CN111944435A - 热熔胶膜及其制备方法、应用、有机硅聚合物 - Google Patents
热熔胶膜及其制备方法、应用、有机硅聚合物 Download PDFInfo
- Publication number
- CN111944435A CN111944435A CN202010837354.7A CN202010837354A CN111944435A CN 111944435 A CN111944435 A CN 111944435A CN 202010837354 A CN202010837354 A CN 202010837354A CN 111944435 A CN111944435 A CN 111944435A
- Authority
- CN
- China
- Prior art keywords
- ethylene
- vinyl acetate
- polyolefin elastomer
- layer
- adhesive film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 86
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- 229920005573 silicon-containing polymer Polymers 0.000 claims abstract description 12
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- 239000000178 monomer Substances 0.000 claims description 29
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- SBKRBXBQFDKYSO-UHFFFAOYSA-N (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C)=C(O)C(C(C)(C)C)=C1 SBKRBXBQFDKYSO-UHFFFAOYSA-N 0.000 description 1
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- STEYNUVPFMIUOY-UHFFFAOYSA-N 4-Hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(O)CC(C)(C)N1CCO STEYNUVPFMIUOY-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
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- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
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- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 230000032683 aging Effects 0.000 description 1
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- OSIVCXJNIBEGCL-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-octoxypiperidin-4-yl) decanedioate Chemical group C1C(C)(C)N(OCCCCCCCC)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(OCCCCCCCC)C(C)(C)C1 OSIVCXJNIBEGCL-UHFFFAOYSA-N 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
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- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于胶膜技术领域,具体涉及一种热熔胶膜及其制备方法、应用、有机硅聚合物。本热熔胶膜包括:内层,即聚烯烃弹性体;外层,即位于内层两表面的乙烯‑醋酸乙烯共聚物;以及中间层,即介于内层与外层之间的有机硅聚合物。通过有机硅聚合物作为中间层,起到连接过渡的作用,提升了EVA与POE层之间的结合力,提高了热熔胶膜在长期使用过程中的稳定性,可应用于太阳能电池板和触摸屏用封装材料领域。
Description
技术领域
本发明属于胶膜技术领域,具体涉及一种热熔胶膜及其制备方法、应用、有机硅聚合物。
背景技术
目前,现有EVA/POE/EVA结构的热熔胶膜因其优良的水汽阻隔性及抗PID等特点,正逐步取代乙烯-醋酸乙烯共聚物胶膜(EVA)成为主要的封装材料。但由于聚烯烃弹性体为非极性树脂,而乙烯-醋酸乙烯共聚物为极性树脂,两种树脂的交联反应活性、熔体粘度和剪切熔体升温速率都有明显的差异,因此胶膜会在共挤后出现分层现象。这种共挤胶膜在长期的老化过程中,会增加两种材料分层的风险,最终导致EVA-POE层的界面之间结合力下降,造成封装材料内部层间的脱层现象,缩短了太阳能电池板和触摸屏的使用寿命。
发明内容
本发明提供了一种热熔胶膜及其制备方法、应用、有机硅聚合物。
为了解决上述技术问题,本发明提供了一种热熔胶膜,包括:内层,即聚烯烃弹性体;外层,即位于内层两表面的乙烯-醋酸乙烯共聚物;以及中间层,即介于内层与外层之间的有机硅聚合物。
第二方面,本发明还提供了一种热熔胶膜的制备方法,包括:将聚烯烃弹性体作为内层、乙烯-醋酸乙烯共聚物作为内层两表面的外层,以共挤方式制成三层共挤复合薄膜;UV辐照,使聚烯烃弹性体中含有特殊极性结构的硅氧烷发生加成反应生成有机硅聚合物,即所述中间层。
第三方面,本发明还提供了一种有机硅聚合物,即所述有机硅聚合物的化学结构式为
第四方面,本发明还提供了一种热熔胶膜作为胶黏剂的应用。
本发明的有益效果是,本发明的熔胶膜及其制备方法、应用、有机硅聚合物通过有机硅聚合物作为中间层,位于内层聚烯烃弹性体与外层乙烯-醋酸乙烯共聚物之间,起到连接过渡的作用,提升了EVA与POE层之间的结合力,提高了热熔胶膜在长期使用过程中的稳定性,可应用于太阳能电池板和触摸屏用封装材料领域。
本发明的其他特征和优点将在随后的说明书中阐述,并且,部分地从说明书中变得显而易见,或者通过实施本发明而了解。本发明的目的和其他优点在说明书、附图中所特别指出的结构来实现和获得。
为使本发明的上述目的、特征和优点能更明显易懂,下文特举较佳实施例,并配合所附附图,作详细说明如下。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案,下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图是本发明的一些实施方式,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是本发明的热熔胶膜的制备工艺流程图;
