CN111100489A - 一种离型硬涂料、一种离型膜和一种光伏组件 - Google Patents
一种离型硬涂料、一种离型膜和一种光伏组件 Download PDFInfo
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- CN111100489A CN111100489A CN201811264920.9A CN201811264920A CN111100489A CN 111100489 A CN111100489 A CN 111100489A CN 201811264920 A CN201811264920 A CN 201811264920A CN 111100489 A CN111100489 A CN 111100489A
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- hard coat
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- hard coating
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Abstract
本发明提供了一种离型硬涂料,包括底部硬涂料组分和上部离型涂料组分,所述底部硬涂料组分包括交联聚合物基质、纳米二氧化硅颗粒;所述上部离型涂料组分包括能与所述底部硬涂料组分发生接枝反应的离型聚合物。该离型硬涂料可以被涂布在诸如PET的基材上,能对抗粘性小广告,并保护基材,防止其受磨损。
Description
技术领域
本发明涉及一种涂料,尤其涉及一种离型硬涂料,一种耐刮擦的离型膜和一种光伏组件。
背景技术
交通工具租赁,尤其是共享单车,以其低碳环保、经济便捷的共享模式,得到越来越多人的关注。人们通过手机就能快速定位到附近的共享单车,并且可以通过手机解锁租用。每辆共享单车上都安装有电子车锁、全球定位系统(GPS),通过固定在车篮里的太阳能电池板持续供电。然而,这些太阳能电池板经常被贴上各种小广告,影响太阳能电池板正常工作。
现有技术中,离型涂料因可以有效地释放压敏胶而被广泛地应用到防粘的离型纸中,但是,离型涂料通常很软并且耐磨性能不好。另外一方面,硬涂料可以提供硬度,并且具有较好地耐久性,防止基材表面磨损,但是,硬涂料的防粘性能不好。在大多数情况下,硬涂料和压敏胶难以被剥离。
美国专利(US6,660,388)公开了一种抗染污性硬涂层,其包括一基本上透明的基板,一包含分散在粘结剂基质中的无机氧化物微粒的硬涂层,和一包含全氟化聚醚的抗污染层。所述薄膜具有非常好的耐磨、耐脏和抗眩光性,以及非常好的层间粘合性和耐久性。
美国专利(US4,472,480)公开了一种低表面能量衬垫,包括已被原位聚合到粘接网的全氟聚醚,粘接网被粘附在基材上。该低表面能量衬垫对压敏胶带的低附着系数的背衬涂层特别有用。
中国发明专利(CN102459378B)公开了一种防污组合物,其为含有具有全氟聚醚基团和活性能量射线反应性基团的化合物(A)和无机微粒(B)的防污组合物,该组合物中的固体成分100质量份中含有20质量份以上、75质量份以下的化合物(A)。
美国专利(US5,104,929)公开了一种透明耐磨涂层,包括分散在乙烯基不饱和脂肪族和/或环脂单体上的胶体二氧化硅颗粒,该二氧化硅颗粒粒径小于100nm,该涂层在保护塑料、木质、金属和陶瓷表面上非常有用。
发明内容
针对现有技术无法同时满足防粘、耐磨、有硬度的要求,本发明提供了一种离型硬涂料,该离型硬涂料可以被涂布在诸如PET的基材上,能对抗粘性小广告,并保护电池板,防止其受冲击和磨损。
为实现本发明的发明目的,本发明的离型硬涂料,包括底部硬涂料组分和上部离型涂料组分,所述底部硬涂料组分包括交联聚合物基质、纳米金属氧化物颗粒;所述上部离型涂料组分包括能与所述底部硬涂料组分发生接枝反应的离型聚合物。
纳米金属氧化物颗粒能增加涂料的硬度,而加入交联聚合物基质,能使涂料底部形成网状结构,涂料的机械结构更强,更稳定,不容易被破坏。
根据本发明的某些实施方式,所述底部硬涂料组分还包括微粒,其粒径在0.5μm~100μm之间。
