WO2018120334A1 - 石墨烯透明导电膜及其制备方法 - Google Patents

石墨烯透明导电膜及其制备方法 Download PDF

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WO2018120334A1
WO2018120334A1 PCT/CN2017/071349 CN2017071349W WO2018120334A1 WO 2018120334 A1 WO2018120334 A1 WO 2018120334A1 CN 2017071349 W CN2017071349 W CN 2017071349W WO 2018120334 A1 WO2018120334 A1 WO 2018120334A1
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graphene
transparent conductive
conductive film
group
vertical alignment
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兰松
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TCL China Star Optoelectronics Technology Co Ltd
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Shenzhen China Star Optoelectronics Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0036—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/22—Electronic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/02—Alignment layer characterised by chemical composition
    • C09K2323/021—Inorganic, e.g. glass or silicon oxide

Definitions

  • the invention relates to a graphene transparent conductive film, and to a method for preparing a graphene transparent conductive film, belonging to the field of liquid crystal displays.
  • a color filter (CF) substrate In a thin film transistor-liquid crystal display (TFT-LCD), a color filter (CF) substrate, a TFT substrate, and a polyimide (PI) material, a liquid crystal material, and a sealant material are generally included.
  • CF color filter
  • PI polyimide
  • a liquid crystal material In a thin film transistor-liquid crystal display (TFT-LCD), a color filter (CF) substrate, a TFT substrate, and a polyimide (PI) material, a liquid crystal material, and a sealant material are generally included.
  • VA vertical alignment
  • a conventional transparent conductive film uses an indium tin oxide (ITO) film prepared by a physical vapor deposition (PVD) method.
  • ITO indium tin oxide
  • PVD physical vapor deposition
  • a strong current bombards the ITO target, and a transparent conductive ITO film is deposited on the substrate.
  • the ITO film does not exhibit bending characteristics under a certain external force, which also limits its application in flexible panels and wearable devices.
  • the cost of indium has gradually increased. Therefore, it is of great application value to find ITO substitutes with high conductivity and light transmittance, simple preparation method and abundant resources.
  • an alignment film commonly used PI material
  • Such alignment films are mainly classified into a friction phase-type PI material and a photo-phase-type PI material, but any alignment material has its own disadvantages.
  • the friction phase is easy to cause dust particles, static electricity, brush marks and other problems to reduce the process yield, while the optical phase material can avoid these problems, but due to limited material properties, heat resistance and aging resistance are not good,
  • the ability to anchor LC molecules is also weak, which affects the quality of the panel.
  • the PI material itself has high polarity and high water absorption, storage and transportation are prone to deterioration, resulting in uneven phase distribution, and PI materials are expensive.
  • the process of film formation on a TFT-LCD is also complicated, resulting in an increase in panel cost.
  • Graphene has good electrical and thermal conductivity, high strength and toughness, and is an ideal substitute for ITO. If a special material can be added to graphene, a graphene material which can conduct electricity and have an alignment effect can be prepared. It will be of great significance to display technology.
  • the present application provides a graphene transparent conductive film having conductive properties and vertical alignment properties, wherein a vertical alignment agent is added to the graphene transparent conductive film, and the vertical alignment agent can reduce liquid crystal molecules.
  • the surface energy in the polymer matrix increases the contact angle so that the liquid crystal molecules are vertically aligned.
  • a graphene transparent conductive film comprising: graphene and a vertical alignment agent; wherein the vertical alignment agent has a structural formula of: RS P -Q n , wherein Q is a sulfonic acid group, n is an integer from 1 to 3; S P is a linking group having the formula -(CH 2 ) m - wherein m is an integer from 1 to 5, wherein one or more -CH 2 - groups
  • R is selected from substituted or unsubstituted C
  • the linking group S P when n is 1, the linking group S P must contain at least two benzene rings or aromatic fused ring structures.
  • the vertical alignment agent of the present invention can be adsorbed on the surface of graphene by a sulfonic acid group, and the vertical chain of the liquid crystal is oriented by a long chain containing a rigid group; the present inventors have found that a benzene ring or aroma in a vertical alignment agent molecule The more the number of fused rings, the better the vertical orientation effect.
  • the particular vertical alignment agent suitable for use in the present invention is selected from
  • a method for preparing a graphene transparent conductive film comprising:
  • step S1 is not particularly limited and may be carried out in accordance with a method generally used in the art.
  • graphene, a surfactant, and water may be mixed, sonicated to make them uniformly mixed, and the graphene solution is prepared.
  • the graphene is not particularly limited, and it is preferable that the graphene is in a powder form and has a particle size of 0.5 to 50 ⁇ m.