图2是含有特殊极性结构的硅氧烷的迁移过程图;
图3是本发明的热熔胶膜的扫描电镜图;
图4是本发明的连接过渡层的红外示意图;
图5是现有EVA/POE/EVA三层结构热熔胶膜的结构示意图;
图6是本发明的连接过渡层在UV辐照前的凝胶渗透色谱图;
图7是本发明的连接过渡层在UV辐照后的凝胶渗透色谱图;
图2中:聚烯烃弹性体1,乙烯-醋酸乙烯共聚物2,有机硅聚合物3,含有特殊极性结构的硅氧烷4。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合附图对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
第一部分:阐述具体技术方案
现有EVA/POE/EVA结构的胶膜中,聚烯烃弹性体为非极性树脂,而乙烯-醋酸乙烯共聚物为极性树脂,两种树脂的交联反应活性、熔体粘度和剪切熔体升温速率都有明显的差异,因此胶膜会在共挤后出现分层现象。为此,见图2,本发明提供了一种热熔胶膜,包括:内层,即聚烯烃弹性体1;外层,即位于内层两表面的乙烯-醋酸乙烯共聚物2;以及中间层,即介于内层与外层之间的有机硅聚合物3,也可以叫连接过渡层。
本发明的热熔胶膜采用内层、两个中间层和两个外层相结合,形成五层复合结构,聚烯烃弹性体和有机硅聚合物被外层的乙烯-醋酸乙烯共聚物所包覆,因此不存在粘辊等问题。采用热压工艺和UV辐照后就能使热熔胶膜的五层复合结构达到交联度使用要求。相较于现有EVA/POE/EVA三层结构的热熔胶膜,本热熔胶膜具有优良的透光率、水汽阻隔性、绝缘性和良品率等优点,并且其中的有机硅聚合物作为连接过渡层,提升了EVA(即乙烯-醋酸乙烯共聚物)与POE(即聚烯烃弹性体)之间的结合力,提高了长期使用过程中的稳定性,可应用于太阳能电池板和触摸屏用封装材料领域。
作为聚烯烃弹性体的一种可选的实施方式。
所述聚烯烃弹性体按质量份数包含以下组分:聚烯烃弹性体母粒92.25份-97.8份;含有特殊极性结构的硅氧烷1份-2.5份;抗氧剂0.1份-1份;热引发剂0.5份-2份;交联单体0.5份-2.5份;光稳定剂0.1份-1份。
可选的,所述聚烯烃弹性体按质量份数包含以下组分:聚烯烃弹性体母粒93份-97.3份;含有特殊极性结构的硅氧烷1.5份-2份;抗氧剂0.5份-0.8份;热引发剂0.8份-1.5份;交联单体1份-2份;光稳定剂0.4份-0.8份。
可选的,含有特殊极性结构的硅氧烷的化学结构式为
具体的,所述有机硅聚合物适于通过硅氧烷发生加成反应生成,其加成反应的反应式为
作为乙烯-醋酸乙烯共聚物的一种可选的实施方式。
所述乙烯-醋酸乙烯共聚物按质量份数包含以下组分:乙烯-醋酸乙烯共聚物母粒91.5份-99.1份;抗氧剂0.1份-1份;热引发剂0.3份-1.5份;交联单体0.3份-2份;硅烷偶联剂0.1份-1份;光稳定剂0.1份-1份。
可选的,所述乙烯-醋酸乙烯共聚物按质量份数包含以下组分:乙烯-醋酸乙烯共聚物母粒93.8份-98.9份;抗氧剂0.2份-0.8份;热引发剂0.5份-1.2份;交联单体0.4份-1.9份;硅烷偶联剂0.2份-0.8份;光稳定剂0.4份-10.8份。
可选的,所述乙烯-醋酸乙烯共聚物内还可以添加一些颜料,在不影响UV光透射情况下,可以制成相应颜色的外层。
本案中的聚烯烃弹性体、乙烯-醋酸乙烯共聚物的组分中,抗氧剂、热引发剂、交联单体、硅烷偶联剂、光稳定剂的组分可以但不限于采用如下原料:
可选的,所述抗氧剂为四(3,5-二叔丁基-4-羟基)苯丙酸季戊四醇酯、三乙二醇醚-二(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯、三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰尿酸、异氰脲酸三(4-叔丁基-3-羟基-2,6-二甲苯基)酯中的一种或其组合物。
