CN106928784A - 透明抗静电膜 - Google Patents
透明抗静电膜 Download PDFInfo
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- CN106928784A CN106928784A CN201610848516.0A CN201610848516A CN106928784A CN 106928784 A CN106928784 A CN 106928784A CN 201610848516 A CN201610848516 A CN 201610848516A CN 106928784 A CN106928784 A CN 106928784A
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Abstract
本发明是一种透明抗静电膜,包括基材及透明石墨烯涂层,基材至少包含第一表面,而透明石墨烯涂层是设置于基材的第一表面上。透明石墨烯涂层具有小于1012ohm/sq的表面电阻值以及波长550nm的可见光的透光度大于70%,且包含多个表面改质的奈米石墨烯片以及载体树脂,其中表面改质的奈米石墨烯片均匀分散于载体树脂中。藉由透明石墨烯涂层的特性,本发明的透明抗静电膜可防制各种静电击穿的风险,并具备电磁波屏蔽的功能,还可维持基材原有的透光度,因而本发明的透明抗静电膜很适合应用于对静电或电磁波敏感的电子元件。
Description
技术领域
本发明有关于一种透明抗静电膜,尤其是利用设置在基材上并由多个表面改质的奈米石墨烯片以及载体树脂所构成的透明石墨烯涂层,以改善整体的抗静电与电磁波屏蔽特性,而且表面改质的奈米石墨烯片可有效分散到载体树脂中,使得透明抗静电膜兼具透光性与抗静电特性。
背景技术
随着科技快速发展以及电气功能的提升,损耗功率也大幅增加,而在电子装置需要更加轻薄短小的需求下,电气操作的功率密度更需要不断提高,因此,需要具抗静电功能的树脂,以保护细小的窄线路,藉以避免静电击穿而失效或损毁,保障产品的使用寿命。
另一方面,电子元件线路的微缩也使得元件之间相互影响的程度益发显著,为避免所述干扰影响,各元件之间常施加一电磁波屏蔽层,对于光电显示元件而言,所述电磁波屏蔽层更需具备高光穿透度,以避免影响视觉感受。
现有技术中,使树脂涂层具抗静电效果,导电粉末如金属粉末、导电碳黑等被大量研究以提升树脂涂层的导电性或降低其电阻。美国专利号US3753765 A及US4085087 A则分别为添加导电碳黑及金属粉末的抗静电涂层案例。然而,导电碳黑不易与树脂进行良好复合,容易从复合体系中脱落,污染基材或环境。金属粉末比重较于树脂高,两种材料混拌复合过程中常导致相分离,使复合材料均匀性低。再者,以导电碳黑或金属粉末作为导电填充材,除前述制作工艺的挑战外,膜层的透明度往往大幅降低,无法兼顾透明度与抗静电两项需求。若希冀制作可见光穿透或半穿透的应用涂层,亦或涂层加工或应用过程需仰赖树脂浆料本身的光穿透性,上述两类填充材则明显受限。
中国专利CN103726323 A公开了一种制作抗静电奈米皮膜树脂层的方法,该专利利用小分子无机盐的吸湿性能,提升膜层的抗静电性。然而,此类材料的特性会因为环境条件影响性能,若在低湿度的环境下,此抗静电添加剂往往无法发挥功效。除无机盐类外,亦有专利公开以导电性聚合物与奈米碳管作为透明导电涂层的抗静电填充剂与填充材。中国专利CN 102333825 A公开以导电性聚合物作为添加剂的抗静电涂层,该涂层宣称具91%光穿透。中国专利CN102388109 A公开以奈米碳管作为添加剂的抗静电涂料,该涂料可披覆于聚合物基材上,防止表面电荷积聚与外力刮伤。然而,导电性聚合物有寿命的问题,无法兼顾耐久性与性能;奈米碳管虽可克服前述问题,但价格却十分昂贵,且有不易分散的问题,对于产品量产化有其技术难度。因此,寻找一性价比高的导电填充物以同时解决透光度与静电问题有其迫切性。
