、US 6,204,443、US 6,320,115、US6,323,416、以及EP 0 769 818中公开了此类稀松布层在太阳能电池层压体中的使用。
此外,应当理解,布置在太阳能电池层受光面上的所有薄膜或片材层均应由透明的材料制成,以允许太阳光高效地透射到太阳能电池组件内。在某些情况下,可包括特殊的薄膜或片材以同时起到包封层和外层的作用。还可以想到,包括在组合件中的任何薄膜或片材层均可以采用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的一个或两个表面进行处理以增强粘附强度,如上所述。
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。可选的具体的太阳能电池预层压构造(从正(光入射)面到背面)包括例如以下构造,其中“ION”是指如上所述的、本发明优选的高熔融流动离聚物包封薄膜或片材:
●玻璃/ION/太阳能电池/ION/玻璃;
●玻璃/ION/太阳能电池/ION/含氟聚合物薄膜;
●含氟聚合物薄膜/ION/太阳能电池/ION/玻璃;
●含氟聚合物薄膜/ION/太阳能电池/ION/含氟聚合物薄膜;
●玻璃/ION/太阳能电池/ION/聚酯薄膜;
●含氟聚合物薄膜/ION/太阳能电池/ION/聚酯薄膜;
●玻璃/ION/太阳能电池/ION/涂布阻挡材料的薄膜/ION/玻璃;
●含氟聚合物薄膜/ION/涂布阻挡材料的薄膜/ION/太阳能电池/ION/涂布阻挡材料的薄膜/ION/含氟聚合物薄膜;
●玻璃/ION/太阳能电池/ION/铝坯料;
●含氟聚合物薄膜/ION/太阳能电池/ION/铝坯料;
●玻璃/ION/太阳能电池/ION/镀锌钢板;
●玻璃/ION/太阳能电池/ION/聚酯薄膜/ION/铝坯料;
●含氟聚合物薄膜/ION/太阳能电池/ION/聚酯薄膜/ION/铝坯料;
●玻璃/ION/太阳能电池/ION/聚酯薄膜/ION/镀锌钢板;
●含氟聚合物薄膜/ION/太阳能电池/ION/聚酯薄膜/ION/镀锌钢板;
●玻璃/ION/太阳能电池/隔音聚(乙烯醇缩丁醛)包封层/玻璃;
●玻璃/ION/太阳能电池/聚(乙烯醇缩丁醛)包封层/含氟聚合物薄膜;
●玻璃/ION/太阳能电池/乙烯乙酸乙烯酯包封层/聚酯薄膜;
●含氟聚合物薄膜/ION/太阳能电池/乙烯-丙烯酸甲酯共聚物包封层/聚酯薄膜;
●玻璃/乙烯-丙烯酸丁酯共聚物包封层/太阳能电池/ION/涂布阻挡材料的薄膜/乙烯-丙烯酸丁酯共聚物包封层/玻璃;
等等。
以上每个实例中优选的含氟聚合物薄膜是含氟聚合物薄膜或含氟聚合物-聚酯-含氟聚合物三层薄膜。以上每个实例中优选的聚酯薄膜是聚(对苯二甲酸乙二醇酯)薄膜。术语“玻璃”旨在指代任何前述类型的玻璃或玻璃替代物的片材。
本发明还提供由上面所公开的太阳能电池预层压组合件制备的太阳能电池层压体。具体地讲,通过使太阳能电池预层压组合件经受下面详细提供的进一步层压处理而形成太阳能电池层压体。
此外,如上所述,在本文使用的层压温度下,高熔融流动离聚物包封薄膜或片材具有比那些由其它低熔融流动离聚物生成的包封薄膜或片材更高的粘附强度,从而可在本文所述的降低了的层压条件下提供太阳能电池层压体结构,并由此可使用简化的生产方法提供太阳能电池层压体结构。
层压方法
本发明还提供制备安全层压体或太阳能电池层压体的简化方法。具体地讲,如上文所提及,与在涉及低熔融流动离聚物的方法中使用的那些材料相比,并入高熔融流动离聚物夹层片材或者高熔融流动离聚物太阳能电池包封薄膜或片材需要降低的层压温度、或减少的循环时间、或这两者。
层压方法可以为高压釜法或非高压釜法。