可选的,所述热引发剂为过氧化异丙苯、二叔丁基过氧化物、过氧化氢二异丙苯、2,5-二甲基-2,5二叔丁基过氧化己烷、4,4-二(叔戊基过氧)戊酸正丁基酯,过氧化2-乙基己基碳酸叔丁酯、3,3-二(叔丁基过氧)丁酸乙酯的一种或其组合物。
可选的,所述交联单体为三烯丙基异氰脲酸酯、三聚氰酸三烯丙酯、三羟甲基丙烷三甲基丙烯酸酯、二甲基丙烯酸二乙二醇酯中的一种或其组合物。
可选的,所述硅烷偶联剂为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)硅烷中的一种或其组合物。由于热熔胶膜中的内层聚烯烃弹性体和中间层有机硅聚合物被外层乙烯-醋酸乙烯共聚物包覆,因此不存在粘辊等问题。由于乙烯-醋酸乙烯共聚物的成本比聚烯烃弹性体成本低,所以热熔胶膜可以通过较低成本即可获得高阻水性和抗PID性。
可选的,所述光稳定剂为双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、聚-{[6-[(1,1,3,3,-四甲基丁基)-亚氨基]-1,3,5,-三嗪-2,4-二基][2-(2,2,6,6,-四甲基哌啶基)-次氨基-六亚甲基-[4-(2,2,6,6,-四甲基派啶基)-次氨基]]、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、聚丁二酸(4-羟基-2,2,6,6-四甲基-1-哌啶乙醇)酯中的一种或其组合物。
在本案中,通过乙烯-醋酸乙烯共聚物与聚烯烃弹性体的原料差异化设计,即保证二者的区别组分仅限于聚烯烃弹性体母粒、乙烯-醋酸乙烯共聚物母粒、含有特殊极性结构的硅氧烷,同时保证热引发剂在聚烯烃弹性体中的质量占比高于其在乙烯-醋酸乙烯共聚物中的质量占比;交联单体在聚烯烃弹性体中的质量占比高于其在乙烯-醋酸乙烯共聚物中的质量占比,以在共挤过程中,所述外层熔融物(乙烯-醋酸乙烯共聚物)的表面能大于内层熔融物(聚烯烃弹性体)。
可选的,所述聚烯烃弹性体与乙烯-醋酸乙烯共聚物的质量比为(10-50):(50-90),可选为(15-45):(50-95)。以及热引发剂在聚烯烃弹性体中的质量占比高于其在乙烯-醋酸乙烯共聚物中的质量占比0.2%-0.5%;交联单体在聚烯烃弹性体中的质量占比高于其在乙烯-醋酸乙烯共聚物中的质量占比0.2%-0.5%。
如图2所示,在共挤过程中,所述外层熔融物(乙烯-醋酸乙烯共聚物1)的表面能大于内层熔融物(聚烯烃弹性体2),以使含有特殊极性结构的硅氧烷4从低表面能迁移至高表面能处,抵达乙烯-醋酸乙烯共聚物与聚烯烃弹性体的界面处,通过UV辐照使硅氧烷发生加成反应生成所述有机硅聚合物3,形成中间层,起到连接过渡的作用。与现有EVA/POE/EVA结构的热熔胶膜(如图5所示)呈现三层结构,且中间有断层,完全不同,其界面处的结合力也会大大提高,可以有效避免热熔胶膜内部层间的脱层现象。
在本案中,含有特殊极性结构的硅氧烷的迁移行为是由乙烯-醋酸乙烯共聚物与聚烯烃弹性体的表面能差值决定的,随着硅氧烷迁移过程的进行,二者之间的表面能差值必然逐渐减小,直到维持各熔融物均处于稳定状态。因此,可以通过原料配方控制乙烯-醋酸乙烯共聚物与聚烯烃弹性体的表面能差值(如外层熔融物的表面张力为35-37mN/m,所述内层熔融物的表面张力为31-33mN/m),使含有特殊极性结构的硅氧烷会大部分迁移至界面处,小部分来不及迁移留在聚烯烃弹性体内,并不会全部集中在界面处,因此在UV辐照后,硅氧烷加成反应生成的有机硅聚合物会将乙烯-醋酸乙烯共聚物与聚烯烃弹性体连接起来,进一步加强界面处的结合力。
