CN105706250A - 粘合膜、太阳能电池用密封件、太阳能电池模块、夹层玻璃用中间膜及夹层玻璃 - Google Patents

粘合膜、太阳能电池用密封件、太阳能电池模块、夹层玻璃用中间膜及夹层玻璃 Download PDF

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CN105706250A
CN105706250A CN201480058920.7A CN201480058920A CN105706250A CN 105706250 A CN105706250 A CN 105706250A CN 201480058920 A CN201480058920 A CN 201480058920A CN 105706250 A CN105706250 A CN 105706250A
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solar
sealing member
laminated
glass
cell
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杉山齐
日高忍
河边纯弥
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CI Kasei Co Ltd
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Abstract

本发明公开了粘合膜及太阳能电池用密封件，所述粘合膜包括：密封用树脂、硅烷偶联剂以及pKb为5～12的碱性化合物。此外，本发明还公开了太阳能电池模块(10)，包括：太阳能电池单元(11)以及夹持太阳能电池单元(11)的一对太阳能电池用密封件(12)，太阳能电池用密封件(12)为本发明的太阳能电池用密封件。

Description

粘合膜、太阳能电池用密封件、太阳能电池模块、夹层玻璃用中间膜及夹层玻璃
技术领域
本发明涉及粘合膜、太阳能电池用密封件、太阳能电池模块、夹层玻璃用中间膜及夹层玻璃。
本申请基于2013年11月5日在日本申请的专利申请第2013-229665号要求优先权，在此援引其内容。
背景技术
为了密封并固定太阳能电池单元，在太阳能模块中广泛使用透明性、加工性、交联性都优异的乙烯-含极性基单体共聚物(乙烯-乙酸乙烯酯共聚物等)的密封用树脂形成的太阳能电池用密封件(以下，还简称为密封件)。此外，密封件中常混合硅烷偶联剂，以提高与配置在太阳能电池模块表面侧的玻璃板等透明保护件或背板等的粘合性(例如，专利文献1)。
但是，保管混合有硅烷偶联剂的密封件时，硅烷偶联剂因密封用树脂中或空气中的水分而水解，进而引起缩合反应易于变质。若硅烷偶联剂因水解或缩合而变质，则出现密封用树脂的交联特性不能如设计的一样，或因硅烷醇基的减少而降低密封件粘合性的问题。
作为能够抑制保管时水解和缩合的硅烷偶联剂，提出了调节缩合反应部位的结构、配位数来降低缩合反应速度的硅烷偶联剂(专利文献2)。但是上述硅烷偶联剂中难以得到粘合性充分的密封件。
现有技术文献
专利文献
专利文献1：日本特开2000-174296号公报
专利文献2：日本特开2008-120952号公报
发明内容
本发明提供硅烷偶联剂不易变质且长期保管后也具有良好粘合性的粘合膜、太阳能电池用密封件、以及使用所述太阳能电池用密封件的太阳能电池模块。
此外，提供了由粘合膜构成的夹层玻璃用中间膜及夹层玻璃。
本发明的粘合膜包括：密封用树脂、硅烷偶联剂以及pKb为5～12的碱性化合物。
本发明的粘合膜中，所述碱性化合物优选pKb为5～12的光稳定剂。
本发明的太阳能电池用密封件由所述粘合膜构成。
本发明的太阳能电池模块包括：太阳能电池单元以及夹持所述太阳能电池单元的一对本发明的所述太阳能电池用密封件。
本发明的夹层玻璃用中间膜由所述粘合膜构成。
本发明的夹层玻璃由一对玻璃板以及由所述一对玻璃板夹持的所述夹层玻璃用中间膜组成。
发明效果
对于本发明的粘合膜，硅烷偶联剂不易变质且长期保管后也具有良好的粘合性。
本发明的太阳能电池模块的粘合膜的粘合性良好而不易发生剥离等不良情况。
附图说明
图1是表示本发明的太阳能电池模块一例的剖面图。
附图标记说明
10太阳能电池模块
11太阳能电池单元
12太阳能电池用密封件
13透明保护件
14背板
15引线串
具体实施方式
<粘合膜>
本发明的粘合膜包括密封用树脂、硅烷偶联剂、以及pKb为5～12的碱性化合物(以下也称为碱性化合物(A))。此外，本发明的粘合膜还可以包括除密封用树脂、硅烷偶联剂和碱性化合物(A)以外的其他添加剂。本发明的密封件由粘合膜构成。