自从2004年英国曼彻斯特大学Andre Geim与Konstantin Novoselov成功利用胶带剥离石墨的方式获得单层石墨烯并获得2010年的诺贝尔物理奖以来,石墨烯的导电性、导热性、抗化性等各种优异性能即不断被产业藉应用于不同的领域。石墨烯(graphene)只具有厚度0.335nm,即仅一个碳原子直径的大小,主要是由sp2混成轨域组成六角形蜂巢排列的二维晶体结构,目前是最薄也是最坚硬的材料,机械强度可远高于钢铁百倍,而比重却仅约钢铁的四分之一,尤其还拥有杰出的导电与导热性质,其中理论电阻达10-6Ω·cm,因此,石墨烯为一极佳的导电材料。
然而,石墨烯在实际应用上最常面临的问题是石墨烯本身很容易聚集、堆叠而结块,即不容易均匀分散,因此,如何防止石墨烯薄片彼此不均匀地堆叠的现象,以获得高均匀性且层数少的石墨烯粉体,一直都是产业界最需解决的技术瓶颈。
中国专利CN103804553A描述了一种石墨烯/聚氯乙烯复合材料,主要利用静电吸附将偶氮引发剂锚固在石墨烯表面,氯乙烯单体再与改质石墨烯进行反应,并原位聚合聚氯乙烯,使得石墨烯与聚氯乙烯间有良好的介面亲和力,进而达到复合材料性能。然而,该专利于锚固过程中未先将石墨烯于去离子水中进行有效分散,而直接进行偶氮锚固。此举将造成偶氮锚固效果与程度受限,原位聚合后恐仍有石墨烯与聚氯乙烯介面亲和力问题。此外,该专利的制备方法需将石墨烯水溶液调整至强碱性,所衍生的强碱水溶液不但对环境不友善,且废水处理费用昂贵。锚固偶氮的石墨烯须于低温且避光环境下储存,造成此法不适于工业量产所用。
另一中国专利CN103450537A公开了一种含高分子量聚乙烯/石墨烯的抗静电复合材料,以高速搅拌机将石墨烯与高密度聚乙烯造粒,再藉由热压成型制备抗静电复合材料。其缺点主要是以高速搅拌机进行高密度聚乙烯与石墨烯两种干粉互混,此法虽可让石墨烯附着或包覆在高密度聚乙烯颗粒表面,进而在热压后形成三维导电网络。但由于两者颗粒密度差异30倍以上,而高密度聚乙烯颗粒偏球形形貌与石墨烯二维片状明显不同,在高速搅拌下甚难均匀。再者,抗静电复合材料对填充物于复合材料中的均匀性要求高,因此以无添加溶剂式进行干粉石墨烯与高密度聚乙烯相互混合的成效相当有限。
中国专利CN102775700B描述了一种PVC/石墨烯抗静电复合材料的制备方法,先以膨胀石墨与PVC母料等混合后,利用磨盘形力化学反应器进行辗磨,再以螺杆挤出机将复合材料熔融挤出,再进行造粒。此法虽可先行制备母粒,有利于后续塑化成不同形状的成品。然而,此复合材料中石墨烯透过磨盘形力化学反应器数次重复辗压形成,膨胀石墨辗压变成石墨烯过程中,新生面不断剥离形成,此时不稳定的新生面若无有效界面活性剂进行稳定与保护,石墨烯会相互团聚,在复合材料成形后团聚处恐无法有效形成抗静电网络,甚至有影响材料机械强度的风险。
另一中国专利CN102627003A描述了一种静电保护层、显示装置和静电保护膜的制备方法。该专利以一层透明导电基体与一层石墨烯相互粘贴,以达抗静电效果。此专利所主张的抗静电层构型虽可达其预期效果,但透过气相沉积法制作石墨烯薄膜耗时、耗能,且尚须搭配转印程序才可将石墨烯层贴附于基体材料上。因此,就制程与价格上考量,此法较不适合应用在工业化量产程序。
有鉴于此,迫切需要发展出工艺简单且可高效率生产并易于实现工业化生产的方法,使得石墨烯能均匀分散于树脂中,其中石墨烯是以简单的方式添加并均匀分散于树脂中,且针对填充材与基体树脂间的介面进行有效提升,使得抗静电涂层具高材料及抗静电稳定性,藉石墨烯的优良导电特性以提供相对较低渗过阀值,进而解决上述现有技术的问题。
