CN110791232A - 一种改性eva胶膜及其制备方法 - Google Patents
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- 239000010703 silicon Substances 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
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- 150000002148 esters Chemical class 0.000 claims description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 6
- DQSYGNJXYMAPMV-UHFFFAOYSA-N 2,6-ditert-butyl-4-(3,5-ditert-butyl-4-hydroxyphenyl)sulfanylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(SC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 DQSYGNJXYMAPMV-UHFFFAOYSA-N 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical group CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 claims description 4
- YEYCMBWKTZNPDH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1 YEYCMBWKTZNPDH-UHFFFAOYSA-N 0.000 claims description 3
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 3
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 3
- WRVWOBJLGCVCSC-UHFFFAOYSA-N tris(1,2,2,6,6-pentamethylpiperidin-3-yl) phosphite Chemical compound CC1(C)N(C)C(C)(C)CCC1OP(OC1C(N(C)C(C)(C)CC1)(C)C)OC1C(C)(C)N(C)C(C)(C)CC1 WRVWOBJLGCVCSC-UHFFFAOYSA-N 0.000 claims description 3
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 claims description 2
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- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims 1
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- 238000004100 electronic packaging Methods 0.000 abstract 1
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- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 37
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 6
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- 125000003700 epoxy group Chemical group 0.000 description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 3
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- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- ICPLYRDBKAGFER-UHFFFAOYSA-N [Si].CC=CF Chemical compound [Si].CC=CF ICPLYRDBKAGFER-UHFFFAOYSA-N 0.000 description 1