  • the surfactant is not particularly limited, and a surfactant known in the art may be selected.
  • the surfactant may be selected such as an anionic surfactant or a cationic surfactant.
  • Surfactants well known in the art such as nonionic surfactants.
  • the surfactant includes a fluorine-containing silane active agent, stearic acid, a sodium dodecyl sulfate surfactant, a quaternary ammonium surfactant, an amino acid surfactant, a betaine surfactant, and a fatty acid.
  • At least one of a glyceride surfactant, a fatty acid sorbitan surfactant, a lecithin surfactant, and a Tween surfactant At least one of a glyceride surfactant, a fatty acid sorbitan surfactant, a lecithin surfactant, and a Tween surfactant.
  • the surfactant is preferably sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate or tetradecyl At least one of sodium sulfate.
  • the mass ratio of the graphene, the surfactant, and the water is 1: (50-500): (2000-10000), preferably 1: (100-300): (3000- 8000).
  • the step S2 comprises: adding a vertical alignment agent and PEDOT-PSS to the graphene solution, sonicating it to make it uniformly mixed, and preparing a graphene transparent conductive film liquid.
  • the mass ratio of the graphene solution, the vertical alignment agent, and the PEDOT-PSS is 1: (0.1-1): (50-100), preferably 1:0.5: (60-80) .
  • PEDOT-PSS is poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid).
  • PEDOT-PSS has high conductivity, high mechanical strength, high visible light transmittance and good stability.
  • the addition of the transparent conductive film can significantly improve the electrical conductivity of the transparent conductive film.
  • the vertical alignment agent has the structural formula: RS P -Q n , wherein Q is a sulfonic acid group, n is an integer of 1-3; and S P is a linking group.
  • the structural formula is -(CH 2 ) m - wherein m is an integer from 1 to 5, wherein one or more -CH 2 - groups may be optionally substituted with a phenylene group, an aromatic fused ring, or a hypocycloalkane.
  • the hydrogen atom may be optionally substituted by a fluorine atom or a chlorine atom; wherein, when n is 1, the linking group S P must contain at least two benzene ring structures or aromatic fused ring
  • the particular vertical alignment agent suitable for use in the present invention may be selected from
  • step S3 is not particularly limited and may be carried out in accordance with conventional techniques in the art.
  • the graphene transparent conductive film liquid is coated on a substrate, and heat-treated to remove moisture in the film liquid to obtain a graphene transparent conductive film.
  • the heat treatment has a treatment temperature of 80 to 140 ° C and a treatment time of 3 to 10 minutes.
  • the heat in the graphene transparent conductive film is removed by heat treatment, and the vertical alignment agent is phase-separated in the graphene solution, the sulfonic acid group is adsorbed in the graphene, and the hydrophobic chain is diffused to the surface of the graphene, thereby preparing A graphene transparent conductive film having a vertical alignment effect.
  • a thin film transistor-liquid crystal display includes: a first substrate, a second substrate, and a liquid crystal material between the first substrate and the second substrate; wherein the first substrate And the above graphene transparent conductive film or the graphene transparent conductive film prepared by the above method is coated on the second substrate.
  • the graphene transparent conductive film of the invention contains a vertical alignment agent, and the vertical alignment agent can reduce the surface energy of the liquid crystal molecules in the polymer matrix, increase the contact angle, and the liquid crystal molecules are vertically arranged; and the graphene transparent conductive film further contains graphite.
  • the olefin and PEDOT-PSS ensure that the conductive film has good electrical conductivity, and therefore the graphene transparent conductive film of the present invention has both electrical conductivity and vertical alignment properties.
  • FIG. 1 is a schematic view showing a preparation process of a graphene transparent conductive film of the present invention
  • FIG. 2 is a schematic structural view of a liquid crystal display of the present invention.
  • the graphene powder, the surfactant and the water are mixed, ultrasonically treated to uniformly mix, and the graphene solution is prepared; wherein the surfactant is sodium dodecyl sulfate;
  • the vertical alignment agent and PEDOT-PSS are added to the graphene solution, and ultrasonically treated to uniformly mix them to obtain a graphene transparent conductive film liquid; wherein, the vertical alignment agent is:
  • the CF substrate and the TFT substrate material are bonded together, sealed with a sealant, and the sealant is cured by ultraviolet irradiation to obtain a liquid crystal cell; and the liquid crystal cell is subjected to ultraviolet irradiation treatment to obtain Thin film transistor - liquid crystal display.
