CN115612440A - 一种双组分无溶剂光伏背板胶黏剂及其制备方法 - Google Patents
一种双组分无溶剂光伏背板胶黏剂及其制备方法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
本发明涉及一种双组分无溶剂光伏背板胶黏剂,本发明的双组分无溶剂光伏背板胶黏剂包括a组分和b组分;a组分包括聚酯多元醇、环氧树脂、增粘树脂、助剂;b组分包括多元异氰酸酯。聚酯多元醇为由二元酸与二元醇进行缩聚酯化反应制得的聚酯多元醇,分子量Mn为1000‑4000,官能度为2,玻璃化转变温度为‑10至20℃。本发明使用的聚酯多元醇官能度为2,所使用的异氰酸酯≥3,改良了胶黏剂的施工性能,提高了交联密度改善了抗老化性能;合成聚酯多元醇所使用的聚单体以脂肪族及脂环族为主,相同黏度下有更高的分子量,内聚力更强且固化后收缩更小,粘结性能更好。
Description
技术领域
本发明属于太阳能电池背板用胶黏剂技术领域,具体涉及一种双组分无溶剂光伏背板胶黏剂及其制备方法,是一种无溶剂太阳能电池背板用胶黏剂组合物。
背景技术
近年来,能源环境问题越来越受到重视,全球新能源产业的蓬勃发展,光伏产业作为可再生能源的重要组成部分,将成为解决全球能源危机的主要方法。
光伏产品有着特殊使用环境,对其各个组件均有较高的要求,背板是光伏组件生产过程中最重要的封装材料,在耐老化、耐高低温、耐水解性、耐击穿等方面都有严格的标准。
用于太阳能背板行业的胶黏剂通常为双组份溶剂型聚氨酯胶黏剂,此类胶黏剂具有稳定的性能,由于其在复合过程中使用到了大量的溶剂,会在复合过程中产生溶剂残留,其使用溶剂使用时溶剂气味大,且使用时易发生火灾爆炸危害,溶剂的使用造成环境污染、安全卫生危害。胶水的制备过程需要经过烘干工序,设备投入大,在成本方面无溶剂复合公寓与干式复合工艺相比,综合可以节约成本约。
现有无溶剂型背板都存在着或多或少的缺陷,如胶黏剂的黏接强度不够、耐老化性能差、生产施工成本高等。如使用聚氨酯预聚体的背板胶,易受水分等的影响,贮存期较短,且生产过程复杂;
CN113773781A,聚酯官能度大于2,固化剂官能度优选≥3,用了聚碳酸酯、环氧树脂、硅烷、抗水解剂。CN113999642A使用了较多的聚碳酸酯、环氧树脂,使用的聚酯官能度大于2,聚碳酸酯成本高,高官能度导致固化后胶黏剂体积收缩较大,产生收缩应力导致粘结强度低;CN109233721A环状聚酯与支链聚酯组合再通过环状聚酯开环反应得到直链聚酯固化,体系较为复杂,可能导致固化后后交联程度不足,抗水性较差的问题。
发明内容
本发明的目的是针对上述技术问题,提供一种双组分无溶剂光伏背板胶黏剂及其制备方法,是一种太阳能电池背板用的胶黏剂组合物,具有优异的耐高温、耐老化以及耐候性。
本发明的目的是通过以下技术方案实现的:
本发明提供了一种双组分无溶剂光伏背板胶黏剂,所述双组分无溶剂光伏背板胶黏剂包括a组分和b组分;
a组分包括按重量份数计的如下成分:70-95份聚酯多元醇、5-20份环氧树脂、1-15份增粘树脂、助剂1.10001-2.5003份;
b组分包括多元异氰酸酯。
作为本发明的一个实施方案,所述的聚酯多元醇为由二元酸与二元醇进行缩聚酯化反应制得的聚酯多元醇,分子量Mn为1000-4000,官能度为2,玻璃化转变温度为-10至20℃。聚酯多元醇的官能度低了不交联,高了粘度大。分子量过高,粘度大,施工困难;分子量小,固化收缩大,以下剥离强度。其它树脂,如聚醚多元醇的耐热较差。
