CN105907354B - 一种耐候性胶粘剂及其在太阳能电池背板上的应用 - Google Patents
一种耐候性胶粘剂及其在太阳能电池背板上的应用 Download PDFInfo
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- CN105907354B CN105907354B CN201610420837.0A CN201610420837A CN105907354B CN 105907354 B CN105907354 B CN 105907354B CN 201610420837 A CN201610420837 A CN 201610420837A CN 105907354 B CN105907354 B CN 105907354B
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Abstract
本发明公开了一种耐候性胶粘剂。所述胶粘剂为含有A组分和B组分的双组份聚氨酯胶粘剂,其中A组分由聚酯多元醇、丙烯酸酯多元醇、聚醚多元醇和助剂组成;B组分主要由异氰酸酯组成。本发明制备的胶粘剂具有较好的初始剥离力,能在环境恶劣的情况下保持较好的粘结力,不易发生黄变,可以应用在耐候性要求较高的场合。
Description
技术领域
本发明涉及胶粘剂技术领域,特别是一种耐候性的胶粘剂。
背景技术
户外工业用途的材料,如建筑材料和太阳能电池背板材料等,长期暴露于室外,对胶粘剂要求具有优异的耐候性能,特别是用于太阳能电池背板材料的胶粘剂,需要比常规户外工业用途材料更高水平的耐候性。
太阳能电池作为绿色能源的实践使用越来越受到重视,并已经取得进展。太阳能电池背板位于太阳能电池板的背面,对电池片起到保护和支撑作用,因此要求背板具有较好的粘结强度、较高的电绝缘性能,能阻隔湿热、氧化,耐水汽、紫外线辐射,和优异的耐冷热冲击等性能。
太阳能电池背板是由多层高分子薄膜经胶粘剂粘合得到复合膜。因此要求在复合背板中使用的胶粘剂在经过长期的湿热、紫外辐射等苛刻的条件后依然保持良好的耐老化性能、粘结强度和黄变值等性能。
CN 103282459 A公开了一种室外聚氨酯胶粘剂,其通过聚酯多元醇、丙烯酸酯多元醇和异氰酸酯反应制得聚氨酯胶粘剂,通过加入羟苯基三嗪的化合物改善其耐紫外老化性能。其胶粘剂固化后的粘结力较好,胶层的柔韧性较好,且耐候性较好。但使用其制得的背板初始粘结力较差,不能满足目前对背板初始粘结力更高的要求。
发明内容:
本发明的目的在于提供一种耐候性好的胶粘剂,所述耐候性胶粘剂具有优异的初始粘结力,低温短时间熟化后,能长时间保持优良的粘结力、耐湿热性能、耐黄变性能等耐候性能。
本发明的另一目的是提供所述耐候性胶粘剂在太阳能电池背板上的应用,它能够简化生产工艺,同时保证太阳能电池背板的性能。
本发明的目的是通过如下技术方案实现的:
一种耐候性胶粘剂,所述胶粘剂由A组分和B组分组成;其中A组分由多元醇组合物和助剂组成;B组分为脂肪族异氰酸酯B1和脂环族异氰酸酯B2的至少一种;其中,
A组分
多元醇组合物 50-80份,
助剂 1-15份,
B组分 5-15份;
所述多元醇组合物的组成及质量百分含量为:
聚醚多元醇A1 5-40%,
聚酯多元醇A2 5-40%,
丙烯酸酯多元醇A3 40-80%。
所述的助剂为环氧树脂、催化剂、紫外线吸收剂、光稳定剂、抗氧剂、抗水解剂中的一种或几种。
