CN103687907A - 偏氟乙烯系树脂组合物、树脂薄膜、太阳能电池用背板以及太阳能电池组件 - Google Patents
偏氟乙烯系树脂组合物、树脂薄膜、太阳能电池用背板以及太阳能电池组件 Download PDFInfo
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- CN103687907A CN103687907A CN201280034750.XA CN201280034750A CN103687907A CN 103687907 A CN103687907 A CN 103687907A CN 201280034750 A CN201280034750 A CN 201280034750A CN 103687907 A CN103687907 A CN 103687907A
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- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
本发明提供即使在直接层叠于乙烯醋酸乙烯酯共聚物(EVA)系密封材料的情况下,在耐湿热性的耐久性评价中也不易发生黄变的偏氟乙烯系树脂组合物、树脂薄膜、太阳能电池用背板以及太阳能电池组件。将至少含有偏氟乙烯树脂和抗氧化剂的偏氟乙烯系树脂组合物进行制膜,从而制成厚度为10~200μm的偏氟乙烯系树脂薄膜,所述偏氟乙烯树脂的通过1H-NMR测定的头尾键接与头头键接的峰值之比(头尾键接/头头键接)为11.5以下,且质均分子量(Mw)为1.30×105以上。而且,将该偏氟乙烯系树脂薄膜与聚对苯二甲酸乙二醇酯系薄膜等电绝缘性树脂薄膜层叠,制成太阳能电池用背板。
Description
技术领域
本发明涉及偏氟乙烯系树脂组合物和使用了该树脂组合物的树脂薄膜、太阳能电池用背板以及太阳能电池组件。更详细而言,涉及在太阳能电池组件等要求耐候性的用途中使用的树脂薄膜的变色抑制技术。
背景技术
近年来,为了应对全球变暖问题而抑制二氧化碳的排放,为此正在推进各种自然能源的利用,其中,尤其是利用了太阳能的太阳能电池备受瞩目。另一方面,太阳能电池组件由于长期在屋外使用,因此对耐久性的要求高,通常,用乙烯醋酸乙烯酯共聚物(EVA)树脂等热塑性树脂密封太阳能电池单元,形成被太阳光照射的面用玻璃覆盖、背面用背板保护的结构。
作为构成该太阳能电池组件的背面保护用背板的耐候性树脂薄膜材料,偏氟乙烯系树脂由于机械强度、耐化学试剂性以及耐候性优异而备受瞩目。而且,以往提出了:使用偏氟乙烯系树脂薄膜与聚对苯二甲酸乙二醇酯薄膜的层叠体作为背板的太阳能电池组件;使用具备涂覆有无机氧化物的透明高防湿薄膜的层叠薄膜作为背板的太阳能电池组件(例如,参照专利文献1、2。)。
另外,背板出于保护太阳能电池单元、配线的目的而设置于太阳能电池组件的最下层,但除了保护目的之外,出于提高太阳光的反射率、提高太阳能电池组件的发电效率的目的,有时使用白色片材(例如,参照专利文献3、4。)。例如,白色的偏氟乙烯系树脂薄膜是通过使偏氟乙烯系树脂组合物含有氧化钛等白色颜料并制成薄膜而得到的。
现有技术文献
专利文献
专利文献1:日本特开2002-83978号公报
专利文献2:日本特开2000-174296号公报
专利文献3:日本特开2009-71236号公报
专利文献4:日本特开2008-28294号公报
发明内容
发明要解决的问题