作为本发明的一个实施方案,所述二元酸包括1,2-环己烷二甲酸、1,3-环己烷二甲酸、1,4-环己烷二甲酸、环戊烷二甲酸、环丁烷二甲酸、甲基六氢苯酐、萘二羧酸、联苯二羧酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、丁二酸、己二酸、癸二酸、月桂二酸中的一种或任意两种以上的组合。二元酸优选多种脂肪族二元酸和脂环族二元酸混合,如己二酸、环戊二甲酸、六氢苯酐、癸二酸中的一种或任意两种以上的组合。
作为本发明的一个实施方案,所述二元醇为脂肪族二元醇,包括乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、己二醇、一缩二丙二醇、一缩二乙二醇、新戊二醇、1,9-壬二醇、3-甲基-戊二醇中的一种或一种以上的组合。
作为本发明的一个实施方案,所述的环氧树脂包括双酚a环氧树脂、双酚f环氧树脂、酚醛环氧树脂、氢化环氧树脂、缩水甘油酯型环氧树脂的一种或一种以上的组合。
作为本发明的一个实施方案,所述的增粘树脂包括松香树脂、氢化松香树脂、萜烯树脂、c5/9石油树脂的一种或一种以上的组合。增粘树脂优选松香树脂和/或萜烯树脂。
作为本发明的一个实施方案,所述助剂包括催化剂0.00001-0.0003份、抗氧剂0.1-0.5份、紫外吸收剂0.5-1份、光稳定剂0.5-1份。
作为本发明的一个实施方案,所述的催化剂为有机金属催化剂。有机金属催化剂优选有机锡催化剂。
作为本发明的一个实施方案,所述抗氧剂包括受阻酚类抗氧剂。所述阻酚类抗氧剂包括2,2’-亚甲基-双-(4-甲基-6-叔丁基)苯酚、2,2’-亚甲基-双-(4-乙基-6-叔丁基)苯酚、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苯甲基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮、3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯、二硬脂基季戊四醇二亚磷酸酯、三(2,4-叔丁基苯基)亚磷酸酯、三(1,2,2,6-五甲基-4-4-哌啶基)亚磷酸酯中的一种或几种。
作为本发明的一个实施方案,所述紫外吸收剂包括2-(2’-羟基-3’-叔丁基-5’-甲基苯基)-5-氯代苯并三唑、2-(2-羟基-3,5-二丁叔基苯基)-5-氯代苯并三唑、2-(2’-羟基-3’,5’-二叔戊基苯基)苯并三唑或2-羟基-4-正辛氧基二苯甲酮中的至少一种。
作为本发明的一个实施方案,所述光稳定剂包括受阻胺光稳定剂。所述受阻胺光稳定剂包括Tinuvin 292,Tinuvin123,光稳定剂944中的至少一种。
作为本发明的一个实施方案,组分b所述的多元异氰酸酯,为平均官能度3~5.5的异氰酸酯及异氰酸酯多聚体。多元异氰酸酯包括三苯基甲烷三异氰酸酯、HDI三聚体、甲苯二异氰酸酯三聚体、二甲基三苯基甲烷四异氰酸酯中一种或多种。官能度过高会导致固化后胶层过硬,剥离不佳;官能度过低会导致交联密度过低,耐老化性不佳。而本专利的异氰酸酯组分为异氰酸酯自聚加成物。
所述的太阳能电池背板用胶黏剂组合物,所述a组分(预聚体组分)和b组分(固化组分)的重量比为(5-15):1。
本发明还提供了一种双组分无溶剂光伏背板胶黏剂的制备方法,所述制备方法包括如下步骤:将聚酯多元醇、环氧树脂、增粘树脂和助剂加热搅拌至熔融,继续搅拌,过滤后冷却即得到组分a;将组分a、组分b按照比例混合后,即得所述双组分无溶剂光伏背板胶黏剂。
