CN110016170B - 一种低水汽透过率聚烯烃弹性体胶膜及制备方法 - Google Patents

一种低水汽透过率聚烯烃弹性体胶膜及制备方法 Download PDF

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CN110016170B
CN110016170B CN201810022942.8A CN201810022942A CN110016170B CN 110016170 B CN110016170 B CN 110016170B CN 201810022942 A CN201810022942 A CN 201810022942A CN 110016170 B CN110016170 B CN 110016170B
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parts
mass
adhesive film
polyolefin elastomer
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CN110016170A (zh
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王龙
熊曦
唐国栋
侯宏兵
周光大
林建华
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Hangzhou First Applied Material Co Ltd
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Hangzhou First Applied Material Co Ltd
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Priority to JP2019571600A priority patent/JP6900519B2/ja
Priority to PCT/CN2018/079449 priority patent/WO2019136823A1/zh
Priority to US16/607,361 priority patent/US11578196B2/en
Priority to EP18899526.0A priority patent/EP3739638A4/en
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Abstract

本发明公开了一种低水汽透过率聚烯烃弹性体胶膜及制备方法，它包括50～100质量份的基体树脂、0～40质量份的改性树脂、0.001～2质量份的活性剂、0.1～3质量份的有机过氧化物、0.02～5质量份的助交联剂、0.02～2质量份的硅烷偶联剂、0.005～2质量份的光稳定剂、0～20质量份的阻水填料。本发明通过加入带有活性基团的改性树脂和活化剂，提高了胶膜的交联度和交联密度，降低了水汽透过率；加入阻水填料进一步提高胶膜阻水性能，保证组件可靠性，延长组件寿命。

Description

一种低水汽透过率聚烯烃弹性体胶膜及制备方法
技术领域
本发明属于光伏封装材料领域，涉及一种用于电子器件封装的具有低水汽透过率的聚烯烃弹性体胶膜及制备方法。
背景技术
能源紧缺和环境问题日益凸显的今天，寻找可再生、环境友好的绿色能源已成为必然趋势。光伏发电是将太阳能转化成电能的过程，具有永久性、清洁性和灵活性三大优点，而且与传统的火力发电、水力发电和核能发电相比，它的制备过程简单，复制性强，因此具有很好的发展前景。