  • the graphene powder, the surfactant and the water are mixed, ultrasonically treated to uniformly mix, and the graphene solution is prepared; wherein the surfactant is sodium lauryl sulfate;
  • the vertical alignment agent and PEDOT-PSS are added to the graphene solution, and ultrasonically treated to uniformly mix them to obtain a graphene transparent conductive film liquid; wherein, the vertical alignment agent is:
  • the CF substrate and the TFT substrate material are bonded together, sealed with a sealant, and the sealant is cured by ultraviolet irradiation to obtain a liquid crystal cell; and the liquid crystal cell is subjected to ultraviolet irradiation treatment to obtain Thin film transistor - liquid crystal display.
  • the graphene powder, the surfactant and the water are mixed, sonicated to make the mixture uniform, and the graphene solution is prepared; wherein the surfactant is sodium dodecylbenzenesulfonate;
  • the vertical alignment agent and PEDOT-PSS are added to the graphene solution, and ultrasonically treated to uniformly mix them to obtain a graphene transparent conductive film liquid; wherein, the vertical alignment agent is:
  • the CF substrate and the TFT substrate material are bonded together, sealed with a sealant, and the sealant is cured by ultraviolet irradiation to obtain a liquid crystal cell; and the liquid crystal cell is subjected to ultraviolet irradiation treatment to obtain Thin film transistor - liquid crystal display.
  • the graphene powder, the surfactant and the water are mixed, sonicated to make the mixture uniform, and the graphene solution is prepared; wherein the surfactant is ammonium lauryl sulfate;
  • the vertical alignment agent and PEDOT-PSS are added to the graphene solution, and ultrasonically treated to uniformly mix them to obtain a graphene transparent conductive film liquid; wherein, the vertical alignment agent is:
  • the CF substrate and the TFT substrate material are bonded together, sealed with a sealant, and the sealant is cured by ultraviolet irradiation to obtain a liquid crystal cell; and the liquid crystal cell is subjected to ultraviolet irradiation treatment to obtain Thin film transistor - liquid crystal display.
  • the graphene powder, the surfactant and the water are mixed, ultrasonically treated to uniformly mix, and the graphene solution is prepared; wherein the surfactant is sodium tetradecyl sulfate;
  • the vertical alignment agent and PEDOT-PSS are added to the graphene solution, which is sonicated to mix them. Evenly, a graphene transparent conductive film liquid is prepared; wherein the vertical alignment agent is:
  • the CF substrate and the TFT substrate material are bonded together, sealed with a sealant, and the sealant is cured by ultraviolet irradiation to obtain a liquid crystal cell; and the liquid crystal cell is subjected to ultraviolet irradiation treatment to obtain Thin film transistor - liquid crystal display.
  • the display effect of the thin film transistor-liquid crystal display prepared in Example 1-5 was examined, and the results are shown in Table 1. It can be seen from the results of Table 1 that the liquid crystal display prepared by the present invention is black without power, and the pretilt angle is 88.5-89.2°, and the dark state effect is good.
  • Example 1 it is good 89.0°
  • Example 2 it is good 88.6°
  • Example 3 it is good 88.5°
  • Example 4 it is good 89.2°
  • Example 5 it is good 89.1°
  • Any numerical value mentioned in the present invention includes all values of one unit at a time from the lowest value to the highest value if there is only two unit intervals between any lowest value and any highest value. For example, if the amount of a component is declared, or the value of a process variable such as temperature, pressure, time, etc. is 50-90, it means in this specification that 51-89, 52-88, ..., and 69 are specifically listed. -71 and 70-71 values. For values other than integers, it is appropriate to consider 0.1, 0.01, 0.001 or 0.0001 as a unit. This is just a few specific examples. In the present application, all possible combinations of numerical values between the lowest and highest values recited are considered to have been disclosed.