发明内容
本发明的主要目的在于提供一种透明抗静电膜,包括基材及透明石墨烯涂层,其中基材至少包含一第一表面,透明石墨烯涂层是设置于基材的第一表面上。透明石墨烯涂层具有小于1012ohm/sq的表面电阻值以及波长550nm可见光的透光度大于70%,且包含多个表面改质的奈米石墨烯片以及载体树脂,其中表面改质的奈米石墨烯片是均匀分散于载体树脂中。
本发明所使用的表面改质的奈米石墨烯片为少层的石墨烯片或多层的石墨烯片,且其中的石墨烯纯度是大于95wt%,厚度为1nm至20nm的区间,而平面横向尺寸是在1um至100um的区间。
本发明的载体树脂可为聚合物树脂,能藉升高温度或在紫外光辐射下以进行固化聚合反应或交联反应。再者,本发明载体树脂的组成成分亦可进一步包含界面活性剂或用于粘度与施工控制的助剂,或其组合。助剂包含稀释剂、可塑剂、交联剂、粘着促进剂、填充剂、流平剂、触变剂(Thixotropic agent)、起始剂或催化剂。
由于本发明所提供的透明抗静电膜具有相当优越的抗静电效能,而且静电消散效能可随表面改质的奈米石墨烯片的添加量增加而提升,因此同时具有可调节的抗静电性及透光性。此外,本发明所揭示的透明抗静电膜可透过网版印刷、刮刀涂覆、轮涂、旋转涂布、刷涂、喷涂等加工方式而设置于基材上,因而相当具有产业利用性。
附图说明
图1为依据本发明的透明抗静电膜的实施例的示意图。
其中,附图标记说明如下:
1 透明抗静电膜
10 基材
20 透明石墨烯涂层
21 表面改质的奈米石墨烯片
23 载体树脂
11 第一表面
12 电子线路
具体实施方式
以下配合图示及元件符号对本发明的实施方式做更详细的说明,使熟悉本领域的技术人员在研读本说明书后能据以实施。
请参阅图1,本发明的透明抗静电膜的实施例的示意图。要注意的是,为清楚展现本发明的主要特点,因此图1只是以示意方式显示其中主要元件之间的相对关系,并非依据实际大小而绘制,所以图中主要元件的厚度、大小、形状、排列、配置等等都只是参考而已,并非用以限定本发明的范围。
如图1所示,本发明的透明抗静电膜1主要是包括基材10及透明石墨烯涂层20,其中基材10至少包含一第一表面11,如图中的上表面,而且第一表面11可形成有电子线路12。透明石墨烯涂层20是设置于基材10的第一表面11上,具有小于1012ohm/sq的表面电阻值以及波长550nm的可见光的透光度大于70%。尤其是,透明石墨烯涂层20包含多个表面改质的奈米石墨烯片21以及载体树脂23,其中表面改质的奈米石墨烯片21是均匀分散于载体树脂22中,形成网路状的导电性结构。再者,表面改质的奈米石墨烯片21占透明抗静电膜1的重量比为0.01-5wt%。
要注意的是,为方便说明本发明的技术特征,图1中的各个表面改质的奈米石墨烯片21是以薄片状的侧面方向显示,即,实际上从图中的观察角度上看,会有一部分的表面改质的奈米石墨烯片21会显示出其正面,或有一部分的表面改质的石墨烯奈米片21会同时显示部分的正面及部分的侧面。
基材10的第一表面11所形成的电子线路可以是集成电路元件或光电显示元件。
一般而言,本发明的透明石墨烯涂层20于波长550nm的可见光下具有大于60%的穿透度,例如70至90%。透明石墨烯涂层20的表面电阻值小于1013ohm/sq,较佳小于1012ohm/sq,最佳的,介于107至1011ohm/sq的表面电阻值。
表面改质的奈米石墨烯片21的堆积密度在0.1g/cm3至0.01g/cm3之间,且其厚度在1nm至20nm的区间、平面横向尺寸在1um至100um的区间,平面横向尺寸与厚度的比值在20至10000的区间,而比表面积为15至750m2/g。
