CN110077073A - 一种聚烯烃膜、制备方法及太阳能电池背板 - Google Patents

一种聚烯烃膜、制备方法及太阳能电池背板 Download PDF

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CN110077073A
CN110077073A CN201910267170.9A CN201910267170A CN110077073A CN 110077073 A CN110077073 A CN 110077073A CN 201910267170 A CN201910267170 A CN 201910267170A CN 110077073 A CN110077073 A CN 110077073A
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polyolefin
phosphate glass
polyolefin film
film according
film
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CN110077073B (zh
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司朋飞
赫茂垒
梁宏陆
邸喜强
田勇
董丽荣
张伊玮
景改峰
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Lucky Film Co Ltd
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Abstract

本发明涉及一种聚烯烃膜、制备方法及太阳能电池背板,所述聚烯烃膜为ABA三层结构,其中B层按如下重量份的组分制成:磷酸盐玻璃5‑20,聚烯烃50‑90,相容剂5‑20。本发明由于添加了钨‑锡‑氟磷酸盐玻璃填料,其片状结构能够有效阻隔水汽、氧气等有害气体的渗透,使得制成的背板阻隔性能显著提高,体系的相容性良好,提升了加工性能,能够满足光伏背板的全天候应用要求。

Description

一种聚烯烃膜、制备方法及太阳能电池背板
技术领域
本发明涉及薄膜技术领域,特别是一种聚烯烃薄膜。
背景技术
太阳能电池背板作为光伏组件的重要封装材料,其阻水性、阻氧性直接影响组件运行安全性、耐久性和发电效率;特别是应用于渔光互补等高湿环境时,水汽和氧气易于通过背板渗透进入组件内部,在长期运行过程中造成胶膜封装失效而产生脱层,因而对电池片和焊带造成侵蚀,从而严重降低光伏组件的发电效率和使用寿命。因此,为了进一步拓展光伏组件应用范围,亟需提高背板的阻隔性。
目前改善背板阻隔性的技术方案主要有在背板结构中设置金属阻隔层、在背板基材中添加层状粘土矿物等。中国专利CN104868003A公开了一种在背板中设置铝箔、铁箔、锡箔、锌箔等金属层作为阻隔层的技术方案,利用金属材料良好的阻隔性,提高了背板的水汽阻隔性,极大的降低了水汽透过率,但成本较高,并且很大程度上降低了背板的绝缘性能。中国专利CN106903959A在所用基材中添加纳米蒙脱土、云母片等无机填料改善背板水汽阻隔性,但效果有限,并且工艺复杂,不利于大量推广应用。