上述耐候性胶粘剂,所述助剂的组成及质量份数为:
上述耐候性胶粘剂,所述聚醚多元醇A1分子量为1000-8000,羟值为20-50mgKOH/g的二官能度聚醚多元醇或三官能度聚醚多元醇中的一种或者两种。
上述耐候性胶粘剂,所述聚酯多元醇A2分子量为1000-8000,羟值为20-60mgKOH/g。
上述耐候性胶粘剂,所述丙烯酸酯多元醇A3分子量为5000-100000,羟值为15-50mgKOH/g。
上述耐候性胶粘剂,所述脂肪族异氰酸酯B1为1,4-二异氰酸酯基丁烷、1,5-二异氰酸酯基戊烷、1,6-二异氰酸酯基己烷、1,6-二异氰酸酯基-2,2,4-三甲基己烷、甲基-2,6-二异氰酸酯基己酸酯(二异氰酸赖氨酸酯)、1,3-双(异氰酸酯基-甲基)苯(亚二甲苯基二异氰酸酯)中的一种或几种;所述的脂环族异氰酸酯B2为5-异氰酸酯基-1-异氰酸酯甲基-1,3,3-三甲基环己烷(异佛尔酮二异氰酸酯)、1,3-双(异氰酸酯甲基)环己烷(氢化亚二甲苯基二异氰酸酯)、双(4-异氰酸酯环己基)甲烷(氢化二苯基甲烷二异氰酸酯)、1,4-二异氰酸酯基环己烷中的一种或几种。
上述耐候性胶粘剂,所述胶粘剂的组成及质量份数为:
A组分
其中,多元醇组合物的组成及百分含量为
聚醚多元醇A1 8-35%;
聚酯多元醇A2 8-35%;
丙烯酸酯多元醇A3 35-75%。
本发明的另一目的是通过如下技术方案实现的:
一种胶粘剂在太阳能电池背板上的应用,在背板支撑层PET上涂布上述胶粘剂,在70℃-100℃温度下,干燥1-5分钟,得到干燥后厚度为5-10μm胶膜,将胶膜与粘结层或耐候层在温度为70℃-90℃和压力0.3-0.5MPa下进行热压复合,在40-60℃下,熟化24-72小时,即得太阳能电池背板。
有益效果
本发明的耐候性胶粘剂,通过聚酯多元醇、丙烯酸酯多元醇和聚醚多元醇的组合使用,与异氰酸酯反应,-OH与-NCO按1:1-1.5比例进行混合,提高了胶粘剂的初始粘结力,并且可以使胶粘剂在低温短时间熟化后,长时间保持优良的粘结力、耐湿热性能、耐黄变性能等耐候性能。
本发明的耐候性胶粘剂,通过优选聚醚多元醇、聚酯多元醇和丙烯酸酯多元醇的分子量和羟值,使得胶粘剂的初始粘结力由1-2N/15mm,提高到4-5N/15mm,并且使其在低温短时间熟化后,长时间保持良好的熟化后剥离力,以及在耐湿热及耐黄变等方面显示更加优异的性能。
本发明的耐候性胶粘剂应用于太阳能电池背板后,由于较高的初始粘结力,可以在涂布复合后可直接进行收卷或者分割,不用再费时熟化,节省时间,提高生产效率。同时由于具有较好的熟化后的剥离力,能够保证太阳能电池背板的使用寿命。
具体实施方式
本发明具有较高耐候性的胶粘剂,由A组分和B组分组成;其中A组分由多元醇组合物和助剂组成;B组分为脂肪族异氰酸酯B1和脂环族异氰酸酯B2的至少一种,其中:
所述多元醇组合物包括聚醚多元醇A1、聚酯多元醇A2和丙烯酸酯多元醇A3,并且,所述的助剂为环氧树脂、催化剂、紫外线吸收剂、光稳定剂、抗氧剂、抗水解剂中的一种或几种。
多元醇组合物的组成及质量百分含量为:
聚醚多元醇A1 5-40%
聚酯多元醇A2 5-40%
丙烯酸酯多元醇A3 40-80%
聚醚多元醇A1分子量为1000-8000,羟值为20-50mgKOH/g,可为二官能度聚醚多元醇和三官能度聚醚多元醇的一种或者两种。