[密封用树脂]
密封用树脂可使用通常作为密封件使用的树脂。
从透明性、加工性以及交联性优异的方面考虑，密封用树脂优选乙烯-含极性基单体共聚物。
所述极性基可列举酯基(-C(O)O-R或R-C(O)O-(但是，R为烷基)等)、羧基等。
作为具有极性基的单体的具体例，可列举例如乙烯基酯(乙酸乙烯酯等)、(甲基)丙烯酸烷基酯((甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯等)、不饱和羧酸((甲基)丙烯酸等)、不饱和二羧酸的酸酐(马来酸酐)、不饱和二羧酸酯(马来酸单甲酯、马来酸二甲酯等)等。
从柔软性和透明性的方面考虑，乙烯-含极性基单体共聚物优选乙烯-乙酸乙烯酯共聚物(以下也称为EVA)、乙烯-(甲基)丙烯酸烷基酯共聚物，尤其优选EVA。
从耐热性、粘合性、柔软性、成型性、耐久性、绝缘性的方面考虑，在全部结构单元(100质量％)中，乙烯-含极性基单体共聚物中具有极性基的单体单元的比例优选为10～40质量％，更优选为15～35质量％。
乙烯-含极性基单体共聚物的质均分子量优选为10000～300000，更优选为100000～170000。乙烯-含极性基单体共聚物的质均分子量为所述下限值以上，则易于得到机械性能良好的密封件。乙烯-含极性基单体共聚物的质均分子量为所述上限值以下，则易于得到加工性优异的密封件。
此外，质均分子量为通过凝胶渗透色谱法测定的值。
并且，密封用树脂还可以使用聚乙烯、聚丙烯、丙烯酸树脂等。
密封用树脂可以单独使用一种，也可以混合使用两种以上。
[硅烷偶联剂]
硅烷偶联剂起到改善太阳能电池单元、透明保护件、背板等与密封件之间的粘合性的作用。硅烷偶联剂可以使用通常在密封件中使用的硅烷偶联剂。
作为硅烷偶联剂的具体例，可列举例如3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基甲基二甲氧基硅烷、烯丙基三甲氧基硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷、3-巯基丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、3-缩水甘油醚氧基丙基甲基二甲氧基硅烷等。
从粘合性方面考虑，硅烷偶联剂优选具有三甲氧基硅烷基的硅烷偶联剂，更优选3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基三乙氧基硅烷。
硅烷偶联剂可以单独使用一种，也可以混合使用两种以上。
[碱性化合物(A)]
碱性化合物(A)是pKb为5～12的碱性化合物。通过使用碱性化合物(A)，可降低保管时密封件中的硅烷偶联剂的水解反应和缩合反应的速度。其结果是由于保管密封件之时能够抑制硅烷偶联剂随时间发生变化，因此可抑制密封件粘合性降低。
此外，可通过日本工业标准JISK2501中和值测定的电位差滴定法测定pKb。
碱性化合物(A)可以是pKb为5～12的碱性化合物，从耐光性高、不易被氧化变色的方面考虑，优选pKb为5～12的光稳定剂(以下也称为光稳定剂(a))。
光稳定剂(a)可列举例如双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯(pKb＝5～6)、聚丁二酸(4-羟基-2,2,6,6-四甲基-1-哌啶乙醇)酯(pKb＝7～8)、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯(pKb＝8～10)、双(1-十一烷氧基-2,2,6,6-四甲基-4-哌啶酮)碳酸酯(pKb＝11～12)等。
碱性化合物(A)可以单独使用一种，也可以混合使用两种以上。
[其他添加剂]
其他添加剂可列举紫外线吸收剂、除光稳定剂(a)外的光稳定剂、抗氧化剂、交联剂、交联助剂、颜料、染料、增塑剂、填料等。本发明的密封件优选包括交联剂，更优选包括交联剂和交联助剂。
交联剂是交联密封用树脂的成分。
交联剂可列举公知的有机过氧化物(过氧化缩酮类、二烷基过氧化物类、过氧化酯类等)、光敏剂等。
交联助剂为具有一个以上(优选两个以上)聚合性不饱和基(乙烯基、烯丙基、(甲基)丙烯酰氧基等)的化合物。
交联助剂可列举例如三烯丙基异氰脲酸酯、三烯丙基氰脲酸酯、三羟甲基丙烷三甲基丙烯酸酯等。
紫外线吸收剂可列举例如二苯甲酮类紫外线吸收剂、苯并三唑类紫外线吸收剂、水杨酸酯类紫外线吸收剂等。