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- MJULMZZKFYNTHK-UHFFFAOYSA-N ethenyl(phenyl)silicon Chemical compound C=C[Si]C1=CC=CC=C1 MJULMZZKFYNTHK-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0892—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms containing monomers with other atoms than carbon, hydrogen or oxygen atoms
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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Abstract
一种改性EVA胶膜及其制备方法,所述改性EVA胶膜按以下重量份配比的原料配制成:改性EVA树脂100份,氟硅树脂2‑5份,纳米氧化物0.5‑2份,交联剂0.5‑1份,紫外光吸收剂0.1‑0.3份,增粘剂0.2‑0.5份,抗氧化剂0.2‑0.4份。所述改性EVA胶膜的制备方法包括以下步骤:(1)在真空下混合均匀、干燥;(2)在循环式辊轧挤压造粒机中进行造粒;(3)挤出流延成型。本发明所制备的改性EVA胶膜透光率高,粘结强度高,耐候性好,使用寿命长,可以广泛应用于太阳能电池封装以及各种电子封装器件。
Description
技术领域
本发明涉及一种改性EVA胶膜及其制备方法,属太阳能光伏组件保护膜材料技术领域。
背景技术
太阳能电池是借助于两层高分子封装膜将硅晶片包裹于其中,再和上下保护层材料玻璃及TPT膜粘结。首先,封装材料必须是透光的,而且透光率要高,这样保证封装后的太阳能电池组件具有足够的光电转换效率。另外,封装材料粘合力必须要强,这样才能更好的固定和保护好太阳能电池;封装材料在封装之前必须是柔软的,易于改变形状,这样才能根据太阳能电池的形状进行封装而不损坏电池片。但是封装固化后它必须是热固性的,因为太阳能组件要在高温的条件下运行,如果是热塑性的就会发生形变,严重地还会流胶,失去了对太阳能电池的保护作用。
太阳能电池组件的核心是电池片,其本身具有长达30年以上的使用寿命;但是目前对电池片起固定、密封和保护作用的透明高分子封装胶的寿命则相对短得多。因此,研制耐老化的太阳能电池组件的封装材料对提高太阳能电池的质量和寿命至关重要。
目前广为使用的太阳能电池胶膜主要是由EVA(乙烯-乙酸乙烯共聚物)添加交联剂等一系列助剂制备的。在长期的户外使用过程中,高分子材料本身的降解和助剂所带来的副反应等都会导致EVA胶膜黄变,透光率降低,从而降低太阳能组件的光电转换效率。与国外产品相比,国内产品的这些性能有待提升。
发明内容
针对现有技术的不足,本发明的目的在于,提供一种具有优异粘结性和耐候性的胶膜及制备方法。
为了解决上述技术问题,本发明提出如下技术方案:一种改性EVA胶膜,由以下原料按重量份配比配制而成:
所述改性EVA树脂,其醋酸乙烯的重量含量为20-30%,硅重量含量为1-5%,环氧值为0.2-0.5,熔融指数为20-50g/10min,其结构通式为:
R1,R2=CH3,CH2CH3,Ph
所述氟硅树脂为甲基乙烯基氟硅树脂、苯基乙烯基氟硅树脂、甲基苯基乙烯基氟硅树脂中的一种或两种以上混合物,其透光率大于98%,折光指数1.45-1.50,乙烯基含量0.5-1%。
所述纳米氧化物是纳米二氧化钛、纳米氧化锌中的一种或两种混合物,粒径为5-10nm。
所述交联剂是2,5-二甲基-2,5-双(叔丁基过氧)己烷,过氧化二异丙苯中的一种或两种混合物。
所述紫外光吸收剂为邻羟基苯甲酸苯酯、2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、2,4-二羟基二苯甲酮、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中的一种。
所述增粘剂为3-异氰酸酯基丙基三乙氧基硅烷、3-异氰酸酯基丙基三甲氧基硅烷中的一种。