聚醚多元醇A1为聚四氢呋喃(PTMG)、聚氧亚丙基二醇(PPG)、聚氧亚乙基二醇(PEG)、四氢呋喃-氧化丙烯共聚二醇等。
聚酯多元醇A2为,分子量为1000-8000,羟值为20-60mgKOH/g。
聚酯多元醇A2通过多元醇与二羧酸及其酸酐的缩聚反应获得,所用二羧酸及其酸酐可以是乙二酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二烷二酸、2-甲基丁二酸、2-甲基己二酸、3-甲基己二酸、3-甲基戊二酸、2-甲基辛二酸、3,8-二甲基癸二酸、3,7-二甲基癸二酸、邻苯二甲酸、对苯二甲酸、间苯二甲酸、乙酸酐、丙酸酐、丁二酸酐、顺丁烯二酸酐和邻苯二甲酸酐等。所用多元醇为乙二醇、丙二醇、丁二醇、戊二醇、己二醇、庚二醇、辛二醇、壬二醇和癸二醇、2-丁基-2-乙基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、2,2-二甲基-1,3-丙二醇、3,3-二甲基-1,5-戊二醇、3,3-二乙基-1,5-戊二醇、2-乙基-2-丁基-1,3-丙二醇等。
丙烯酸酯多元醇A3分子量为5000-100000,羟值为15-50mgKOH/g,丙烯酸酯多元醇可为含有羟基基团的(甲基)丙烯酸酯的均聚物或共聚物。带有羟基基团的(甲基)丙烯酸酯均聚物如(甲基)丙烯酸-2-羟乙酯、(甲基)丙烯酸-2-羟丙酯、(甲基)丙烯酸-3-羟丙酯、甘油单(甲基)丙烯酸酯、丙烯酸-4-羟丁酯等;包括(甲基)丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸-2-乙基己基酯、(甲基)丙烯酸二环戊酯、(甲基)丙烯酸异冰片酯、苯乙烯和乙烯基甲苯等单体与带有羟基基团的(甲基)丙烯酸酯的共聚物。本发明选用的三种多元醇,在一定范围内其分子量增大,则初始剥离力相应增大,熟化后剥离力减小,耐湿热性能下降;但分子量过大或过小,都会导致耐湿热性能下降;在一定范围内其羟值增大,初始剥离力相应增大,熟化后剥离力增大,耐湿热性能减小。本发明选用三种多元醇的组合使用,通过分子量和羟值优选,在初始剥离力、熟化后剥离力和耐湿热性能之间做出平衡,使得到的胶粘剂应用于太阳能电池背板时,初始剥离力满足收卷的要求,同时,熟化后的剥离力和耐湿热性满足太阳能电池背板长寿命的应用要求。
脂肪族异氰酸酯B1为1,4-二异氰酸酯基丁烷、1,5-二异氰酸酯基戊烷、1,6-二异氰酸酯基己烷、1,6-二异氰酸酯基-2,2,4-三甲基己烷、甲基-2,6-二异氰酸酯基己酸酯(二异氰酸赖氨酸酯)、1,3-双(异氰酸酯基-甲基)苯(亚二甲苯基二异氰酸酯)中的一种或几种。
脂环族异氰酸酯B2为5-异氰酸酯基-1-异氰酸酯甲基-1,3,3-三甲基环己烷(异佛尔酮二异氰酸酯)、1,3-双(异氰酸酯甲基)环己烷(氢化亚二甲苯基二异氰酸酯)、双(4-异氰酸酯环己基)甲烷(氢化二苯基甲烷二异氰酸酯)、1,4-二异氰酸酯基环己烷中的一种或几种。
本发明的耐候性胶粘剂,可以含有环氧树脂,优选缩水甘油醚类环氧树脂、缩水甘油酯类环氧树脂、缩水甘油胺类环氧树脂、线型脂肪族类环氧树脂、脂环族类环氧树脂一种或几种。
本发明耐候性胶粘剂,可以含有催化剂,优选金属催化剂和胺基催化剂。金属催化剂如锡类催化剂(十二酸三甲基锡、三甲基锡氢氧化物、双十二酸二丁基锡、顺丁烯二二丁基锡等)、铅基催化剂(油酸铅、环烷酸铅、辛烯酸铅等)和其他金属催化剂(环烷酸金属盐如环烷酸钴)。胺基催化剂如三亚乙基二胺、四甲基乙二胺等。