经发明人研究发现,在底部硬涂料组分中添加微米级别的粒子,涂料经固化后,不仅能产生发雾、磨砂的效果,而且,微粒加入后涂料表面变粗糙,与涂料接触的压敏胶膜(如小广告胶膜)的接触面积变小,涂料的离型效果更好。此外,微粒的粒径大小对本发明的技术效果有一定影响,微粒的粒径不能太大,如果太大,会影响底部硬涂料组分的涂膜溶液的稳定性,同样的,微粒的粒径也不能太小,如果太小,不能产生发雾、磨砂的效果,而且离型效果不佳。因此,微粒的粒径在0.5μm~100μm之间,能有较好的发雾、磨砂效果,并且提高离型力。
根据本发明的某些实施方式,所述微粒选自微米级的聚合物颗粒,微米级的无机金属氧化物颗粒,微米级的金属盐颗粒及其组合。
优选地,所述微米级的聚合物颗粒选自聚甲基丙烯酸甲酯(PMMA),聚苯乙烯(PS)及其组合。
优选地,所述微米级的无机金属氧化物颗粒选自氧化硅,氧化铝,氧化钛及其组合。
优选地,所述微米级的金属盐颗粒选自碳酸钙,硫酸钙,硫酸镁及其组合。
根据本发明的某些实施方式,所述交联聚合物基质包括多官能度的丙烯酸酯,选自三羟甲基丙烷三丙烯酸酯(trimethylolpropane triacrylate),三(2-羟乙基异氰脲酸酯)三丙烯酸酯(tris(2-hydroxyethylisocyanurate)triacrylate),季戊四醇三丙烯酸酯(pentaerythritol triacrylate),季戊四醇四丙烯酸酯(pentaerythritoltetraacrylate),二-三羟甲基丙烷四丙烯酸酯(di-trimethylolpropanetetraacrylate),乙氧基化季戊四醇四丙烯酸酯(ethoxylated pentaerythritoltetraacrylate),双季戊四醇五丙烯酸酯(dipentaerythritol pentaacrylate)及其组合。
根据本发明的某些实施方式,所述纳米金属氧化物颗粒选自纳米二氧化硅颗粒,纳米氧化铝,纳米氧化锆,纳米氧化锌及其组合。其中,优选纳米二氧化硅颗粒。更优选地,所述纳米二氧化硅颗粒的粒径小于100nm。最优选地,所述纳米二氧化硅颗粒的粒径小于50nm。
根据本发明的某些实施方式,所述底部硬涂料组分经过光引发聚合。在底部硬涂料组分中添加光引发剂,通过光引发剂吸收强紫外灯光发射的紫外量子,引发聚合交联和接枝反应,不仅能促使底部硬涂料组分固化,而且还促使底部硬涂料组分和上部离型涂料组分化学键和,牢牢锁住上部离型涂料组分,防止上部离型涂料组分脱落。
根据本发明的某些实施方式,所述离型聚合物选自氟化聚烯烃,全氟聚醚丙烯酸酯,聚氟硅酮及其组合。其中,优选聚氟硅酮。
根据本发明的某些实施方式,所述底部硬涂料组分的厚度在1μm~250μm之间。优选地,厚度在25μm~100μm之间。底部离型涂料组分的厚度不宜过薄,厚度小于1μm会影响硬度和耐磨性,太厚会影响涂料固化。
根据本发明的某些实施方式,所述上部离型涂料组分的厚度小于500nm。优选地,厚度小于100nm。上部离型涂料组分的厚度要求非常薄,从而表现出涂层的硬度和耐磨性。
本发明还提供一种离型膜,包括基材,所述基材表面涂布本发明所述的离型硬涂料。
根据本发明的某些实施方式,所述基材包括至少一层聚合物基材,所述聚合物基材可选自聚对苯二甲酸乙二醇酯(PET),聚氯乙烯(PVC),聚甲基丙烯酸甲酯(PMMA),聚酰胺(PI),聚氨酯(PU),聚碳酸酯(PC)。
根据本发明的某些实施方式,所述基材的表面粗燥度小于100μm。
根据本发明的某些实施方式,所述离型膜的剥离力在0.5g/in~2.0g/in之间。
经发明人深入研究发现,底部硬涂料组分表面的粗糙度以及基材表面的粗糙度均能影响离型效果。底部硬涂料组分表面越粗糙,离型膜的离型效果越好,同样的,基材表面越粗糙,离型膜的离型效果越好,因此,可以对基材表面进行压花处理,增加基材表面的粗糙度,从而减少基材与胶的接触面积,提高离型力。但是,如果基材表面过于粗糙,离型膜的结构会不稳定,并且耐磨性会变差。
本发明还提供一种光伏组件,包括光伏电池,所述光伏电池的表面涂布本发明所述的离型硬涂料或本发明所述的离型膜。
附图说明
为了让本发明的上述和其它目的、特征及优点能更加明显易懂,下面结合附图和具体实施方式对本发明作进一步说明。本领域技术人员应该理解,附图旨在示意性地阐明本发明的优选实施方式,图中各个部件并非按比例绘制。
图1为根据本发明某些具体实施方式的离型硬涂料的结构示意图;
图2~3为根据本发明某些具体实施方式的离型膜的结构示意图。
具体实施方式
以下,将结合附图对根据本发明的一些具体实施方式进行更为详细的说明。应当理解,在不脱离本发明的范围或精神的情况下,本领域技术人员能够根据本说明书的教导设想其他各种实施方案并能够对其进行修改。因此,以下的具体方式是说明性的而非限制性的。