在示例性方法中,叠合玻璃片材、前包封层、太阳能电池组件、后包封层和背衬层(例如,薄膜)以及玻璃盖板,并在热、压力和真空(例如,在约27-28英寸(689-711mm)汞柱的范围内)下层压在一起以除去空气。优选地,玻璃片材经过洗涤和干燥。典型的玻璃类型为90密耳厚的退火低铁玻璃。在示例性过程中,将本发明的预层压组合件放入能够维持真空的袋子(“真空袋”)内,在该袋子上使用真空管或吸真空的其它装置抽出袋内空气,在保持真空的情况下密封袋子,将密封后的袋子放在高压釜中约10至约50分钟,其中高压釜的温度为约100℃至约180℃,压力为约150至约250,优选约200psig(约15巴)。优选地,在约100℃至约120℃的温度下对该袋子进行约20至约45分钟的热压处理。更优选地,在约110℃至约120℃的温度下对该袋子进行约20至约40分钟的热压处理。可以用真空环代替真空袋。在US 3,311,517中公开了一种类型的真空袋。本发明的高熔融流动离聚物薄膜和片材提供了较低的层压温度和/或更快的层压循环时间等期望优点,具体取决于层压机的选择。
通过压送辊方法可以除去预层压组合件内存留的任何空气。例如,可以将预层压组合件在烘箱内加热约15至约60(优选约30)分钟,其中烘箱温度为约80℃至约120℃,或优选介于约90℃和约100℃之间。此后,让加热过的预层压组合件通过一组压送辊,以便挤出太阳能电池外层、太阳能电池组件和包封层之间的空隙空间内的空气,并密封组合件的边缘。根据构造材料和所采用的确切条件,该方法可提供最终的太阳能电池模块,或可以提供所谓的预压组合件。
然后,可以将预压组合件放在充入空气的高压釜中,高压釜中的温度升至约100℃至约160℃,或优选介于约110℃和约120℃之间,压力升至介于约100psig和约300psig之间,或优选约200psig(14.3巴)。将这些条件保持约15分钟至约1小时,或优选约20至约50分钟,然后在没有新空气进入高压釜的情况下使空气冷却。在冷却约10至约30(优选约20)分钟后,释放多余的空气压力并从高压釜中取出太阳能电池层压体。该方法不应认为具有限制性。基本上本领域内已知的任何层压方法均可在本文中使用。
非高压釜层压方法已在例如US 3,234,062、US 3,852,136、US4,341,576、US 4,385,951、US 4,398,979、US 5,536,347、US5,853,516、US 6,342,116、US 5,415,909、US 2004-0182493、US 2003-0148114A1、EP 1 235 683B1、WO 91/01880、以及WO 03/057478A1中有所公开。一般来讲,非高压釜方法包括加热预层压组合件或预压组合件,并且任选地施加真空、压力或这两者。例如,预压件可以连续通过加热烘箱和压送辊。光伏层压方法的商业实例包括Meier Vakuumtechnik GmbH,Bocholt,Germany的Icolam真空层压系统。
在制备太阳能电池层压体时,如果需要,可使用本领域已公开的任何方法来密封层压体的边缘以减少水分和空气的进入,以及减少影响太阳能电池效率和寿命的可能的降解。合适的封边材料包括但不限于:丁基橡胶、多硫化物、硅氧烷、聚氨酯、聚丙烯弹性体、聚苯乙烯弹性体、嵌段弹性体、苯乙烯-乙烯-丁烯-苯乙烯(SEBS)等。
实施例
以下实施例旨在对本发明进行例证,并非旨在以任何方式来限制本发明的范围。
方法
下列方法用于下文提出的实施例中。
熔融指数
使用2160g的负荷在190℃下按照ASTM D1238测量熔融指数(MI)。类似的ISO测试为ISO 1133。
I.层压方法1
堆叠(叠合)下述层压层以形成实施例中所述的预层压组合件。对包含作为入射层或背板层的薄膜层的组合件,在薄膜层上布置玻璃盖板。然后将预层压组合件放入Meier ICOLAM 10/08层压机(Meier VakuumtechnikGmbH,Bocholt,Germany)中。层压循环包括5.5分钟的抽真空步骤(3英寸汞柱的真空)和在115℃下5.5分钟的加压步骤(2巴的压力)。仅实施例11、16、20、52、57和60中包括附加步骤以固化组合物,即在维持加压条件下于145℃保持5分钟。然后取出层压体。
II.层压方法2