本发明的耐候性胶粘剂,优选含有硅烷的化合物,例如(甲基)丙烯酰氧基烷基三烷氧基硅烷、(甲基)丙烯酰氧基烷基烷基烷氧基硅烷、乙烯基三烷氧基硅烷、乙烯基烷基烷氧基硅烷、环氧硅烷、巯基硅烷和异氰尿酸酯硅烷。然而,硅烷化合物不仅限于这些硅烷化合物。
本发明的耐候性胶粘剂,使用的紫外线吸收剂优选羟苯基三嗪的化合物和苯并三唑的化合物如TINUVIN405、TINUVIN479、TINUVIN477、TINUVIN234、TINUVIN571等。
本发明的耐候性胶粘剂,使用的抗氧剂优选受阻酚的化合物,如IRGANOX1010、IRGANOX1035、IRGANOX1076、IRGANOX1135等。
本发明的耐候性胶粘剂,使用的光稳定剂优选受阻胺的化合物,如,TINUVIN765、TINUVIN111FDL、TINUVIN123、TINUVIN144等。
本发明具有较高耐候性的胶粘剂,使用的抗水解剂,例如N,N′-二-邻甲苯基碳二酰亚胺,N,N′-二苯基碳二酰亚胺,N,N′-二-2,6-二甲基苯基碳化二亚胺,2-恶唑啉、2-甲基-2-恶唑啉、2-苯基-2-恶唑啉等中的一种或几种本发明具有较高耐候性的胶粘剂,可使用酮类和/或酯类溶剂,如丙酮、环己酮、甲乙酮、乙酸乙酯、乙酸丁酯等。可以为其中的任意一种或至少两种的混合物。
耐候性胶粘剂制备工艺
将聚酯多元醇、聚醚多元醇、丙烯酸酯多元醇及溶剂添加到反应釜中混合均匀,再向反应釜中添加催化剂、紫外线吸收剂、光稳定剂、抗氧剂、抗水解剂等助剂,混合均匀。再添加异氰酸酯组合物B,搅拌10-40min,即可得到所述胶粘剂。
背板复合工艺
在背板支撑层PET上涂布上述胶粘剂,在70℃-100℃温度下,干燥1-5分钟,得到干燥后厚度为5-10μm胶膜,将胶膜与粘结层或耐候层在温度为70℃-90℃和压力0.3-0.5MPa下进行热压复合,40-60℃,24-72小时熟化,即得太阳能电池背板。
背板中粘结层为聚乙烯、超高分子量聚乙烯组成的膜材料,,可在其中添加各种添加剂等。背板中的耐候层通常为氟系聚合物组成的膜材料,可以是:氟化聚烯烃以及聚烯烃-氟化聚烯烃共聚物,具体有聚氟乙烯(PVF)、聚偏氟乙烯(PVDF)、聚三氟氯乙烯(PCTFE)、聚乙烯四氟(ETFE)、聚四氟乙烯(PTFE)、四氟乙烯全氟烷基乙烯基醚共聚物(FPA)、四氟乙烯-六氟丙烯共聚物(FEP)等。
背板中所使用的支撑层PET、粘结层、和耐候层,可以对其进行电晕处理,火焰处理,等离子处理等的表面处理,提高涂布面以及粘合面的粘合性。
以下给出几个实施例。
为更好的说明和理解本发明,将提出几个实施例和对比例对本发明做进一步描述,但这些实施例并非只在对本发明的实施方式进行限制。
实施例1
A组分包括聚醚多元醇A1,为聚氧亚丙基二醇,其分子量为1000,羟值为50mgKOH/g,用量占多元醇组合物总量的5%,共4.13g;
聚酯多元醇A2,由邻苯二甲酸酐与2-丁基-2-乙基-1,3-丙二醇缩聚制得,其分子量为8000,羟值为20mgKOH/g,用量占多元醇组合物总量的40%,共33.00g;
丙烯酸酯多元醇A3,由甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸丁酯和甲基丙烯酸-2-羟乙酯共聚获得的丙烯酸酯多元醇,其分子量为100000,羟值为15mgKOH/g,用量占多元醇组合物总量的55%,共45.39g。