表面改质的奈米石墨烯片21具有至少一表面改质层,其化学结构为Mx(R)y(R’)z,其中M是一金属元素,可选自硅、钛、锆以及铝的其中的至少一个,R是一亲水性官能基,R’是一亲油性官能基,0≦x≦6,1≦y≦20,且1≦z≦20,亲水性官能基及亲油性官能基分别化学键结至表面改质的奈米石墨烯片21与载体树脂23。
具体而言,R是选自烷氧基、羰基、羧基、酰氧基、酰氨基、伸烷氧基以及伸烷氧羧基的至少一个,R’是选自乙烯基、脂肪环氧烷基、苯乙烯基、甲基丙烯酰氧基、丙烯酰氧基、脂肪基胺基、氯丙烷基、脂肪基氢硫基、脂肪基硫离子基、异氰酸基、脂肪基尿素基、脂肪基羧基、脂肪基羟基、环己烷基、苯基、脂肪基甲酰基、乙酰基以及苯甲酰基的至少一个。
表面改质的奈米石墨烯片21的氧含量为1-20wt%。
本发明的载体树脂22可选自光学树脂(Optical Clear Resin)。具体而言,载体树脂21可选自聚丙烯酸酯、聚乙烯基醚、聚偏氟乙烯、聚对苯二甲酸乙烯酯、聚氨酯、聚氧化乙烯、聚丙烯腈、聚丙烯酰胺、聚丙烯酸甲酯、聚甲基丙烯酸甲酯、聚醋酸乙烯酯、聚乙烯吡咯烷酮、聚四甘醇二丙烯酸酯、聚酰亚胺、醋酸纤维素、醋酸丁酸纤维素、醋酸丙酸纤维素、乙基纤维素、氰乙基纤维素、氰乙基聚乙烯醇、羧甲基纤维素、聚氯乙烯、聚烯烃以及硅酮树脂的至少一个。此外,载体树脂21也可选自热固型树脂或可光固化型树脂。
透明石墨烯涂层20可进一步包含至少一种助剂,例如:一导电助剂、至少一界面活性剂、一黏度调变助剂、一偶合剂以及一触变剂,用以调整有关透明导电石墨烯涂层的导电、加工、粘着以及透光等性质。
导电助剂可选自导电高分子、无机盐类以及有机盐类的至少一个,用以辅助表面改质的奈米石墨烯片达到抑制静电效果,并且可平衡整体材料成本。
界面活性剂可选自饱和脂肪酸、不饱和脂肪酸以及多元不饱和脂肪酸的至少一个,其中饱和脂肪酸包含硬脂酸、月桂酸、棕榈酸以及肉豆蔻酸的至少一个;不饱和脂肪酸包含棕榈烯酸以及油酸的至少一个;而多元不饱和脂肪酸包含亚麻油酸以及次亚麻油酸的至少一个。
粘度调变助剂可选自对苯二甲酸酯类、酯肪酸酯类、磷酸酯类、环氧酯类或高分子聚酯类的至少一个。
偶合剂的化学结构为Mx(R)y(R’)z,M是金属元素,R是亲水性官能基,R’是亲油性官能基,0≦x≦6,1≦y≦20,且1≦z≦20,其中亲水性官能基及亲油性官能基用以使得表面改质的奈米石墨烯片21与载体树脂23能在其间产生化学键结而结合,用以调整当奈米石墨烯片的比表面积较小时,其表面改质层数量可能不足的问题。偶合剂包含但不限于硅烷类、钛酸酯类、锆酸酯类、铝锆酸酯类以及铝酸酯类。
触变剂可选自二氧化硅、膨润土、氢化蓖麻油、聚酰胺蜡、高岭土、石绵、氯化烯化合物、金属皂、羟乙基纤维素、聚乙烯醇以及聚丙烯酸盐的至少一个。
为进一步显示本发明的透明抗静电膜的具体功效藉以使得熟知现有技术的人士者能更加清楚了解整体的操作方式,下文中将以示范性实例详细说明实际的操作方式。
以下实验示例皆使用表面改质的奈米石墨烯片,表面改质的步骤包含奈米石墨烯片官能基化步骤以及表面改质层形成步骤。奈米石墨烯片官能基化步骤先将奈米石墨烯片与加热的氢氧化钾、双氧水或硫酸等反应而在奈米石墨烯片表面形成COOH、OH官能基,亦可用紫外光或臭氧进行改质获得官能基化的奈米石墨烯片。表面改质层形成步骤将官能基化的奈米石墨烯片再加入偶合剂进一步反应以在官能基化的奈米石墨烯片的表面形成一表面改质层。该偶合剂的化学结构为Mx(R)y(R’)z,M是一金属元素,包含硅、钛、锆及铝的至少其中之一,R是一亲水性官能基,R’是一亲油性官能基,0≦x≦6,1≦y≦20,且1≦z≦20,该亲水性官能基及该亲油性官能基可使得所述表面改质的奈米石墨烯片与该载体树脂之间产生化学键结而结合。表面改质的奈米石墨烯片的氧含量为1-20wt%。
