CN116285516A - 光伏钢化玻璃用涂料、涂层及其制备方法 - Google Patents
光伏钢化玻璃用涂料、涂层及其制备方法 Download PDFInfo
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- CN116285516A CN116285516A CN202310042609.4A CN202310042609A CN116285516A CN 116285516 A CN116285516 A CN 116285516A CN 202310042609 A CN202310042609 A CN 202310042609A CN 116285516 A CN116285516 A CN 116285516A
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Classifications
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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Abstract
本发明属于光伏涂料技术领域,具体涉及一种光伏钢化玻璃用涂料、涂层及其制备方法,包括以下质量份数的原材料:氟树脂:60‑100份;颜填料:50‑75份;分散剂:1‑4份;改性聚合物:5‑26份;流平剂:0.5‑1.0份;抗氧剂:0.2‑0.6份;封闭型氰酸酯固化剂:6‑18份;催化剂:0.1‑0.4份;溶剂:35‑60份;其中所述改性聚合物是以端羟基聚丁二烯、甘油和马来酸酐为主链,分子链两端以N,N‑(氨丙基三乙氧基)硅烷封端;采用聚合物改性的方式,在传统热固型涂层的基础上,提高了热固型涂层与胶膜的剥离强度以及热固型涂层与玻璃的附着力,并且在短长期湿热老化后剥离强度有很好的保持力,优于传统的玻璃镀釉涂层。
Description
技术领域
本发明属于光伏涂料技术领域,具体涉及一种光伏钢化玻璃用涂料、涂层及其制备方法。
背景技术
近几年,随着双面电池技术的日趋成熟,双面双玻组件应运而生。玻璃作为一种无机材料,水汽透过率为零,透光率优异,其自身在耐候的持久性上获得普遍认可,因此钢化玻璃成为了光伏组件配套使用的一种重要材料。为了实现双面电池组件发电效率的提升以及特殊外观需求,在玻璃上某些特殊位置印刷白色、黑色或其它颜色的涂层也就被开发了出来,这种印刷了涂层的玻璃称为网格玻璃。这里所述的网格即电池片与电池片之间以及电池片与铝边框之间的间隙在玻璃上所对应的区域。而在这些区域印刷涂料再进行烘烤后形成的玻璃即为网格玻璃。为了方便组件厂自动化生产,这些涂层印刷的宽度会比电池片所对应的区域宽出1-3mm。而其印刷涂层用的玻璃为正面压花玻璃或背面浮法玻璃。
目前市场上主流的网格玻璃所使用的涂料为镀釉涂料,涂料的主要成分为低熔点玻璃粉、颜填料、分散剂、溶剂以及少量树脂,涂料固化工艺为100-150℃*1-2min溶剂挥发以及600-700℃*2-3min玻璃粉熔融成釉,颜填料会被玻璃釉包裹,其它有机组分均会被热分解而挥发消失。这种涂料的固化过程也是玻璃同步进行钢化处理的过程,需经过急速升温和降温。因固化后的涂层和钢化玻璃的膨胀系数不一致,导致玻璃表面应力集中,再加上玻璃需要叠压放置运输,因此这种网格玻璃存在很高的碎片率。如今电池片的尺寸越做越大,玻璃的大小也在原有的基础上增加了20-40%,这就导致了玻璃在印刷镀釉涂料后的碎片率更高。现有网格玻璃的碎片率在0.3-0.8%,玻璃厂家苦不堪言。此外,这种网格玻璃上的镀釉涂层中使用了低熔点玻璃粉,低熔点玻璃粉为了降低熔点,需要玻璃高温混合时加入钠钾类的碱金属组分,这种钠钾类碱金属成分会在晶硅组件封装后长期使用时游离出来,产生PID失效,即电势诱导衰减,影响光伏组件的使用寿命。此外,传统的镀釉涂层在PCT短期湿热老化和双85长期湿热老化后与胶膜的剥离强度衰减明显,水汽容易渗透进入组件内,导致组件漏电失效。