通常,作为用于密封太阳能电池单元的密封材料,使用EVA树脂,在该EVA系密封材料上热压接使用了偏氟乙烯系树脂薄膜的背板。然而,对于EVA系密封材料与偏氟乙烯系树脂薄膜直接接触的结构的太阳能电池组件的情况,在高温高湿的条件下进行耐久性试验时,存在背板(偏氟乙烯系树脂薄膜)变成黄色的问题。
因而,本发明的主要目的在于,提供即使在直接层叠于乙烯醋酸乙烯酯共聚物(EVA)系密封材料的情况下,在耐湿热性的耐久性评价中也不易发生变色的偏氟乙烯系树脂组合物、树脂薄膜、太阳能电池用背板以及太阳能电池组件。
用于解决问题的方案
本发明人为了解决前述课题而进行了深入实验研究,结果明确了偏氟乙烯系树脂薄膜的变色是因密封材料中使用的太阳能电池组件用EVA树脂所含有的受阻胺系光稳定剂引起的。具体而言,发现了:长时间置于高温/高湿的环境下时,由于EVA树脂中的受阻胺系光稳定剂,EVA系密封材料与偏氟乙烯系树脂薄膜的界面局部产生碱性气氛,由此,偏氟乙烯系树脂薄膜产生脱氟反应,生成多烯结构。
因而,本发明人研究了用于抑制EVA系密封材料与偏氟乙烯系树脂薄膜的界面产生碱性气氛的方法,发现通过使偏氟乙烯系树脂薄膜含有特定结构的偏氟乙烯系树脂和抗氧化剂,能够大幅抑制耐湿热性的耐久性评价中的变色,从而完成了本发明。
即,本发明的偏氟乙烯系树脂组合物至少含有偏氟乙烯树脂和抗氧化剂,所述偏氟乙烯树脂的通过1H-NMR测定的头尾键接(head to tail)与头头键接(head to head)的峰值之比(头尾键接/头头键接)为11.5以下,且质均分子量(Mw)为1.30×105以上。
该偏氟乙烯系树脂组合物中,相对于树脂成分总质量,可以含有50质量%以上的前述偏氟乙烯树脂。
另外,前述抗氧化剂例如可以相对于100质量份树脂成分配混0.01~5质量份。
另一方面,作为树脂成分,除含有前述偏氟乙烯树脂外,相对于树脂成分总质量,可以含有5~50质量%的范围的甲基丙烯酸酯系树脂。
另外,相对于树脂成分100质量份,还可以配混5~30质量份的氧化钛。
本发明的偏氟乙烯系树脂薄膜由前述的偏氟乙烯系树脂组合物制成,厚度为10~200μm。
另外,本发明的太阳能电池用背板使用了前述的偏氟乙烯系树脂薄膜。
进而,本发明的太阳能电池组件使用了该太阳能电池背板。
发明的效果
根据本发明,由于含有特定结构的偏氟乙烯树脂和抗氧化剂,因此能够实现即使在直接层叠于乙烯醋酸乙烯酯共聚物(EVA)系密封材料的情况下,在耐湿热性的耐久性评价中也不易产生黄变的偏氟乙烯系树脂薄膜。
附图说明
图1为本发明的第四实施方式的太阳能电池组件的结构的示意性剖视图。
具体实施方式
以下,针对用于实施本发明的方式,参照附图进行详细说明。需要说明的是,本发明不限定于以下说明的实施方式。
(第一实施方式)
首先,针对本发明的第一实施方式的偏氟乙烯系树脂组合物(以下也简称为树脂组合物。)进行说明。本实施方式的树脂组合物至少含有具有特定的分子链结构和分子量的偏氟乙烯树脂(PVDF树脂)、以及抗氧化剂。
[树脂成分]
本实施方式的树脂组合物中,树脂成分的50质量%以上为PVDF树脂。而且含有为均聚物、且分子链中的头尾键接与头头键接的比率R(=头尾键接/头头键接)为11.5以下、且质均分子量(Mw)为1.30×105以上的PVDF树脂。通过含有这种分子链结构的PVDF树脂,在用于太阳能电池用背板时,在长期耐湿热性的耐久性评价中能够防止碱性气氛的发生、抑制黄色系的变色。
此处,PVDF树脂是否为均聚物可以通过19F-NMR来确认。另外,比率R是通过1H-NMR在通常的评价条件(溶剂:DMSO-d6、测定温度:60℃、测定频率:500MHz)下测定的头尾键接(2.87ppm)与头头键接(1.0ppm)的峰值之比。