实验示例1~4以表面改质的奈米石墨烯片进行半透明可剥胶测试实例,添加前述表面改质的奈米石墨烯片后,可剥胶达抗静电的功效,且依然维持半透明度。
[实验示例1]
配方内容包含聚氯乙烯60wt%、环氧树脂10wt%、酚醛树脂10wt%、磷苯二甲酸酯10%、硬脂酸钡2wt%、磷酸三苯酯2.5wt%、碳酸钙2wt%、二氧化硅2wt%、表面改质奈米石墨烯片为1.5wt%,其中聚氯乙烯、环氧树脂及酚醛树脂作为载体树脂,磷苯二甲酸酯作为粘度调整剂,硬脂酸钡、磷酸三苯酯及二氧化硅作为提高内聚强度与附着力功效。
首先,依据上述配方比例进行预混合,而后用行星式高速混拌机以公转速1600rpm,自转速880rpm,历时5分钟均匀混合。接着,再添加占载体树脂的0.5wt%的钛酸酯作为偶合剂,以公转速1600rpm,自转速352rpm,经过3分钟均匀混合,可得到包含表面改质层的奈米石墨烯片的透明浆料。然后以刮刀法方式将包含表面改质的奈米石墨烯片的透明浆料涂布于玻璃基材上,透明石墨烯涂层的厚度约30μm,并进行150度烘箱或热板的加热烘烤处理30分钟,以固化透明石墨烯涂层而形成所需的透明抗静电膜。
[实验示例2]
配方内容包含聚氯乙烯60wt%、环氧树脂10wt%、酚醛树脂10wt%、磷苯二甲酸酯10%、硬脂酸钡2wt%、磷酸三苯酯2.5wt%、碳酸钙2wt%、二氧化硅2wt%、表面改质奈米石墨烯片为1.5wt%,其中聚氯乙烯、环氧树脂及酚醛树脂作为载体树脂,磷苯二甲酸酯作为粘度调整剂,硬脂酸钡、磷酸三苯酯及二氧化硅作为提高内聚强度与附着力功效。
于实验示例2,将表面改质的奈米石墨烯片预先分散于正己烷,再将含有表面改质的奈米石墨烯片的正己烷添加入载体树脂中并以叶片搅拌进行混和。混和均匀后减以压浓缩机去除正己烷。而后用行星式高速混拌机以公转速1600rpm,自转速880rpm,经过5分钟均匀混合。再添加占载体树脂的0.7wt%的钛酸酯作为偶合剂,以公转速1600rpm,自转速352rpm,经过3分钟均匀混合,可得到包含表面改质的奈米石墨烯片的透明浆料。接着,以网版印刷方式将包含表面改质的奈米石墨烯片的透明浆料涂布于玻璃基材上,透明石墨烯涂层的厚度约30μm并进行150度烘箱或热板的加热烘烤处理30分钟以固化透明石墨烯涂层,形成所需的透明抗静电膜。
[实验示例3]
实验示例3所使用的配方如同实验示例2,将上述表面改质奈米石墨烯片预先分散于正己烷,与实验示例2不同的是,移除正己烷后,再将经正己烷润湿的奈米石墨烯添加入树脂载体中,而后用行星式高速混拌机以公转速1600rpm,自转速880rpm,经过5分钟均匀混合。再添加占树脂载体的0.7wt%的钛酸酯作为偶合剂,以公转速1600rpm,自转速352rpm,经过3分钟均匀混合,可得到包含表面改质的奈米石墨烯片的透明浆料。接着,以网版印刷法方式将包含表面改质的奈米石墨烯片的透明浆料涂布于玻璃基材上,透明石墨烯涂层的厚度约30μm,接着进行150度烘箱或热板的加热烘烤处理30分钟以固化透明石墨烯涂层,形成所需的透明抗静电膜。
[实验示例4]
配方内容包含聚氯乙烯65wt%、环氧树脂12wt%、酚醛树脂10wt%、对苯二甲酸二辛酯11wt%、表面改质的奈米石墨烯片2wt%,其中聚氯乙烯、环氧树脂及酚醛树脂作为载体树脂,对苯二甲酸二辛酯作为粘度调变助剂。