发明内容
本发明提供了一种光伏钢化玻璃用涂料、涂层及其制备方法,以解决传统镀釉网格玻璃附着力的问题。
为了解决上述技术问题,本发明提供了一种光伏钢化玻璃用涂料,包括以下质量份数的原材料:氟树脂:60-100份;颜填料:50-75份;分散剂:1-4份;改性聚合物:5-26份;流平剂:0.5-1.0份;抗氧剂:0.2-0.6份;封闭型氰酸酯固化剂:6-18份;催化剂:0.1-0.4份;溶剂:35-60份;其中所述改性聚合物是以端羟基聚丁二烯、甘油和马来酸酐为主链,分子链两端以N,N-(氨丙基三乙氧基)硅烷封端。
又一方面,本发明还提供了一种光伏钢化玻璃用涂料的制备方法,包括以下步骤:步骤S1,颜填料研磨:将溶剂和氟树脂混合并搅拌均匀,加入分散剂,500-1000转/min搅拌5-10min;将搅拌机转速升至1000-2000转,缓慢加入颜填料,搅拌30-60min,使颜填料分散均匀,即制得所需待研磨浆料;将待研磨浆料接入研磨机中,研磨机转速1000-1500转/min,锆珠粒径0.6-0.8mm,以5-10L/min的流量研磨2-4遍,测试浆料细度≤5-10μm即可,即制得所需颜填料浆料;步骤S2,涂料成品制备:将上述颜填料研磨浆料、剩余氟树脂、改性聚合物、流平剂、抗氧剂、封闭型固化剂、催化剂以及剩余溶剂混合并1000转/min高速分散10min,再将无需研磨的颜填料加入,2000转/min高速分散30-60min,过滤,分装,即为涂料成品。
第三方面,本发明还提供了一种改性聚合物的制备方法,包括以下步骤:步骤S1,将丙二醇甲醚醋酸酯加入反应容器中,通入氮气,升温至70~125℃,加入甘油,持续搅拌分散,制得甘油溶液A;步骤S2,将马来酸酐使用丙二醇甲醚醋酸酯按照6:4重量比进行溶解,制得60%马来酸酐溶液B;步骤S3,将马来酸酐溶液B滴加入甘油溶液A中,70~125℃反应1-2h,制得甘油和马来酸酐的预聚物C;步骤S4,将端羟基聚丁二烯缓慢加至预聚物C中,持续通入氮气,搅拌,升温至120~180℃,反应2-6小时,直至无反应产物水流出,得到反应产物D;步骤S5,将N,N-(氨丙基三乙氧基)硅烷缓慢滴加入反应产物D中,持续通入氮气,保持温度80-140℃,反应2-4小时,直至无反应产物水流出再保温1-2小时,冷却,包装,即制得的最终产物为所述改性聚合物。
第四方面,本发明还提供了一种光伏钢化玻璃用涂层,包括:如前所述的光伏钢化玻璃用涂料。
第五方面,本发明还提供了一种如前所述的光伏钢化玻璃用涂层的制备方法,包括以下步骤:步骤S1,按需取用如前所述的涂料成品,300-500转/min搅拌5-10min并加入适量溶剂调至合适粘度;步骤S2,根据涂层膜厚需求,选择合适的丝网印刷网版,将涂料印刷至玻璃表面,采用滚轮传送的方式通过低中高温度段烘箱烘烤2-4min,涂料充分固化交联,样板冷却至60℃以下,电晕处理,即为光伏钢化玻璃用涂层。
本发明的有益效果是,本发明的光伏钢化玻璃用涂料、涂层及其制备方法具有如下优点:
(1)采用聚合物改性的方式,在传统热固型涂层的基础上,提高了热固型涂层与胶膜的剥离强度以及热固型涂层与玻璃的附着力,并且在短长期湿热老化后剥离强度有很好的保持力,优于传统的玻璃镀釉涂层;