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Abstract

一种石墨烯透明导电膜，包括石墨烯和垂直取向剂。其制备方法包括将石墨烯、表面活性剂和水混合制得石墨烯溶液；然后加入垂直取向剂，制得石墨烯透明导电膜液；将膜液涂布在基板上，加热即得。该垂直取向剂可降低液晶分子在聚合物基体中的表面能，增加接触角，使液晶分子垂直排列。

Description

一种石墨烯透明导电膜及其制备方法
本申请要求享有2016年12月30日提交的名称为“一种石墨烯透明导电膜及其制备方法”的中国专利申请CN201611252503.3的优先权，其全部内容通过引用并入本文中。
技术领域
本发明涉及一种石墨烯透明导电膜，还涉及一种石墨烯透明导电膜的制备方法，属于液晶显示器领域。
背景技术
在薄膜晶体管-液晶显示器(TFT-LCD)中，通常包括彩色滤光片(CF)基板、TFT基板以及这两者之间的聚酰亚胺(PI)材料、液晶材料和框胶材料。针对常见的垂直配向(VA)显示模式而言，需要在CF基板、TFT基板上同时有一层透明到导电膜，该透明导电膜的主要作用是在CF基板和TFT基板之间形成电场，驱动液晶分子偏转，从而实现亮暗的显示。
目前传统的透明导电膜使用的是由物理气相溅射(PVD)的方法制备出的氧化铟锡(ITO)薄膜。在PVD装置中，强电流轰击ITO靶材，在基板上沉积得到透明导电ITO薄膜。但是由于ITO的本身氧化物的物理特性，ITO薄膜并不能在一定外力作用下展现弯折特性，这也限制了其在柔性面板，可穿戴设备上的应用。另一方面，随着国家政策的导向，铟的成本也逐渐涨高。所以寻找高导电性和透光率、制备方法简单、资源丰富的ITO替代品具有很强的应用价值。
另外，在CF基板和TFT基板上，还分别有一层薄膜材料，其主要作用是使液晶分子按一定方向排列，我们称之为配向膜(常用PI材料)。这种配向膜主要分为摩擦配相型PI材料和光配相型PI材料，但是，无论那种配向材料都会有各自的缺点。首先摩擦配相向容易造成粉尘颗粒、静电残留、刷痕等问题降低工艺良率，而光配相材料虽然可以避免这些问题，但由于材料特性受限，耐热性和耐老化性不佳，同时锚定LC分子的能力也较弱，从而影响面板的品质；其次，PI材料本身就具有高极性和高吸水性，存储和运送容易造成变质而导致配相不均，并且PI材料价格昂贵，在TFT-LCD上成膜的工艺也较为复杂，导致面板成本提高。
石墨烯具有良好的导电导热性能，强度和韧性也较高，是ITO的理想替代材料，如果能够在石墨烯中在添加一些特殊的材料，制备出既可以导电有具有配向效果的石墨烯材料，对显示器技术来说将具有重大的意义。
发明内容
为了解决现有技术存在的问题，本申请提供一种具有导电性能和垂直取向性能的石墨烯透明导电膜，该石墨烯透明导电膜内添加有垂直取向剂，所述垂直取向剂可以降低液晶分子在聚合物基体中的表面能，增加接触角，使液晶分子垂直排列。
根据本发明的一个方面，提供一种石墨烯透明导电膜，包括：石墨烯和垂直取向剂；所述垂直取向剂的结构通式为：R-SP-Qn，其中，Q为磺酸基，n为1-3的整数；SP为连接基团，其结构通式为-(CH2)m-，式中m为1-5的整数，其中的一个或多个-CH2-基团可任选地被亚苯基、芳香稠环、亚环烷基、-O-、-S-、-CO-、-COO-、-OCO-、-OCOO-、-OCH2-、-CH2O-、-CH＝CH-、-CF＝CF-、-C≡C-、-CH＝CH-COO-或-OCO-CH＝CH-基团取代；R选自取代或未取代的C3-20的直链或支链烷基，其中一个或多个-CH2-基团可任选地被-O-、-CONH-、-COO-、-OCO-、-CO-、或-CH＝CH-基团取代，其中一个或多个氢原子可任选地被氟原子或氯原子取代。
根据本发明的一个优选实施例，在所述结构通式R-SP-Qn中，当n为1时，所述连接基团SP中须含有至少两个苯环或芳香稠环结构。
本发明的垂直取向剂可依靠磺酸基吸附在石墨烯表面，依靠含有刚性基团的长链达到使得液晶垂直取向的目的；本发明人在研究中发现，垂直取向剂分子中苯环或芳香稠环的个数越多，其垂直取向效果越好。
在一些具体的实施例中，适用于本发明的具体的垂直取向剂选自
Figure PCTCN2017071349-appb-000001
Figure PCTCN2017071349-appb-000002
Figure PCTCN2017071349-appb-000003
中的一种或多种。
根据本发明的另一个方面，提供一种石墨烯透明导电膜的制备方法，包括：
