CN105462238B - 一种用于光伏电池的挤出型背板及其制备方法 - Google Patents

一种用于光伏电池的挤出型背板及其制备方法 Download PDF

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CN105462238B
CN105462238B CN201511019415.4A CN201511019415A CN105462238B CN 105462238 B CN105462238 B CN 105462238B CN 201511019415 A CN201511019415 A CN 201511019415A CN 105462238 B CN105462238 B CN 105462238B
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fire retardant
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CN105462238A (zh
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罗吉江
符书臻
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New Materials Co Ltdsuzhou Duchamps
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Abstract

本发明公开了一种用于光伏电池的挤出型背板，包括上表层、芯层和下表层；其中，所述上表层由聚酰胺树脂、填料、阻燃剂、添加剂组成；芯层由聚丙烯树脂和接枝聚乙烯改性的聚酰胺树脂、填料、阻燃剂、添加剂组成；下表层由聚酰胺树脂、阻燃剂、偶联剂、添加剂组成；阻燃剂由表面处理过的纳米级无机阻燃剂和红磷组成；纳米级无机阻燃剂选自10~100nm的氢氧化铝和/或氢氧化镁；所使用的表面处理剂为1~5nm的乙烯基笼型聚倍半硅氧烷。本发明的挤出型背板的阻燃效果良好，燃烧测试后达到A级；还能够保证阻燃剂对该挤出型背板的力学性能、耐老化性能、阻水性能、绝缘性能等无影响。

Description

一种用于光伏电池的挤出型背板及其制备方法
技术领域
本发明涉及一种用于光伏电池的挤出型背板及其制备方法。
背景技术
随着不可再生能源的衰竭及愈发严重的环境问题，作为清洁能源的太阳能受到前所未有的关注和重视。太阳能发电(又称为光伏发电)是有效利用太阳能的主要途径之一，而作为太阳能发电的核心部件，太阳能电池组件的可靠性直接决定了太阳能发电的效能。
光伏组件主要由低铁钢化玻璃、热塑性封装胶膜、电池片串、热塑性封装胶膜、背板共五层结构层压封装而成。在实际使用过程中，有可能由于组件材料存在缺陷、系统设计缺陷及热斑效应等原因导致组件起火，造成不可估量的经济损失和环境破坏，因此要对背板进行防火处理。
当前市场上的背板主要有涂覆型背板、复合型背板及共挤出型背板，其中，涂覆型背板和复合型背板主要是将氟碳涂料或氟膜与PET基材结合，通过对PET基材进行改性来达到阻燃效果。例如，公开号为CN103262259A的专利公开了一种光伏组件用阻燃背板，通过用结晶矿物质硅酸盐薄片如云母、蛭石、煅烧粘土、二氧化硅、滑石粉、硅钙石及其组合对基体层改性，制成阻燃片材后附着氟膜制成背板。又如，公告号为CN204257675U的实用新型专利公开了一种阻燃型太阳能电池背板，包括阻燃基材层和涂布于阻燃基材层两面的含氟涂层共三层结构。然而，上述方案中主要通过对背板中的PET基材进行阻燃改性，导致背板电性能及机械性能下降，影响背板整体的封装效果，降低组件的使用寿命。
而对于挤出型背板，中国发明专利CN103057223A公开了一种聚酰胺太阳能背板，通过多层共挤装置将内表层、芯层和外表层进行三层共挤得到背板材料。然而，其并没有关于阻燃性的内容记载。