另外,还有在材料中添加磷酸盐玻璃来改善材料的阻隔性的技术方案。磷酸盐玻璃是一种具有网状结构的无机玻璃,通过掺杂不同的金属阳离子,可以调控其结构和玻璃化转变温度(Tg)等特性,常见的掺杂金属包括铅、锌、锡、钨等。其中锡-氟磷酸盐玻璃的Tg范围为55-155℃,在大多数聚合物的加工温度范围内以流体存在,因而易于通过熔融共混等常见工艺进行加工。在实际配方设计中,可根据所应用树脂对象的加工特性和制品使用环境条件,选择特定Tg的锡-氟磷酸盐玻璃。此外,引入钨元素还可提高制品的耐化学品性,满足腐蚀性较强场合的应用。锡氟磷酸盐玻璃可通过熔融挤出、拉伸等工艺调控其分散形态,实现聚合物材料增强和增加水汽、氧气阻隔性。例如,中国专利CN106867239A制备了一种极性聚合物/磷酸盐玻璃复合材料,用于提高聚烯烃材料阻氧性和韧性,但存在以下几点不足:首先,无机的锡-氟磷酸盐玻璃未经过表面改性,与有机聚合物相容性差,导致分散性差;其次,极性聚合物母粒与非极性聚烯烃材料相容性差,用于改性聚烯烃材料加工难度大;再次,需要使用专用的层倍增器,此设备并非常规的聚合物加工设备,价格昂贵,不利于推广应用;最后,无机锡-氟磷酸盐材料的填充必然影响聚烯烃材料的粘结性,不满足作为光伏背板材料的应用要求。
发明内容
本发明用于克服上述已有技术之缺陷,提供一种聚烯烃膜、制备方法及太阳能电池背板,它通过硅烷表面处理或磺化技术增强无机玻璃与聚合物基体的相容性,同时使无机玻璃实现片状分散,达到满足光伏背板粘结层材料的应用要求和提高阻隔性的目的,除此之外,它还能有效降低所复合的太阳能背板的水汽和氧气透过率,以提高太阳能组件的运行效率和使用寿命。
本发明的技术问题是通过如下技术方案解决的。
一种聚烯烃膜,所述聚烯烃膜为ABA三层结构,其中B层按如下重量份的组分制成:
磷酸盐玻璃5-20,
聚烯烃50-90,
相容剂5-20。
上述聚烯烃膜,所述磷酸盐玻璃的玻璃化转变温度(Tg)范围为50℃-150℃,优选80℃-110℃。
上述聚烯烃膜,所述磷酸盐玻璃经过硅烷表面处理:将硅烷偶联剂配制成5-40wt%浓度的硅烷偶联剂溶液,然后按照磷酸盐玻璃:硅烷偶联剂=(50:1)—(5:1)的重量比混合搅拌,然后进行干燥,完成对磷酸盐玻璃的硅烷表面处理。
上述聚烯烃膜,所述磷酸盐玻璃中掺杂2.5-5重量份三氧化钨(WO3)以引入金属钨阳离子。
上述聚烯烃膜,所述聚烯烃为低密度聚乙烯、线性低密度聚乙烯、高密度聚乙烯、均聚聚丙烯或共聚聚丙烯,熔融指数为0.5-3.0g/10min。
上述聚烯烃膜,所述相容剂为马来酸酐接枝聚乙烯或马来酸酐接枝聚丙烯,接枝率为0.6%-3%。
上述聚烯烃膜,所述聚烯烃膜为共挤结构,其中A层含有89-97%的聚烯烃、0.2-2%的抗水解剂、0.5-3%的紫外吸收剂、0.5-1%的光稳定剂和0.5-5%的钛白粉或氧化镁等无机填料。
上述聚烯烃膜,所述B层厚度为10-60μm,所述A层厚度为10-60μm。
一种制备上述聚烯烃膜的方法,制备按如下步骤进行:
①将相容剂、磷酸盐玻璃粉末充分干燥,按一定配比称重并混合均匀,加入双螺杆挤出机在200-250℃进行熔融共混、造粒,制成母粒;
②将上述母粒与干燥后的聚烯烃熔融共混、造粒,制成B层材料;
③将B层材料加入用于挤出中间层的挤出机,将称量好的A层材料各组分加入用于挤出两侧层的挤出机,经熔融共挤、铸片,然后在磷酸盐玻璃的Tg以上的加工温度下进行双轴拉伸,使液态的磷酸盐玻璃在外界力场作用下变形取向,冷却后形成平行于膜表面的二维片状存在于聚合物基体中。