作为本发明的一个实施方案,所述加热温度为60-150℃。搅拌时间为20-40min。双组分无溶剂光伏背板胶黏剂的使用方法为将a、b组分按照比例混合后,加入连续混合进样系统即可涂布使用。
与现有技术相比,本发明具有如下有益效果:
(1)本发明的创新点在于,使用的聚酯多元醇官能度为2,较低的交联度使得聚酯生产和指标控制更加简单,尤其使用了脂环族二元酸,在保证耐水解性能的同时,大幅降低了树脂粘度,改善了施工性能;使用的异氰酸酯≥3,提高了交联密度改善了抗老化性能;同时使用较低粘度的主树脂和固化剂,使得涂布复合工艺更好控制。
(2)发明不添加其他配方常用的聚碳酸酯和硅烷偶联剂,成本更低廉且与基材亲和性更好,添加增粘树脂改善了浸润性粘结强度更高,而且降低了熔融粘度。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
本实施例涉及一种双组份无溶剂光伏背板胶黏剂:由组分(A)和组分(B)组成,其中组分(A)由10份的环氧树脂、5份的松香增粘树脂、0.00001份月桂酸二丁基锡、0.1份抗氧剂1010、0.5份紫外吸收剂2-(2’-羟基-3’-叔丁基-5’-甲基苯基)-5-氯代苯并三唑、0.5份光稳定剂Tinuvin 292,余量为聚酯多元醇a,共计100份;80℃加热搅拌至熔融,继续搅拌30min,过滤后冷却即得到。
聚酯多元醇a由1,2-环己烷二甲酸酐、1,6-己二醇、新戊二醇进行缩聚酯化反应制得,其比例为58:22:20,制得的聚酯多元醇分子量Mn为4000,玻璃化转变温度为-10℃;
组分(B)为六亚甲基二异氰酸酯(HDI)三聚体,官能度为5;
将预主剂与固化组分按7.5:1的重量比混合均匀后,加入连续混合进样系统涂布使用,涂布温度70℃,复合上25μm厚的PVDF膜,放入60℃烘箱熟化2天。
实施例2
本实施例涉及一种双组份无溶剂光伏背板胶黏剂:由组分(A)和组分(B)组成,其中组分(A)由10份的环氧树脂、5份的松香增粘树脂、月桂酸二丁基锡0.0001份、0.5份抗氧剂1010、0.5份紫外吸收剂2-(2’-羟基-3’-叔丁基-5’-甲基苯基)-5-氯代苯并三唑、0.5份光稳定剂Tinuvin 292,余量为聚酯多元醇b,共计100份。80℃加热搅拌至熔融,继续搅拌30min,过滤后冷却即得到;
聚酯多元醇b由邻苯二甲酸酐、己二酸、新戊二醇、3-甲基戊二醇进行缩聚酯化反应制得,其比例为51:5.5:16:27.5,制得的聚酯多元醇分子量Mn为3000,玻璃化转变温度为-1℃;
组分(B)为六亚甲基二异氰酸酯(HDI)三聚体,官能度为4.2;
将预聚体组分与固化组分按10:1的重量比混合均匀后,加入连续混合进样系统涂布使用,涂布温度80℃,复合上25μm厚的PVDF膜,放入60℃烘箱熟化2天。
实施例3
本实施例涉及一种双组份无溶剂光伏背板胶黏剂:由组分(A)和组分(B)组成,其中组分(A)由20份的环氧树脂、1份的松香增粘树脂、月桂酸二丁基锡0.0003份、0.5份抗氧剂1010、1份紫外吸收剂2-(2’-羟基-3’-叔丁基-5’-甲基苯基)-5-氯代苯并三唑、1份光稳定剂Tinuvin 292,余量为聚酯多元醇c,共计100份。80℃加热搅拌至熔融,继续搅拌30min,过滤后冷却即得到;
聚酯多元醇c由间苯二甲酸,癸二酸、1,5-戊二醇、一缩二乙二醇进行缩聚酯化反应制得,其比例为41:21:30:8,制得的聚酯多元醇分子量Mn为2000,玻璃化转变温度为7℃;
组分(B)为六亚甲基二异氰酸酯(HDI)三聚体,官能度为4.2;