所述抗氧剂为受阻分类抗氧剂和辅助抗氧剂组成;其质量比为5:1,为2,6-二叔丁基对甲基苯酚和双十二碳醇酯、双(3,5-二叔丁基-4-羟基苯基)硫醚和双十四碳醇酯中的一种。
本发明一种改性EVA胶膜的制备方法,包括以下步骤:
(1)按照配方配比将改性EVA树脂、氟硅树脂、纳米氧化物、交联剂、紫外吸收剂、增粘剂、抗氧化剂进行混合均匀,得到混合料,然后在0.070-0.085MPa下真空干燥4h-6h,冷却至室温备用;
(2)将步骤(1)得到的干燥混合物投入到循环式辊轧挤压造粒机进行造粒;
(3)将步骤(2)得到的粒料倒入流延机进行共混熔融、挤出,经平模头流延成型,得到透明改性EVA胶膜成品。
本发明的工作原理如下,本发明通过对EVA树脂进行改性,在EVA的结构引入了环氧基基团和硅氧烷基团,降低醋酸乙烯酯的含量,使得树脂能迅速固化,使用强度、耐腐蚀性、耐碱性能提高;另外硅烷氧基的引入,易于解决配方组分之间的湿润性与粘结性,引入环氧基团,有利于提高其交联密度,提高的力学强度;在EVA胶膜中加入了氟硅树脂,不仅提高了其折光光率、韧性,还提高了其热稳定性、耐候性以及耐化学品性,另外通过添加纳米氧化物,提升薄膜的致密性、抗老化性,添加3-异氰酸酯基硅烷类增粘剂提升胶膜的粘结强度,延长其使用寿命。
本发明的有益效果在于,本发明通过对EVA树脂进行改性,使得树脂能迅速固化,使用强度、耐腐蚀性、耐碱性能提高;在EVA胶膜中加入了氟硅树脂,不仅提高了其折光光率、韧性,还提高了其热稳定性、耐候性以及耐化学品性;改性后的EVA胶膜完全适用于太阳能电池的封装,也适用于电子器件的封装。
具体实施方式
实施例1
本实施例一种改性EVA胶膜的制备方法,其包括以下步骤:
(1)将100份醋酸乙烯重量含量为20%,硅重量含量为5%,环氧值为0.2,熔融指数为20g/10min的改性EVA树脂、2份乙烯基含量0.5%的甲基乙烯基氟硅树脂、0.5份纳米二氧化钛、0.5份2,5-二甲基-2,5-双(叔丁基过氧)己烷交联剂、0.1份邻羟基苯甲酸苯酯、0.2份3-异氰酸酯基丙基三乙氧基硅烷、0.167份2,6-二叔丁基对甲基苯酚和0.033份双十二碳醇酯进行混合均匀,得到混合料,然后在0.070MPa下真空干燥4h,冷却至室温备用。
(2)将步骤(1)得到的干燥混合物投入到循环式辊轧挤压造粒机进行造粒。
(3)将步骤(2)得到的粒料倒入流延机进行共混熔融、挤出,经平模头流延成型,得到透明改性EVA胶膜成品。
实施例2
本实施例一种改性EVA胶膜的制备方法,包括以下步骤:
(1)将100份醋酸乙烯重量含量为30%,硅重量含量为1%,环氧值为0.5,熔融指数为50g/10min的改性EVA树脂、5份乙烯基含量1.0%的苯基乙烯基氟硅树脂、2份纳米氧化锌、1份过氧化二异丙苯、0.3份2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、0.5份3-异氰酸酯基丙基三甲氧基硅烷、0.33双(3,5-二叔丁基-4-羟基苯基)硫醚和0.07份双十四碳醇酯进行混合均匀,得到混合料,然后在0.085MPa下真空干燥6h,冷却至室温备用。
(2)将步骤(1)得到的干燥混合物投入到循环式辊轧挤压造粒机进行造粒。
(3)将步骤(2)得到的粒料倒入流延机进行共混熔融、挤出,经平模头流延成型,得到透明改性EVA胶膜成品。
实施例3
本实施例一种改性EVA胶膜的制备方法,包括以下步骤:
(1)将100份醋酸乙烯重量含量为25%,硅重量含量为2%,环氧值为0.3,熔融指数为40g/10min的改性EVA树脂、3份乙烯基含量0.6%的甲基苯基乙烯基氟硅树脂、1份纳米二氧化钛、1份2,5-二甲基-2,5-双(叔丁基过氧)己烷、0.2份2,4-二羟基二苯甲酮、0.3份3-异氰酸酯基丙基三乙氧基硅烷、0.25份2,6-二叔丁基对甲基苯酚和0.05份双十二碳醇酯进行混合均匀,得到混合料,然后在0.080MPa下真空干燥4h,冷却至室温备用。
(2)将步骤(1)得到的干燥混合物投入到循环式辊轧挤压造粒机进行造粒。
(3)将步骤(2)得到的粒料倒入流延机进行共混熔融、挤出,经平模头流延成型,得到透明改性EVA胶膜成品。
实施例4
本实施例一种改性EVA胶膜的制备方法,包括以下步骤:
(1)将100份醋酸乙烯重量含量为23%,硅重量含量为4%,环氧值为0.4,熔融指数为30g/10min的改性EVA树脂、4份乙烯基含量0.8%的苯基乙烯基硅树脂、0.5份纳米二氧化钛、0.5份纳米氧化锌、1份过氧化二异丙苯、0.2份三(1,2,2,6,6-五甲哌啶基)亚磷酸酯、0.4份3-异氰酸酯基丙基三甲氧基硅烷、0.25份双(3,5-二叔丁基-4-羟基苯基)硫醚和0.05份双十四碳醇酯进行混合均匀,得到混合料,然后在0.085MPa下真空干燥6h,冷却至室温备用。