目前光伏组件的封装材料主要采用乙烯醋酸乙烯酯共聚物(EVA)。但是EVA材料自身分子结构决定了EVA胶膜存在水汽透过率偏高、耐候性较差等不足。随着电池技术的发展，各种新型高效电池片如N型电池、PERC电池、双面电池等相继面世，对封装材料的性能提出了更高的要求。此外，在渔光互补等项目中，组件的工作环境湿度很高，也需要有更低水汽透过率的封装材料来为组件长期高效工作保驾护航。这些新型高效电池片或特殊水汽环境对封装材料的水汽阻隔性能提出了更高要求。如何降低封装材料的水汽阻隔性能提升光伏组件的寿命是行业需要解决的问题。
如果降低基体树脂EVA中的醋酸乙烯酯(VA)含量，随着极性官能团比例的下降，可相应增加封装材料的阻隔性，但会带来透光率降低的问题，不利于光伏电池发电量的提升。极端的情形是不采用极性单体共聚物作为基体树脂，如专利CN106752997A(公开号)、专利CN102863916B(公开号)等，采用茂金属催化的乙烯和α-烯烃单体比如丁烯、戊烯、辛烯等进行共聚得到的聚合物作为基体树脂进行封装，由于分子链中没有不饱和键，所有耐候性和阻水性均明显好于EVA，但这种改进方式只能在聚合过程中进行实现，而在封装胶膜制作过程无法进行二次改良
为了提高封装胶膜的阻水性能，常见的方法是在胶膜中添加吸水剂，通过物理吸附或者化学反应的方式，减缓水汽在胶膜中的扩散。如专利CN103756579A添加了离子聚合物、专利CN104962216A(公开号)添加了二环己基碳二亚胺、1-乙基-(3-二甲基氨基丙基)碳酰二亚胺。这种方法对胶膜阻水性能的提升效果比较有限，且当吸水剂吸附饱和或者全部和水反应后就失去阻水效果，并不能完全保证组件长期使用的可靠性。
基于上述情况，目前开发一种具有低水汽透过率的新胶膜，保证光伏组件长期高效工作是很有必要的。
发明内容
本发明的目的是弥补现有技术的不足，提供一种交联型低水汽透过率的聚烯烃弹性体封装胶膜。过氧化物和助交联剂可以引发聚烯烃弹性体交联，通过添加含有活性基团的聚烯烃弹性体和活化剂，进一步提高胶膜的交联密度和交联度，再配合阻水填料，保证胶膜的高效阻水特性。本发明不仅适用于透明烯烃胶膜，也适用于有色胶膜。对于有色胶膜，除了过氧化物交联体系，还可以用紫外辐射、电子辐射交联等方式对胶膜进行预处理，提高胶膜的交联度和交联密度，进一步改善胶膜的阻水性能。通过本发明制备的聚烯烃弹性体封装胶膜，具有超低的水汽透过率和优异的耐候性，能为组件在户外长期高效工作提供可靠保证。
本发明的目的是通过以下技术方案实现的：一种用于电子器件封装的低水汽透过率聚烯烃弹性体胶膜，它包括：50～100质量份的基体树脂、0～40质量份的改性树脂、0.001～2质量份的活性剂、0.1～3质量份的有机过氧化物、0.02～5质量份的助交联剂、0.02～2质量份的硅烷偶联剂、0.005～2质量份的光稳定剂、0～20质量份的阻水填料。
进一步地，所述胶膜的厚度为0.01～1mm。
进一步地，所述基体树脂由乙烯分别与丙烯、丁烯、戊烯、己烯、辛烯发生共聚反应而形成的聚合物的一种或多种按任意配比混合组成，基体树脂的熔融指数为0.5～45g/10min。
进一步地，所述改性树脂由具有以下结构式(1)的改性树脂～具有结构式(14)的改性树脂的一种或多种按任意配比混合组成：
Figure BDA0001544136870000031
Figure BDA0001544136870000041
其中，a、b、c、d为自然数，X1选自甲基、乙基、丙基、丁基、己基；R1、R2和R3分别独立地为碳原子个数为1～10的烷基；X2和X3为可以参与交联反应的活性基团，通过含有X2和X3基团的单体参与共聚或者通过自由基引发的接枝反应的方式引入聚烯烃弹性体分子链；所述X2选自卤素、氨基、羧基、羟基、醛基、巯基、酸酐基、丙烯酰胺基、磺酸基、环氧基、氰基、异氰酸酯基、碳碳双键、碳碳三键、酰氯基，其含量为0.05％～15wt％。所述X3选自亚氨基，磷酸二酯基、碳碳双键、碳碳三键，其含量为0.05％～15wt％。
进一步地，所述活性剂含有两个或者两个以上活性基团，所述活性基团选自卤素、羧基、氨基、羟基、巯基、酸酐基、丙烯酰胺基、异氰酸酯基、醛基、磺酸基、硅烷偶联基、酰氯基。