将预聚体组分与固化组分按10:1的重量比混合均匀后,加入连续混合进样系统涂布使用,涂布温度80℃,复合上25μm厚的PVDF膜,放入60℃烘箱熟化2天。
实施例4
本实施例涉及一种双组份无溶剂光伏背板胶黏剂:由组分(A)和组分(B)组成,其中组分(A)由10份的环氧树脂、15份的松香增粘树脂、月桂酸二丁基锡0.0003份、0.5份抗氧剂1010、1份紫外吸收剂2-(2’-羟基-3’-叔丁基-5’-甲基苯基)-5-氯代苯并三唑、1份光稳定剂Tinuvin 292,余量为聚酯多元醇d,共计100份。80℃加热搅拌至熔融,继续搅拌30min,过滤后冷却即得到;
聚酯多元醇d由1-2-环己烷二甲酸酐,间苯二甲酸、1,6-己二醇、一缩二丙二醇进行缩聚酯化反应制得,其比例为26:29:21:24,制得的聚酯多元醇分子量Mn为2000,玻璃化转变温度为-5℃;
组分(B)为六亚甲基二异氰酸酯(HDI)三聚体,官能度为4.2;
将预聚体组分与固化组分按12:1的重量比混合均匀后,加入连续混合进样系统涂布使用,涂布温度80℃,复合上25μm厚的PVDF膜,放入60℃烘箱熟化2天。
实施例5
本实施例涉及一种双组份无溶剂光伏背板胶黏剂:由组分(A)和组分(B)组成,其中组分(A)由8份的环氧树脂、3份的松香增粘树脂、月桂酸二丁基锡0.0003份、0.5份抗氧剂1010、1份紫外吸收剂2-(2’-羟基-3’-叔丁基-5’-甲基苯基)-5-氯代苯并三唑、1份光稳定剂Tinuvin 292,余量为聚酯多元醇e,共计100份。80℃加热搅拌至熔融,继续搅拌30min,过滤后冷却即得到;
聚酯多元醇e由邻苯二甲酸酐,1-2-环己烷二甲酸酐、新戊二醇、一缩二丙二醇进行缩聚酯化反应制得,其比例为38:18:27:15,制得的聚酯多元醇分子量Mn为1000,玻璃化转变温度为20℃;
组分(B)为六亚甲基二异氰酸酯(HDI)三聚体,官能度为4.2;
将预聚体组分与固化组分按5:1的重量比混合均匀后,加入连续混合进样系统涂布使用,涂布温度80℃,复合上25μm厚的PVDF膜,放入60℃烘箱熟化2天。
对比例1
取与实施例相同PET膜,在PET膜一侧涂布市售溶剂型聚氨酯胶PA-3018,涂胶量为10g/m2复合与实施例相同的氟膜,采用与实施例相同的涂布固化处理方法。
对比例2
本对比例的胶粘剂与实施例1基本相同,不同之处仅在于:组分A中聚酯多元醇f由邻苯二甲酸酐,新戊二醇,己二醇,丙三醇比例为57:19:22:1进行缩聚酯化反应制得,其制得的聚酯多元醇分子量Mn为3000,官能度大于2,玻璃化转变温度为34℃。
对比例3
本对比例的胶粘剂与实施例2基本相同,不同之处仅在于:组分A中聚酯多元醇f由邻苯二甲酸酐,新戊二醇,己二醇比例为57:20:22行缩聚酯化反应制得,其制得的聚酯多元醇分子量Mn较大为6000,官能度等于2,玻璃化转变温度为34℃。
对比例4
本对比例的胶粘剂与实施例1基本相同,不同之处仅在于:未添加增粘树脂;
表1实施例与对比例性能对比
通过上述数据可以看出实施例所述胶黏剂与市售溶剂型胶黏剂性能接近。
需要说明的是,上述胶黏剂胶膜的各项性能指标是通过以下的方法来进行测定的:
1.剥离强度
测试方法参照国家标准GB/T2790《胶粘剂180°剥离强度试验方法挠性材料对刚性材料》。样品以100mm/min速度在拉力机上测定PVDF与PET间的粘结强度,记录剥离强度数值。
2、恒定耐湿热老化性能
按GB/T2423.3试验方法进行湿热老化试验。