除非另外指明,否则本说明书和权利要求中使用的表示特征尺寸、数量和物理特性的所有数字均应理解为由术语“约”来修饰。因此,除非有相反的说明,否则本说明书和所附权利要求书中列出的数值参数均是近似值,根据本发明的教导,本领域普通技术人员能够适当改变这些近似值,获得所需特性。用端点表示的数值范围包括该范围内的所有数字,例如,1至5包括1、1.1、1.3、1.5、2、2.75、3、3.80、4和5等。
除非另外指明,否则实施例所用的原料,均为市售工业品,通过商业渠道可以购得。
离型硬涂料
本发明的某些方面提供了一种离型硬涂料,如图1所示,离型硬涂料(10)包括底部硬涂料组分(11)和上部离型涂料组分(12),所述底部硬涂料组分包括交联聚合物基质、纳米金属氧化物颗粒;所述上部离型涂料组分包括能与底部硬涂料组分(11)发生接枝反应的离型聚合物。
1)底部硬涂料组分
a.纳米二氧化硅
纳米金属氧化物颗粒可优选纳米二氧化硅颗粒,以增加涂料的硬度。优选的,纳米二氧化硅颗粒的粒径小于100nm。更优选地,所述纳米二氧化硅颗粒的粒径小于50nm。本发明中,通过商业途径可以获得溶于水或水醇(water-alcohol)的无机硅溶胶(inorganicsilica sols),可选自E.I.duPont de Nemours and Co.,Inc.(Wilmington,DE,USA)的商品名为LUDOX SM的硅溶胶,Nyacol Co.(Ashand,MA,USA)的商品名为NYACOL的硅溶胶,Ondea Nalco Chemical Co.(Oak Brook,IL,USA)的商品名为NALCO 2326的硅溶胶(平均粒径5nm,pH10.5,固含量15%),Ondea Nalco Chemical Co.的商品名为NALCO 2327的硅溶胶(平均粒径20nm),Ondea Nalco Chemical Co.的商品名为Nalco 2329K的硅溶胶(平均粒径75nm),Ondea Nalco Chemical Co.的商品名为NALCO 1115和NALCO 1130的硅溶胶,RemetCorp.(Utica,NY,USA)的商品名为REMASOL SP30的硅溶胶。除了可以选择球形纳米二氧化硅颗粒,同时也可以选择非球形(即,针形)二氧化硅颗粒,可选自Nissan化学公司(东京,日本)的商品名为SNOWTEX-UP的水性悬浮液,该悬浮液混合物由20-21%(重量百分比)非球形二氧化硅、小于0.35%(重量百分比)Na2O和水组成,其中,针形二氧化硅颗粒的平均直径为9~15nm,长度约为40~300nm,悬浮液的粘度在25℃时小于100mPa.s,pH值大约为9~10.5,比重在20℃约为1.13;可选自Nissan化学公司的商品名为SNOWTEX-PS-S的水性悬浮液,该悬浮液中的针形二氧化硅颗粒具有珍珠串形态,悬浮液混合物由20-21%(重量百分比)珍珠串形态的二氧化硅、小于0.2%(重量百分比)Na2O和水组成,其中,二氧化硅颗粒的直径约为18~25nm,长度约为80~150nm,动态光散射方法下的颗粒尺寸为80~150nm,悬浮液的粘度在25℃时小于100mPa.s,pH值大约为9~10.5,比重在20℃约为1.13;可选自Nissan化学公司的商品名为SNOWTEX-PS-M的水性悬浮液,该悬浮液中的针形二氧化硅颗粒具有珍珠串形态,悬浮液混合物由20-21%(重量百分比)珍珠串形态的二氧化硅、小于0.2%(重量百分比)Na2O和水组成,其中,二氧化硅颗粒的直径约为10~15nm,长度约为80~120nm。
b.交联聚合物基质
加入交联聚合物基质,能使涂料底部形成网状结构,涂料的机械结构更强,更稳定,不容易被破坏。交联聚合物基质包括多官能度的丙烯酸酯,可选自SurfaceSpecialties(Smyrna,GA,USA)的商品名为TMPTA-N的三羟甲基丙烷三丙烯酸酯,SartomerInc.(Exton,PA,USA)的商品名为SR368的三(2-羟乙基异氰脲酸酯)三丙烯酸酯,SartomerInc.的商品名为SR444的季戊四醇三丙烯酸酯,Sartomer Inc.的商品名为SR295的季戊四醇四丙烯酸酯,Sartomer Inc.的商品名为SR355的二-三羟甲基丙烷四丙烯酸酯,SartomerInc.的商品名为SR494的乙氧基化季戊四醇四丙烯酸酯,以及Sartomer Inc.的商品名为SR399的双季戊四醇五丙烯酸酯。