首先,依据上述比例将对苯二甲酸二辛酯与表面改质的奈米石墨片进行混合,再用行星式高速混拌机以公转速1600rpm,自转速880rpm,历时5分钟均匀混合。添加聚氯乙烯65wt%、环氧树脂12wt%以及酚醛树脂10wt%,并且进一步添加占载体树脂的1wt%的钛酸酯作为偶合剂,以公转速1600rpm,自转速352rpm,经过3分钟均匀混合,可得到包含表面改质的奈米石墨烯片的透明浆料。接着,以刮刀法方式将包含表面改质的奈米石墨烯片的透明浆料涂布于玻璃基材上,透明石墨烯涂层的厚度约30μm,并进行150度烘箱或热板的加热烘烤处理30分钟以固化透明石墨烯涂层,形成所需的透明抗静电膜。
上述实验示例的测试结果如表一所示。
表一
一般而言,容易积蓄静电的绝缘材料的表面电阻通常大于1013ohm/sq,而抗静电材料所需求的表面电阻较佳介于106至1011ohm/sq。从实验示例1、2、3、4与对比例的实验结果中,显而易见的是本发明的透明抗静电膜能有效排除静电,且透明石墨烯涂层具良好的光学可穿透性。值得一提的是,透明石墨烯涂层不会影响现有电子线路的化学及物理性质,从而透明石墨烯涂层可直接设置于表面形成有电子线路的基材上,因此本发明的透明抗静电膜确实具有极高的产业利用性。
再者,本发明的透明抗静电膜亦可应用于光学感压胶,实验示例5~6以表面改质的奈米石墨烯片进行光学感压胶测试实例,添加本案的表面改质的奈米石墨烯片后,光学感压胶达抗静电的功效,且依然良好的透明度。实施例如下所示:
[实验示例5]
载体树脂包含丙烯酸树脂40wt%以及水60wt%。以载体树脂的重量计算,添加0.3wt%的表面改质的奈米石墨烯片以及1wt%的PEDOT:PSS入载体树脂中,接着,以刮刀法方式将包含表面改质的奈米石墨烯片的透明浆料涂布于聚对苯二甲酸乙二酯的基材上,透明石墨烯涂层的厚度约10μm,并进行100度烘箱或热板的加热烘烤处理30分钟以固化透明石墨烯涂层,形成所需的透明抗静电膜。
[实验示例6]
载体树脂包含聚甲基丙烯酸甲酯40wt%、乙酸乙酯60wt%。以载体树脂的重量计算,添加0.05wt%的表面改质的奈米石墨烯片以及1wt%的钠烷基磺酸盐入载体树脂中,其中钠烷基磺酸盐做为导电助剂。接着,以刮刀法方式将包含表面改质的奈米石墨片的透明浆料涂布于聚对苯二甲酸乙二酯基材上,涂层厚度约10μm,并进行100度烘箱或热板的加热烘烤处理30分钟以固化涂层,形成所需的透明抗静电膜。
表二
从实验示例5、6与对比例的实验结果中,显而易见的是本发明的透明抗静电膜能有效排除静电,且透明石墨烯涂层于波长550nm的可见光的透光度接近90%。
再者,本发明的透明抗静电膜亦可应用于塑胶载具,实验示例7~8以表面改质的奈米石墨烯片进行抗静电涂层测试实例,添加本案的表面改质的奈米石墨烯片后,树脂涂料可达抗静电的功效,且依然良好的透明度。实施例如下所示:
[实验示例7]
载体树脂包含聚甲基丙烯酸甲酯20wt%以及乙酸乙酯80wt%。以载体树脂的重量计算,添加0.25wt%的表面改质的奈米石墨烯片以及0.25wt%的钠烷基磺酸盐入载体树脂中,接着,以刮刀法方式将包含表面改质的奈米石墨烯片的透明浆料涂布于聚碳酸脂的基材上,透明石墨烯涂层的厚度约15μm,并进行80度烘箱或热板的加热烘烤处理30分钟以固化透明石墨烯涂层,形成所需的透明抗静电膜。
[实验示例8]
载体树脂包含三聚氰胺-甲醛树脂40wt%、水60wt%。以载体树脂的重量计算,添加0.05wt%的表面改质的奈米石墨烯片以及1.2wt%的PEDOT:PSS入载体树脂中,其中PEDOT:PSS做为导电助剂。接着,以刮刀法方式将包含表面改质的奈米石墨片的透明浆料涂布于聚碳酸脂基材上,涂层厚度约15μm,并进行130度烘箱或热板的加热烘烤处理1小时以固化涂层,形成所需的透明抗静电膜。
表二
从实验示例7、8与对比例的实验结果中,显而易见的是本发明的透明抗静电膜能有效排除静电,且透明石墨烯涂层于波长550nm的可见光的透光度接近85%。