(2)本发明降低了网格玻璃的碎片率,传统镀釉网格玻璃从生产运输至组件厂使用过程中的碎片率在0.3-0.8%,落球试验条件下则有6片碎1-2片的碎片率;而本发明的热固型涂层不涉及玻璃的钢化成型过程,仅需在100-240℃条件下固化交联,涂层不会在玻璃表面形成很大的集中应力,因此不会碎片;即使在更大尺寸的玻璃应用上也有极大的优势;
(3)本发明解决了了PID失效的问题,因镀釉涂层的低熔点玻璃粉中存在钠钾等碱金属成分,在长期湿热条件下,钠钾离子会迁移到晶硅电池片表面而导致电池片失效;而本发明使用的热固型涂层无碱金属成分,PID试验结果显示其无PID失效的问题。
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。
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是本发明的光伏钢化玻璃用涂料的制备及使用方法的工艺流程图。
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。
现有技术方案中,主要为低熔点玻璃粉和颜填料为成膜物的镀釉涂料。这种涂料在固化后主要有两个缺点:湿热老化后剥离强度明显衰减、碎片率高和PID失效。
湿热老化后剥离强度衰减:镀釉涂层在600-700℃高温下会热分解掉所有有机成分,仅留下颜填料和玻璃成分,胶膜中的聚烯烃成分和偶联剂与釉层不能形成有效或足够多的化学键合(胶膜中不能加入过多偶联剂,不然会影响胶膜的耐湿热性能),特别是在湿热老化后,这种化学键合会被逐渐侵蚀破坏,从而使得釉层和胶膜剥离强度明显衰减。
碎片率高:涂料在固化过程也是玻璃同步进行钢化处理过程,需经过急速升温和降温的过程。因固化后的涂层和钢化玻璃的膨胀系数不一致,导致玻璃表面应力集中,再加上玻璃需要叠压放置运输,因此这种网格玻璃存在很高的碎片率。如今电池片的尺寸越做越大,玻璃的大小也在原有的基础上增加了20-40%,这就导致了常规镀釉网格玻璃的碎片率更高。
PID失效:网格玻璃上的镀釉涂层中使用了低熔点玻璃粉,低熔点玻璃粉为了降低熔点,需要玻璃高温混合时加入钠钾类的碱金属组分,这种钠钾类碱金属成分会在晶硅组件封装后长期使用时游离出来,钠钾离子迁移至电池片表面,会与电池片表面的银栅线发生电腐蚀反应,从而腐蚀电池栅线,导致填充因子低、串联电阻高,组件性能衰减,产生PID失效,即电势诱导衰减,影响光伏组件的使用寿命。
本发明的单组分热固型白色\黑色\彩色氟碳涂料,采用丝网印刷的方式进行施工,低温烘烤,快速固化。通过聚合物改性和配方设计,提高网格涂层与胶膜的初始和湿热老化后的剥离强度,降低网格玻璃的碎片率,解决PID失效问题。
本发明提供了一种光伏钢化玻璃用涂料,包括以下质量份数的原材料:氟树脂:60-100份;颜填料:50-75份;分散剂:1-4份;改性聚合物:5-26份;流平剂:0.5-1.0份;抗氧剂:0.2-0.6份;封闭型氰酸酯固化剂:6-18份;催化剂:0.1-0.4份;溶剂:35-60份;其中所述改性聚合物是以端羟基聚丁二烯、甘油和马来酸酐为主链,分子链两端以N,N-(氨丙基三乙氧基)硅烷封端,所制备的改性聚合物的分子链带有侧羟基,可与涂料中的-NCO基团反应;分子链两端为12个硅氧烷结构,可与玻璃表面的硅羟基发生亲核取代反应,脱出乙醇,形成稳定的-Si-O-Si-共价键结构,相比于普通单一偶联剂末端仅有2-3个硅氧烷结构,12个硅氧烷会有更好的附着力性能优势;分子链中的-C=C-双键结构与光伏EVA/POE胶膜层压热贴合时,在胶膜中引发剂的作用下,-C=C-双键结构会与胶膜形成交联反应,从而使得涂层与胶膜具有优异的剥离强度,且在湿热老化后剥离强度衰减小。