本发明还提供一种太阳能电池背板,所述太阳能电池背板使用上述任一项所述的聚烯烃膜。
有益效果:
1.本发明中的聚烯烃膜,由于添加了钨-锡-氟磷酸盐玻璃,其片状结构能够有效阻隔水汽、氧气等有害气体的渗透,使得制成的背板的阻隔性能显著提高,接近玻璃的阻隔水平,能够有效保护电池片和焊带等核心部件,提高组件运行效率和安全性,同时延长组件使用寿命;
2.本发明中的钨-锡-氟磷酸盐玻璃经过表面处理,相容剂以非极性的聚烯烃为主链,并接枝极性基团,使得体系的相容性良好,提升了加工性能;
3.本发明的聚烯烃膜为ABA三层共挤结构,在中间层两侧分别设置PET粘结层和EVA胶膜粘结层,保持了优异的粘结性能,能够满足光伏背板的全天候应用要求。
具体实施方式
本发明使用马来酸酐接枝聚烯烃作为相容剂,同时使用硅烷偶联剂对磷酸盐玻璃进行表面处理,改善了磷酸盐玻璃与聚烯烃材料的相容性,制备马来酸酐接枝聚烯烃/磷酸盐玻璃母粒,然后与聚烯烃材料进行共混挤出,在磷酸盐玻璃的Tg以上的温度范围进行双轴拉伸制成聚烯烃膜,冷却定型后磷酸盐玻璃以片状分散于聚烯烃基体内,这种共混材料具有较好的相容性,能够大幅提高聚烯烃材料的水汽阻隔性。
本发明中的磷酸盐玻璃使用5-20重量份。磷酸盐玻璃是提高聚烯烃阻隔性的关键组分,含量过低会对水汽阻隔的提升作用较差;含量过高将对制品的断裂伸长率等机械性能产生不利影响。
磷酸盐玻璃经硅烷偶联剂表面处理。硅烷偶联剂及表面处理工艺条件没有特殊要求,现有技术中常用的硅烷偶联剂及工艺条件都可用于本发明中。
本发明中的聚烯烃重量份数为50-90。聚烯烃质量份过少将降低制品整体极性,影响对极性水汽分子的阻隔性,质量份过大将减少磷酸盐玻璃的占比,同样不利于提高制品水汽阻隔性。
聚烯烃基体材料的熔融指数为0.5-3.0g/10min。熔融指数大于3.0g/10min的聚烯烃材料在双向拉伸环节不易加工成膜。
本发明中的相容剂重量份数为5-20,一般为马来酸酐接枝聚烯烃,接枝率0.6-3.0%。马来酸酐的接枝率过低,不能明显提高聚烯烃的极性,达不到增加相容性的目的;接枝率过高,将导致聚烯烃/磷酸盐玻璃复合材料制品整体的极性强,降低制品对水汽的阻隔性。
本发明使用的抗水解剂、紫外吸收剂、光稳定剂、钛白粉等助剂应采用适于聚合物的抗水解剂、紫外吸收剂、光稳定剂和钛白粉等助剂。
制备按以下步骤进行:
(1)马来酸酐接枝聚烯烃/磷酸盐玻璃母粒的制备
将马来酸酐接枝聚烯烃和经过硅烷偶联剂表面处理后的磷酸盐充分干燥除去水分,然后按设定质量比混合均匀,马来酸酐接枝聚烯烃与磷酸盐的质量比范围为(1-4):1,然后加入双螺杆挤出机,在190-250℃温度下进行熔融共混,切粒干燥后制得马来酸酐接枝聚烯烃/磷酸盐玻璃母粒。
(2)聚烯烃与马来酸酐接枝聚烯烃/磷酸盐玻璃母粒的共混
将50-90质量份的聚烯烃与10-50质量份的马来酸酐接枝聚烯烃/磷酸盐玻璃母粒混合均匀,然后加入双螺杆挤出机,在190-250℃进行熔融共混,切粒干燥,用于后续的三层共挤中间层材料。
(3)熔融共挤及双向拉伸
使用三层共挤出机和双轴拉伸工艺制备聚烯烃/磷酸盐玻璃膜。将上述步骤(2)中所得的共混材料加入中间A层挤出机中,同时将89-97%的聚烯烃、0.2-2%的抗水解剂、0.5-3%的紫外吸收剂、0.5-1%的光稳定剂和0.5-5%的钛白粉或氧化镁等无机填料按比例混合均匀,用于挤出B层。然后经双轴拉伸和热定型,使磷酸盐玻璃沿平行于膜层的方向取向,制得聚烯烃膜。其中纵向拉伸比为7.5-9.0,横向拉伸比为4.5-5.5。