S1：将石墨烯、表面活性剂和水混合，制得石墨烯溶液；
S2：向所述石墨烯溶液中加入垂直取向剂和PEDOT-PSS，混合，制得石墨烯透明导电膜液；
S3：将所述石墨烯透明导电膜液涂布在基板上，去除膜液中的水分，即可制得石墨烯透明导电膜。
根据本发明的制备方法，对于步骤S1没有特别的限定，可按照本领域常用方法进行。例如，可将石墨烯、表面活性剂和水混合，对其进行超声处理以使其混合均匀，制得所述石墨烯溶液。
根据本发明的一个优选实施例，对所述石墨烯没有特别限定，优选所述石墨烯为粉状，其粒度为0.5～50um。
根据本发明的一些优选实施例，对所述表面活性剂没有特别限定，选择本行业公知的表面活性剂即可。所述表面活性剂可以选择如阴离子表面活性剂、阳离子表面活性剂 和非离子表面活性剂等本行业公知的表面活性剂。所述表面活性剂包括含氟类硅烷活性剂、硬脂酸、十二烷基磺酸钠类表面活性剂、季铵类表面活性剂、氨基酸类表面活性剂、甜菜碱型表面活性剂、脂肪酸甘油酯类表面活性剂、脂肪酸山梨坦类表面活性剂、卵磷脂类表面活性剂和吐温系列表面活性剂中的至少一种。
在一些具体的实施例中，所述表面活性剂优选为十二烷基硫酸钠、十二烷基硫酸铵、十二烷基磺酸钠、十二烷基苯磺酸钠或十四烷基硫酸钠中的至少一种。
根据本发明的一些实施方式，所述石墨烯、表面活性剂和水的质量之比为1:(50-500):(2000-10000)，优选为1:(100-300):(3000-8000)。
根据本发明的制备方法，所述步骤S2包括：向所述石墨烯溶液中加入垂直取向剂和PEDOT-PSS，对其进行超声处理以使其混合均匀，制得石墨烯透明导电膜液。
在一些具体实施例中，所述石墨烯溶液、垂直取向剂和PEDOT-PSS的质量之比为1:(0.1-1):(50-100)，优选为1:0.5:(60-80)。
PEDOT-PSS即聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)，PEDOT-PSS具有高导电率、高机械强度、高可见光透射率和稳定性好的特点，将其加入透明导电膜中，可显著提高透明导电膜的导电性能。
根据本发明的一些优选实施例，所述垂直取向剂的结构通式为：R-SP-Qn，其中，Q为磺酸基，n为1-3的整数；SP为连接基团，其结构通式为-(CH2)m-，式中m为1-5的整数，其中的一个或多个-CH2-基团可任选地被亚苯基、芳香稠环、亚环烷基、-O-、-S-、-CO-、-COO-、-OCO-、-O-CO-O-、-OCH2-、-CH2O-、-CH＝CH-、-CF＝CF-、-C≡C-、-CH＝CH-COO-或-OCO-CH＝CH-基团取代；R选自取代或未取代的C3-20的直链或支链烷基，其中一个或多个-CH2-基团可任选地被-O-、-CONH-、-COO-、-OCO-、-CO-、或-CH＝CH-基团取代，其中一个或多个氢原子可任选地被氟原子或氯原子取代；其中，当n为1时，所述连接基团SP中须含有至少两个苯环结构或芳香稠环结构。
在一些具体的实施例中，适用于本发明的具体的垂直取向剂可选自
Figure PCTCN2017071349-appb-000004
Figure PCTCN2017071349-appb-000005
Figure PCTCN2017071349-appb-000006
中的一种或多种。
根据本发明的一些优选实施例，对于步骤S3没有特别的限定，可按照本领域的常规技术进行。例如，将所述石墨烯透明导电膜液涂布在基板上，对其进行加热处理以去除膜液中的水分，即可制得石墨烯透明导电膜。
根据本发明的一个实施方式，所述加热处理的处理温度为80-140℃，处理时间为3-10min。
通过热处理以去除了石墨烯透明导电膜内的水分，同时垂直取向剂会在石墨烯溶液中发生相分离，磺酸基吸附在石墨烯中，疏水性链扩散到石墨烯表面，即可制备出具有垂直取向效果的石墨烯透明导电膜。
根据本发明的再一个方面，提供一种薄膜晶体管-液晶显示器，包括：第一基板、第二基板和位于所述第一基板和第二基板之间的液晶材料；其中，所述第一基板和第二基板上涂布有上述石墨烯透明导电膜或上述方法制备的石墨烯透明导电膜。
本发明石墨烯透明导电膜内含有垂直取向剂，垂直取向剂可以降低液晶分子在聚合物基体中的表面能，增加接触角，使得液晶分子垂直排列；同时该石墨烯透明导电膜内还含有石墨烯和PEDOT-PSS，保证了导电膜具有很好的导电性能，因此本发明的石墨烯透明导电膜同时具有导电性能和垂直取向性能。
附图说明
附图用来提供对本发明的进一步理解，并且构成说明书的一部分，与本发明的实施例共同用于解释本发明，并不构成对本发明的限制。在附图中：