因此，有必要开发一种具有极佳阻燃性的挤出型背板，同时满足背板的力学性能，以满足太阳能电池组件的使用要求。
发明内容
本发明的发明目的是提供一种用于光伏电池的挤出型背板及其制备方法。
为达到上述发明目的，本发明采用的技术方案是：一种用于光伏电池的挤出型背板，包括上表层、芯层和下表层，所述上表层、芯层和下表层的质量比为10～20：60～80：10～20；
其中，所述上表层由聚酰胺树脂、填料、阻燃剂、添加剂组成；
所述芯层由聚丙烯树脂和接枝聚乙烯改性的聚酰胺树脂、填料、阻燃剂、添加剂组成；
所述下表层由聚酰胺树脂、阻燃剂、偶联剂、添加剂组成；
所述添加剂由抗氧剂、紫外吸收剂、光稳定剂组成；
所述填料选自玻璃纤维、碳纤维、钛白粉和云母中的一种或几种；
所述阻燃剂由表面处理过的纳米级无机阻燃剂和红磷组成；所述纳米级无机阻燃剂选自10～100nm的氢氧化铝和/或氢氧化镁；所使用的表面处理剂为1～5nm的乙烯基笼型聚倍半硅氧烷；
所述偶联剂为硅烷偶联剂或钛酸酯偶联剂。
本发明的挤出型背板是三层共挤结构，每一层均加入阻燃剂进行阻燃改性，在不降低背板原有性能的基础上，提高阻燃性能；尤其是还能够保证背板对组件的封装效果，耐老化性能和力学性能略有提升。
所述红磷配合氢氧化铝、氢氧化镁等无机阻燃剂使用，具有较好的协效性，可以有效的抑制聚合物燃烧时产生烟雾。
所述填料选自5～20微米的玻璃纤维、碳纤维、钛白粉或云母中的一种或几种。
紫外吸收剂与光稳定剂配合使用，对背板的抗紫外老化性能具有良好的协效性。
上述技术方案中，所述抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂264、抗氧剂164、抗氧剂DNP或抗氧剂CA。
上述技术方案中，所述紫外吸收剂为邻羟基苯甲酸苯酯、2，4-二羟基二苯甲酮、2-羟基-4-正辛氧基二苯甲酮或2-(2′-羟基-3′，5′-二叔苯基)-5-氯化苯并三唑。
上述技术方案中，所述光稳定剂为三(1，2，2，6，6-五甲哌啶基)亚磷酸酯、4-苯甲酰氧基-2，2，6，6-四甲基哌啶或六甲基磷酰三胺。
上述技术方案中，所述填料为经过表面活性处理的填料，所使用的处理剂为硅烷偶联剂。
上述技术方案中，所述上表层各组分以质量计量为：聚酰胺树脂65～85份、填料0～15份、抗氧剂0.1～1份、紫外吸收剂0.05～0.5份、光稳定剂0.1～0.5份、阻燃剂5～40份；
所述芯层各组分以质量计量为：聚酰胺树脂5～75份、聚丙烯树脂5～75份、接枝聚乙烯树脂5～50份、填料0～15份、抗氧剂0.1～1份、紫外吸收剂0.05～0.5份、光稳定剂0.1～0.5份、阻燃剂5～40份；
所述下表层各组分以质量计量为：聚酰胺树脂70～85份、填料0～15份、抗氧剂0.1～1份、紫外吸收剂0.05～0.5份、光稳定剂0.1～0.5份、阻燃剂5～40份、偶联剂0.5～1份。
本发明同时请求保护一种挤出型背板的制备方法，包括如下步骤：按上述的配比将上表层、芯层和下表层的物料分别加入到三层共挤出片材机组的A螺杆、B螺杆以及C螺杆中，同时在螺杆挤出机熔融挤出，经流延、冷却、牵引、卷取即得到所述用于光伏电池的挤出型背板。
本发明的机理如下：通过对多层共挤背板中的每一层结构都添加纳米无机阻燃剂及笼型聚倍半硅氧烷进行改性；使用纳米无机阻燃剂氢氧化铝、氢氧化镁等一方面可以提高聚合物的力学性能，另一方面具有较好的阻燃性和抑烟性，氢氧化物在燃烧时受热分解吸收大量的热量，使聚合物表面温度降低，同时分解产生水蒸汽有蓄热和释放高分子表面气体浓度的作用；但是，纳米材料易出现团聚现象，因此添加笼型聚倍半硅氧烷进行处理；笼型聚倍半硅氧烷是以SI-O交替连接的硅氧骨架组成无机内核，形成八个以硅原子为顶角的六面体，每个硅原子上所连接的基团可以是惰性基团或反应性基团，其中反应性基团可以与聚合物分子发生接枝或聚合反应，实现分子级分散，提高聚合物性能。本发明使用的是乙烯基笼型聚倍半硅氧烷，乙烯基笼型聚倍半硅氧烷可以与聚合物进行接枝反应，同时增加纳米阻燃剂与聚合物的相容性，使纳米阻燃剂分散性好，减少纳米材料易团聚的缺点；同时，笼型聚倍半硅氧烷结合纳米材料改性聚合物，可以提高复合物的力学性能，并能使复合材料有效的延迟燃烧，增加材料的阻燃性能。