进而,质均分子量(Mw)可以通过GPC(Gel Permeation Chromatography:凝胶渗透色谱法)进行测定。此时的测定条件例如为,洗脱液:N,N′-二甲基甲酰胺(含有10mmol/L溴化锂)、标准物质:聚环氧乙烷和聚乙二醇、柱温度:50℃。
另一方面,在PVDF树脂的分子链中的头尾键接与头头键接的比率R(=头尾键接/头头键接)超过11.5的情况下,或者,在PVDF树脂的质均分子量(Mw)不足1.30×105的情况下,制成薄膜时,在后述耐久性评价中,变色为黄色系的颜色的倾向变强,无法获得前述的效果。需要说明的是,从薄膜的制膜性的观点出发,PVDF树脂的键接比R优选为8.0以上,PVDF树脂的质均分子量(Mw)优选为2.00×105以下。
具有这种分子链结构和分子量的PVDF树脂的含量没有特别限定,相对于树脂成分的总质量优选为50质量%以上。由此,能够进一步提高抑制黄变的效果。
本实施方式的树脂组合物中,也可以与前述的PVDF树脂一起还含有甲基丙烯酸酯系树脂。该情况下,理想的是,甲基丙烯酸酯系树脂的配混量相对于树脂成分总质量为5~50质量%。通过像这样配混甲基丙烯酸酯系树脂,能够提高与其它原材料的粘接性。
本实施方式的树脂组合物中配混的甲基丙烯酸酯系树脂是指甲基丙烯酸甲酯的均聚物或甲基丙烯酸甲酯与其它单体(不足50质量%)的共聚物。作为能够与甲基丙烯酸甲酯共聚的单体,例如可列举出碳原子数为2~4的甲基丙烯酸酯;丙烯酸甲酯、丙烯酸丁酯等碳原子数1~8的丙烯酸酯;苯乙烯、α-甲基苯乙烯、丙烯腈、丙烯酸及其它烯属不饱和单体等。
需要说明的是,本实施方式的树脂组合物还可以在不损害本发明的效果的范围内根据需要配混除前述具有特定的分子链结构和分子量的PVDF树脂以外的PVDF树脂、除甲基丙烯酸酯系树脂以外的树脂。
[抗氧化剂]
本实施方式的树脂组合物中,与前述具有特定的分子链结构和分子量的PVDF树脂共同配混抗氧化剂。由此,在用于太阳能电池用的背面保护片时,在长期的耐湿热性的耐久性评价中,能够显著地抑制黄色系的变色。本实施方式的树脂组合物中配混的抗氧化剂可以是具有作为自由基捕获剂的作用的酚系抗氧化剂、具有作为过氧化物分解剂的作用的亚磷酸酯系抗氧化剂中的任意种,通过将它们组合使用,能够期待协同效应。
作为酚系抗氧化剂的具体例,可列举出2,6-二叔丁基-4-甲基苯酚、正十八烷基-3-(3’,5’-二叔丁基-4’-羟基苯基)丙酸酯、四-[亚甲基-3-(3’,5’-二叔丁基-4-羟基苯基)丙酸酯]甲烷、三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯、三乙二醇-双-[3-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯]、2,2’-亚甲基双-(4-甲基-6-叔丁基苯酚)、4-4’-硫代双-(3-甲基-6-叔丁基苯酚)、4-4’-丁叉基双-(3-甲基-6-叔丁基苯酚)等。
另外,作为亚磷酸酯系抗氧化剂,可列举出三壬基苯基亚磷酸酯、二硬脂基季戊四醇二亚磷酸酯、三(2,4-二叔丁基苯基亚磷酸酯、四(2,4-二叔丁基苯基)-4,4’-亚联苯基二亚磷酸酯等。
进而,抗氧化剂的配混量没有特别限定,从抑制黄变的效果和制造成本的观点出发,相对于树脂成分100质量份,优选设为0.01~5质量份,更优选设为0.1~2质量份。
[氧化钛]