堆叠(叠合)下述层压体层以形成实施例中所述的预层压组合件。对包含作为入射层或背板层的薄膜层的组合件,在薄膜层上布置玻璃盖板。然后将该预层压组合件放入真空袋内,将真空袋密封,并通过施加真空除去真空袋内的空气。将真空袋放入烘箱内,并加热到90至100℃维持30分钟,以除去组合件之间包含的任何空气。然后如上所述,使该预压组合件在压力为200psig(14.8巴)的充空气高压釜中于115℃下经受30分钟的热压处理。然后在没有新空气进入高压釜的情况下冷却空气。冷却20分钟之后,当空气温度小于约50℃时,释放多余压力,并将层压体从高压釜中取出。
实施例1至20
按照层压方法1组装和层压下表1所述12x12英寸(305x305mm)层压体结构。
表1
层压体结构
●ION 1为20mil(0.51mm)厚的压花的离聚物A片材,离聚物A为包含15重量%的甲基丙烯酸聚合残基的乙烯-甲基丙烯酸共聚物并具有30g/10min的MI,其中甲基丙烯酸用锌离子中和了20%。
●ION 2为60mil(1.52mm)厚的压花的三层片材,其具有(i)两(2)个2mil(0.06mm)厚的由离聚物B和TINUVIN 328(Ciba SpecialtyChemicals公司)的共混物形成的表面层,离聚物B为包含18重量%的甲基丙烯酸聚合残基的乙烯-甲基丙烯酸共聚物并具有50g/10min的MI,其中甲基丙烯酸用钠离子中和了10%,TINUVIN328的含量按共混物的总重量计为0.15重量%,以及(ii)由乙烯-甲基丙烯酸共聚物形成的芯层,乙烯-甲基丙烯酸共聚物包含18重量%的甲基丙烯酸聚合残基并具有1g/10min的MI,其中甲基丙烯酸用钠离子中和了35%。
●ION 3为15mil(0.38mm)厚的压花的三层片材,其具有(i)两(2)个1mil(0.03mm)厚的离聚物C表面层,离聚物C为包含19重量%的甲基丙烯酸聚合残基的乙烯-甲基丙烯酸共聚物并具有100g/10min的MI,其中甲基丙烯酸用锌离子中和了7.5%,以及(ii)乙烯-丙烯酸异丁酯-甲基丙烯酸共聚物芯层,乙烯-丙烯酸异丁酯-甲基丙烯酸共聚物包含10重量%的丙烯酸异丁酯聚合残基和10重量%的甲基丙烯酸聚合残基并具有1g/10min的MI,其中甲基丙烯酸用锌离子中和了70%。
●ION 4为1mil(0.03mm)厚的离聚物D的薄膜,离聚物D为包含19重量%的甲基丙烯酸聚合残基的乙烯-甲基丙烯酸共聚物并具有200g/10mi n的MI,其中甲基丙烯酸用锌离子中和了5%。
●ION 5为20mil(0.51mm)厚的压花的离聚物E片材,离聚物E为包含22重量%的甲基丙烯酸聚合残基的乙烯-甲基丙烯酸共聚物并具有75g/10min的MI,其中甲基丙烯酸用锌离子中和了7.5%。
●ION 6为20mil(0.51mm)厚的压花的离聚物F片材,离聚物F为组合物,按组合物的总重量计,其包含99.5重量%的离聚物A和0.5重量%的N-β-(氨基乙基)-γ-氨基丙基三甲氧基硅烷。
●ION 7为90mil(2.25mm)厚的压花的三层片材,其具有(i)两(2)个1mil(0.03mm)厚的离聚物G表面层,离聚物G为组合物,按组合物的总重量计,其包含99.25重量%的离聚物B和0.25重量%的N-β-(氨基乙基)-γ-氨基丙基三甲氧基硅烷,以及(ii)乙烯-丙烯酸正丁酯共聚物芯层,乙烯-丙烯酸正丁酯共聚物包含35重量%的丙烯酸正丁酯聚合残基并具有3g/10min的MI。
●ION 8为20mil(0.51mm)厚的压花的三层片材,其具有(i)两(2)个2mil(0.06mm)厚的离聚物H表面层,离聚物H为组合物,按组合物的总重量计,其包含99.875重量%的离聚物C和0.125重量%的N-β-(氨基乙基)-γ-氨基丙基三甲氧基硅烷,以及(ii)乙烯-甲基丙烯酸共聚物芯层,乙烯-甲基丙烯酸共聚物包含22重量%的甲基丙烯酸聚合残基并具有1.5g/10min的MI,其中甲基丙烯酸用钠离子中和了35%。