B组份为脂肪族异氰酸酯B1,1,6-二异氰酸酯基己烷,7.10g。
助剂为双酚A型缩水甘油醚环氧树脂,4.48g,催化剂二月桂酸二丁基锡,0.04g,偶联剂乙烯基三烷氧基硅烷,0.90g,紫外线吸收剂TINUVIN571,0.55g,光稳定剂TINUVIN765,0.55g,抗氧剂IRGANOX1135,0.28g,抗水解剂N,N′-二苯基碳二酰亚胺,3.58g。
溶剂为乙酸乙酯,300g。
将聚酯多元醇、聚醚多元醇、丙烯酸酯多元醇及溶剂添加到反应釜中混合均匀,再向反应釜中加入上述助剂,混合均匀。再添加B1,1,6-二异氰酸酯基己烷,搅拌20min,即可得到所述胶粘剂。
在背板支撑层PET上涂布上述胶粘剂,在70℃温度下,干燥5分钟,得到干燥后厚度为10μm胶膜,将胶膜与PE膜在温度为70℃和压力0.5MPa下进行热压复合,40℃,72小时熟化。
实施例2
A组分包括聚醚多元醇A1,为聚四氢呋喃,其分子量为8000,羟值为20mgKOH/g,用量占多元醇组合物总量的40%,共30.43g;聚酯多元醇A2,由邻苯二甲酸酐和2,4-二丁基-1,5-戊二醇缩聚制得,其分子量为1000,羟值为60mgKOH/g,用量占多元醇组合物总量的5%,共3.81g;丙烯酸酯多元醇A3,使用丙烯酸丁酯、甲基丙烯酸环己酯、甲基丙烯酸-2-羟乙酯和甲基丙烯酸丁酯获得的丙烯酸酯多元醇,其分子量为5000,羟值为50mgKOH/g,用量占多元醇组合物总量的55%,共41.84g。
B组份为脂肪族异氰酸酯B1,1,6-二异氰酸酯基己烷,13.44g。
其它助剂包括环氧树脂为双酚A型缩水甘油醚,4.5g,催化剂为二月桂酸二丁基锡,0.04g,偶联剂为乙烯基三烷氧基硅烷,0.91g,紫外线吸收剂为TINUVIN571,0.58g,光稳定剂为TINUVIN765,0.58g,抗氧剂为IRGANOX1135,0.29g,抗水解剂为N,N′-二苯基碳二酰亚胺,3.58g。
溶剂为乙酸乙酯,300g。
将聚酯多元醇、聚醚多元醇、丙烯酸酯多元醇及溶剂添加到反应釜中混合均匀,再向反应釜中添加催化剂、紫外线吸收剂、光稳定剂、抗氧剂、抗水解剂等助剂,混合均匀。再添加异氰酸酯组合物B,搅拌20min,即可得到所述胶粘剂。
在背板支撑层PET上涂布上述胶粘剂,在100℃温度下,干燥1分钟,得到干燥后厚度为10μm胶膜,将胶膜与ETFE膜在温度为90℃和压力0.3MPa下进行热压复合,60℃,24小时熟化。
实施例3
A组分包括聚醚多元醇A1,为聚氧亚乙基二醇,其分子量为3000,羟值为30mgKOH/g,用量占多元醇组合物总量的25%,共19.40g;聚酯多元醇A2,由2-甲基丁二酸与3,3-二甲基-1,5-戊二醇缩聚而得,其分子量为2000,羟值为45mgKOH/g,用量占多元醇组合物总量的25%,共19.40g;丙烯酸酯多元醇A3,为(甲基)丙烯酸-2-羟丙酯均聚物,其分子量为50000,羟值为30mgKOH/g,用量占多元醇组合物总量的50%,共38.80g。
B组份为脂肪族异氰酸酯B1,1,6-二异氰酸酯基己烷,12.01g。
其它助剂包括环氧树脂为双酚A型缩水甘油醚,4.47g,催化剂为二月桂酸二丁基锡,0.04g,偶联剂为乙烯基三烷氧基硅烷,0.89g,紫外线吸收剂为TINUVIN571,0.56g,光稳定剂为TINUVIN765,0.56g,抗氧剂为IRGANOX1135,0.28g,抗水解剂为N,N′-二苯基碳二酰亚胺,3.59g。