图1为本发明石墨烯透明导电膜的制备过程示意图；
图2为本发明液晶显示器结构示意图。
具体实施方式
以下结合具体的实施例对本发明的技术方案作一步的说明。
实施例1
(1)按照如下质量份备料：
石墨烯粉             1
表面活性剂           200
水                   5000
将将石墨烯粉、表面活性剂和水混合，对其进行超声处理以使其混合均匀，制得所述石墨烯溶液；其中，表面活性剂为十二烷基磺酸钠；
(2)按照如下质量份备料：
石墨烯溶液            1
垂直取向剂            0.5
PEDOT-PSS             60
将垂直取向剂和PEDOT-PSS加入石墨烯溶液中，对其进行超声处理以使其混合均匀，制得石墨烯透明导电膜液；其中，垂直取向剂为：
Figure PCTCN2017071349-appb-000007
(3)将上述石墨烯透明导电膜液涂布在TFT基板和CF基板上，然后加热至120℃，烘烤3min，以去除石墨烯膜内的水分，即可制备出具有垂直取向效果的石墨烯透明导电膜；
(4)在真空环境下，将CF基板和TFT基板材料贴合在一起，以密封胶密封，通过紫外照射的方式对密封胶进行固化，得到液晶盒；对液晶盒进行紫外照射处理，即得到薄膜晶体管-液晶显示器。
实施例2
(1)按照如下质量份备料：
石墨烯粉             1
表面活性剂           100
水                   8000
将将石墨烯粉、表面活性剂和水混合，对其进行超声处理以使其混合均匀，制得所述石墨烯溶液；其中，表面活性剂为十二烷基硫酸钠；
(2)按照如下质量份备料：
石墨烯溶液             1
垂直取向剂             0.1
PEDOT-PSS              80
将垂直取向剂和PEDOT-PSS加入石墨烯溶液中，对其进行超声处理以使其混合均匀，制得石墨烯透明导电膜液；其中，垂直取向剂为：
Figure PCTCN2017071349-appb-000008
(3)将上述石墨烯透明导电膜液涂布在TFT基板和CF基板上，然后加热至100℃，烘烤5min，以去除石墨烯膜内的水分，即可制备出具有垂直取向效果的石墨烯透明导电 膜；
(4)在真空环境下，将CF基板和TFT基板材料贴合在一起，以密封胶密封，通过紫外照射的方式对密封胶进行固化，得到液晶盒；对液晶盒进行紫外照射处理，即得到薄膜晶体管-液晶显示器。
实施例3
(1)按照如下质量份备料：
石墨烯粉             1
表面活性剂           500
水                   2000
将将石墨烯粉、表面活性剂和水混合，对其进行超声处理以使其混合均匀，制得所述石墨烯溶液；其中，表面活性剂为十二烷基苯磺酸钠；
(2)按照如下质量份备料：
石墨烯溶液             1
垂直取向剂             0.3
PEDOT-PSS              75
将垂直取向剂和PEDOT-PSS加入石墨烯溶液中，对其进行超声处理以使其混合均匀，制得石墨烯透明导电膜液；其中，垂直取向剂为：
Figure PCTCN2017071349-appb-000009
(3)将上述石墨烯透明导电膜液涂布在TFT基板和CF基板上，然后加热至80℃，烘烤10min，以去除石墨烯膜内的水分，即可制备出具有垂直取向效果的石墨烯透明导电膜；
(4)在真空环境下，将CF基板和TFT基板材料贴合在一起，以密封胶密封，通过紫外照射的方式对密封胶进行固化，得到液晶盒；对液晶盒进行紫外照射处理，即得到薄膜晶体管-液晶显示器。
实施例4
(1)按照如下质量份备料：
石墨烯粉             1
表面活性剂           50
水                   10000
将将石墨烯粉、表面活性剂和水混合，对其进行超声处理以使其混合均匀，制得所述石墨烯溶液；其中，表面活性剂为十二烷基硫酸铵；
(2)按照如下质量份备料：
石墨烯溶液             1
垂直取向剂             0.8
PEDOT-PSS              100
将垂直取向剂和PEDOT-PSS加入石墨烯溶液中，对其进行超声处理以使其混合均匀，制得石墨烯透明导电膜液；其中，垂直取向剂为：
Figure PCTCN2017071349-appb-000010