进一步,见图1,本发明还提供了一种热熔胶膜的制备方法,包括:将聚烯烃弹性体作为内层、乙烯-醋酸乙烯共聚物作为内层两表面的外层,以共挤方式制成三层共挤复合薄膜;UV辐照,使聚烯烃弹性体中含有特殊极性结构的硅氧烷发生加成反应生成有机硅聚合物,即所述中间层。具体的,所述热熔胶膜包含五层结构:内层聚烯烃弹性体;两个外层乙烯-醋酸乙烯共聚物;介于内层与外层之间的两个中间层有机硅聚合物。
作为共挤方式的一种可选的实施方式。
所述共挤方式包括:将聚烯烃弹性体的各组分混合熔融,形成内层熔融物;将乙烯-醋酸乙烯共聚物的各组分混合熔融,形成外层熔融物;将外层熔融物分别置于内层熔融物的上、下表面,内层熔融物中的含有特殊极性结构的硅氧烷迁移至内层熔融物与外层熔融物的界面处;通过模具热压挤出,得到三层共挤复合薄膜。
可选的,所述外层熔融物的表面能大于内层熔融物,以使含有特殊极性结构的硅氧烷从低表面能迁移至高表面能处;其中所述外层熔融物的表面张力为35-37mN/m;所述内层熔融物的表面张力为31-33mN/m。
进一步,本发明提供了一种有机硅聚合物,其化学结构式为
进一步,本发明提供了一种热熔胶膜作为胶黏剂的应用。
所述胶黏剂例如但不限于应用于太阳能电池板领域和触摸屏用封装材料领域。
第二部分:列举部分实施例
实施例1
(1)内层的聚烯烃弹性体采用聚烯烃弹性体母粒95kg,含有特殊极性结构的硅氧烷1.2kg,抗氧剂0.5kg,热引发剂1.6kg,交联单体1.5kg,光稳定剂0.2kg,进行制备;外层的乙烯-醋酸乙烯共聚物采用乙烯-醋酸乙烯共聚物母粒96.2kg,抗氧剂0.6kg,热引发剂0.8kg,交联单体1.6kg,硅烷偶联剂0.4kg,光稳定剂0.2kg,进行制备。
(2)将一份聚烯烃弹性体原料和两份乙烯-醋酸乙烯共聚物原料分别加入相应的进料筒,通过100℃挤出后,得到内层熔融物和两个外层熔融物;然后分别通过分配器分配和共挤模头,得到三层共挤复合薄膜,再进行UV辐照后,得到五层复合结构的热熔胶膜。
实施例2
(1)内层的聚烯烃弹性体采用聚烯烃弹性体母粒94.8kg,含有特殊极性结构的硅氧烷1.6kg,抗氧剂0.5kg,热引发剂1.5kg,交联单体1.4kg,光稳定剂0.2kg,进行制备;外层的乙烯-醋酸乙烯共聚物采用乙烯-醋酸乙烯共聚物母粒97.1kg,抗氧剂0.5kg,热引发剂0.6kg,交联单体1.2kg,硅烷偶联剂0.4kg,光稳定剂0.2kg,进行制备。
(2)将一份聚烯烃弹性体原料和两份乙烯-醋酸乙烯共聚物原料分别加入相应的进料筒,通过100℃挤出后,得到内层熔融物和两个外层熔融物;然后分别通过分配器分配和共挤模头,得到三层共挤复合薄膜,再进行UV辐照后,得到五层复合结构的热熔胶膜。
实施例3
(1)内层的聚烯烃弹性体采用聚烯烃弹性体母粒95.1kg,含有特殊极性结构的硅氧烷1.6kg,抗氧剂0.5kg,热引发剂1.4kg,交联单体1.2kg,光稳定剂0.2kg,进行制备;外层的乙烯-醋酸乙烯共聚物采用乙烯-醋酸乙烯共聚物母粒96.5kg,抗氧剂0.5kg,热引发剂0.9kg,交联单体1.3kg,硅烷偶联剂0.6kg,光稳定剂0.2kg,进行制备。
(2)将一份聚烯烃弹性体原料和两份乙烯-醋酸乙烯共聚物原料分别加入相应的进料筒,通过100℃挤出后,得到内层熔融物和两个外层熔融物;然后分别通过分配器分配和共挤模头,得到三层共挤复合薄膜,再进行UV辐照后,得到五层复合结构的热熔胶膜。
实施例4
(1)内层的聚烯烃弹性体采用聚烯烃弹性体母粒93.3kg,含有特殊极性结构的硅氧烷2.3kg,抗氧剂0.4kg,热引发剂1.6kg,交联单体2.2kg,光稳定剂0.2kg,进行制备;外层的乙烯-醋酸乙烯共聚物采用乙烯-醋酸乙烯共聚物母粒97.6kg,抗氧剂0.6kg,热引发剂0.8kg,交联单体0.5kg,硅烷偶联剂0.3kg,光稳定剂0.2kg,进行制备。