(2)将步骤(1)得到的干燥混合物投入到循环式辊轧挤压造粒机进行造粒。
(3)将步骤(2)得到的粒料倒入流延机进行共混熔融、挤出,经平模头流延成型,得到透明改性EVA胶膜成品。
实施例5
本实施例一种改性EVA胶膜的制备方法,包括以下步骤:
(1)将100份醋酸乙烯重量含量为25%,硅重量含量为2%,环氧值为0.2,熔融指数为40g/10min的改性EVA树脂、2份乙烯基含量0.9%的甲基苯基乙烯基氟硅树脂、0.5份纳米二氧化钛、0.5份纳米氧化锌、1份过氧化二异丙苯、0.2份4-苯甲酰氧基-2,2,6,6-四甲基哌啶、0.3份3-异氰酸酯基丙基三甲氧基硅烷、0.25份双(3,5-二叔丁基-4-羟基苯基)硫醚和0.05份双十四碳醇酯进行混合均匀,得到混合料,然后在0.075MPa下真空干燥4h,冷却至室温备用。
(2)将步骤(1)得到的干燥混合物投入到循环式辊轧挤压造粒机进行造粒。
(3)将步骤(2)得到的粒料倒入流延机进行共混熔融、挤出,经平模头流延成型,得到透明改性EVA胶膜成品。
按照本发明实施例1-5所制备的改性EVA胶膜进行性能测试,其结果如表1所示。所测试的胶膜材料的厚度为0.5mm,粘结强度按照GB/T 2790测试,黄变指数按照GB2409-80测试,透光率按照GB2410-1989测试。
表1各实施例胶膜性能测试结果
胶膜 | 折射率 | 粘结强度(N/cm) | 透光率(%) | 黄变指数 |
实施例1 | 1.48 | 94 | 90 | 0.2 |
实施例2 | 1.50 | 96 | 92 | 0.2 |
实施例3 | 1.46 | 95 | 90 | 0.2 |
实施例4 | 1.49 | 92 | 91 | 0.2 |
实施例5 | 1.48 | 98 | 90 | 0.2 |
由表1可知,本实施例制备的改性EVA胶膜,粘结强度在90N/cm以上,透光率在90%以上,黄变指数小。其各项性能指标得到了很大程度的提高。
Claims (9)
2.根据权利要求1所述的一种改性EVA胶膜,其特征在于,所述改性EVA胶膜由以下原料按重量份配比配制而成:
改性EVA树脂100份;氟硅树脂2-5份;纳米氧化物0.5-2份;交联剂0.5-1份;紫外光吸收剂0.1-0.3份;增粘剂0.2-0.5份;抗氧化剂0.2-0.4份。
3.根据权利要求1所述的一种改性EVA胶膜,其特征在于,所述氟硅树脂为甲基乙烯基氟硅树脂、苯基乙烯基氟硅树脂、甲基苯基乙烯基氟硅树脂中的一种或两种以上混合物,其透光率大于98%,折光指数为1.45-1.50,乙烯基含量0.5-1%。
4.根据权利要求1所述的一种改性EVA胶膜,其特征在于,所述纳米氧化物是纳米二氧化钛、纳米氧化锌中的一种或两种混合物,粒径为5-10nm。
5.根据权利要求1所述的一种改性EVA胶膜,其特征在于,所述交联剂是2,5-二甲基-2,5-双(叔丁基过氧)己烷,过氧化二异丙苯中的一种或两种混合物。
6.根据权利要求1所述的一种改性EVA胶膜,其特征在于,所述紫外光吸收剂为邻羟基苯甲酸苯酯、2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑、2,4-二羟基二苯甲酮、三(1,2,2,6,6-五甲哌啶基)亚磷酸酯或4-苯甲酰氧基-2,2,6,6-四甲基哌啶中的一种。
7.根据权利要求1所述的一种改性EVA胶膜,其特征在于,所述增粘剂为3-异氰酸酯基丙基三乙氧基硅烷、3-异氰酸酯基丙基三甲氧基硅烷中的一种。
8.根据权利要求1所述的改性EVA胶膜,其特征在于,所述抗氧剂为受阻分类抗氧剂和辅助抗氧剂组成;其质量比为5:1,为2,6-二叔丁基对甲基苯酚和双十二碳醇酯、双(3,5-二叔丁基-4-羟基苯基)硫醚和双十四碳醇酯中的一种。
9.一种如权利要求1所述改性EVA胶膜的制备方法,其特征在于,所述方法包括以下步骤:
(1)按照配方配比将改性EVA树脂、氟硅树脂、纳米氧化物、交联剂、紫外吸收剂、增粘剂和抗氧化剂进行混合均匀,得到混合料,然后在0.070-0.085MPa下真空干燥4h-6h,冷却至室温备用;
(2)将步骤(1)得到的干燥混合物投入到循环式辊轧挤压造粒机进行造粒;
(3)将步骤(2)得到的粒料倒入流延机进行共混熔融、挤出,经平模头流延成型,得到透明改性EVA胶膜成品。
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