(3)将上述石墨烯透明导电膜液涂布在TFT基板和CF基板上，然后加热至90℃，烘烤8min，以去除石墨烯膜内的水分，即可制备出具有垂直取向效果的石墨烯透明导电膜；
(4)在真空环境下，将CF基板和TFT基板材料贴合在一起，以密封胶密封，通过紫外照射的方式对密封胶进行固化，得到液晶盒；对液晶盒进行紫外照射处理，即得到薄膜晶体管-液晶显示器。
实施例5
(1)按照如下质量份备料：
石墨烯粉             1
表面活性剂           300
水                   3000
将将石墨烯粉、表面活性剂和水混合，对其进行超声处理以使其混合均匀，制得所述石墨烯溶液；其中，表面活性剂为十四烷基硫酸钠；
(2)按照如下质量份备料：
石墨烯溶液             1
垂直取向剂             1
PEDOT-PSS              50
将垂直取向剂和PEDOT-PSS加入石墨烯溶液中，对其进行超声处理以使其混合均 匀，制得石墨烯透明导电膜液；其中，垂直取向剂为：
Figure PCTCN2017071349-appb-000011
(3)将上述石墨烯透明导电膜液涂布在TFT基板和CF基板上，然后加热至140℃，烘烤6min，以去除石墨烯膜内的水分，即可制备出具有垂直取向效果的石墨烯透明导电膜；
(4)在真空环境下，将CF基板和TFT基板材料贴合在一起，以密封胶密封，通过紫外照射的方式对密封胶进行固化，得到液晶盒；对液晶盒进行紫外照射处理，即得到薄膜晶体管-液晶显示器。
对实施例1-5制备的薄膜晶体管-液晶显示器进行显示效果检测，结果见表1。由表1结果可知，本发明制备的液晶显示器在不加电的情况下显黑色，预倾角为88.5-89.2°，暗态效果好。
表1
显示模式 暗态效果 预倾角
实施例1 好 89.0°
实施例2 好 88.6°
实施例3 好 88.5°
实施例4 好 89.2°
实施例5 好 89.1°
在本发明中的提到的任何数值，如果在任何最低值和任何最高值之间只是有两个单位的间隔，则包括从最低值到最高值的每次增加一个单位的所有值。例如，如果声明一种组分的量，或诸如温度、压力、时间等工艺变量的值为50-90，在本说明书中它的意思是具体列举了51-89、52-88……以及69-71以及70-71等数值。对于非整数的值，可以适当考虑以0.1、0.01、0.001或0.0001为一单位。这仅是一些特殊指明的例子。在本申请中，以相似方式，所列举的最低值和最高值之间的数值的所有可能组合都被认为已经公开。
应当注意的是，以上所述的实施例仅用于解释本发明，并不构成对本发明的任何限制。通过参照典型实施例对本发明进行了描述，但应当理解为其中所用的词语为描述性 和解释性词汇，而不是限定性词汇。可以按规定在本发明权利要求的范围内对本发明作出修改，以及在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例，但是并不意味着本发明限于其中公开的特定例，相反，本发明可扩展至其他所有具有相同功能的方法和应用。
附图标记说明
1          基板
2          石墨烯透明导电膜液
3          垂直取向剂
4          表面活性剂
5          石墨烯
6          液晶分子

Claims (17)

  1. 一种石墨烯透明导电膜，包括：石墨烯和垂直取向剂；所述垂直取向剂的结构通式为：R-SP-Qn；其中，Q为磺酸基，n为1-3的整数；SP为连接基团，其结构通式为-(CH2)m-，式中m为1-5的整数，其中的一个或多个-CH2-基团可任选地被亚苯基、芳香稠环基、亚环烷基、-O-、-S-、-CO-、-COO-、-OCO-、-OCOO-、-OCH2-、-CH2O-、-CH＝CH-、-CF＝CF-、-C≡C-、-CH＝CH-COO-或-OCO-CH＝CH-基团取代；R选自取代或未取代的C3-20的直链或支链烷基，其中一个或多个CH2基团可任选地被-O-、-CONH-、-COO-、-OCO-、-CO-、或-CH＝CH-基团取代，其中一个或多个氢原子可任选地被氟原子或氯原子取代。
  2. 根据权利要求1所述的石墨烯透明导电膜，其中，在所述结构通式R-SP-Qn中，当n为1时，所述连接基团SP中含有至少两个苯环或芳香稠环结构。
  3. 根据权利要求1所述的石墨烯透明导电膜，其中，所述垂直取向剂选自
    Figure PCTCN2017071349-appb-100001
    Figure PCTCN2017071349-appb-100002