进一步地，所述有机过氧化物由叔丁基过氧化碳酸异丙酯、2,5-二甲基-2,5-(双叔丁过氧基)己烷、叔丁基过氧化碳酸-2-乙基己酯、1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷、1,1-双(叔戊基过氧)-3,3,5-三甲基环己烷、1,1-双(叔戊基过氧)环己烷、1,1-双(叔丁基过氧)环己烷、2,2-双(叔丁基过氧)丁烷、过氧化2-乙基己基碳酸叔戊酯、2,5-二甲基2,5-二甲基2,5-二甲基2,5-双(苯甲酰过氧)-己烷、过氧化碳酸叔戊酯、过氧化3,3,5三甲基己酸叔丁酯的一种或多种按任意配比混合组成；所述助交联剂由三烯丙基异氰尿酸酯、三聚氰酸三烯丙酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇三丙烯酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、乙氧化三羟甲基丙烷三丙烯酸酯、丙氧化三羟甲基丙烷三丙烯酸酯、乙氧化甘油三丙烯酸酯、丙氧化甘油三丙烯酸酯、季戊四醇四丙烯酸酯、乙氧化季戊四醇四丙烯酸酯、三羟甲基丙烷四丙烯酸酯、双三羟甲基丙烷四丙烯酸酯、双三羟甲基丙烷四甲基丙烯酸酯、丙氧化季戊四醇四丙烯酸酯、2,4,6-三(2-丙烯基氧基)-1,3,5-三嗪、三环葵烷二甲醇二丙烯酸酯、丙氧化新戊二醇二丙烯酸酯、乙氧化双酚A二丙烯酸酯、乙氧化双酚A二甲基丙烯酸酯、2-丁基-2-乙基-1,3-丙二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯的一种或多种按任意配比混合组成；所述硅烷偶联剂由乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三过氧化叔丁基硅烷、乙烯基三乙酰氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷、γ-氨丙基三乙氧基硅烷、γ-甲基丙烯酸酰氧基丙基三甲氧基硅烷、γ-缩水甘油醚氧丙基三甲基硅烷、3-氨丙基三甲基硅烷的一种或多种按任意配比混合组成；所述光稳定剂由双(2,2,6,6-四甲基-4-哌啶基)葵二酸酯、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)葵二酸酯、4-(甲基)丙烯酰氧基-2,2,6,6-四甲基哌啶与α-烯类单体聚合得到的接枝共聚物、4-羟基-2,2,6,6-四甲基-1-哌啶醇、3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯、葵二酸双-2,2,6,6-四甲基哌啶醇和三(1,2,2,6,6-五甲基-4-哌啶基)亚磷酸酯的一种或多种按任意配比混合组成。
进一步地，所述吸水填料为多孔吸附型材料或能吸附水汽形成结晶水的化合物。
进一步地，所述吸水填料由分子筛、沸石、硅藻土、活性炭、多孔二氧化硅、多孔三氧化二铝、炭黑、氧化钙、碳酸钙、氯化钙、硫酸镁、氯化镁、硫酸铜、硫酸钠、硫酸钙、硫酸锌、氢氧化钙的一种或多种按任意配比混合组成。
一种上述低水汽透过率聚烯烃弹性体胶膜的制备方法，该方法具体为：按照50～100质量份的基体树脂、0～40质量份的改性树脂、0.001～2质量份的活性剂、0.1～3质量份的有机过氧化物、0.02～5质量份的助交联剂、0.02～2质量份的硅烷偶联剂、0.005～2质量份的光稳定剂、0～20质量份的阻水填料取材，将所有组分混合后加入挤出机，经过T型模头流延成膜，得到超低水汽透过率聚烯烃弹性体胶膜。
进一步地，经过T型模头流延成膜后，再通过辐照剂量为0.01～0.1kWh/m2的紫外光或者辐照剂量为0.2～100KGY电子束等方式进行处理，使基体树脂、改性树脂与活性剂、有机过氧化物、助交联剂发生交联、接枝等反应。