c.微粒
经发明人研究发现,如果在底部硬涂料组分中添加一些微粒,该微粒的粒径在0.5μm~100μm之间,如微米级的聚合物颗粒,微米级的无机金属氧化物颗粒,微米级的金属盐颗粒,涂料经固化后,不仅能产生发雾、磨砂的效果,而且,能使涂料表面变粗糙,胶的接触面积变小,涂料的离型效果更好。微粒的大小对涂料的性能有一定影响,如果微粒太大,不仅降低涂料的离型力,影响抗粘性能,而且还影响涂料的磨砂效果以及抗反射性能。微米级的金属氧化物颗粒可选自W.R.Grace(Columbia,MD,USA)的商品名为Syloid的微米氧化硅(平均粒径5-10μm)。微米级的聚合物颗粒或微珠可选自Sigma-Aldrich,Cospheric LLC(Santa Barbara,CA,USA),J Color Chemicals,Spherotech(Lake Forest,IL,USA),中国杭州三墩工业园,Microbeads(N-2021Skedsmokorset,挪威),Bangs Laboratories(Fisher,IN,USA),Polysciences Inc.(Warrington,PA,USA)及Techpolymer(MtPleasant,TN,USA)的微珠产品。
底部硬涂料组分的厚度不宜过薄,优选地,厚度在1μm~250μm之间,底部离型涂料组分的厚度小于1μm会阻碍离型硬涂料固化。更优选地,厚度在25μm~100μm之间。
2)上部离型涂料组分
通过接枝反应,离型聚合物与底部硬涂料组分结合在一起,并且提供较好的离型效果。优选地,表面接枝离型聚合物可选自全氟聚醚丙烯酸酯,聚氟硅酮。全氟聚醚丙烯酸酯可以根据美国专利US6,841,190公开的方法获得;聚氟硅酮可以购自于Shin-EtsuSilicones of America,Inc.(Akron,OH,USA),商品名为X-70-201S。
上部离型涂料组分的厚度非常薄,优选地,厚度小于100nm。上部离型涂料组分的厚度增加会影响上部离型涂料组分和底部硬涂料组分之间的结合力,导致部分上部离型涂料组分脱落,从而影响离型效果。
离型膜
本发明的某些方面提供一种离型膜,如图2所示,离型膜(1)包括基材(20),所述基材(20)表面涂布本发明所述的离型硬涂料(10)。离型硬涂料(10)包括底部硬涂料组分(11)和上部离型涂料组分(12)。基材(20)可选用聚合物基材,如Mitsubishi公司的商品名为3SAC的聚对苯二甲酸乙二醇酯(PET)。
如图3所示,基材(20)经压花处理后表面不平整,粗糙度增加了。基材表面的粗糙度对离型效果有一定影响,基材表面越粗糙,离型膜的离型效果越好。但是,如果基材表面太粗糙,离型膜的耐磨性会变差,结构不稳定,因此,基材的表面粗糙度小于100μm较好。
应当理解,图3示例性地示出了基材经压花处理后表面的形状,本领域技术人员可以理解的是,为了实现相同或相似的技术效果,基材表面可以是其他形状。
实施例
以下提供的实施例和对比例有助于理解本发明,并且这些实施例和对比例仅用于对本发明进行示例性说明,而不应将它们理解为对本发明范围的限制。
在本发明的实施例和对比例中采用的原料如表1所示。
表1
制备、测试本发明的是实施例和对比例所采用的部分仪器如表2所示。
表2
仪器 | 型号 | 生产商 |
老化测试机 | QUV-SPRAY | Q-lab Corporation |
凹印涂布机 | YS Gravure | Yasui Seiki |
紫外灯 | H Bulb | Fusion |
剥离测试机 | SP2000 | I-MASS |
胶带 | 232 | 3M Company |
胶带 | 2003 | 3M Company |
钢丝绒 | Scotch Brite | 3M Company |
制备表面功能化纳米二氧化硅有机溶液
将400克纳米二氧化硅颗粒(Nalco 2329K,二氧化硅平均粒径为75nm)注入1quart(0.95升)的反应容器中;将450克丙二醇甲醚(268895)、9.2克3-(甲基丙烯酰氧基)丙基三甲氧基硅烷(SIM6487)、0.23克水溶受阻胺光稳定剂(PROSTAB 5128,抑制剂含量5wt.%)混合后,边搅拌边加入反应容器中。密封并加热反应容器,在80℃下加热16小时,形成表面功能化二氧化硅分散液。继续将混合分散液旋转、蒸发水分,形成42.4wt.%纳米二氧化硅1-甲氧-2-丙醇有机溶液。