除光稳定剂(a)外的光稳定剂可列举例如双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯(4≤pKb<5)、3-(2,2,6,6-四甲基-4-哌啶基)-2-甲基-1-丙烯-3-酮(4≤pKb<5)等。
[各成分的比例]
相对于100质量份密封用树脂，本发明的密封件中的硅烷偶联剂的含量优选为0.1～2质量份，更优选为0.2～1.0质量份。若硅烷偶联剂的含量为所述下限值以上，则易于得到优异的粘合性。若硅烷偶联剂的含量为前述上限值以下，则有利于成本。
本发明的密封件包含交联剂时，相对于100质量份密封用树脂，交联剂的含量优选为大于0质量份且5质量份以下，更优选为大于0质量份且2质量份以下。
本发明的密封件包含交联助剂时，相对于100质量份密封用树脂，交联助剂的用量优选为大于0质量份且5质量份以下，更优选为大于0质量份且2质量份以下。
密封件的厚度可以根据太阳能电池模块适当设置，优选0.05～1mm。若密封件的厚度设为所述下限值以上，则容易密封太阳能电池单元。若密封件的厚度设为所述上限值以下，则太阳能电池模块可变得更薄。
[密封件的制造方法]
没有特别限定本发明的密封件的制造方法，可列举的方法有例如混合密封用树脂、硅烷偶联剂和碱性化合物(A)、以及根据需要使用的其他添加剂得到树脂组合物后，将所述树脂组合物片状化。
片状化的方法可列举例如使用T模的挤出成型法、加压成型法。此外，树脂组合物为溶液的情况时，在剥离片上涂布树脂组合物，经过干燥，可片状化。
[作用效果]
在以上说明的本发明的密封件中，由于包括特定pKb的低碱性的碱性化合物(A)，因此可在保管密封件时抑制硅烷偶联剂因水解或缩合而随时间发生变化。并且，由于不必通过调节硅烷偶联剂的缩合反应部位的结构或配位数来降低缩合反应的速度，因此充分得到硅烷偶联剂的粘合性。
可见，本发明的密封件即使长期保管后也具有良好的粘合性，可以制造出不易发生剥离等不良情况的太阳能电池模块。
<太阳能电池模块>
下面结合图1说明本发明的太阳能电池模块的一例。
如图1所示，本实施例中的太阳能电池模块10包括：多个太阳能电池单元11、11……、一对太阳能电池用密封件12、12(以下也称为密封件12)、透明保护件13以及背板14。
太阳能电池单元11被一对密封件12、12夹持并固定。并且密封件12、12配置在透明保护件13和背板14之间。
密封件12是本发明的密封件。
[太阳能电池单元]
太阳能电池单元可列举例如具有接合p型和n型半导体的结构的pn接合型太阳能电池元件。
pn接合型太阳能电池元件可列举例如硅系(单晶硅系、多晶硅系、非晶硅系)、化合物系(GaAs系、CIS系、CdTe-CdS系)等。
本实施例中，多个太阳能电池单元11通过具有导线和焊接部的引线串15串联电连接。
[透明保护件]
透明保护件13可使用为保护太阳能电池单元的表面侧通常使用的部件，可列举例如玻璃板、树脂板。
从透光性的方面考虑，玻璃板优选为表面凹凸的浮法玻璃。浮法玻璃的材料优选为铁量少的白板玻璃(高透射玻璃)。
[背板]
背板14可使用作为太阳能电池模块的背板通常使用的材料。
背板14的材料可列举例如聚氟乙烯、聚酯(聚对苯二甲酸乙二醇酯等)、聚烯烃(聚乙烯等)、玻璃、金属(铝等)等。
背板14可以是单层，也可以是多层。
[太阳能电池模块的制造方法]
本发明的太阳能电池模块的制造方法除使用本发明的密封件外可采用公知的制造方法。
作为制造太阳能电池模块10的制造方法可列举例如以下方法。
通过引线串15电连接的多个太阳能电池单元11、11……夹在一对密封件12、12之间，且将密封件12、12夹在透明保护件13和背板14之间。然后进行加热，使密封件12、12之间、密封件12和透明保护件13之间、密封件12和背板14之间相互粘接。
密封件12包含交联剂时，优选加热至交联剂的分解温度以上。若加热至交联剂的分解温度以上，则可以交联密封件12中包含的密封用树脂，更能提高密封件12的耐久性。
[作用效果]
如上说明的本发明的太阳能电池模块由于使用粘合性良好的本发明的密封件，因此不易发生剥离等不良情况。
此外，本发明的太阳能电池模块并不限于上述太阳能电池模块10。
例如，还可以使用由所述粘合膜构成的夹层玻璃用中间膜。
此外，还可以使用由一对玻璃板和由所述一对玻璃板夹持的所述玻璃用中间膜组成的夹层玻璃。
实施例
下面通过实施例详细说明本发明，但是本发明并不限于以下记载内容。
[化合物]
下面示出所使用化合物的缩写。
(密封用树脂)
EVA-1：乙烯-乙酸乙烯酯共聚物(产品名“SEETECVE700”，乙酸乙烯酯单元的比例：28质量％，湖南石油化学公司制造)
(光稳定剂)