本发明的有益效果是，本发明内容不限于聚烯烃弹性体体系，同样适用于EVA胶膜、PE胶膜、EMMA胶膜中。通过加入改性的树脂和活性剂的方式，提高胶膜的交联密度和交联度，再配合适当的阻水填料，可以大大提高高分子材料的阻水性能。其中基体树脂、活化剂、交联剂、有机过氧化物中的两种或多种可以发生增加阻隔性的化学反应。
具体实施方式
下面结合具体实施例对本发明做进一步描述，但本发明的保护范围不仅局限于实施例。
实施例1
包括以下质量份的组分：80份熔融指数为5g/10min的聚烯烃弹性体，牌号C5070D(SABIC Innovative Plastics)，20份含有2.5％氨基的乙烯辛烯共聚物改性树脂，0.26份乙二酸，0.65份叔丁基过氧化碳酸异丙酯，0.6份三烯丙基异氰尿酸酯，0.5份乙烯基三乙氧基硅烷，0.04份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯，0.2份分子筛，记为S-1。
实施例2
包括以下质量份的组分：65份熔融指数为15g/10min的聚烯烃弹性体，牌号C13060D(SABIC Innovative Plastics)，35份含有1.0％羧基的乙烯和戊烯共聚物改性树脂，0.20份1,4-丁二胺，0.40过氧化3,3,5三甲基己酸叔丁酯，0.35三烯丙基异氰尿酸酯B，0.5份乙烯基三甲氧基硅烷，0.08份4-羟基-2,2,6,6-四甲基-1-哌啶醇，0.25份二氧化硅，记为S-2。
实施例3
包括以下质量份的组分：80份熔融指数为30g/10min的聚烯烃弹性体，牌号C30070D(SABIC Innovative Plastics)，20份含有2.0％异氰酸酯基的乙烯丁烯共聚物改性树脂，0.22份1,3-丙二醇，0.65份1,1-双(过氧化叔丁基)-3,3,5-三甲基环己烷，0.6份三烯丙基异氰尿酸酯，0.5份乙烯基三乙氧基硅烷，0.02份4-羟基-2,2,6,6-四甲基-1-哌啶醇，0.2份硫酸镁，记为S-3。
实施例4
包括以下质量份的组分：60份熔融指数为0.5g/10min的聚烯烃弹性体，牌号8150(Dow)，40份含有0.2％异氰酸酯基的乙烯和己烯共聚物改性树脂，0.30份1,4-丁二酸，0.35份1,1-双(过氧化叔丁基)-3,3,5-三甲基环己烷，0.3三羟甲基丙烷三丙烯酸酯，0.5份乙烯基三甲氧基硅烷，0.005份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯，0.2份氯化钙，记为S-4。
实施例5
包括以下质量份的组分：60份熔融指数为5g/10min的聚烯烃弹性体，牌号8200(Dow)，40份含有1.0％羟基的乙烯戊烯共聚物改性树脂，2.0份1,5-戊二磺酸，0.1份叔丁基过氧化碳酸-2-乙基己酯，0.02份季戊四醇四丙烯酸酯，0.8份乙烯基三乙酰氧基硅烷，0.5份分子筛，0.02份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯，记为S-5。
实施例6
包括以下质量份的组分：60份熔融指数为5g/10min的聚烯烃弹性体，牌号8200(Dow)，40份含有1.0％羟基的乙烯戊烯共聚物改性树脂，0.22份甲苯二异氰酸酯，0.55份3,3,5三甲基己酸叔丁酯，0.5份三羟甲基丙烷三丙烯酸酯，1.0份乙烯基三甲氧基硅烷，0.07份4-羟基-2,2,6,6-四甲基-1-哌啶醇，0.5份硫酸钙，记为S-6。
实施例7
包括以下质量份的组分：70份熔融指数为20g/10min的聚烯烃弹性体8200(Dow)和C30070D(SABIC Innovative Plastics)的混合物，30份含有1.5％羟基的乙烯丁烯共聚物改性树脂，0.24份1，6-己二酸，0.55份份叔丁基过氧化碳酸-2-乙基己酯，0.5份季戊四醇四丙烯酸酯，0.5份乙烯基三甲氧基硅烷，0.05份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯，0.5份氯化镁记为S-7。