本实施方式的树脂组合物中也可以配混氧化钛。PVDF树脂由于耐候性优异,因此能够充分地确保树脂薄膜自身的耐候性,通过配混氧化钛,在用于太阳能电池用背板时,能够提高太阳光的反射率、提高太阳能电池组件的发电效率。
其中,氧化钛的配混量相对于树脂成分100质量份不足5质量份时,可能无法充分地获得提高太阳光的反射率的效果。另外,相对于100质量份树脂成分配混超过30质量份的氧化钛时,可能在树脂组合物中的分散变得不均一、或薄膜的制膜困难。因此,在配混氧化钛时,相对于100质量份树脂成分优选设为5~30质量份。
作为在本实施方式的树脂组合物中配混的氧化钛,优选为通过氯化物法或硫酸盐法而得到的金红石型或锐钛矿型晶体形态的氧化钛。例如,在通过氯化物法制造氧化钛的情况下,将TiCl4氧化而制成TiO2颗粒。另外,在通过硫酸盐法制造氧化钛(TiO2)的情况下,将硫酸和含钛的矿石溶解,使所得溶液经由一系列工序而生成TiO2。
在实用方面,理想的是,使用因耐候性劣化而导致的着色少的金红石型的晶体结构的氧化钛。另外,为了提高树脂组合物中的分散性、且降低树脂分解作用,特别优选在最外侧表面形成有无机覆盖层的氧化钛。
氧化钛的粒径以通过沉降法算出的平均粒径计优选为0.05~2.0μm。这是因为,氧化钛的粒径小于0.05μm时,会因可见光的透射而显示透明性,另外,氧化钛的粒径超过2μm时,在树脂组合物中的分散性劣化而变得容易聚集。
需要说明的是,本实施方式的树脂组合物中,除了前述的氧化钛以外,作为无机颜料,可以配混氧化锌、硫化锌或硫酸钡等,另外,为了提高遮蔽性,也可以配混除氧化钛以外的金属氧化物。进而,本实施方式的树脂组合物中,除了前述的各成分以外,还可以添加抗氧化剂、分散剂、偶联剂、热稳定剂、表面活性剂、抗静电剂、防雾剂以及紫外线吸收剂等。
如上详述那样,本实施方式的偏氟乙烯系树脂组合物由于含有具有特定的分子链结构和分子量的PVDF树脂、以及抗氧化剂,因此能够获得以下的偏氟乙烯系树脂薄膜,该薄膜的制膜性优异,即使在直接层叠于EVA系密封材料的情况下,在耐湿热性的耐久性评价中也不易产生黄变。
(第二实施方式)
接着,针对本发明的第二实施方式的偏氟乙烯系树脂薄膜(以下也简称为树脂薄膜。)进行说明。本实施方式的树脂薄膜是将前述第一实施方式的树脂组合物制膜而得到的,其厚度为10~200μm。需要说明的是,树脂薄膜的厚度不足10μm时,有时机械强度不足,另外,超过200μm时,制膜性降低。
[制造方法]
本实施方式的树脂薄膜的制造方法没有特别限定,可以将第一实施方式的树脂组合物通过例如熔融挤出成形等一般的方法进行制膜。各种制膜方法之中,优选的是,通过挤出机使用薄膜用T模具进行制膜的方法。另外,原料可以使用进行了熔融混炼的树脂组合物,也可以将各原料配混后直接供给到单螺杆或双螺杆的挤出机,以例如150~260℃的温度将它们熔融,通过薄膜用T模具挤出,从而进行制膜。
本实施方式的偏氟乙烯系树脂薄膜由于含有具有特定的分子链结构和分子量的PVDF树脂、以及抗氧化剂,因此即使在直接层叠于EVA系密封材料的情况下,也能够抑制碱性气氛的产生。因此,本实施方式的偏氟乙烯系树脂薄膜即使在高温/高湿的环境下进行长期耐久性试验,也不易黄变,作为太阳能电池的背板用是极其有用的。
(第三实施方式)
接着,针对本发明的第三实施方式的太阳能电池用背板(以下也简称为背板。)进行说明。本实施方式的背板是通过将前述的第二实施方式的偏氟乙烯系树脂薄膜与例如聚对苯二甲酸乙二醇酯(PET)系薄膜等电绝缘性树脂薄膜层叠并贴合而得到的。