试验条件:85℃,相对湿度85%,2000h。试验前、后对试样按照国家标准GB/T2790《胶粘剂180°剥离强度试验方法挠性材料对刚性材料》进行剥离力测定。
3、玻璃化转变温度
测试方法参照国家标准GB/T 27816-2011《色漆和清漆用漆基玻璃化转变温度的测定》
4、分子量
测试方法参照国家标准GB/T27810-2011《色漆和清漆用漆基凝胶渗透色谱法用四氢呋喃做洗脱剂》。
本发明具体应用途径很多,以上所述仅是本发明的优选实施方式。应当指出,以上实施例仅用于说明本发明,而并不用于限制本发明的保护范围。对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进,这些改进也应视为本发明的保护范围。
Claims (10)
1.一种双组分无溶剂光伏背板胶黏剂,其特征在于,所述双组分无溶剂光伏背板胶黏剂包括a组分和b组分;
a组分包括按重量份数计的如下成分:70-95份聚酯多元醇、5-20份环氧树脂、1-15份增粘树脂、助剂1.10001-2.5003份;
b组分包括多元异氰酸酯。
2.根据权利要求1所述的双组份太阳能电池背板用胶黏剂组合物,其特征在于,所述的聚酯多元醇为由二元酸与二元醇进行缩聚酯化反应制得的聚酯多元醇,分子量Mn为1000-4000,官能度为2,玻璃化转变温度为-10至20℃。
3.根据权利要求2所述的双组份太阳能电池背板用胶黏剂组合物,其特征在于,所述二元酸包括1,2-环己烷二甲酸、1,3-环己烷二甲酸、1,4-环己烷二甲酸、环戊烷二甲酸、环丁烷二甲酸、甲基六氢苯酐、萘二羧酸、联苯二羧酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、丁二酸、己二酸、癸二酸、月桂二酸中的一种或任意两种以上的组合。
4.根据权利要求2所述的双组份太阳能电池背板用胶黏剂组合物,其特征在于,所述二元醇为脂肪族二元醇,包括乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、己二醇、一缩二丙二醇、一缩二乙二醇、新戊二醇、1,9-壬二醇、3-甲基-戊二醇中的一种或一种以上的组合。
5.根据权利要求1所述的双组份太阳能电池背板用胶黏剂组合物,其特征在于,所述的环氧树脂包括双酚a环氧树脂、双酚f环氧树脂、酚醛环氧树脂、氢化环氧树脂、缩水甘油酯型环氧树脂的一种或一种以上的组合。
6.根据权利要求1所述的双组份太阳能电池背板用胶黏剂组合物,其特征在于,所述的增粘树脂包括松香树脂、氢化松香树脂、萜烯树脂、c5/9石油树脂的一种或一种以上的组合。
7.根据权利要求1所述的双组份太阳能电池背板用胶黏剂组合物,其特征在于,所述助剂包括催化剂0.00001-0.0003份、抗氧剂0.1-0.5份、紫外吸收剂0.5-1份、光稳定剂0.5-1份。
8.根据权利要求1所述的双组份太阳能电池背板用胶黏剂组合物,其特征在于,组分b所述的多元异氰酸酯,为平均官能度3~5.5的异氰酸酯及异氰酸酯多聚体。
9.根据权利要求1所述的双组份太阳能电池背板用胶黏剂组合物,其特征在于,其特征在于,所述a组分和b组分的重量比为(5-15):1。
10.一种如权利要求1所述的双组分无溶剂光伏背板胶黏剂的制备方法,其特征在于,所述制备方法包括如下步骤:将聚酯多元醇、环氧树脂、增粘树脂和助剂加热搅拌至熔融,继续搅拌,过滤后冷却即得到组分a;将组分a、组分b按照比例混合后,即得所述双组分无溶剂光伏背板胶黏剂。
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