溶剂为乙酸乙酯,300g。
将聚酯多元醇、聚醚多元醇、丙烯酸酯多元醇及溶剂添加到反应釜中混合均匀,再向反应釜中添加催化剂、紫外线吸收剂、光稳定剂、抗氧剂、抗水解剂等助剂,混合均匀。再添加异氰酸酯组合物B,搅拌20min,即可得到所述胶粘剂。
在背板支撑层PET上涂布上述胶粘剂,在90℃温度下,干燥2分钟,得到干燥后厚度为5μm胶膜,将胶膜与PVDF膜在温度为80℃和压力0.4MPa下进行热压复合,50℃,48小时熟化。
实施例4
A组分包括聚醚多元醇A1,为聚氧亚丙基二醇,其分子量为3000,羟值为30mgKOH/g,用量占多元醇组合物总量的30%,共22.4g;聚酯多元醇A2,由邻苯二甲酸酐和2,4-二丁基-1,5-戊二醇缩聚制得,其分子量为2000,羟值为45mgKOH/g,用量占多元醇组合物总量的30%,共22.4g;丙烯酸酯多元醇A3,为(甲基)丙烯酸-2-羟乙酯均聚物,其分子量为50000,羟值为30mgKOH/g,用量占多元醇组合物总量的40%,共29.87g。
B组份为脂肪族异氰酸酯B2,异佛尔酮二异氰酸酯,12.01g。
其它助剂包括环氧树脂为双酚A型缩水甘油醚,4.47g,催化剂为二月桂酸二丁基锡,0.04g,偶联剂为乙烯基三烷氧基硅烷,0.90g,紫外线吸收剂为TINUVIN571,0.57g,光稳定剂为TINUVIN765,0.57g,抗氧剂为IRGANOX1135,0.28g,抗水解剂为N,N′-二苯基碳二酰亚胺,3.60g。
溶剂为乙酸乙酯,300g。
将聚酯多元醇、聚醚多元醇、丙烯酸酯多元醇及溶剂添加到反应釜中混合均匀,再向反应釜中添加催化剂、紫外线吸收剂、光稳定剂、抗氧剂、抗水解剂等助剂,混合均匀。再添加异氰酸酯组合物B,搅拌20min,即可得到所述胶粘剂。
在背板支撑层PET上涂布上述胶粘剂,在90℃温度下,干燥2分钟,得到干燥后厚度为8μm胶膜,将胶膜与PVF膜在温度为80℃和压力0.5MPa下进行热压复合,50℃,72小时熟化。
实施例5
A组分包括聚醚多元醇A1,为聚四氢呋喃,其分子量为3000,羟值为30mgKOH/g,用量占多元醇组合物总量的10%,共7.72g;聚酯多元醇A2,由邻苯二甲酸酐与2-丁基-2-乙基-1,3-丙二醇缩聚制得,其分子量为2000,羟值为45mgKOH/g,用量占多元醇组合物总量的10%,共7.72g;丙烯酸酯多元醇A3,丙烯酸-4-羟丁酯,其分子量为50000,羟值为30mgKOH/g,用量占多元醇组合物总量的80%,共61.73g。
B组份为脂肪族异氰酸酯B1和脂环族异氰酸酯B2的1:1混合物,1,6-二异氰酸酯基己烷,6.22g;异佛尔酮二异氰酸酯,6.22g。
其它助剂包括环氧树脂为双酚A型缩水甘油醚,4.48g,催化剂为二月桂酸二丁基锡,0.04g,偶联剂为乙烯基三烷氧基硅烷,0.90g,紫外线吸收剂为TINUVIN571,0.56g,光稳定剂为TINUVIN765,0.56g,抗氧剂为IRGANOX1135,0.28g,抗水解剂为N,N′-二苯基碳二酰亚胺,3.57g。
溶剂为乙酸乙酯,300g。
将聚酯多元醇、聚醚多元醇、丙烯酸酯多元醇及溶剂添加到反应釜中混合均匀,再向反应釜中添加催化剂、紫外线吸收剂、光稳定剂、抗氧剂、抗水解剂等助剂,混合均匀。再添加异氰酸酯组合物B,搅拌20min,即可得到所述胶粘剂。