由于上述技术方案运用，本发明与现有技术相比具有下列优点：
1.本发明设计了一种三层共挤结构的挤出型背板，每一层均加入阻燃剂进行阻燃改性，在不降低背板原有性能的基础上，提高了阻燃性能，实验证明：本发明的挤出型背板的阻燃效果良好，燃烧测试后达到A级；此外，还能够保证阻燃剂对该挤出型背板的力学性能、耐老化性能、阻水性能、绝缘性能等无影响，使背板不仅具有极佳的阻燃性，而且还具有良好的力学性能、耐老化性能、阻水性能、绝缘性能，可以满足太阳能电池组件的使用要求；
2.实验证明，本发明所使用的纳米级无机阻燃剂对挤出型背板的力学性能有增益效果，取得了显著的效果；
3.本发明的制备方法简单易行，适于推广应用。
具体实施方式
下面结合实施例对本发明作进一步描述：
实施例一
一种用于光伏电池的挤出型背板，其制备方法如下：
(1)填料的表面处理：称取一定量的硅烷偶联剂KH550(为玻璃纤维质量的1％)，加入少量乙醇水溶液；称取玻璃纤维放置于高速混合机中，在高速搅拌的同时升温至60℃，逐滴加入偶联剂溶液；滴加完毕后继续高速混合20min；混合完毕后将处理好的玻璃纤维取出，在鼓风干燥箱内120℃下干燥1h，备用；
(2)纳米阻燃剂的制备：在容器中加入乙醇，将其加热到60℃，然后在搅拌下依次加入水和一定量的笼型聚倍半硅氧烷，水和笼型聚倍半硅氧烷的摩尔比为3:1；在搅拌分散1min后，将纳米氢氧化铝加入，继续在60℃搅拌30min；然后先在60～70℃去除液体，去除液体后再在鼓风干燥箱内120℃下干燥1h，得到表面处理的纳米氢氧化铝，备用；
(3)改性聚酰胺树脂的制备：将25份聚酰胺树脂、65份聚丙烯树脂、5份接枝聚乙烯树脂高速混合均匀，经双螺杆挤出机180～240℃熔融挤出造粒，得到改性聚酰胺树脂备用；
挤出型阻燃背板的制备：将70份的聚酰胺树脂加入干燥器，在80℃条件下干燥4小时后投入高速搅拌机中，加入3份钛白粉、7份处理过的玻璃纤维、1份抗氧剂1010、0.5份2，4-二羟基二甲苯苯酮、0.3份六甲基磷酰三胺、15份表面处理过的纳米氢氧化铝、6份红磷，搅拌30分钟，转速500～700r/min，将物料充分混合均匀；将混合好的物料投入三层共挤出机组的A螺杆；
将75份制好的改性聚酰胺树脂加入干燥器内，在80℃条件下干燥4小时，然后投入到高速混合机中，加入1.5份的钛白粉、4.5份处理过的玻璃纤维、3份红磷、0.5份的抗氧剂1010、0.5份的2，4-二羟基二甲苯酮、0.3份的六甲基磷酰三胺、15份表面处理过的纳米氢氧化铝，搅拌30min，转速500～700r/min，将物料混合均匀；将混合好的物料投入到三层共挤出机组的B螺杆；
将75份的聚酰胺树脂加入干燥器，在80℃条件下干燥4小时后投入高速搅拌机中，加入1份钛白粉、7份表面处理过的玻璃纤维、1份抗氧剂1010、0.5份2，4-二羟基二甲苯苯酮、0.3份六甲基磷酰三胺、15份表面处理过的纳米氢氧化铝、2份红磷，0.5份硅烷偶联剂KH550，搅拌30分钟，转速500～700r/min，将物料充分混合均匀；将混合好的物料投入三层共挤出机组的C螺杆；
将三种物料同时在180～240℃的螺杆挤出机中熔融挤出，螺杆控制转速为85～110r/min，物料在螺杆内停留大约3～5min，上表层、芯层、下表层三种物料通过分配器按质量比20：60：20进行分配，进入模具后经冷却、牵引、卷取等工序得到成品S1，检测结果见表1。
实施例二
一种挤出型阻燃背板，其制备方法如下：