(2)将一份聚烯烃弹性体原料和两份乙烯-醋酸乙烯共聚物原料分别加入相应的进料筒,通过100℃挤出后,得到内层熔融物和两个外层熔融物;然后分别通过分配器分配和共挤模头,得到三层共挤复合薄膜,再进行UV辐照后,得到五层复合结构的热熔胶膜。
实施例5
(1)内层的聚烯烃弹性体采用聚烯烃弹性体母粒94.6kg,含有特殊极性结构的硅氧烷1.9kg,抗氧剂0.4kg,热引发剂1.2kg,交联单体1.7kg,光稳定剂0.2kg,进行制备;外层的乙烯-醋酸乙烯共聚物采用乙烯-醋酸乙烯共聚物母粒95.6kg,抗氧剂0.2kg,热引发剂1.4kg,交联单体1.8kg,硅烷偶联剂0.8kg,光稳定剂0.2kg,进行制备。
(2)将一份聚烯烃弹性体原料和两份乙烯-醋酸乙烯共聚物原料分别加入相应的进料筒,通过100℃挤出后,得到内层熔融物和两个外层熔融物;然后分别通过分配器分配和共挤模头,得到三层共挤复合薄膜,再进行UV辐照后,得到五层复合结构的热熔胶膜。
实施例6
(1)内层的聚烯烃弹性体采用聚烯烃弹性体母粒92.25kg,含有特殊极性结构的硅氧烷1kg,抗氧剂1kg,热引发剂2kg,交联单体2.5kg,光稳定剂1kg,进行制备;外层的乙烯-醋酸乙烯共聚物采用乙烯-醋酸乙烯共聚物母粒91.5kg,抗氧剂0.1kg,热引发剂0.3kg,交联单体0.3kg,硅烷偶联剂0.1kg,光稳定剂0.1kg,进行制备。
(2)将一份聚烯烃弹性体原料和两份乙烯-醋酸乙烯共聚物原料分别加入相应的进料筒,通过100℃挤出后,得到内层熔融物和两个外层熔融物;然后分别通过分配器分配和共挤模头,得到三层共挤复合薄膜,再进行UV辐照后,得到五层复合结构的热熔胶膜。
实施例7
(1)内层的聚烯烃弹性体采用聚烯烃弹性体母粒97.8kg,含有特殊极性结构的硅氧烷2.5kg,抗氧剂0.1kg,热引发剂0.5kg,交联单体0.5kg,光稳定剂0.1kg,进行制备;外层的乙烯-醋酸乙烯共聚物采用乙烯-醋酸乙烯共聚物母粒99.1kg,抗氧剂1kg,热引发剂1.5kg,交联单体2kg,硅烷偶联剂1kg,光稳定剂1kg,进行制备。
(2)将一份聚烯烃弹性体原料和两份乙烯-醋酸乙烯共聚物原料分别加入相应的进料筒,通过100℃挤出后,得到内层熔融物和两个外层熔融物;然后分别通过分配器分配和共挤模头,得到三层共挤复合薄膜,再进行UV辐照后,得到五层复合结构的热熔胶膜。
对比例1
(1)内层的聚烯烃弹性体采用聚烯烃弹性体母粒96.5kg,抗氧剂0.2kg,热引发剂1.2kg,交联单体1.6kg,硅烷偶联剂0.5kg,光稳定剂0.2kg,进行制备;外层的乙烯-醋酸乙烯共聚物采用乙烯-醋酸乙烯共聚物母粒94.8kg,抗氧剂0.4kg,热引发剂1.4kg,交联单体2.0kg,硅烷偶联剂1.0kg,光稳定剂0.4kg,进行制备。
(2)将一份聚烯烃弹性体原料和两份乙烯-醋酸乙烯共聚物原料分别加入相应的进料筒,通过100℃挤出后,得到内层熔融物和两个外层熔融物;然后分别通过分配器分配和共挤模头,得到三层共挤复合薄膜,再进行UV辐照后,得到热熔胶膜。
第三部分:性能参数对比分析
本部分对实施例1-5制备的五层复合结构的热熔胶膜与原料中不添加含有特殊极性结构的硅氧烷制备的热熔胶膜(对比例1)、现有热熔胶膜(对比例2),与光伏玻璃之间进行层压,在145℃下层压15分钟并检测性能,结果如表1所示。
表1热熔胶膜的性能对比
由表1可以看出,本案的五层复合结构的热熔胶膜具有较高的层压剥离力,主要原因是由于含有特殊极性结构的硅氧烷从聚烯烃弹性体内迁移至乙烯-醋酸乙烯共聚物与聚烯烃弹性体的界面处,通过UV辐照使硅氧烷发生加成反应生成所述有机硅聚合物,形成中间层,从而起到连接过渡的作用,形成五层复合结构的热熔胶膜,如图3所示,其内层与外层之间没有明显的断层,也印证了热熔胶膜较高的层压剥离力。