制备硬涂料混合物
1.不含微粒的硬涂料混合物
将51.5份可固化粘合的季戊四醇三丙烯酸酯(SR444)倒入反应容器中,在大约49℃下加热,将88份纳米二氧化硅胶体(Nalco 2327,二氧化硅平均粒径为20nm)加入装有季戊四醇三丙烯酸酯(SR444)的反应容器中,经混合后,混合物中含有32.4份的纳米二氧化硅胶体,再加入15.6份的DMA(274135),再将0.15份的BHT(W218405)和0.02份硫代二苯胺(P14831)混合后加入反应容器中。在100±20mm Hg大气压,52℃±2℃温度条件下,将混合物蒸发,直到大部分液体挥发,干制样品中仍留有少量水,并用异丙醇/蒸馏水(14/1,固含量50%)混合溶液稀释干制样品,然后用异丙醇/蒸馏水(14/1,固含量25%)混合溶液进一步稀释样品,在稀释后的样品中加入光引发剂(IRGACURE 184),以提供可光固化的混合物。
2.含有微粒的硬涂料混合物
根据本发明公开的制备表面功能化纳米二氧化硅有机溶液的方法,制得功能化二氧化硅有机溶液。将51.5份可固化粘合的季戊四醇三丙烯酸酯(SR444)倒入反应容器中,在大约49℃下加热,将88份功能化纳米二氧化硅(平均粒径为75nm)加入装有季戊四醇三丙烯酸酯(SR444)的反应容器中,经混合后,混合物中含有32.4份的纳米二氧化硅胶体,再加入15.6份的DMA(274135),再将0.15份的BHT(W218405)和0.02份硫代二苯胺(P14831)混合后加入反应容器中。在100±20mm Hg大气压,52℃±2℃温度条件下,将混合物蒸发,直到大部分液体挥发,干制样品中仍留有少量水,并用异丙醇/蒸馏水(14/1,固含量50%)混合溶液稀释干制样品,然后用异丙醇/蒸馏水(14/1,固含量25%)混合溶液进一步稀释样品,在稀释后的样品中加入光引发剂(IRGACURE184),以提供可光固化的混合物。最后,在可光固化的混合物中加入粒径为3μm、粘接率为3%的PMMA粒子(PMPMS-1.4)。
实施例1
根据本发明公开的制备硬涂料混合物(不含微粒)的方法,制得不含微粒的硬涂料混合物。用#3线棒将硬涂料混合物涂布于PET(Hostaphan 3SAC)上,在50℃下烘干10分钟,并置于紫外灯(H Bulb)中以线速20fpm,100%紫外光照进行固化。
用#5线棒将0.7%的全氟聚醚丙烯酸酯(通过美国专利US6,841,190公开的结构获得)氟化溶液(Novec HFE7600)涂布于上述固化后的底部硬涂料组分上,空气中晾干5分钟,并置于紫外灯(H Bulb)中以线速20fpm,25%紫外光照进行固化,制得样品1。
实施例2
根据本发明公开的制备硬涂料混合物(不含微粒)的方法,制得不含微粒的硬涂料混合物。用#3线棒将混合物涂布于聚氯乙烯膜(Scotchcal3630)上,在50℃下烘干10分钟,并置于紫外灯(H Bulb)中以线速40fpm,100%紫外光照以及氮气环境下进行固化。
用#5线棒将0.7%的全氟聚醚丙烯酸酯(通过美国专利US6,841,190公开的结构获得)氟化溶液(Novec HFE7600)涂布于上述固化后的底部硬涂料组分上,空气中晾干5分钟,并置于紫外灯(H Bulb)中以线速20fpm,25%紫外光照以及氮气环境下进行固化,制得样品2。
实施例3
根据本发明公开的制备硬涂料混合物(含有微粒)的方法,制得含有微粒的硬涂料混合物。
使用凹印涂布机,在PET(Hostaphan 3SAC)上,涂布含有PMMA粒子的可光固化的混合物,置于70℃烤箱烘干0.75分钟,并置于紫外灯(H Bulb)中以线速40fpm,100%紫外光照以及氮气环境下进行固化,最终形成5μm厚度的磨砂硬涂层。
用#5线棒将0.5%的全氟聚醚丙烯酸酯(通过美国专利US6,841,190公开的结构获得)氟化溶液(Novec HFE7600)涂布于上述磨砂硬涂料上,空气中晾干5分钟,并置于紫外灯(H Bulb)中以线速20fpm,25%紫外光照以及氮气环境下进行固化,最终形成50nm厚度的离型涂层,制得样品3。
实施例4
根据本发明公开的制备硬涂料混合物(含有微粒)的方法,制得含有微粒的硬涂料混合物。
使用凹印涂布机,在PET(Hostaphan 3SAC)上,涂布含有PMMA粒子的可光固化的混合物,置于70℃烤箱烘干0.75分钟,并置于紫外灯(H Bulb)中以线速40fpm,100%紫外光照以及氮气环境下进行固化,最终形成5μm厚度的磨砂硬涂层。