(1)填料的表面处理：称取一定量的硅烷偶联剂KH550(为碳纤维质量的1％)，加入少量乙醇水溶液；称取碳纤维放置于高速混合机中，在高速搅拌的同时升温至60℃，逐滴加入偶联剂溶液；滴加完毕后继续高速混合20min；混合完毕后将处理好的碳纤维取出，在鼓风干燥箱内120℃下干燥1h，备用；
(2)纳米阻燃剂的制备：在容器中加入乙醇，将其加热到60℃，然后在搅拌下依次加入水和一定量的笼型聚倍半硅氧烷，水和笼型聚倍半硅氧烷的摩尔比为3:1；在搅拌分散1min后，将纳米氢氧化镁加入，继续在60℃搅拌30min；然后先在60～70℃去除液体，去除液体后再在鼓风干燥箱内120℃下干燥1h，得表面处理的纳米氢氧化镁，备用；
(3)改性聚酰胺树脂的制备：将35份聚酰胺树脂、50份聚丙烯树脂、10份接枝聚乙烯树脂高速混合均匀，经双螺杆挤出机180～240℃熔融挤出造粒，得到改性聚酰胺树脂备用；
挤出型阻燃背板的制备：将70份的聚酰胺树脂加入干燥器，在80℃条件下干燥4小时后投入高速搅拌机中，加入1份钛白粉、5份处理过的碳纤维、1份抗氧剂1076、0.7份邻羟基苯甲酸苯酯、0.2份三(1，2，2，6，6-五甲哌啶基)亚磷酸酯、20份表面处理过的纳米氢氧化镁、5份红磷，搅拌30分钟，转速500～700r/min，将物料充分混合均匀；将混合好的物料投入三层共挤出机组的A螺杆；
将75份制好的改性聚酰胺树脂加入干燥器内，在80℃条件下干燥4小时，然后投入到高速混合机中，加入1.5份的钛白粉、5.5份处理过的碳纤维、0.5份的抗氧剂1076、0.5份邻羟基苯甲酸苯酯、0.3份三(1，2，2，6，6-五甲哌啶基)亚磷酸酯、15份表面处理过的纳米氢氧化镁、3份红磷，，搅拌30min，转速500～700r/min，将物料混合均匀；将混合好的物料投入到三层共挤出机组的B螺杆；
将85份的聚酰胺树脂加入干燥器，在80℃条件下干燥4小时后投入高速搅拌机中，加入2份钛白粉、6份表面处理过的碳纤维、1份抗氧剂1076、0.7份邻羟基苯甲酸苯酯、0.2份三(1，2，2，6，6-五甲哌啶基)亚磷酸酯、5份表面处理过的纳米氢氧化镁、1份红磷，，0.5份硅烷偶联剂KH550，搅拌30分钟，转速500～700r/min，将物料充分混合均匀；将混合好的物料投入三层共挤出机组的C螺杆；
将三种物料同时在180～240℃的螺杆挤出机中熔融挤出，螺杆控制转速为85～110r/min，物料在螺杆内停留大约3～5min，上表层、芯层、下表层三种物料通过分配器按质量比20：60：20进行分配，进入模具后经冷却、牵引、卷取等工序得到成品S2，检测结果见表1。
对比例一
一种挤出型背板，其制备方法如下：
(1)改性聚酰胺树脂的制备：将25份聚酰胺树脂、75份聚丙烯树脂、5份接枝聚乙烯树脂高速混合均匀，经双螺杆挤出机180～240℃熔融挤出造粒，得到改性聚酰胺树脂备用。
挤出型背板的制备：将90份的聚酰胺树脂加入干燥器，在80℃条件下干燥4小时后投入高速搅拌机中，加入3份钛白粉、7份玻璃纤维、1份抗氧剂1010、0.5份2，4-二羟基二甲苯苯酮、0.3份六甲基磷酰三胺，搅拌30分钟，转速500～700r/min，将物料充分混合均匀；将混合好的物料投入三层共挤出机组的A螺杆；
将95份制好的改性聚酰胺树脂加入干燥器内，在80℃条件下干燥4小时，然后投入到高速混合机中，加入1.5份钛白粉、4.5份玻璃纤维、0.5份抗氧剂1010、0.5份2，4-二羟基二甲苯酮、0.3份六甲基磷酰三胺，搅拌30min，转速500～799r/min，将物料混合均匀；将混合好的物料投入到三层共挤出机组的B螺杆；
将90份的聚酰胺树脂加入干燥器，在80℃条件下干燥4小时后投入高速搅拌机中，加入3份钛白粉、7份玻璃纤维、1份抗氧剂1010、0.5公斤2，4-二羟基二甲苯苯酮、0.3份六甲基磷酰三胺、0.5份硅烷偶联剂KH550，搅拌30分钟，转速500～700r/min，将物料充分混合均匀；将混合好的物料投入三层共挤出机组的C螺杆；