在其中一个实施例中,所述改性聚合物包括以下质量份数的各组分:端羟基聚丁二烯:20.0-180.0份;甘油:0.5-3.0份;马来酸酐:4.0-8.0份;N,N-(氨丙基三乙氧基)硅烷:7.0-9.0份;丙二醇甲醚醋酸酯:21.0-50.0份;所述端羟基聚丁二烯的分子量Mn为1000~4500;所述马来酸酐需使用丙二醇甲醚醋酸酯进行溶解后滴加使用。
在其中一个实施例中,所述氟树脂为FEVE树脂中的四氟乙烯-乙烯基醚树脂、四氟乙烯-乙烯基酯树脂、三氟氯乙烯-乙烯基醚、三氟氯乙烯-乙烯基酯树脂树脂中的一种或多种;所述氟树脂的羟值为50-80mgKOH/g;具体如东氟化工ZHM-2或HLR-6氟树脂、长兴41011氟树脂、大金GK-570氟树脂等;氟树脂的加入是为了提升涂层的耐候性以及耐脏污性能,是涂层的主要成膜物之一。
在其中一个实施例中,所述封闭型聚异氰酸酯固化剂为封闭型HDI三聚体、封闭型H6XDI加成物、封闭型XDI加成物中的一种或多种。具体如科思创的3175封闭型异氰酸酯固化剂;封闭型聚异氰酸酯固化剂每个分子带有两个以上被封闭的-NCO基团,封闭型固化剂在常温下不具有活性,在高温下解封释放封闭剂,使-NCO基团被释放出来,-NCO基团可与涂料组分中的-OH反应形成网状交联结构,使得涂层的物理和化学性能得以长久稳定保持。
在其中一个实施例中,所述颜填料为钛白粉、沉淀硫酸钡、立德粉、氧化锌、碳酸钙、铜铬黑、铁铬黑、炭黑、苯胺黑、铁红、镉红、立索尔红、大红、镉黄、铅铬黄、群青、酞青蓝、孔雀蓝、铬绿、锌绿、钴紫、群青紫、二氧化硅、高岭土、膨润土、玻璃粉、空心玻璃微珠、氧化铝粉、PTFE微粉、PVDF微粉、PE蜡粉、PP蜡粉中的一种或多种;颜填料的加入主要是为了赋予色彩,提升遮盖力;还对涂料的流变性、耐候性、耐化学品性、耐热性、涂膜的机械性能、手感有一定影响,颜填料的加入还可以降低涂料的成本;有些颜填料还对涂层的阻燃性、导电性有影响。
在其中一个实施例中,所述分散剂为阴离子型润湿分散剂、阳离子型润湿分散剂、非离子型润湿分散剂、两性型润湿分散剂、高分子型超分散剂、受控自由基型超分散剂中的一种或多种;具体如Efka PU 4010;分散剂是一种在分子内同时具有亲油性和亲水性两种相反性质的表面活性剂,能减少完成分散过程所需要的时间和能量,改性粒子表面性质,调整颜料粒子的运动性,从而提高粉料的稳定性,避免凝絮沉降。
在其中一个实施例中,所述流平剂为丙烯酸流平剂、有机硅流平剂、氟硅流平剂以及高沸点溶剂中的一种或多种;所述高沸点溶剂的沸点在150℃以上;具体如BYK-300;流平剂通过有限的相容性迁移到湿膜表面,影响漆膜表面张力,促使涂料在干燥过程中形成一个平整、均匀的涂层,改善涂料对底材的渗透性,减少涂刷时产生的斑点、痕迹等外观瑕疵。
在其中一个实施例中,所述抗氧剂为受阻胺、受阻酚、亚磷酸酯类、硫代二丙酸酯类、硫醇类中的一种或多种;具体如1010、1076、164、168等抗氧剂;抗氧剂是延缓或抑制聚合物受热氧化分解的一类物质,可延缓聚合物的老化并延长其使用寿命。
在其中一个实施例中,所述催化剂为有机锡类、有机锌类、有机铋类、胺类中的一种或多种;具体如二丁基锡二月桂酸酯;催化剂的加入是为了降低封闭型催化剂的解封温度,催化涂层中-OH、-COOH、氨基、环氧基等活性基团等与-NCO基团加速反应,提高生产效率,避免涂层中各组分反应不完全出现涂层发粘和性能不佳的问题。
在其中一个实施例中,所述溶剂为醋酸丁酯、甲苯、二甲苯、乙酸乙酯、丙二醇甲醚醋酸酯、正丁醇、丙酮、丁酮、200号溶剂油中的一种或多种;溶剂能够将有机反应物溶解形成均相体系,使得涂层中的各组分充分均匀反应交联。根据烘烤温度来选择不同沸点的溶剂,以确保涂层不发粘以及有足够的交联固化时间。