在背板支撑层PET上涂布上述胶粘剂,在90℃温度下,干燥2分钟,得到干燥后厚度为8μm胶膜,将胶膜与PE膜在温度为80℃和压力0.5MPa下进行热压复合,50℃,72小时熟化。
对比例1
A组分包括聚酯多元醇A2,由邻苯二甲酸酐和2,4-二丁基-1,5-戊二醇缩聚制得,其分子量为2000,羟值为45mgKOH/g,用量占多元醇组合物总量的30%,共23.19g;丙烯酸酯多元醇A3,由甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸丁酯和甲基丙烯酸-2-羟乙酯获得的丙烯酸酯多元醇,其分子量为50000,羟值为30mgKOH/g,用量占多元醇组合物总量的70%,共54.11g。
B组份为脂肪族异氰酸酯B1,1,6-二异氰酸酯基己烷,12.23g。
其它助剂包括环氧树脂为双酚A型缩水甘油醚,4.49g,催化剂为二月桂酸二丁基锡,0.04g,偶联剂为乙烯基三烷氧基硅烷,0.89g,紫外线吸收剂为TINUVIN571,0.58g,光稳定剂为TINUVIN765,0.58g,抗氧剂为IRGANOX1135,0.29g,抗水解剂为N,N′-二苯基碳二酰亚胺,3.60g。
溶剂为乙酸乙酯,300g。
将聚酯多元醇、聚醚多元醇、丙烯酸酯多元醇及溶剂添加到反应釜中混合均匀,再向反应釜中添加催化剂、紫外线吸收剂、光稳定剂、抗氧剂、抗水解剂等助剂,混合均匀。再添加异氰酸酯组合物B,搅拌20min,即可得到所述胶粘剂。
在背板支撑层PET上涂布上述胶粘剂,在90℃温度下,干燥2分钟,得到干燥后厚度为8μm胶膜,将胶膜与PE膜在温度为80℃和压力0.5MPa下进行热压复合,50℃,72小时熟化。
实施例1-5及对比例1配方及测试得到结果如表1。
表1:
测试方法及标准
初始剥离力样品制备
在背板支撑层PET上涂布上述胶粘剂,在70℃-100℃温度下,干燥1-5分钟,得到干燥后厚度为5-10μm胶膜,将胶膜与粘结层或耐候层在温度为70℃-90℃和压力0.3-0.5MPa下进行热压复合,所得复合膜裁成200mm*15mm样片,获得用于确认初始剥离力的样品。
熟化后剥离力样品制备
在背板支撑层PET上涂布上述胶粘剂,在70℃-100℃温度下,干燥1-5分钟,得到干燥后厚度为5-10μm胶膜,将胶膜与粘结层或耐候层在温度为70℃-90℃和压力0.3-0.5MPa下进行热压复合,40-60℃,24-72小时熟化,所得复合膜裁成200mm*15mm样片,以获得用于确认熟化后剥离力的样品。
用于确认背板耐候性样品的制备
在背板支撑层PET上涂布上述胶粘剂,在70℃-100℃温度下,干燥1-5分钟,得到干燥后厚度为5-10μm胶膜,将胶膜与粘结层或耐候层在温度为70℃-90℃和压力0.3-0.5MPa下进行热压复合,40-60℃,24-72小时熟化,所得复合膜裁成100mm*150mm样片,分别置于用于确认固化背板耐湿热特性的高速加压寿命试验机(PCT)和用于确认泛黄程度的UV辐射测试仪中进行测试。
评价
初始剥离力
使用拉伸强度测试机将用于确认初始剥离力的样品在室温环境下在100mm/min的测试速率下经受180°剥离测试。
熟化后剥离力
使用拉伸强度测试机将用于确认熟化后剥离力的样品在室温环境下在100mm/min的测试速率下经受180°剥离测试。