以下给出几个实施例,对本发明做进一步说明,但是本发明的实施方式并不限于这些实施例。
实施例1
i)选用低密度聚乙烯(LDPE)、经硅烷表面处理的磷酸盐玻璃粉末、PE-MAH作为原料,在烘箱中于85℃真空干燥24h,以除去吸附的水分。
ii)造粒:分别称取100kg PE-MAH和100kg磷酸盐玻璃粉,混合均匀后加入双螺杆挤出机中进行熔融共混,挤出后冷却、切粒,制得PE-MAH/磷酸盐玻璃母料。挤出机各区温度为220℃。
iii)共挤:取50kg步骤(i)所得母粒与50kg聚乙烯切片混合均匀,加入A层挤出机,用于挤出聚烯烃膜的中间层;将89kg聚乙烯切片、2kg抗水解剂、3kg紫外吸收剂、1kg光稳定剂、5kg钛白粉混合均匀,加入B层挤出机,用于挤出设置于两侧的聚烯烃层;
iv)铸片及双向拉伸:步骤(ii)所述的三层材料经模头共挤出后进行流延、铸片,然后按照3倍的纵向、横向拉伸比进行纵向、横向拉伸,经热定型、收卷工序制得聚烯烃膜。
v)对所得聚烯烃膜进行表面电晕处理,以增加其表面能,用于复合太阳能电池背板。
太阳能电池背板结构:
粘结层为上述聚烯烃膜,厚度为60μm,基材为PET膜,厚度为250μm,耐候层为PVF膜,厚度为25μm。
实施例2
i)选用聚丙烯(PP)、经硅烷表面处理的磷酸盐玻璃粉末、PP-MAH作为原料,在烘箱中于85℃真空干燥24h,以除去吸附的水分。
ii)造粒:分别称取400kg PE-MAH和100kg磷酸盐玻璃粉末,混合均匀后加入双螺杆挤出机中进行熔融共混,挤出后冷却、切粒,制得PE-MAH/磷酸盐玻璃母料。挤出机各区温度为220℃。
iii)共挤:取90kg步骤(i)所得母粒与10kg聚乙烯切片混合均匀,加入A层挤出机,用于挤出聚烯烃膜的中间层;将97kg聚乙烯切片、0.2kg抗水解剂、0.5kg紫外吸收剂、0.5kg光稳定剂、0.5kg钛白粉混合均匀,加入B层挤出机,用于挤出设置于两侧的聚烯烃层;
iv)铸片及双向拉伸:步骤(ii)所述的三层材料经模头共挤出后进行流延、铸片,然后按照3倍的纵向、横向拉伸比进行纵向、横向拉伸,经热定型、收卷工序制得聚烯烃膜。
v)对所得聚烯烃膜进行表面电晕处理,用于复合太阳能电池背板。
太阳能电池背板结构:
粘结层为上述聚烯烃膜,厚度为60μm,基材为PET膜,厚度为250μm,耐候层为PVF膜,厚度为25μm。
实施例3
i)选用聚丙烯(PP)、经硅烷表面处理的磷酸盐玻璃粉末、PP-MAH作为原料,在烘箱中于85℃真空干燥24h,以除去吸附的水分。
ii)造粒:分别称取200kg PE-MAH和100kg磷酸盐玻璃粉,混合均匀后加入双螺杆挤出机中进行熔融共混,挤出后冷却、切粒,制得PE-MAH/磷酸盐玻璃母料。挤出机各区温度为220℃。
iii)共挤:取45kg步骤(i)所得母粒与10kg聚乙烯切片混合均匀,加入A层挤出机,用于挤出聚烯烃膜的中间层;将93kg聚乙烯切片、1.1kg抗水解剂、1.75kg紫外吸收剂、0.75kg光稳定剂、3.4kg钛白粉混合均匀,加入B层挤出机,用于挤出设置于两侧的聚烯烃层;