用#5线棒将1%的全氟聚醚丙烯酸酯(通过美国专利US6,841,190公开的结构获得)氟化溶液(Novec HFE7600)涂布于上述磨砂硬涂料上,空气中晾干5分钟,并置于紫外灯(H Bulb)中以线速20fpm,25%紫外光照以及氮气环境下进行固化,最终形成100nm厚度的离型涂层,制得样品4。
实施例5
根据本发明公开的制备硬涂料混合物(含有微粒)的方法,制得含有微粒的硬涂料混合物。
使用凹印涂布机,在PET(Hostaphan 3SAC)上,涂布含有PMMA粒子的可光固化的混合物,置于70℃烤箱烘干0.75分钟,并置于紫外灯(H Bulb)中以线速40fpm,100%紫外光照以及氮气环境下进行固化,最终形成5μm厚度的磨砂硬涂层。
用#5线棒将2%的全氟聚醚丙烯酸酯(通过美国专利US6,841,190公开的结构获得)氟化溶液(Novec HFE7600)涂布于上述磨砂硬涂料上,空气中晾干5分钟,并置于紫外灯(H Bulb)中以线速20fpm,25%紫外光照以及氮气环境下进行固化,最终形成200nm厚度的离型涂层,制得样品5。
实施例6
根据本发明公开的制备硬涂料混合物(含有微粒)的方法,制得含有微粒的硬涂料混合物。
使用凹印涂布机,在PET(Hostaphan 3SAC)上,涂布含有PMMA粒子的可光固化的混合物,置于70℃烤箱烘干,并置于紫外灯(H Bulb)中以线速40fpm,100%紫外光照以及氮气环境下进行固化,最终形成5μm厚度的磨砂硬涂层。
使用反向接触微型凹印涂布机(三螺旋纹),将0.7%的全氟聚醚丙烯酸酯(通过美国专利US6,841,190公开的结构获得)氟化溶液(Novec HFE7600)涂布于上述磨砂硬涂料上,湿厚度为0.5mils,涂布线速度为30ft/min,置于70℃下烤箱烘干,并置于紫外灯(HBulb)中以100%紫外光照以及氮气环境下进行固化,制得样品6。
实施例7
根据本发明公开的制备硬涂料混合物(含有微粒)的方法,制得含有微粒的硬涂料混合物。
使用凹印涂布机,在PET(Hostaphan 3SAC)上,涂布含有PMMA粒子的可光固化的混合物,置于70℃烤箱烘干,并置于紫外灯(H Bulb)中以线速40fpm,100%紫外光照以及氮气环境下进行固化,最终形成5μm厚度的磨砂硬涂层。
使用反向接触微型凹印涂布机(三螺旋纹),将0.7%的全氟聚醚丙烯酸酯(通过美国专利US6,841,190公开的结构获得)氟化溶液(Novec HFE7600)涂布于上述磨砂硬涂料上,湿厚度为0.5mils,涂布线速度为30ft/min,置于70℃下烤箱烘干,并置于紫外灯(HBulb)以75%紫外光照以及氮气环境下进行固化,制得样品7。
实施例8
根据本发明公开的制备硬涂料混合物(含有微粒)的方法,制得含有微粒的硬涂料混合物。
使用凹印涂布机,在PET(Hostaphan 3SAC)上,涂布含有PMMA粒子的可光固化的混合物,置于70℃烤箱烘干,并置于紫外灯(H Bulb)中以线速40fpm,100%紫外光照以及氮气环境下进行固化,最终形成5μm厚度的磨砂硬涂层。
使用反向接触微型凹印涂布机(三螺旋纹),将0.7%的全氟聚醚丙烯酸酯(通过美国专利US6,841,190公开的结构获得)氟化溶液(Novec HFE7600)涂布于上述磨砂硬涂料上,湿厚度为0.5mils,涂布线速度为30ft/min,置于70℃下烤箱烘干,并置于紫外灯(HBulb)中以50%紫外光照,以及小于氮气环境下进行固化,制得样品8。
实施例9
在棱镜线性排布的棱镜膜(通过美国专利US2008/0291541公开的结构获得)上,用#5线棒将0.5%的全氟聚醚丙烯酸酯(通过美国专利US6,841,190公开的方法获得)氟化溶液(Novec HFE7600)涂布于上述磨砂硬涂料上,空气中晾干5分钟,并置于紫外灯(HBulb)中以线速20fpm,25%紫外光照以及氮气环境下进行固化,最终形成50nm厚度的离型涂层,制得样品9。
实施例10
在棱镜线性排布的棱镜膜(通过美国专利US2008/0291541公开的结构获得)上,用#5线棒将含有50ppm铂催化剂(SIP6832.2)氟硅酮溶液(X-70-201S),涂布于上述磨砂硬涂料上,置于80℃烤箱烘干15分钟,制得样品10。
实施例11