a-1：双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯(pKb＝5～6，产品名“JF-95”，城北化学工业公司制造)
a-2：聚丁二酸(4-羟基-2,2,6,6-四甲基-1-哌啶乙醇)酯(pKb＝7～8，产品名“Tinuvin622”，BASF日本公司制造)
a-3：双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯(pKb＝8～10，产品名“Tinuvin123”，BASF日本公司制造)
a-4：双(1-十一烷氧基-2,2,6,6-四甲基-4-哌啶酮)碳酸酯(pKb＝11～12，产品名“LA-81”，ADEKA公司制造)
e-1：双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯(4≤pKb<5，产品名“JF-90”，城北化学工业公司制造)
e-2：3-(2,2,6,6-四甲基-4-哌啶基)-2-甲基-1-丙烯-3-酮(4≤pKb<5，产品名“LA-87”，ADEKA公司制造)
(硅烷偶联剂)
b-1：3-甲基丙烯酰氧基丙基三甲氧基硅烷(产品名“KBM-503”，信越有机硅公司制造)
(交联剂)
c-1：叔丁基过氧化-2-乙基己基单碳酸酯(产品名“KayahekisaAD”，化药AKZO公司制造)
(交联助剂)
d-1：三烯丙基异氰脲酸酯(产品名“TAIC(注册商标)”，日本化成公司制造)
[实施例1]
混合100质量份EVA-1、0.2质量份碱性化合物光稳定剂(a-1)、0.2质量份硅烷偶联剂(b-1)、0.5质量份交联剂(c-1)、以及0.5质量份交联助剂(d-1)，得到树脂组合物。通过单螺杆挤出机将所得树脂组合物挤出成型得到片状的密封件。
[实施例2～8]
除如表1所示更改各成分的组成外，通过以实施例1相同的方式得到密封件。
[比较例1～5]
除如表2所示更改各成分的组成外，通过以实施例1相同的方式得到密封件。
[剥离强度]
准备多个以150μm厚度的烯烃薄膜包装的所得密封件的样本，分别在23℃×85％RH和30℃×60％RH的两种条件下进行保管。对于每种条件下保管6个月后和保管12个月后的样本，按照如下方法测定了剥离强度。
从保管的样本中剥掉烯烃薄膜，叠加在20cm的四方形的压纹白板玻璃上，通过层压机在150℃中进行5分钟真空脱气后，在压力0.1MPa中压制12分钟后得到试验片。对于所述试验片，使用180°拉力试验机(岛津制作所制造“AG-5000A”)，在23℃×50％RH条件下，进行180°剥离试验，测定了剥离强度(N/cm)。
剥离强度的测定结果如表1和表2所示。
[表1]
[表2]
如表1所示，包括pKb为5～12的碱性化合物的光稳定剂的实施例1～8的密封件中，在23℃×85％RH和30℃×60％RH的任一条件下进行保管之后，经过12个月后的剥离强度也为36N/cm以上，抑制了粘合性降低。
另一方面，如表2所示，包括pKb不足5的光稳定剂但不包括pKb为5～12的碱性化合物的比较例1～5的密封件中，在23℃×85％RH和30℃×60％RH的任一条件下进行保管之后，经过12个月后的剥离强度不到19N/cm，密封件的粘合性明显降低。
工业实用性
根据本发明，可提供硅烷偶联剂不易变质且长期保管后也具有良好粘合性的粘合膜、太阳能电池用密封件、以及使用所述太阳能电池用密封件的太阳能电池模块。此外，提供了由粘合膜组成的夹层玻璃用中间膜及夹层玻璃。

Claims (6)

1.一种粘合膜，其特征在于，包括：密封用树脂、硅烷偶联剂以及pKb为5～12的碱性化合物。
2.根据权利要求1所述的粘合膜，其特征在于，所述碱性化合物是pKb为5～12的光稳定剂。
3.一种太阳能电池用密封件，其特征在于，所述太阳能电池用密封件由权利要求1或2所述的粘合膜构成。
4.一种太阳能电池模块，其特征在于，包括：太阳能电池单元以及夹持所述太阳能电池单元的一对权利要求3所述的太阳能电池用密封件。
5.一种夹层玻璃用中间膜，其特征在于，所述夹层玻璃用中间膜由权利要求1或2所述的粘合膜构成。
6.一种夹层玻璃，其特征在于，所述夹层玻璃由一对玻璃板以及由所述一对玻璃板夹持的权利要求5所述的夹层玻璃用中间膜组成。
CN201480058920.7A 2013-11-05 2014-11-04 粘合膜、太阳能电池用密封件、太阳能电池模块、夹层玻璃用中间膜及夹层玻璃 Pending CN105706250A (zh)

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