如图1所示,本发明还提供了一种光伏钢化玻璃用涂料的制备方法,包括以下步骤:步骤S1,颜填料研磨:将溶剂和氟树脂混合并搅拌均匀,加入分散剂,500-1000转/min搅拌5-10min;将搅拌机转速升至1000-2000转,缓慢加入颜填料,搅拌30-60min,使颜填料分散均匀,即制得所需待研磨浆料;将待研磨浆料接入研磨机中,研磨机转速1000-1500转/min,锆珠粒径0.6-0.8mm,以5-10L/min的流量研磨2-4遍,测试浆料细度≤5-10μm即可,即制得所需颜填料浆料;步骤S2,涂料成品制备:将上述颜填料研磨浆料、剩余氟树脂、改性聚合物、流平剂、抗氧剂、封闭型固化剂、催化剂以及剩余溶剂混合并1000转/min高速分散10min,再将无需研磨的颜填料加入,2000转/min高速分散30-60min,过滤,分装,即为涂料成品。
本发明还提供了一种改性聚合物的制备方法,包括以下步骤:步骤S1,将丙二醇甲醚醋酸酯加入反应容器中,通入氮气,升温至70~125℃,加入甘油,持续搅拌分散,制得甘油溶液A;步骤S2,将马来酸酐使用丙二醇甲醚醋酸酯按照6:4重量比进行溶解,制得60%马来酸酐溶液B;步骤S3,将马来酸酐溶液B滴加入甘油溶液A中,70~125℃反应1-2h,制得甘油和马来酸酐的预聚物C;步骤S4,将端羟基聚丁二烯缓慢加至预聚物C中,持续通入氮气,搅拌,升温至120~180℃,反应2-6小时,直至无反应产物水流出,得到反应产物D;步骤S5,将N,N-(氨丙基三乙氧基)硅烷缓慢滴加入反应产物D中,持续通入氮气,保持温度80-140℃,反应2-4小时,直至无反应产物水流出再保温1-2小时,冷却,包装,即制得的最终产物为所述改性聚合物。
在其中一个实施例中,所述改性聚合物的化学反应式为:
本发明还提供了一种光伏钢化玻璃用涂层,包括:如前所述的光伏钢化玻璃用涂料。
本发明还提供了一种如前所述的光伏钢化玻璃用涂层的制备方法,包括以下步骤:步骤S1,按需取用如前所述的涂料成品,300-500转/min搅拌5-10min并加入适量溶剂调至合适粘度;步骤S2,根据涂层膜厚需求,选择合适的丝网印刷网版,将涂料印刷至玻璃表面,采用滚轮传送的方式通过低中高温度段烘箱烘烤2-4min,涂料充分固化交联,样板冷却至60℃以下,电晕处理,即为光伏钢化玻璃用涂层。
实施例1:
按照表1所示的配方比例进行涂料配制、搅拌、丝印。烘箱烘烤温度110-220℃,烘烤时间2min;电晕强度4.5kW。
表1
实施例2:
按照表2所示的配方比例进行涂料配制、搅拌、丝印。烘箱烘烤温度110-240℃,烘烤时间2min;电晕强度4.5kW。
表2
类型 | 具体组成/比例 | 用量/重量份 |
氟树脂 | HLR-6氟树脂 | 86 |
颜填料 | 钛白粉:沉淀硫酸钡:膨润土=6:2:1 | 72 |
分散剂 | BYK-111 | 2.9 |
改性聚合物 | 改性聚合物 | 12 |
流平剂 | BYK-306 | 0.8 |
抗氧剂 | 1076 | 0.5 |
封闭型固化剂 | 三井G282封闭型固化剂 | 11 |
催化剂 | 有机锡催化剂 | 0.2 |
溶剂 | 乙酸丁酯 | 38 |
实施例3:
按照表3所示的配方比例进行涂料配制、搅拌、丝印。烘箱烘烤温度110-220℃,烘烤时间2min;电晕强度4.5kW。
表3
类型 | 具体组成/比例 | 用量/重量份 |
氟树脂 | ZHM-2氟树脂 | 96 |
颜填料 | 炭黑:玻璃粉:二氧化硅=4:3:1 | 56 |
分散剂 | BYK-163 | 1.5 |
改性聚合物 | 改性聚合物 | 20 |
流平剂 | BYK-300 | 0.8 |
抗氧剂 | 1010 | 0.6 |
封闭型固化剂 | 科思创3175封闭型固化剂 | 17 |