固化后背板耐湿热特性
在PCT(高速加压寿命试验机)中剥离力下降程度
将上面提及的用于确认固化背板耐湿热特性的每种样品置于高速加压寿命试验机中,在保持在加压环境下在120℃和0.1MPa下确认50h剥离力下降程度和100h后背板表观情况。评价标准如下:
PCT 50h后剥离力下降程度:
好:剥离强度下降50%或者更少,
中:剥离强度下降大于50%或者更少并且小于70%,
差:剥离强度下降大于70%,
PCT 100h后背板表观情况:
好:不起泡、不缩边,
中:起泡并且不缩边,或者缩边不起泡,
差:脱落,
泛黄程度。
将上面提及的用于确认泛黄程度的每种样品置于UV辐射测试仪中,使得复合膜侧对应于待辐射的表面,随后在60℃和50%RH下在1,000W/m2的照度条件下进行辐射使用色差仪,测量辐射前后的色差(Δb)并且评价泛黄程度。评价标准如下:
好:Δb小于5。
中:Δb为5或更大并且小于10。
差:Δb为10或更大。
如表1所示,实施例1-5的胶粘剂在初始剥离力、固化后剥离力和固化背板耐湿热特性及泛黄程度之间的总体平衡方面是优异的,同时由于提高的初始剥离力,能够直接进行收卷或切割工序而不会分层,节约了时间,提高了效率。
如上所述,这些实施例和对比例证实了聚醚多元醇、聚酯多元醇和丙烯酸酯多元醇复合时,胶粘剂初始剥离力明显提高,熟化后剥离力和耐候性能优异。
Claims (2)
1.一种耐候性胶粘剂,其特征在于,所述胶粘剂由A组分和B组分组成;其中A组分由多元醇组合物和助剂组成;B组分为脂肪族异氰酸酯B1和脂环族异氰酸酯B2的至少一种;
A组分
多元醇组合物 50-80份,
助剂 1-15份;
B组分 5-15份;
所述多元醇组合物的组成及质量百分含量为:
聚醚多元醇A1 5-40%
聚酯多元醇A2 5-40%
丙烯酸酯多元醇A3 40-80%;
所述助剂的组成及质量份数为:
环氧树脂 1-8份,
催化剂 0-1份,
紫外线吸收剂 0-2份,
光稳定剂 0-2份,
抗氧剂 0-1份,
抗水解剂 0-5份;
所述聚醚多元醇A1分子量为1000-8000,羟值为20-50 mgKOH/g的二官能度聚醚多元醇或三官能度聚醚多元醇中的一种或者两种;
所述聚酯多元醇A2分子量为1000-8000,羟值为20-60 mgKOH/g;
所述丙烯酸酯多元醇A3分子量为5000-100000,羟值为15-50mgKOH/g;
所述脂肪族异氰酸酯B1为1,4-二异氰酸酯基丁烷、1,5-二异氰酸酯基戊烷、1,6-二异氰酸酯基己烷、1,6-二异氰酸酯基-2,2,4-三甲基己烷、甲基-2,6-二异氰酸酯基己酸酯(二异氰酸赖氨酸酯)、1,3-双(异氰酸酯基-甲基)苯中的一种或几种;所述的脂环族异氰酸酯B2为 异佛尔酮二异氰酸酯、1,3-双(异氰酸酯甲基)环己烷、双(4-异氰酸酯环己基)甲烷(氢化二苯基甲烷二异氰酸酯)、1,4-二异氰酸酯基环己烷中的一种或几种。
2.一种如权利要求1所述的胶粘剂在太阳能电池背板上的应用,其特征在于,在背板支撑层PET上涂布上述胶粘剂,在70℃-100℃温度下,干燥1-5分钟,得到干燥后厚度为5-10μm胶膜,将胶膜与粘结层或耐候层在温度为70℃-90℃和压力0.3-0.5MPa下进行热压复合,在40-60℃下,熟化24-72小时,即得太阳能电池背板。
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