实施例8
包括以下质量份的组分：60份熔融指数为15g/10min的聚烯烃弹性体8402(Dow)和8200(Dow)的混合物，40份含有1.5％磺酸基的乙烯辛烯共聚物改性树脂，0.30份3-氨基-1-丁醇，0.5份叔丁基过氧化碳酸-2-乙基己酯，0.5三羟甲基丙烷三丙烯酸酯，0.4份乙烯基三乙氧基硅烷，0.05份4-羟基-2,2,6,6-四甲基-1-哌啶醇，0.15份硫酸钠，记为S-8。
实施例9
包括以下质量份的组分：70份熔融指数为10g/10min的聚烯烃弹性体8402(Dow)和8200(Dow)的混合物，30份含有1.5％磺酸基的乙烯辛烯共聚物改性树脂，0.30份1,3-二烯丙基脲，0.5份叔丁基过氧化碳酸-2-乙基己酯，0.5乙氧化三羟甲基丙烷三丙烯酸酯，0.3份乙烯基三乙酰氧基硅烷，2份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯，0.2份硫酸镁，记为S-9。
实施例10
包括以下质量份的组分：95份熔融指数为10g/10min的聚烯烃弹性体8402(Dow)和8200(Dow)的混合物，5份含有2.0％磺酸基的乙烯辛烯共聚物改性树脂，0.001份1,4-己二硫醇，0.5份1,1-双(叔丁基过氧)环己烷，0.5乙氧化三烯丙基异氰尿酸酯，0.3份乙烯基三甲氧基硅烷，0.09份4-羟基-2,2,6,6-四甲基-1-哌啶醇，0.2份氯化钙，记为S-10。
实施例11
包括以下质量份的组分：90份熔融指数为20g/10min的聚烯烃弹性体8200(Dow)和C30070D(SABIC Innovative Plastics)的混合物，10份含有0.1％酰氯基团的乙烯辛烯共聚物改性树脂，0.08份4-氨基-1-丁酸，0.5份叔丁基过氧化碳酸-2-乙基己酯，0.5份三羟甲基丙烷三甲基丙烯酸酯，0.2份乙烯基三乙氧基硅烷，0.08份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯，0.1份氯化钙，0.1份硫酸镁，记为S-11。
实施例12
包括以下质量份的组分：60份熔融指数为10g/10min的聚烯烃弹性体8200(Dow)和8402(Dow)的混合物，40份含有0.1％酰氯基团的乙烯辛烯共聚物改性树脂，0.95份乙二酸，0.5份叔丁基过氧化碳酸-2-乙基己酯，0.5份三羟甲基丙烷三甲基丙烯酸酯，2.0份乙烯基三甲氧基硅烷，1.2份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯，记为S-12。
实施例13
包括以下质量份的组分：70份熔融指数为5g/10min的聚烯烃弹性体，牌号8200(Dow)，30份含有3.0％酸酐基团的乙烯辛烯共聚物改性树脂，0.65份1,4-丁二醇，0.5份叔丁基过氧化碳酸-2-乙基己酯，0.5份三羟甲基丙烷三甲基丙烯酸酯，0.6份乙烯基三乙酰氧基硅烷，1.0份4-羟基-2,2,6,6-四甲基-1-哌啶醇，0.1份碳酸钙，0.1份硫酸镁、记为S-13。
实施例14
包括以下质量份的组分：70份熔融指数为5g/10min的聚烯烃弹性体，牌号8200(Dow)，30份含有3.0％酸酐基团的乙烯辛烯共聚物改性树脂，0.65份4-氨基-1-丁醇，0.5份叔丁基过氧化碳酸-2-乙基己酯，0.5份三羟甲基丙烷三甲基丙烯酸酯，0.3份乙烯基三乙酰氧基硅烷，0.02份4-羟基-2,2,6,6-四甲基-1-哌啶醇，0.2份分子筛记为S-14。
实施例15