将三种物料同时在180～240℃的螺杆挤出机中熔融挤出，螺杆控制转速为85～110r/min，物料在螺杆内停留大约3～5min，上表层、芯层、下表层三种物料通过分配器按质量比20：60：20进行分配，进入模具后经冷却、牵引、卷取等工序得到成品B1，检测结果见表1。
表1 实施例及对比例中各背板的性能表征
由上表可见，本发明的挤出型背板的阻燃效果良好，燃烧测试后达到A级；此外，还能够保证阻燃剂对该挤出型背板的力学性能、耐老化性能、阻水性能、绝缘性能等无影响，使背板不仅具有极佳的阻燃性，而且还具有良好的力学性能、耐老化性能、阻水性能、绝缘性能，可以满足太阳能电池组件的使用要求。
上述各实施例及对比例中的表征方法采用如下标准：
收缩率 CQC3308光伏组件封装用背板认证技术规范；
吸水率 GB/T 1034塑料吸水性试验方法；
水蒸气透过率 GB/T 21529塑料薄膜和薄片水蒸气透过率的测定；
湿热老化 CQC3308光伏组件封装用背板认证技术规范；
体积电阻率 GB/T 1410固体绝缘材料体积电阻率和表面电阻率试验方法。
局部放电测试/V CQC3308光伏组件封装用背板认证技术规范
与EVA剥离强度 CQC3308光伏组件封装用背板认证技术规范
阻燃性能 GB/T 2408塑料燃烧性能的测定。

Claims (4)

1.一种用于光伏电池的挤出型背板，包括上表层、芯层和下表层，其特征在于：所述上表层、芯层和下表层的质量比为10~20：60~80：10~20；
其中，所述上表层由聚酰胺树脂、填料、阻燃剂、添加剂组成；
所述芯层由聚丙烯树脂和接枝聚乙烯改性的聚酰胺树脂、填料、阻燃剂、添加剂组成；
所述下表层由聚酰胺树脂、阻燃剂、偶联剂、添加剂、填料组成；
所述添加剂由抗氧剂、紫外吸收剂、光稳定剂组成；
所述填料选自玻璃纤维、碳纤维、钛白粉和云母中的一种或几种；
所述阻燃剂由表面处理过的纳米级无机阻燃剂和红磷组成；所述纳米级无机阻燃剂选自10~100nm的氢氧化铝和/或氢氧化镁；所使用的表面处理剂为1~5nm的乙烯基笼型聚倍半硅氧烷；
所述偶联剂为硅烷偶联剂或钛酸酯偶联剂；
所述上表层各组分以质量计量为：聚酰胺树脂65~85份、填料0~15份、抗氧剂0.1~1份、紫外吸收剂0.05~0.5份、光稳定剂0.1~0.5份、阻燃剂5~40份；
所述芯层各组分以质量计量为：聚酰胺树脂5~75份、聚丙烯树脂5~75份、接枝聚乙烯树脂5~50份、填料0~15份、抗氧剂0.1~1份、紫外吸收剂0.05~0.5份、光稳定剂0.1~0.5份、阻燃剂5~40份；
所述下表层各组分以质量计量为：聚酰胺树脂70~85份、填料0~15份、抗氧剂0.1~1份、紫外吸收剂0.05~0.5份、光稳定剂0.1~0.5份、阻燃剂5~40份、偶联剂0.5~1份；
所述紫外吸收剂为邻羟基苯甲酸苯酯、2，4-二羟基二苯甲酮、2-羟基-4-正辛氧基二苯甲酮或2-（2′-羟基-3′，5′-二叔苯基）-5-氯化苯并三唑；
所述光稳定剂为三（1，2，2，6，6-五甲哌啶基）亚磷酸酯、4-苯甲酰氧基-2，2，6，6-四甲基哌啶或六甲基磷酰三胺。
2.根据权利要求1所述的用于光伏电池的挤出型背板，其特征在于：所述抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂264、抗氧剂164、抗氧剂DNP或抗氧剂CA。
3.根据权利要求1所述的用于光伏电池的挤出型背板，其特征在于：所述填料为经过表面活性处理的填料，所使用的处理剂为硅烷偶联剂。
4.一种如权利要求1所述的挤出型背板的制备方法，其特征在于，包括如下步骤：按权利要求1所述的配比将上表层、芯层和下表层的物料分别加入到三层共挤出片材机组的A螺杆、B螺杆以及C螺杆中，同时在螺杆挤出机熔融挤出，经流延、冷却、牵引、卷取即得到所述用于光伏电池的挤出型背板。
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