●ION 9为15mil(0.38mm)厚的压花的离聚物I片材,离聚物I为组合物,按组合物的总重量计,其包含99.875重量%的离聚物D和0.125重量%的γ-缩水甘油醚氧基丙基三乙氧基硅烷。
●ION 10为1mil(0.03mm)厚的离聚物J薄膜,离聚物J为组合物,按组合物的总重量计,其包含99.875重量%的离聚物E、0.30重量%的TINUVIN 1577(Ciba Specialty Chemicals公司的产品)、0.30重量%的CHIMASSORB 944(Ciba Specialty Chemicals公司的产品)、以及0.125重量%的γ-甲基丙烯酰氧基丙基三甲氧基硅烷。
●ION 11为90mil(2.25mm)厚的压花的离聚物K片材,离聚物K为组合物,按组合物的总重量计,其包含98.5重量%的离聚物A和1.5重量%的1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷。
●ION 12为15mil(0.38mm)厚的压花的离聚物L片材,离聚物L为组合物,按组合物的总重量计,其包含98.0重量%的离聚物B和2.0重量%的1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷。
●ION 13为20mil(0.51mm)厚的压花的离聚物M片材,离聚物M为组合物,按组合物的总重量计,其包含97.5重量%的离聚物C、0.5重量%的CYASORB UV-1164(Cytec Industries)和2.5重量%的1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷。
●ION 14为1mil(0.03mm)厚的离聚物N薄膜,离聚物N为组合物,按组合物的总重量计,其包含93.0重量%的离聚物D、5.0重量%的异氰尿酸三烯丙酯和2.0重量%的1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷。
●ION 15为20mil(0.51mm)厚的压花的三层片材,其具有(i)两(2)个1mil(0.03mm)厚的离聚物O表面层,离聚物O为组合物,按组合物的总重量计,其包含95.0重量%的离聚物E、3重量%的三羟甲基丙烷三丙烯酸酯和2.0重量%的1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷,以及(ii)乙烯-丙烯酸甲酯共聚物芯层,乙烯-丙烯酸甲酯共聚物包含25重量%的丙烯酸甲酯聚合残基并具有5g/10min的MI。
●ION 16为1mil(0.03mm)厚的离聚物P薄膜,离聚物P为组合物,按组合物的总重量计,其包含98.0重量%的离聚物A、0.5重量%的乙烯基三甲氧基硅烷和1.5重量%的1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷。
●ION 17为20mil(0.51mm)厚的压花的离聚物Q片材,离聚物Q为组合物,按组合物的总重量计,其包含97.75重量%的离聚物B、0.25重量%的γ-甲基丙烯酰氧基丙基三甲氧基硅烷和2.0重量%的1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷。
●ION 18为15mil(0.38mm)厚的压花的三层片材,其具有(i)两(2)个1mil(0.03mm)厚的离聚物R表面层,离聚物R为组合物,按组合物的总重量计,其包含97.375重量%的离聚物C、0.125重量%的N-β-(N-乙烯基苄基氨基乙基)-γ-氨基丙基三甲氧基硅烷和2.5重量%的1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷,以及(ii)乙烯-甲基丙烯酸共聚物芯层,乙烯-甲基丙烯酸共聚物包含18重量%的甲基丙烯酸聚合残基并具有1.5g/10min的MI,甲基丙烯酸用钠离子中和了70%。