包括以下质量份的组分：70份熔融指数为15g/10min的聚烯烃弹性体8200(Dow)和8402(Dow)的混合物，30份含有3.0％磺酸基团的乙烯辛烯共聚物改性树脂，0.65份对苯二酰胺，0.5份叔丁基过氧化碳酸-2-乙基己酯，0.5份三羟甲基丙烷三甲基丙烯酸酯，0.3份乙烯基三乙酰氧基硅烷，0.02份4-羟基-2,2,6,6-四甲基-1-哌啶醇，0.2份分子筛记为S-15。
实施例16
包括以下质量份的组分：60份熔融指数为20g/10min的聚烯烃弹性体8200(Dow)和C30070D(SABIC Innovative Plastics)的混合物，30份含有3.0％酸酐基团的乙烯辛烯共聚物改性树脂，0.65份1,4-丁二醇，0.5份叔丁基过氧化碳酸-2-乙基己酯，0.5份三羟甲基丙烷三甲基丙烯酸酯，0.2份乙烯基三乙氧基硅烷，0.06份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯，4份三氧化二铝，6份碳酸钙，记为S-16。
实施例17
包括以下质量份的组分：50份熔融指数为5g/10min的聚烯烃弹性体，牌号8200(Dow)，40份含有1.5％异氰酸酯基团的乙烯辛烯共聚物改性树脂，0.25份1,6-己二硫醇，0.5份叔丁基过氧化碳酸-2-乙基己酯，0.5份三羟甲基丙烷三甲基丙烯酸酯，0.2份乙烯基三甲氧基硅烷，0.08份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯，10份二氧化硅，5份氯化钙，5份碳酸钙，记为S-17。
实施例18
包括以下质量份的组分：70份熔融指数为20g/10min的聚烯烃弹性体8200(Dow)和C30070D(SABIC Innovative Plastics)的混合物，30份含有3.0％磺酸基团的乙烯辛烯共聚物改性树脂，0.50份1,4-丁二胺，0.3份叔丁基过氧化碳酸-2-乙基己酯，0.3份三羟甲基丙烷三甲基丙烯酸酯，0.2份乙烯基三甲氧基硅烷，0.09份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯，0.5份炭黑，记为S-18。
实施例19
包括以下质量份的组分：100份熔融指数为5g/10min的聚烯烃弹性体，牌号8200(Dow)，0.26份乙二酸，0.65份叔丁基过氧化碳酸异丙酯，0.6份三烯丙基异氰尿酸酯，0.5份乙烯基三乙氧基硅烷，0.06份4-羟基-2,2,6,6-四甲基-1-哌啶醇，0.2份分子筛，记为S-19。
实施例20
包括以下质量份的组分：100份熔融指数为5g/10min的聚烯烃弹性体，牌号8200(Dow)，0.26份1,3-丙二醇，0.65份叔丁基过氧化碳酸异丙酯，0.6份三烯丙基异氰尿酸酯，0.5份乙烯基三乙酰氧基硅烷，0.05份4-羟基-2,2,6,6-四甲基-1-哌啶醇，0.2份分子筛，记为S-20。
对比例1
包括以下质量份的组分：100份熔融指数为5g/10min的聚烯烃弹性体，牌号C5070D(SABIC Innovative Plastics)0.65份叔丁基过氧化碳酸异丙酯，0.6份三烯丙基异氰尿酸酯，0.5份乙烯基三甲氧基硅烷，0.08份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯，0.2份分子筛，记为C-1。
对比例2
包括以下质量份的组分：80份熔融指数为5g/10min的聚烯烃弹性体，牌号8200(Dow)，20份含有2.5％氨基的乙烯丁烯共聚物改性树脂，0.65份叔丁基过氧化碳酸异丙酯，0.6份三烯丙基异氰尿酸酯，0.5份乙烯基三乙氧基硅烷，0.05份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯，0.2份分子筛，记为C-2。
对比例3
包括以下质量份的组分：100份熔融指数为25g/10min的乙烯醋酸乙烯酯，0.65份叔丁基过氧化碳酸异丙酯，0.6份三烯丙基异氰尿酸酯，0.5份乙烯基三乙氧基硅烷，0.06份4-羟基-2,2,6,6-四甲基-1-哌啶醇，0.2份分子筛记为C-5。