需要说明的是,这些薄膜的贴合可以利用各种粘接剂进行粘接。另外,PET系薄膜等其它树脂薄膜是出于对背板赋予电绝缘性、遮蔽性、水蒸汽阻隔性(防湿性)的目的而层叠的。
本实施方式的背板由于使用偏氟乙烯系树脂薄膜,且该薄膜含有具有特定的分子链结构和分子量的PVDF树脂、以及抗氧化剂,因此即使在直接层叠于EVA系密封材料的情况下,也能够抑制碱性气氛的产生。因此,即使进行长时间的耐湿热性的耐久性评价,与EVA系密封材料接触的面的黄变程度也极小。
(第四实施方式)
接着,针对本发明的第四实施方式的太阳能电池组件进行说明。图1是本实施方式的太阳能电池组件的结构的示意性剖视图。如图1所示,本实施方式的太阳能电池组件10的光伏元件即太阳能电池单元5被EVA系密封材料2密封。
并且,被太阳光6照射的面层叠有由玻璃等制成的透明基板1,背面侧层叠有前述第三实施方式的背板3,它们的周围设置有框架4。需要说明的是,EVA系密封材料2与背板3可以通过100~150℃的加热压制进行贴合。
关于本实施方式的太阳能电池组件10,由于背板3使用了含有具有特定的分子链结构和分子量的PVDF树脂、以及抗氧化剂的偏氟乙烯系树脂薄膜,因此尽管背板3直接层叠于EVA系密封材料2,在耐湿热性的耐久性评价中也能够抑制背板3的黄变。
实施例
以下,列举出本发明的实施例和比较例,对本发明的效果进行说明。本实施例中,通过以下示出的方法制作实施例和比较例的偏氟乙烯系树脂薄膜,对其耐湿热性进行评价。
<原料>
(1)偏氟乙烯(PVDF)树脂
作为PVDF树脂,使用下述表1示出的树脂。需要说明的是,下述表1所示的No.A~F的PVDF树脂均为均聚物。
[表1]
(2)甲基丙烯酸酯系树脂(Mitsubishi Rayon Co.,Ltd.制HIPETHBS000):
包含丙烯酸丁酯(n-BA)和甲基丙烯酸丁酯(BMA)的橡胶成分的甲基丙烯酸酯系树脂。MFR(230℃、10kg载重)为4~7g/10分钟。
(3)氧化钛(Dupont Corporation制R960):
粒径为约0.35μm。纯钛成分为约89质量%。
(4)抗氧化剂(ADEKA CORPORATION制2112):
亚磷酸酯系抗氧化剂
<评价试样的制作方法>
(实施例1)
首先,通过φ30mm的双螺杆挤出机对相对于100质量份No.A的偏氟乙烯树脂配混有22质量份氧化钛、1质量份抗氧化剂的混合物进行混炼,制作复合物。接着,利用φ40mm的单螺杆挤出机以250℃的挤出温度使用T模具将该复合物进行薄膜成形,得到厚度为30μm的薄膜。
(实施例2)
使用相对于含有80质量%No.A的偏氟乙烯树脂、20质量%甲基丙烯酸酯系树脂的树脂成分100质量份配混有22质量份氧化钛、1质量份抗氧化剂的混合物,用与前述实施例1同样的方法和条件得到厚度为30μm的薄膜。
(实施例3)
除了使用No.B的偏氟乙烯树脂以外,用与前述实施例2同样的方法和条件得到厚度为30μm的薄膜。
(比较例1)
除了使用No.C的偏氟乙烯树脂以外,用与前述实施例2同样的方法和条件得到厚度为30μm的薄膜。
(比较例2)
除了不配混抗氧化剂以外,用与前述实施例3同样的方法和条件得到厚度为30μm的薄膜。
(比较例3~5)
除了使用No.D~F的偏氟乙烯树脂以外,用与前述实施例2同样的方法和条件得到厚度为30μm的薄膜。
<评价方法>
(PVDF树脂特性)
(1)比率R(头尾键接/头头键接)
针对实施例和比较例中使用的No.A~F的PVDF树脂,通过下述的测定器和测定条件下进行评价,通过2.87ppm的峰值与1.0ppm的峰值的比率,算出头尾键接与头头键接之比(R值)。