●ION 19为20mil(0.51mm)厚的压花的三层片材,其具有(i)两(2)个2mil(0.06mm)厚的离聚物S表面层,离聚物S为组合物,按组合物的总重量计,其包含92.875重量%的离聚物D、5.0重量%的异氰尿酸三烯丙酯、0.125重量%的γ-甲基丙烯酰氧基丙基三甲氧基硅烷和2.0重量%的1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷,以及(ii)乙烯-甲基丙烯酸共聚物芯层,乙烯-甲基丙烯酸共聚物包含22重量%的甲基丙烯酸聚合残基并具有0.5g/10min的MI,甲基丙烯酸用锌离子中和了35%。
●ION 20为90mil(2.25mm)厚的压花的离聚物T片材,离聚物T为组合物,按组合物的总重量计,其包含94.875重量%的离聚物E,3重量%的三羟甲基丙烷三丙烯酸酯,0.125重量%的N-β-(N-乙烯基苄基氨基乙基)-γ-氨基丙基三甲氧基硅烷、CYASORB UV-1164和TINUVIN 123,以及2.0重量%的1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷。
●PVB A为40mil(1.02mm)厚的隔音聚(乙烯醇缩丁醛)片材,其包含百分之(pph)一百的羟基数为15的聚(乙烯醇缩丁醛)并用48.5pph的增塑剂四乙二醇二庚酸酯增塑处理,以与PCT专利申请WO2004/039581中所公开的那些方式相似的方式制备。
实施例21至40
按照上面的层压方法2组装和层压上表1中所述的12x12英寸(305x305mm)太阳能电池层压体结构。
实施例41至60
按照上面的层压方法1组装和层压下表2中所述的12x12英寸(305x305mm)太阳能电池预层压结构。层1和层2分别构成入射层和前板包封层,层4和层5分别构成背板包封层和背衬层。
表2
太阳能电池预层压结构
实施例61至80
按照上面的层压方法2组装和层压上表2中所述的12x12英寸(305x305mm)太阳能电池预层压结构。层1和层2分别构成入射层和前板包封层,层4和层5分别构成背板包封层和背衬层。
比较实施例CE1、实施例81
在比较实施例CE1中,将50克低熔融流动离聚物添加到预热至90℃的配有50cc混炼头的Brabender流变仪(C.W.Brabender Ins truments,Inc.,So.Hackensack,NJ)中混炼1分钟以上,混炼叶片的速度设为8rpm,该低熔融流动离聚物为包含15重量%的甲基丙烯酸聚合残基的乙烯-甲基丙烯酸共聚物并具有5g/10min的MI,甲基丙烯酸用锌离子中和了23%。然后将混炼叶片的速度增至30rpm,继续混炼聚合物树脂1分钟,之后安全销由于高转矩被切断,而混炼马达电流为5A。然后停止该过程。
在实施例81中,将50克高熔融流动离聚物添加到预热至90℃的配有50cc混炼头的Brabender流变仪中混炼1分钟以上,混炼叶片的速度设为8rpm,该高熔融流动离聚物为包含15重量%的甲基丙烯酸聚合残基的乙烯-甲基丙烯酸共聚物并具有100g/10min的MI,甲基丙烯酸用锌离子中和了11.9%。然后将混炼叶片的速度增至30rpm,继续混炼聚合物树脂5分钟,之后得到均匀的聚合物熔融体,同时混合马达电流为1A并且聚合物熔融温度为101℃。然后停止该过程。
这些结果表明,由于掺入了有机过氧化物,高熔融流动离聚物(实施例81)能够在足够低的温度(约90℃)下通过商业上可行的和可规模化的挤出复合设备进行复合,而相应的低熔融流动离聚物(比较实施例CE1)则无法达到这一点。
Claims (17)
1.一种包含离聚物组合物的聚合物薄膜或片材,所述离聚物组合物包含α烯烃和具有3至8个碳原子的α,β-烯键式不饱和羧酸的离聚共聚物,所述α,β-烯键式不饱和羧酸的含量按所述离聚共聚物的总重量计约1至约30重量%,其中使用一种或多种金属离子中和所述羧酸,按所述离聚共聚物中羧酸根的总摩尔数计,中和了1至100摩尔%含量的羧酸,并且其中所述离聚共聚物具有约20至约300g/10min的熔融指数。