对比例4
包括以下质量份的组分：90份熔融指数为25g/10min的乙烯醋酸乙烯酯，0.65份叔丁基过氧化碳酸异丙酯，0.6份三烯丙基异氰尿酸酯，0.5份乙烯基三乙氧基硅烷，0.07份4-羟基-2,2,6,6-四甲基-1-哌啶醇，4份钛白粉，6份氯化钙，记为C-6。
将上述实施例和对比例中组分按比例混合后加入挤出机，通过螺杆精密挤出，经过T型模头流延成膜，以上例中为便于比较，流延成膜厚度统一为0.5mm。
通过上述实施例得到的封装胶膜应用于太阳能电池组件的封装，经下述测试方法进行评价，评价结果列于表1：
1.封装胶膜的交联度
测试方法参照标准GB/T 29848《光伏组件封装用乙烯-醋酸乙烯酯共聚物(EVA)胶膜》。2.水汽透过率
测试方法参照标准GB/T 29848《光伏组件封装用乙烯-醋酸乙烯酯共聚物(EVA)胶膜》3.恒定耐湿热老化性能
测试方法参照标准GB/T 29848《光伏组件封装用乙烯-醋酸乙烯酯共聚物(EVA)胶膜》，试验温度为85℃，试验相对湿度为85％，老化时间为1000h。试验前后按照国标GB 2409《塑料黄色指数试验方法》测定黄变指数(ΔYI)。
表1.实施例和对比例样品测试汇总
Figure BDA0001544136870000111
测试结果表明，根据本发明方案制备的聚烯烃弹性体胶膜，具有很低的水汽透过率和优异的耐候性，是一种理想的高分子封装材料，可以用于光伏组件、电子设备、显示器件等封装。该结果证明通过引入带有活性基团的活性树脂和活性剂，引发活性基团反应，提高胶膜的交联密度和交联度，是一种提高材料阻水性能的好方法。再配合适当的阻水填料，就能得到阻水性能优异的封装材料。这种方法不仅适用于聚烯烃弹性体胶膜，还可以推广到EVA、EMMA等材料。它提高了材料阻水性能的同时，还改善了材料的耐候性。可用于制备透明胶膜，也可以用不制备有色胶膜，例如黑色、白色等。

Claims (6)

1.一种用于电子器件封装的低水汽透过率聚烯烃弹性体胶膜，其特征在于，它包括：50～100质量份的基体树脂、5～40质量份的改性树脂、0.001～2质量份的活性剂、0.1～3质量份的有机过氧化物、0.02～5质量份的助交联剂、0.02～2质量份的硅烷偶联剂、0.005～2质量份的光稳定剂、0～20质量份的阻水填料；
所述改性树脂由具有以下结构式(1)的改性树脂～具有结构式(14)的改性树脂的一种或多种按任意配比混合组成：
Figure FDA0002705803370000011
Figure FDA0002705803370000021
其中，a、b、c、d为自然数，X1选自甲基、乙基、丙基、丁基、己基；R1、R2和R3分别独立地为碳原子个数为1～10的烷基；X2和X3为参与交联反应的活性基团，通过含有X2和X3基团的单体参与共聚或者通过自由基引发的接枝反应的方式引入聚烯烃弹性体分子链；所述X2选自卤素、氨基、羧基、羟基、醛基、巯基、酸酐基、丙烯酰胺基、磺酸基、环氧基、氰基、异氰酸酯基、碳碳双键、碳碳三键、酰氯基，其含量为0.05％～15wt％；所述X3选自亚氨基，磷酸二酯基、碳碳双键、碳碳三键，其含量为0.05％～15wt％；
所述活性剂含有两个或者两个以上活性基团，所述活性基团选自卤素、羧基、氨基、羟基、巯基、酸酐基、丙烯酰胺基、异氰酸酯基、醛基、磺酸基、硅烷偶联基、酰氯基；
所述阻水填料由分子筛、沸石、硅藻土、活性炭、多孔二氧化硅、多孔三氧化二铝、氧化钙、碳酸钙、氯化钙、硫酸镁、氯化镁、硫酸铜、硫酸钠、硫酸钙、硫酸锌、氢氧化钙的一种或多种按任意配比混合组成。
2.根据权利要求1所述的低水汽透过率聚烯烃弹性体胶膜，其特征在于，所述胶膜的厚度为0.01～1mm。
3.根据权利要求1所述的低水汽透过率聚烯烃弹性体胶膜，其特征在于，所述基体树脂由乙烯分别与丙烯、丁烯、戊烯、己烯、辛烯发生共聚反应而形成的聚合物的一种或多种按任意配比混合组成，基体树脂的熔融指数为0.5～45g/10min。