综上所述,本发明的主要特点在于奈米石墨烯片的表面改质层,可提高石墨烯在载体树脂中的相容性以及亲和性,使得奈米石墨烯片均匀分散于载体树脂,解决现有石墨烯甚至是奈米碳管不易分散的问题,进一步检验实施示例1-8的透明抗静电膜,其雾度小于30%或刮刀细度小于15um,充分说明表面改质的奈米石墨烯片系均匀分散于载体树脂,符合光学等级的要求。因此本发明的透明抗静电膜可有效抑制静电,进而避免静电对基材的冲击,更可达成电磁波屏蔽的效果,且兼顾光学透明度,因此非常适用于需要抗静电或电磁波屏蔽,且须维持透光性诉求的光电显示元件或集成电路元件。
此外,本发明的透明抗静电膜可透过石墨烯、树脂、表面改质剂与其他任选添加剂的混合形成,比如利用行星式高速混拌机、高剪切分散设备、超音波震荡设备或其他可将材料均匀混和的设备。因此,不需要额外设计的特殊设备,即可满足制造含有表面改质的奈米石墨烯片的透明抗静电膜所需,达到降低成本的经济性,增强市场上的产品竞争力。
以上所述仅为用以解释本发明的较佳实施例,并非企图据以对本发明做任何形式上的限制,因此,凡有在相同的发明精神下所作有关本发明的任何修饰或变更,皆仍应包括在本发明意图保护的范畴。
Claims (18)
1.一种透明抗静电膜,其特征在于,包括:
一基材,至少包含一第一表面;以及
一透明石墨烯涂层,设置于该基材的第一表面上,具有小于1012ohm/sq的表面电阻值以及波长550nm的可见光的透光度大于70%,且包含多个表面改质的奈米石墨烯片以及一载体树脂,其中所述表面改质的奈米石墨烯片均匀分散于该载体树脂中。
2.根据权利要求1所述的透明抗静电膜,其特征在于,该基材的材质为玻璃、塑胶或晶圆的任一个。
3.根据权利要求1所述的透明抗静电膜,其特征在于,该基材的第一表面上进一步形成有电子线路,该透明石墨烯涂层设置于该电子线路上。
4.根据权利要求1所述的透明抗静电膜,其特征在于,所述表面改质的奈米石墨烯片占该透明石墨烯涂层的重量比为0.01-5wt%。
5.根据权利要求1所述的透明抗静电膜,其特征在于,该透明石墨烯涂层的表面电阻值介于107至1011ohm/sq。
6.根据权利要求1所述的透明抗静电膜,其特征在于,所述表面改质的奈米石墨烯片均匀分散于该载体树脂是指该透明石墨烯涂层的雾度小于30%或刮板细度小于15um。
7.根据权利要求1所述的透明抗静电膜,其特征在于,所述表面改质的奈米石墨烯片具有介于0.1g/cm3至0.001g/cm3的一堆积密度、介于1nm至20nm的一厚度、介于1um至100um的一平面横向尺寸以及介于15至750m2/g的一比表面积。
8.根据权利要求1所述的透明抗静电膜,其特征在于,各该表面改质的石墨烯奈米片具有化学结构为Mx(R)y(R’)z的至少一表面改质层,其中M是一金属元素,包含硅、钛、锆以及铝的至少一个,R是一亲水性官能基,R’是一亲油性官能基,0≦x≦6,1≦y≦20,且1≦z≦20,该亲水性官能基及该亲油性官能基分别化学键结至所述表面改质的奈米石墨烯片与该载体树脂。
9.根据权利要求8所述的透明抗静电膜,其特征在于,R是选自烷氧基、羰基、羧基、酰氧基、酰氨基、伸烷氧基以及伸烷氧羧基的至少一个,R’是选自乙烯基、脂肪环氧烷基、苯乙烯基、甲基丙烯酰氧基、丙烯酰氧基、脂肪基胺基、氯丙烷基、脂肪基氢硫基、脂肪基硫离子基、异氰酸基、脂肪基尿素基、脂肪基羧基、脂肪基羟基、环己烷基、苯基、脂肪基甲酰基、乙酰基以及苯甲酰基的至少一个。
10.根据权利要求1所述的透明抗静电膜,其特征在于,所述表面改质的奈米石墨烯片的氧含量为1-20wt%。