2.权利要求1的聚合物薄膜或片材,其中所述离聚物组合物还包含选自硅烷偶联剂、有机过氧化物、以及它们的组合的添加剂。
3.一种包含夹层和附加层的制品,所述夹层由权利要求1或2的聚合物薄膜或片材形成,所述附加层选自玻璃、其它聚合物夹层片材、聚合物薄膜层、以及金属薄膜或片材。
4.权利要求1或2的聚合物薄膜或片材或者权利要求3的制品,其中(a)所述α烯烃为乙烯;(b)所述α,β-烯键式不饱和羧酸选自丙烯酸、甲基丙烯酸、衣康酸、马来酸、马来酸酐、富马酸、一甲基马来酸、以及它们的混合物;(c)所述离聚共聚物包含约10至约25重量%的α,β-烯键式不饱和羧酸;(d)使用一种或多种金属离子中和所述羧酸,按所述离聚共聚物中羧酸根的总摩尔数计,中和了2至40摩尔%含量的羧酸;(e)所述离聚共聚物具有约30至约200g/10min的熔融指数;以及(f)所述夹层具有约0.1至约250mil(约0.003至约6.35mm)的厚度。
5.权利要求2的聚合物薄膜或片材或者权利要求3或4的制品,其中按所述离聚物组合物的总重量计,所述离聚物组合物包含约0.01至约5重量%的硅烷偶联剂,并且所述硅烷偶联剂选自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-环氧基环己基)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、以及它们的混合物。
6.权利要求2的聚合物薄膜或片材或者权利要求3或4的制品,其中按所述离聚物组合物的总重量计,所述离聚物组合物包含约0.01至约10重量%的有机过氧化物,并且所述有机过氧化物选自: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、正丁基-4,4-双(叔丁基过氧)戊酸酯、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、叔丁基过氧苯甲酸酯、过氧化苯甲酰以及它们的混合物。
7.权利要求3至6中任一项的制品,所述制品为安全玻璃层压体,其中所述附加层为玻璃片材,并且所述夹层具有约10至约250mil(约0.25至约6.35mm)的厚度并且被层压到所述玻璃片材上。
8.权利要求3至6中任一项的制品,所述制品为太阳能电池预层压组合件,并且其中所述组合件包括包含一个或多个太阳能电池的太阳能电池组件,所述聚合物薄膜或片材具有约0.1至约20mil(约0.003至约0.5mm)的厚度。
9.权利要求8的制品,所述制品还包括位于所述聚合物薄膜或片材的相对侧上、与所述太阳能电池组件相邻的第二聚合物层,其中所述第二聚合物层包含选自下列的聚合物组合物:聚(乙烯醇缩醛)、乙烯乙酸乙烯酯、聚氨酯、聚氯乙烯、聚乙烯、聚烯烃嵌段弹性体、乙烯丙烯酸酯共聚物、α烯烃和α,β-烯键式不饱和羧酸的共聚物及其离聚物、硅氧烷弹性体以及环氧树脂。
10.权利要求8或9的制品,所述制品还包括(A)入射层,所述入射层由透明材料形成并且在所述组合件的受光面上充当外层,和/或(B)背衬层,所述背衬层由玻璃、塑料薄膜或片材、或者金属薄膜或片材形成并且在所述组合件的背面充当外层。
11.一种制造制品的方法,其中所述制品为太阳能电池模块,所述方法包括:(i)提供权利要求8-10中任一项所述的太阳能电池预层压组合件,和(ii)层压所述预层压组合件以形成所述太阳能电池模块。
12.权利要求13的方法,其中通过使所述组合件经受热和任选的真空处理来实施所述层压步骤(ii)。
13.一种通过权利要求11或12的方法制备的制品。