催化剂 | 有机锡催化剂:有机铋催化剂=1:1 | 0.3 |
溶剂 | 丙二醇甲醚醋酸酯 | 52 |
实施例4:
按照表4所示的配方比例进行涂料配制、搅拌、丝印。烘箱烘烤温度110-230℃,烘烤时间2min;电晕强度4.5kW。
表4
实施例5:
按照表5所示的配方比例进行涂料配制、搅拌、丝印。烘箱烘烤温度110-230℃,烘烤时间2min;电晕强度4.5kW。
表5
类型 | 具体组成/比例 | 用量/重量份 |
氟树脂 | 41011氟树脂 | 76 |
颜填料 | 钛白粉:PTFE微粉:膨润土=6:1:1 | 65 |
分散剂 | BYK-110 | 1.3 |
改性聚合物 | 改性聚合物 | 14 |
流平剂 | BYK-300 | 0.6 |
抗氧剂 | 1010 | 0.5 |
封闭型固化剂 | 科思创3370封闭型固化剂 | 14 |
催化剂 | 有机锡催化剂 | 0.3 |
溶剂 | 丙二醇甲醚醋酸酯 | 47 |
实施例测试结果:
表6初始性能
表7老化性能
附:PID试验参考IEC TS 62804-2:2022;落球试验参考GB/T 15763.2-2005抗冲击性试验。
由上述测试结果可以看出:
(1)1、2、3、4、5组实施例都为热固型网格玻璃涂层,对比镀釉型网格玻璃涂层,5组热固型涂层在初始性能上与镀釉型涂层基本一致,无明显差异;
(2)在PCT和双85湿热老化方面,镀釉型涂层的剥离强度衰减明显,不如热固型涂层;
(3)在PID试验方面,镀釉型网格玻璃内的釉层有电击穿风险,电池片会失效,而热固型涂层则无异常;
(4)在落球试验方面,镀釉型网格玻璃有一定的碎片概率,而热固涂层型网格玻璃则不会碎片。
由此可见,本发明虽然需要增加涂层烘烤和电晕工序,但也降低了玻璃的碎片率,减少了玻璃厂收到的客诉及索赔,从长期来看是正收益的;且光伏组件越做越大,玻璃越大,其碎片概率也越大,在玻璃大尺寸的趋势下,采用热固型涂层进行网格印刷也是明智之选。
同时,热固型涂层网格玻璃所生产的组件无PID失效风险,且涂层在长期湿热老化条件下涂层性能无明显衰减,可有效的延长组件的使用寿命。
综上所述,本发明的光伏钢化玻璃用涂料、涂层及其制备方法,采用聚合物改性的方式,在传统热固型涂层的基础上,提高了热固型涂层与胶膜的剥离强度以及热固型涂层与玻璃的附着力,并且在短长期湿热老化后剥离强度有很好的保持力,优于传统的玻璃镀釉涂层。
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)
1.一种光伏钢化玻璃用涂料,其特征在于,包括以下质量份数的原材料:
氟树脂:60-100份;
颜填料:50-75份;
分散剂:1-4份;
改性聚合物:5-26份;
流平剂:0.5-1.0份;
抗氧剂:0.2-0.6份;
封闭型氰酸酯固化剂:6-18份;
催化剂:0.1-0.4份;
溶剂:35-60份;其中
所述改性聚合物是以端羟基聚丁二烯、甘油和马来酸酐为主链,分子链两端以N,N-(氨丙基三乙氧基)硅烷封端。
2.如权利要求1所述的光伏钢化玻璃用涂料,其特征在于,所述改性聚合物包括以下质量份数的各组分:
端羟基聚丁二烯:20.0-180.0份;
甘油:0.5-3.0份;
马来酸酐:4.0-8.0份;
N,N-(氨丙基三乙氧基)硅烷:7.0-9.0份;
丙二醇甲醚醋酸酯:21.0-50.0份;
所述端羟基聚丁二烯的分子量Mn为1000~4500;
所述马来酸酐需使用丙二醇甲醚醋酸酯进行溶解后滴加使用。
3.如权利要求1所述的光伏钢化玻璃用涂料,其特征在于,
所述氟树脂为FEVE树脂中的四氟乙烯-乙烯基醚树脂、四氟乙烯-乙烯基酯树脂、三氟氯乙烯-乙烯基醚、三氟氯乙烯-乙烯基酯树脂树脂中的一种或多种;