11.根据权利要求1所述的透明抗静电膜,其特征在于,该载体树脂是选自聚偏氟乙烯、聚甲基丙烯酸甲酯、聚对苯二甲酸乙烯酯、聚氨酯、聚氧化乙烯、聚丙烯腈、聚丙烯酰胺、聚丙烯酸甲酯、聚甲基丙烯酸甲酯、聚醋酸乙烯酯、聚乙烯吡咯烷酮、聚四甘醇二丙烯酸酯、聚酰亚胺、醋酸纤维素、醋酸丁酸纤维素、醋酸丙酸纤维素、乙基纤维素、氰乙基纤维素、氰乙基聚乙烯醇、羧甲基纤维素、聚氯乙烯、聚烯烃以及硅酮树脂的至少一个。
12.根据权利要求1所述的透明抗静电膜,其特征在于,该透明石墨烯涂层进一步包含一导电助剂、一界面活性剂、一粘度调变助剂、一偶合剂以及一触变剂的至少一个。
13.根据权利要求12所述的透明抗静电膜,其特征在于,该导电助剂是选自导电高分子、无机盐类以及有机盐类的至少一个。
14.根据权利要求12所述的透明抗静电膜,其特征在于,该界面活性剂是选自一饱和脂肪酸、一不饱和脂肪酸以及一多元不饱和脂肪酸的至少一个,其中该饱和脂肪酸包含硬脂酸、月桂酸、棕榈酸以及肉豆蔻酸的至少一个,该不饱和脂肪酸包含棕榈烯酸以及油酸的至少一个,该多元不饱和脂肪酸包含亚麻油酸以及次亚麻油酸的至少一个。
15.根据权利要求12所述的透明抗静电膜,其特征在于,该粘度调变助剂选自对苯二甲酸酯类、酯肪酸酯类、磷酸酯类、环氧酯类以及高分子聚酯类的至少一个。
16.根据权利要求12所述的透明抗静电膜,其特征在于,该偶合剂的化学结构为Mx(R)y(R’)z,M是一金属元素,R是一亲水性官能基,R’是一亲油性官能基,0≦x≦6,1≦y≦20,且1≦z≦20,该亲水性官能基及该亲油性官能基用以于所述表面改质的奈米石墨烯片与该载体树脂之间产生化学键结。
17.根据权利要求16所述的透明抗静电膜,其特征在于,该偶合剂选自硅烷类、钛酸酯类、锆酸酯类、铝锆酸酯类以及铝酸酯类的至少一个。
18.根据权利要求12所述的透明抗静电膜,其特征在于,该触变剂选自二氧化硅、膨润土、氢化蓖麻油、聚酰胺蜡、高岭土、石绵、氯化烯化合物、金属皂、羟乙基纤维素、聚乙烯醇以及聚丙烯酸盐的至少一个。
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CN107236372A (zh) * | 2017-07-19 | 2017-10-10 | 刘世德 | 电磁波屏蔽薄膜及其制备方法 |
CN108148397A (zh) * | 2017-12-22 | 2018-06-12 | 山东凯恩新材料科技有限公司 | 一种导热聚酰胺封装材料的研究及制备方法 |
CN109994431A (zh) * | 2017-12-29 | 2019-07-09 | 矽品精密工业股份有限公司 | 封装结构 |
CN108676347A (zh) * | 2018-05-18 | 2018-10-19 | 许水仙 | 一种聚氨酯塑料专用抗静电剂的制备方法 |
WO2020224258A1 (zh) * | 2019-05-05 | 2020-11-12 | 深圳第三代半导体研究院 | 一种高导热碳膜及其制备方法 |
CN112430346A (zh) * | 2020-12-10 | 2021-03-02 | 河南银金达新材料股份有限公司 | 一种pet抗静电膜材料及其制备方法 |
CN112430346B (zh) * | 2020-12-10 | 2023-03-31 | 河南银金达新材料股份有限公司 | 一种pet抗静电膜材料及其制备方法 |
CN112848247A (zh) * | 2020-12-18 | 2021-05-28 | 重庆和泰润佳股份有限公司 | 一种透气膜的吹制方法 |
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