在棱镜线性排布的棱镜膜(通过美国专利US2008/0291541公开的结构获得)上,用#5线棒将含有50ppm的铂催化剂(SIP6832.2)的10%氟硅酮溶液(氟硅酮X-70-201S,溶剂FS thinner)涂布于上述磨砂硬涂料上,置于80℃烤箱烘干15分钟,制得样品11。
实施例12
在棱镜线性排布的棱镜膜(通过美国专利US2008/0291541公开的结构获得)上,用#5线棒将100克硅离型剂(SYL-OFFTMSL 100)、3克硅交联剂(SYL-OFFTMSL 2)、0.05克加成催化剂(SYL-OFFTMSL 3000)的混合液体,涂布于上述磨砂硬涂料上,置于80℃烤箱烘干15分钟,制得样品12。
测试方法
本发明通过“剥离力测试”来评价离型膜的防粘性能,通过“刮擦测试”来评价离型膜的耐磨性能,通过“老化测试”来评价离型膜的耐久性能,通过“硬度测试”来评价离型膜的硬度。
剥离力测试
将样品与3M 232胶带层压,根据FTM 10测试标准,使用剥离测试机对样品进行测试,将测试结果记录于表3-1中。本行业内,一般认为剥离力值小于15,就满足防粘要求。并且,剥离力数值越小,认为该样品的防粘性能越好。
刮擦测试
将样品与3M 2008胶带层压,根据FTM10测试标准,使用剥离测试机对样品进行测试,将测试结果记录于表3-2中。使用0#钢丝绒,在Taber Abraser4000上以200g的力在样品表面摩擦100个来回,并将刮擦后的样品与3M 2008胶带层压,根据FTM10测试标准,使用剥离测试机对样品进行测试,将测试结果记录于表3-2中,比较刮擦前和刮擦后的剥离力数值。刮擦前、后都满足防粘要求,认为该样品的耐磨性能良好;刮擦前、后的剥离力值变化不大,认为该样品的耐磨性能极好。
老化测试
将样品与3M 2008胶带层压,根据FTM10测试标准,使用剥离测试机对样品进行测试,将测试结果记录于表3-3中。根据ASTM154-4标准,将样品涂层面朝外放入紫外老化箱(QUV Accelerated Weathering Tester,Q-lab Corporation),紫外老化250小时,取出样品,观察颜色和外观变化,并将老化后的样品与3M 2008胶带层压,根据FTM10测试标准,使用剥离测试机对样品进行测试,将测试结果记录于表3-3中。比较老化前和老化后的剥离力数值。老化前、后都满足防粘要求,认为该样品的耐久性能良好;老化前、后的剥离力值变化不大,认为该样品的耐久性能极好。
硬度测试
根据GB/T6739-2006测试标准,使用标准硬度的三菱试验铅笔(4H),用Elcometer3086铅笔硬度测试仪,以1kg的压力,铅笔芯与样品表面的夹角为45°,在样品表面划5~10mm,在不同位置重复测定5次,通过目测样品表面是否有磨痕(或墨痕数量)来判定样品的硬度,将测试结果记录于表3-4中。
表3-1
剥离力值(g/in) | |
实施例1 | 10.1 |
实施例2 | 7.4 |
实施例3 | 3.7 |
实施例4 | 2.3 |
实施例5 | 1.6 |
实施例6 | 1.8 |
实施例7 | 1.2 |
实施例8 | 0.8 |
实施例9 | 0.5 |
实施例10 | 0.5 |
实施例11 | 3.5 |
实施例12 | 4.7 |
表3-2
刮擦前剥离力值(g/in) | 刮擦后剥离力值(g/in) | |
实施例9 | 1.8 | 14.4 |
实施例10 | 4.0 | 4.8 |
表3-3
老化前剥离力值(g/in) | 老化后剥离力值(g/in) | |
实施例8 | 4.8 | 6.5 |
实施例9 | 1.8 | 13.9 |
实施例10 | 4.0 | 4.4 |
表3-4
硬度 | |
实施例7 | 4H |
由表3-1的测试结果可知,根据本发明的某些具体实施方式的离型膜具有至少满足要求的防粘性能,其中,实施例3~12的离型膜的防粘性能特别好。由表3-2的测试结果可知,根据本发明的某些具体实施方式的离型膜的耐磨性能良好。由表3-4的测试结果可知,根据本发明的某些具体实施方式的离型膜的耐久性能良好,尤其实施例10,不仅防粘性能好,而且在经过刮擦测试或老化测试以后,剥离力值几乎没有变化,其耐磨性能和耐久性能都极好。另外,由表3-4的测试结果可知,根据本发明的某些具体实施方式的离型膜的硬度可以达到4H。
上述本发明的具体实施例仅例示性的说明了本发明的原理及其功效,而非用于限制本发明,熟知本领域的技术人员应明白,在不偏离本发明的精神和范围的情况下,对本发明所作的任何改变和改进都在本发明的范围内。本发明的保护范围,应以本发明所附的权利要求书所界定的范围为准。