如图4所示,在其他组分不变的基础上,改变硅氧烷的添加量,以通过红外光谱验证有机硅聚合物的生成。在红外光谱中表现为在1250cm-1的Si-C的特征峰的强、弱和无。其中A代表加入18份硅氧烷,B代表加入1.2份硅氧烷,C代表不加入硅氧烷。可以看出,五层复合结构的热熔胶膜中添加加入1.8份硅氧烷,其有机硅聚合物的生成量最大,热熔胶膜的层压剥离力最高。
如图6和图7所示,连接过渡层在UV辐照前后的分子量发生变化,即具有特殊极性结构的硅氧烷经加成聚合后得到有机硅聚合物。
综上所述,本发明的熔胶膜及其制备方法、应用、有机硅聚合物通过聚烯烃弹性体内的含有特殊极性结构的硅氧烷迁移至乙烯-醋酸乙烯共聚物与聚烯烃弹性体的界面处,在UV辐照后,使硅氧烷发生加成反应生成所述有机硅聚合物,即所述中间层,从而起到连接过渡的作用,形成五层复合结构的热熔胶膜,提升了EVA与POE层之间的结合力,提高了热熔胶膜在长期使用过程中的稳定性,可应用于太阳能电池板和触摸屏用封装材料领域。
以上述依据本发明的理想实施例为启示,通过上述的说明内容,相关工作人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。
Claims (10)
1.一种热熔胶膜,其特征在于,包括:
内层,即聚烯烃弹性体;
外层,即位于内层两表面的乙烯-醋酸乙烯共聚物;以及
中间层,即介于内层与外层之间的有机硅聚合物。
2.根据权利要求1所述的热熔胶膜,其特征在于,
所述聚烯烃弹性体按质量份数包含以下组分:
聚烯烃弹性体母粒,92.25份-97.8份;
含有特殊极性结构的硅氧烷,1份-2.5份;
抗氧剂,0.1份-1份;
热引发剂,0.5份-2份;
交联单体,0.5份-2.5份;
光稳定剂,0.1份-1份。
4.根据权利要求2所述的热熔胶膜,其特征在于,
所述乙烯-醋酸乙烯共聚物按质量份数包含以下组分:
乙烯-醋酸乙烯共聚物母粒,91.5份-99.1份;
抗氧剂,0.1份-1份;
热引发剂,0.3份-1.5份;
交联单体,0.3份-2份;
硅烷偶联剂,0.1份-1份;
光稳定剂,0.1份-1份。
5.根据权利要求4所述的热熔胶膜,其特征在于,
热引发剂在聚烯烃弹性体中的质量占比高于其在乙烯-醋酸乙烯共聚物中的质量占比;
交联单体在聚烯烃弹性体中的质量占比高于其在乙烯-醋酸乙烯共聚物中的质量占比;以及
所述聚烯烃弹性体与乙烯-醋酸乙烯共聚物的质量比为(10-50):(50-90)。
6.一种热熔胶膜的制备方法,其特征在于,包括:
将聚烯烃弹性体作为内层、乙烯-醋酸乙烯共聚物作为内层两表面的外层,以共挤方式制成三层共挤复合薄膜;
UV辐照,使聚烯烃弹性体中含有特殊极性结构的硅氧烷发生加成反应生成有机硅聚合物,即所述中间层。
7.根据权利要求6所述的制备方法,其特征在于,
所述共挤方式包括:
将聚烯烃弹性体的各组分混合熔融,形成内层熔融物;
将乙烯-醋酸乙烯共聚物的各组分混合熔融,形成外层熔融物;
将外层熔融物分别置于内层熔融物的上、下表面,内层熔融物中的含有特殊极性结构的硅氧烷迁移至内层熔融物与外层熔融物的界面处;
通过模具热压挤出,得到所述三层共挤复合薄膜。
8.根据权利要求7所述的制备方法,其特征在于,
所述外层熔融物的表面能大于内层熔融物,以使含有特殊极性结构的硅氧烷从低表面能迁移至高表面能处;其中
所述外层熔融物的表面张力为35-37mN/m;
所述内层熔融物的表面张力为31-33mN/m。
10.一种热熔胶膜作为胶黏剂的应用。
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