所述氟树脂的羟值为50-80mgKOH/g。
4.如权利要求1所述的光伏钢化玻璃用涂料,其特征在于,
所述封闭型聚异氰酸酯固化剂为封闭型HDI三聚体、封闭型H6XDI加成物、封闭型XDI加成物中的一种或多种。
5.如权利要求1所述的光伏钢化玻璃用涂料,其特征在于,
所述颜填料为钛白粉、沉淀硫酸钡、立德粉、氧化锌、碳酸钙、铜铬黑、铁铬黑、炭黑、苯胺黑、铁红、镉红、立索尔红、大红、镉黄、铅铬黄、群青、酞青蓝、孔雀蓝、铬绿、锌绿、钴紫、群青紫、二氧化硅、高岭土、膨润土、玻璃粉、空心玻璃微珠、氧化铝粉、PTFE微粉、PVDF微粉、PE蜡粉、PP蜡粉中的一种或多种;
所述分散剂为阴离子型润湿分散剂、阳离子型润湿分散剂、非离子型润湿分散剂、两性型润湿分散剂、高分子型超分散剂、受控自由基型超分散剂中的一种或多种;
所述流平剂为丙烯酸流平剂、有机硅流平剂、氟硅流平剂以及高沸点溶剂中的一种或多种;
所述抗氧剂为受阻胺、受阻酚、亚磷酸酯类、硫代二丙酸酯类、硫醇类中的一种或多种;
所述催化剂为有机锡类、有机锌类、有机铋类、胺类中的一种或多种;
所述溶剂为醋酸丁酯、甲苯、二甲苯、乙酸乙酯、丙二醇甲醚醋酸酯、正丁醇、丙酮、丁酮、200号溶剂油中的一种或多种。
6.一种如权利要求1所述光伏钢化玻璃用涂料的制备方法,其特征在于,包括以下步骤:
步骤S1,颜填料研磨:将溶剂和氟树脂混合并搅拌均匀,加入分散剂,500-1000转/min搅拌5-10min;将搅拌机转速升至1000-2000转,缓慢加入颜填料,搅拌30-60min,使颜填料分散均匀,即制得所需待研磨浆料;将待研磨浆料接入研磨机中,研磨机转速1000-1500转/min,锆珠粒径0.6-0.8mm,以5-10L/min的流量研磨2-4遍,测试浆料细度≤5-10μm即可,即制得所需颜填料浆料;
步骤S2,涂料成品制备:将上述颜填料研磨浆料、剩余氟树脂、改性聚合物、流平剂、抗氧剂、封闭型固化剂、催化剂以及剩余溶剂混合并1000转/min高速分散10min,再将无需研磨的颜填料加入,2000转/min高速分散30-60min,过滤,分装,即为涂料成品。
7.一种如权利要求1所述的改性聚合物的制备方法,其特征在于,包括以下步骤:
步骤S1,将丙二醇甲醚醋酸酯加入反应容器中,通入氮气,升温至70~125℃,加入甘油,持续搅拌分散,制得甘油溶液A;
步骤S2,将马来酸酐使用丙二醇甲醚醋酸酯按照6:4重量比进行溶解,制得60%马来酸酐溶液B;
步骤S3,将马来酸酐溶液B滴加入甘油溶液A中,70~125℃反应1-2h,制得甘油和马来酸酐的预聚物C;
步骤S4,将端羟基聚丁二烯缓慢加至预聚物C中,持续通入氮气,搅拌,升温至120~180℃,反应2-6小时,直至无反应产物水流出,得到反应产物D;
步骤S5,将N,N-(氨丙基三乙氧基)硅烷缓慢滴加入反应产物D中,持续通入氮气,保持温度80-140℃,反应2-4小时,直至无反应产物水流出再保温1-2小时,冷却,包装,即制得的最终产物为所述改性聚合物。
9.一种光伏钢化玻璃用涂层,其特征在于,包括:
如权利要求1所述的光伏钢化玻璃用涂料。
10.一种如权利要求9所述的光伏钢化玻璃用涂层的制备方法,其特征在于,包括以下步骤:
步骤S1,按需取用如权利要求6所述的涂料成品,300-500转/min搅拌5-10min并加入适量溶剂调至合适粘度;
步骤S2,根据涂层膜厚需求,选择合适的丝网印刷网版,将涂料印刷至玻璃表面,采用滚轮传送的方式通过低中高温度段烘箱烘烤2-4min,涂料充分固化交联,样板冷却至60℃以下,电晕处理,即为光伏钢化玻璃用涂层。
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