·测定器:NMR(BrukerAVANCEIII500)
·核种:1H(-NMR)
·溶剂:DMSO-d6
·测定温度:60℃
·测定频率:500MHz
(b)质均分子量(Mw)
针对实施例和比较例中使用的No.A~F的PVDF树脂,使用GPC装置用下述测定条件进行评价。
·柱:ShodexGPC KD-806×2+KD802
·洗脱液:N,N′-二甲基甲酰胺(溴化锂:含有10mmol/L)
·标准物质:聚环氧乙烷和聚乙二醇
·柱温度:50℃
(薄膜的耐湿热性)
从通过前述方法制作的实施例和比较例的树脂薄膜中切出10cm见方的试样,利用加压机在加热温度230℃、压力5MPa的条件下,将其与太阳能电池组件用EVA树脂薄膜(EVA系密封材料)贴合,从而制作层叠物。然后,针对这些试样,作为耐湿热性评价,基于JIS C8990,使用环境试验仪在温度85℃±2℃、相对湿度85%±5%的条件下进行1000小时的湿热试验(damp heattest)。
然后,对于EVA贴合面的薄膜的黄变度,基于JIS K7105进行色差测定,算出ΔYI(黄色指数)值,根据该值进行评价。此时,如果ΔYI值为10以下则判断为实用上不存在问题的水平。将其结果总结示于下述表2。
[表2]
如上述表2所示那样,与比较例1~5的树脂薄膜相比,在本发明范围内制作的实施例1~3的树脂薄膜的黄变度大幅降低。具体而言,分别比较所使用的PVDF树脂的头尾键接与头头键接之比(R)显示为近似值的实施例2与比较例1、实施例3与比较例3时,与PVDF树脂的质均分子量不足1.30×105的比较例1、3相比,PVDF树脂的质均分子量为1.30×105以上的实施例2、3的黄变度少。
另外,比较所使用的PVDF树脂的分子量显示近似值的实施例3与比较例4时,与PVDF树脂的头尾键接与头头键接之比(R)超过11.5的比较例4相比,PVDF树脂的头尾键接与头头键接之比(R)为11.5以下的实施例3的黄变度少。
由以上结果可以确认:根据本发明,能够实现即使在直接层叠于由乙烯醋酸乙烯酯共聚物树脂形成的密封材料的情况下,在耐湿热性的耐久性评价中也不易发生黄变的偏氟乙烯系树脂薄膜。
附图标记说明
1 透明基板
2 EVA系密封材料
3 背板
4 框架
5 太阳能电池单元
6 太阳光
10 太阳能电池组件
Claims (8)
1.一种偏氟乙烯系树脂组合物,其至少含有偏氟乙烯树脂和抗氧化剂,
所述偏氟乙烯树脂的通过1H-NMR测定的头尾键接与头头键接的峰值之比即头尾键接/头头键接为11.5以下、质均分子量(Mw)为1.30×105以上。
2.根据权利要求1所述的偏氟乙烯系树脂组合物,其特征在于,相对于树脂成分总质量,含有50质量%以上的所述偏氟乙烯树脂。
3.根据权利要求1或2所述的偏氟乙烯系树脂组合物,其特征在于,相对于100质量份树脂成分,含有0.01~5质量份的所述抗氧化剂。
4.根据权利要求2或3所述的偏氟乙烯系树脂组合物,其特征在于,相对于树脂成分总质量,含有5~50质量%的甲基丙烯酸酯系树脂。
5.根据权利要求1~4中任一项所述的聚偏氟乙烯系树脂组合物,其特征在于,相对于100质量份树脂成分,含有5~30质量份的氧化钛。
6.一种偏氟乙烯系树脂薄膜,其由权利要求1~5中任一项所述的偏氟乙烯系树脂组合物制成,厚度为10~200μm。
7.一种太阳能电池组件用背板,其使用了权利要求6所述的偏氟乙烯系树脂薄膜。
8.一种太阳能电池组件,其使用了权利要求7所述的背板。
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