14.一种包含离聚物组合物和添加剂的聚合物组合物,其中(i)所述离聚物组合物包含α烯烃和具有3至8个碳原子的α,β-烯键式不饱和羧酸的共聚物,所述α,β-烯键式不饱和羧酸的含量按所述离聚共聚物的总重量计约1至约30重量%,其中使用一种或多种金属离子中和所述羧酸,按所述离聚共聚物中羧酸根的总摩尔数计,中和了1至100摩尔%含量的羧酸,(ii)所述离聚共聚物具有约20至约300g/10min的熔融指数,以及(iii)所述添加剂选自硅烷偶联剂、有机过氧化物、以及它们的组合。
15.权利要求15的聚合物组合物,其中(A)所述离聚共聚物具有约30至约200g/10min的熔融指数,(B)所述α烯烃为乙烯,(C)所述α,β-烯键式不饱和羧酸选自丙烯酸、甲基丙烯酸、衣康酸、马来酸、马来酸酐、富马酸、一甲基马来酸、以及它们的混合物,(D)按所述离聚共聚物的总重量计,所述离聚物组合物包含约10至约25重量%的得自所述α,β-烯键式不饱和羧酸的重复单元,以及(E)使用一种或多种金属离子中和所述羧酸,按所述离聚共聚物中羧酸根的总摩尔数计,中和了2至40摩尔%含量的羧酸。
16.权利要求15或16的聚合物组合物,其中按所述组合物的总重量计,所述聚合物组合物包含约0.01至约5重量%的硅烷偶联剂,所述硅氧烷偶联剂选自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-环氧基环己基)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、以及它们的混合物。
17.权利要求15或16的聚合物组合物,其中按所述聚合物组合物的总重量计,所述聚合物组合物包含约0.01至约10重量%的有机过氧化物,所述有机过氧化物选自: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、正丁基-4,4-双(叔丁基过氧)戊酸酯、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、叔丁基过氧苯甲酸酯、过氧化苯甲酰以及它们的混合物。
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CN111231473A (zh) * | 2020-01-17 | 2020-06-05 | 江西赛欧特科新材料有限公司 | 一种有机硅复合聚氨酯的合成革及其制备方法 |
CN111231473B (zh) * | 2020-01-17 | 2021-12-07 | 江西赛欧特科新材料有限公司 | 一种有机硅复合聚氨酯的合成革及其制备方法 |
CN114196330A (zh) * | 2021-08-16 | 2022-03-18 | 江苏奥天利新材料有限公司 | 一种离聚物型夹层玻璃中间膜及其制备方法 |
Also Published As
Publication number | Publication date |
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EP2118179A1 (en) | 2009-11-18 |
US20140182664A1 (en) | 2014-07-03 |
WO2008100612A1 (en) | 2008-08-21 |
US8691372B2 (en) | 2014-04-08 |
JP5300743B2 (ja) | 2013-09-25 |
US20080199690A1 (en) | 2008-08-21 |
ATE525421T1 (de) | 2011-10-15 |
JP2010519346A (ja) | 2010-06-03 |
EP2118179B1 (en) | 2011-09-21 |
KR20090113375A (ko) | 2009-10-30 |
ES2370744T3 (es) | 2011-12-22 |
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