Claims (21)
1.一种离型硬涂料,包括底部硬涂料组分和上部离型涂料组分,其特征在于,所述底部硬涂料组分包括交联聚合物基质、纳米金属氧化物颗粒;所述上部离型涂料组分包括能与所述底部硬涂料组分发生接枝反应的离型聚合物。
2.根据权利要求1所述的离型硬涂料,其特征在于,所述底部硬涂料组分还包括微粒,所述微粒的粒径在0.5μm~100μm之间。
3.根据权利要求2所述的离型硬涂料,其特征在于,所述微粒选自微米级的聚合物颗粒,微米级的无机金属氧化物颗粒,微米级的金属盐颗粒及其组合。
4.根据权利要求3所述的离型硬涂料,其特征在于,所述微米级的聚合物颗粒选自聚甲基丙烯酸甲酯(PMMA),聚苯乙烯(PS)及其组合。
5.根据权利要求3所述的离型硬涂料,其特征在于,所述微米级的无机金属氧化物颗粒选自氧化硅,氧化铝,氧化钛及其组合。
6.根据权利要求3所述的离型硬涂料,其特征在于,所述微米级的金属盐颗粒选自碳酸钙,硫酸钙,硫酸镁及其组合。
7.根据权利要求1所述的离型硬涂料,其特征在于,所述交联聚合物基质包括多官能度的丙烯酸酯,选自三羟甲基丙烷三丙烯酸酯(trimethylolpropane triacrylate),三(2-羟乙基异氰脲酸酯)三丙烯酸酯(tris(2-hydroxyethylisocyanurate)triacrylate),季戊四醇三丙烯酸酯(pentaerythritol triacrylate),季戊四醇四丙烯酸酯(pentaerythritoltetraacrylate),二-三羟甲基丙烷四丙烯酸酯(di-trimethylolpropanetetraacrylate),乙氧基化季戊四醇四丙烯酸酯(ethoxylated pentaerythritoltetraacrylate),双季戊四醇五丙烯酸酯(dipentaerythritol pentaacrylate)及其组合。
8.根据权利要求1所述的离型硬涂料,其特征在于,所述纳米金属氧化物颗粒选自纳米二氧化硅颗粒,纳米氧化铝,纳米氧化锆,纳米氧化锌及其组合。
9.根据权利要求8所述的离型硬涂料,其特征在于,所述纳米金属氧化物颗粒的粒径小于100nm。
10.根据权利要求9所述的离型硬涂料,其特征在于,所述纳米金属氧化物颗粒的粒径小于50nm。
11.根据权利要求1-10中任意一项所述的离型硬涂料,其特征在于,所述底部硬涂料组分经过光引发聚合。
12.根据权利要求1所述的离型硬涂料,其特征在于,所述离型聚合物选自氟化聚烯烃,全氟聚醚丙烯酸酯,聚氟硅酮及其组合。
13.根据权利要求1所述的离型硬涂料,其特征在于,所述底部硬涂料组分的厚度在1μm~250μm之间。
14.根据权利要求13所述的离型硬涂料,其特征在于,所述底部硬涂料组分的厚度在25μm~100μm之间。
15.根据权利要求1所述的离型硬涂料,其特征在于,所述上部离型涂料组分的厚度小于500nm。
16.根据权利要求15所述的离型硬涂料,其特征在于,所述上部离型涂料组分的厚度小于100nm。
17.一种离型膜,包括基材,其特征在于,所述基材表面涂布根据权利要求1-16中任意一项所述的离型硬涂料。
18.根据权利要求17所述的离型膜,其特征在于,所述基材包括至少一层聚合物基材,所述聚合物基材可选自聚对苯二甲酸乙二醇酯(PET),聚氯乙烯(PVC),聚甲基丙烯酸甲酯(PMMA),聚酰胺(PI),聚氨酯(PU),聚碳酸酯(PC)。
19.根据权利要求17所述的离型膜,其特征在于,所述基材的表面粗糙度小于100μm。
20.根据权利要求17所述的离型膜,其特征在于,所述离型膜的剥离力在0.5g/in~2.0g/in之间。
21.一种光伏组件,包括光伏电池,其特征在于,所述光伏电池的表面涂布根据权利要求1-16中任意一项所述的离型硬涂料或根据权利要求17-20中任意一项所述的离型膜。
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CN111100489B (zh) | 2022-03-15 |
WO2020084531A1 (en) | 2020-04-30 |
EP3870662A4 (en) | 2022-07-27 |
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