iv)铸片及双向拉伸:步骤(ii)所述的三层材料经模头共挤出后进行流延、铸片,然后按照3倍的纵向、横向拉伸比进行纵向、横向拉伸,经热定型、收卷工序制得聚烯烃膜。
v)对所得高聚烯烃膜进行表面电晕处理,用于复合太阳能电池背板。
太阳能电池背板结构:
粘结层为上述聚烯烃膜,厚度为60μm,基材为PET膜,厚度为250μm,耐候层为PVF膜,厚度为25μm。
对比例1
复合型太阳能电池背板,粘结层为普通PE膜,厚度为60μm,基材为PET膜,厚度为250μm,耐候层为PVF膜,厚度为25μm。
对实施例1-2的太阳能电池背板和对比例1的太阳能电池背板进行性能测试,结果见表1。
表1
注:测试方法:
1、层间粘结力测试:
按GB/T 8808(软质复合塑料材料剥离试验方法)中方法A的规定用万能拉力试验机测试PET与聚烯烃膜的剥离强度。
2、水汽透过率测试:
按ASTM F-1249利用调制红外线传感器的水蒸气透过塑料薄膜和薄板的穿透率的标准试验方法测试样品的水汽透过率。

Claims (10)

1.一种聚烯烃膜,其特征在于,所述聚烯烃膜为ABA三层结构,其中B层按如下重量份的组分制成:
磷酸盐玻璃 5-20,
聚烯烃 50-90,
相容剂 5-20。
2.根据权利要求1所述的聚烯烃膜,其特征在于,所述磷酸盐玻璃的玻璃化转变温度(Tg)范围为50-150℃。
3.根据权利要求2所述的聚烯烃膜,其特征在于,所述磷酸盐玻璃经过硅烷表面处理:所述磷酸盐玻璃经过硅烷表面处理:将硅烷偶联剂配制成5-40wt%浓度的硅烷偶联剂溶液,然后按照磷酸盐玻璃:硅烷偶联剂=(50:1)—(5:1)的重量比混合搅拌,然后进行干燥即完成对磷酸盐玻璃的硅烷表面处理。
4.根据权利要求3所述的聚烯烃膜,其特征在于,所述磷酸盐玻璃中掺杂2.5-5重量份三氧化钨(WO3)以引入金属钨阳离子。
5.根据权利要求1所述的聚烯烃膜,其特征在于,所述聚烯烃为低密度聚乙烯、线性低密度聚乙烯、高密度聚乙烯、均聚聚丙烯或共聚聚丙烯,熔融指数为0.5-3.0g/10min。
6.根据权利要求1所述的聚烯烃膜,其特征在于,所述相容剂为马来酸酐接枝聚乙烯或马来酸酐接枝聚丙烯,接枝率为0.6%-3%。
7.根据权利要求1所述的聚烯烃膜,其特征在于,所述聚烯烃膜为共挤结构,其中A层含有89-97%的聚烯烃、0.2-2%的抗水解剂、0.5-3%的紫外吸收剂、0.5-1%的光稳定剂和0.5-5%的钛白粉或氧化镁等无机填料。
8.根据权利要求1所述的聚烯烃膜,其特征在于,所述B层厚度为10-60μm,所述A层厚度为10-60μm。
9.一种制备上述聚烯烃膜的方法,其特征在于,制备按如下步骤进行:
①将相容剂、磷酸盐玻璃粉末充分干燥,按一定配比称重并混合均匀,加入双螺杆挤出机在200-250℃进行熔融共混、造粒,制成母粒;
②将上述母粒与干燥后的聚烯烃熔融共混、造粒,制成B层材料;
③将B层材料加入用于挤出中间层的挤出机,将称量好的A层材料各组分加入用于挤出两侧层的挤出机,经熔融共挤、铸片,然后在磷酸盐玻璃的Tg以上的加工温度下进行双轴拉伸,使液态的磷酸盐玻璃在外界力场作用下变形取向,冷却后形成平行于膜表面的二维片状存在于聚合物基体中。
10.一种太阳能电池背板,其特征在于,所述太阳能电池背板使用如权利要求1-9中任一项所述的聚烯烃膜。
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