    Figure PCTCN2017071349-appb-100003
    中的一种或多种。
  4. 一种石墨烯透明导电膜的制备方法，包括：
    S1：将石墨烯、表面活性剂和水混合，制得石墨烯溶液；
    S2：向所述石墨烯溶液中加入垂直取向剂和PEDOT-PSS，混合制得石墨烯透明导电膜液；
    S3：将所述石墨烯透明导电膜液涂布在基板上，去除膜液中的水分，即可制得石墨烯透明导电膜。
  5. 根据权利要求4所述的制备方法，其中，所述步骤S1包括：将石墨烯、表面活性剂和水混合，对其进行超声处理以使其混合，制得所述石墨烯溶液。
  6. 根据权利要求5中所述的制备方法，其中，所述石墨烯、表面活性剂和水的质量之比为1:(50-500):(2000-10000)。
  7. 根据权利要求4所述的制备方法，其中，所述步骤S2包括：向所述石墨烯溶液中加入垂直取向剂和PEDOT-PSS，对其进行超声处理以使其混合，制得石墨烯透明导电膜液。
  8. 根据权利要求7所述的制备方法，其中，所述石墨烯溶液、垂直取向剂和PEDOT-PSS的质量之比为1:(0.1-1):(50-100)。
  9. 根据权利要求7所述的制备方法，其中，所述垂直取向剂的结构通式为：R-SP-Qn，其中，Q为磺酸基，n为1-3的整数；SP为连接基团，其结构通式为-(CH2)m-，式中m为1-5的整数，其中的一个或多个-CH2-基团可任选地被亚苯基、芳香稠环、亚环烷基、-O-、-S-、-CO-、-COO-、-OCO-、-O-CO-O-、-OCH2-、-CH2O-、-CH＝CH-、-CF＝CF-、-C≡C-、-CH＝CH-COO-或-OCO-CH＝CH-基团取代；R选自取代或未取代的C3-20的直链或支链烷基，其中一个或多个-CH2-基团可任选地被-O-、-CONH-、-COO-、-OCO-、-CO-、或-CH＝CH-基团取代，其中一个或多个氢原子可任选地被氟原子或氯原子取代。
  10. 根据权利要求9所述的制备方法，其中，在所述结构通式R-SP-Qn中，当n为1时，所述连接基团SP中须含有至少两个苯环结构或芳香稠环结构。
  11. 根据权利要求4所述的制备方法，其中，所述步骤S3包括：将所述石墨烯透明 导电膜液涂布在基板上，对其进行加热处理以去除膜液中的水分，即可制得石墨烯透明导电膜。
  12. 根据权利要求11所述的制备方法，其中，所述加热处理的处理温度为80-140℃，处理时间为3-10min。
  13. 一种液晶显示器，包括：第一基板、第二基板和位于所述第一基板和第二基板之间的液晶材料；其中，所述第一基板和第二基板上涂布有石墨烯透明导电膜；
    其中，所述石墨烯透明导电膜包括石墨烯和垂直取向剂；所述垂直取向剂的结构通式为：R-SP-Qn；其中，Q为磺酸基，n为1-3的整数；SP为连接基团，其结构通式为-(CH2)m-，式中m为1-5的整数，其中的一个或多个-CH2-基团可任选地被亚苯基、芳香稠环基、亚环烷基、-O-、-S-、-CO-、-COO-、-OCO-、-OCOO-、-OCH2-、-CH2O-、-CH＝CH-、-CF＝CF-、-C≡C-、-CH＝CH-COO-或-OCO-CH＝CH-基团取代；R选自取代或未取代的C3-20的直链或支链烷基，其中一个或多个-CH2-基团可任选地被-O-、-CONH-、-COO-、-OCO-、-CO-、或-CH＝CH-基团取代，其中一个或多个氢原子可任选地被氟原子或氯原子取代。
  14. 根据权利要求13所述的液晶显示器，其中，在所述结构通式R-SP-Qn中，当n为1时，所述连接基团SP中含有至少两个苯环或芳香稠环结构。
  15. 根据权利要求13所述的液晶显示器，其中，所述石墨烯透明导电膜通过如下方法制备：
    S1：将石墨烯、表面活性剂和水混合，制得石墨烯溶液；
    S2：向所述石墨烯溶液中加入垂直取向剂和PEDOT-PSS，混合制得石墨烯透明导电膜液；
    S3：将所述石墨烯透明导电膜液涂布在基板上，去除膜液中的水分，即可制得石墨烯透明导电膜。
  16. 根据权利要求15所述的液晶显示器，其中，所述石墨烯、表面活性剂和水的质量之比为1:(50-500):(2000-10000)。
  17. 根据权利要求15所述的液晶显示器，其中，所述石墨烯溶液、垂直取向剂和PEDOT-PSS的质量之比为1:(0.1-1):(50-100)。
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