4.根据权利要求1所述的低水汽透过率聚烯烃弹性体胶膜，其特征在于，所述有机过氧化物由叔丁基过氧化碳酸异丙酯、2,5-二甲基-2,5-(双叔丁过氧基)己烷、叔丁基过氧化碳酸-2-乙基己酯、1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷、1,1-双(叔戊基过氧)-3,3,5-三甲基环己烷、1,1-双(叔戊基过氧)环己烷、1,1-双(叔丁基过氧)环己烷、2,2-双(叔丁基过氧)丁烷、过氧化2-乙基己基碳酸叔戊酯、2,5-二甲基2,5-二甲基2,5-二甲基2,5-双(苯甲酰过氧)-己烷、过氧化碳酸叔戊酯、过氧化3,3,5三甲基己酸叔丁酯的一种或多种按任意配比混合组成；所述助交联剂由三烯丙基异氰尿酸酯、三聚氰酸三烯丙酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇三丙烯酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、乙氧化三羟甲基丙烷三丙烯酸酯、丙氧化三羟甲基丙烷三丙烯酸酯、乙氧化甘油三丙烯酸酯、丙氧化甘油三丙烯酸酯、季戊四醇四丙烯酸酯、乙氧化季戊四醇四丙烯酸酯、三羟甲基丙烷四丙烯酸酯、双三羟甲基丙烷四丙烯酸酯、双三羟甲基丙烷四甲基丙烯酸酯、丙氧化季戊四醇四丙烯酸酯、2,4,6-三(2-丙烯基氧基)-1,3,5-三嗪、三环葵烷二甲醇二丙烯酸酯、丙氧化新戊二醇二丙烯酸酯、乙氧化双酚A二丙烯酸酯、乙氧化双酚A二甲基丙烯酸酯、2-丁基-2-乙基-1,3-丙二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯的一种或多种按任意配比混合组成；所述硅烷偶联剂由乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三过氧化叔丁基硅烷、乙烯基三乙酰氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷、γ-氨丙基三乙氧基硅烷、γ-甲基丙烯酸酰氧基丙基三甲氧基硅烷、γ-缩水甘油醚氧丙基三甲基硅烷、3-氨丙基三甲基硅烷的一种或多种按任意配比混合组成；所述光稳定剂由双(2,2,6,6-四甲基-4-哌啶基)葵二酸酯、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)葵二酸酯、4-(甲基)丙烯酰氧基-2,2,6,6-四甲基哌啶与α-烯类单体聚合得到的接枝共聚物、4-羟基-2,2,6,6-四甲基-1-哌啶醇、3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯、葵二酸双-2,2,6,6-四甲基哌啶醇和三(1,2,2,6,6-五甲基-4-哌啶基)亚磷酸酯的一种或多种按任意配比混合组成。
5.一种权利要求1所述低水汽透过率聚烯烃弹性体胶膜的制备方法，其特征在于，该方法具体为：按照50～100质量份的基体树脂、5～40质量份的改性树脂、0.001～2质量份的活性剂、0.1～3质量份的有机过氧化物、0.02～5质量份的助交联剂、0.02～2质量份的硅烷偶联剂、0.005～2质量份的光稳定剂、0～20质量份的阻水填料取材，将所有组分混合后加入挤出机，经过T型模头流延成膜，得到超低水汽透过率聚烯烃弹性体胶膜。
6.根据权利要求5所述的方法，其特征在于，经过T型模头流延成膜后，再通过辐照剂量为0.01～0.1kWh/m2的紫外光或者辐照剂量为0.2～100KGY电子束的方式进行处理，使基体树脂、改性树脂与活性剂、有机过氧化物、助交联剂发生交联、接枝的反应。
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