WO2018040955A1 - 一种化学接枝改性的pet/纳米银线透明导电膜的制备 - Google Patents

一种化学接枝改性的pet/纳米银线透明导电膜的制备 Download PDF

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WO2018040955A1
WO2018040955A1 PCT/CN2017/098060 CN2017098060W WO2018040955A1 WO 2018040955 A1 WO2018040955 A1 WO 2018040955A1 CN 2017098060 W CN2017098060 W CN 2017098060W WO 2018040955 A1 WO2018040955 A1 WO 2018040955A1
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transparent conductive
silver wire
nano silver
pet
preparation
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PCT/CN2017/098060
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English (en)
French (fr)
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段镶锋
段曦东
李晓丰
毛志浩
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广东纳路纳米科技有限公司
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Publication of WO2018040955A1 publication Critical patent/WO2018040955A1/zh

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    • 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
    • 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
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys

Definitions

  • the invention relates to the technical field of flexible transparent conductive films, in particular to the preparation of a chemical graft modified PET/nano-silver transparent conductive film.
  • the transparent conductive film is a film which has both conductivity and high light transmittance, and is widely used in the field of electronic components such as liquid crystal displays, touch panels and solar cells. Future mobile terminals, wearable devices, smart home appliances and other products have strong demand for touch panels. At the same time, with the large size and low cost of touch panels, and traditional ITO films can not be applied to flexible surfaces, conductivity and light transmission. Factors such as rate are not easy to overcome, and many manufacturers have begun to study alternatives to ITO, including nano-silver wires, metal meshes, carbon nanotubes, and graphene. From the perspective of market reaction, the proportion of film products produced by applying new material technologies is increasing year by year.
  • the nano silver wire technology can quickly produce large-area touch panels by using a printing process, and has a small bending radius, and the resistance change rate is small when bending, and is applied to a device with a flexible curved surface display.
  • the substrate materials used in the existing flexible curved surface equipment are mostly polyethylene terephthalate (PET) films, the PET macromolecular chain structure is regular, the crystallinity is high, and there is no strong polar group in the molecule. Therefore, its surface affinity is poor.
  • PET polyethylene terephthalate
  • the main methods used are surface coating, surface oxidation, plasma, high-energy radiation, ultraviolet radiation, etc., but this affects the bulk properties of PET or can not reach To long-term modification effect. It can be seen that the prior art still has large defects.
  • the present invention adopts the following technical solutions:
  • the preparation of the chemical graft modified PET/nano-silver transparent conductive film of the invention comprises: removing the surface of the PET substrate, preparing the nano silver wire mixture, and preparing the transparent conductive film;
  • the surface of the PET substrate is modified to include: the PET substrate is selected from the optical grade coating PET treated by the double-sided hardening layer, and the PET substrate is treated, washed and dried by using a mixed solvent of acetone and ethanol;
  • the preparation of the nano silver wire mixture comprises: adding 0.1-10 g of a coupling agent to a nano silver wire ethanol solution having a concentration of 0.01-10 mg/ml, and the obtained coupling agent-nano silver wire ethanol solution is heated to 30-150. Stirring at °C for 30-240min to obtain a nano silver wire mixture;
  • the preparation of the transparent conductive film comprises: immersing the surface-depleted PET substrate into the nano silver wire mixture, the reaction temperature is controlled at 30-120 ° C, the time is 30-180 min, and after the reaction is finished, the water is repeatedly washed by the distilled water, and then The transparent conductive film was prepared by baking in an oven at 60-180 ° C for 30-240 min.
  • the coupling agent is added in an amount of 0.1 to 5 g, and the concentration of the nanosilver ethanol solution is 0.01 to 5 mg/ml.
  • the coupling agent-nanosilver ethanol solution is heated to 30-120 ° C for 30-150 min.
  • the reaction temperature is controlled at 30-100 ° C for 30-150 min; the oven baking temperature is 60-120 ° C, and the time is 30-150 min.
  • the PET substrate has a thickness of 50 um, 100 um, 125 um and is provided with a protective film.
  • the absolute ethanol to acetone volume ratio is one.
  • the coupling agent is a mercaptosilane coupling agent KH-580 or a mercaptosilane coupling agent. KH-590.
  • the coupling agent is a mercaptosilane coupling agent KH-590.
  • the transparent conductive film prepared by the present invention has a thickness of 50 to 600 nm, preferably 50 to 300 nm.
  • the invention adopts a nano silver wire instead of the nano silver particle as a thin film conductive material dispersed in the ethanol, and the conductive purpose is achieved by contacting the silver wires with each other;
  • the surface of the nano silver wire is chemically modified with a coupling agent by the coordination of the thiol group at one end of the silane coupling agent with the nano silver, and the siloxane group at the other end of the coupling agent is combined with the hardened layer on the surface of the PET to form a chemical bond.
  • the form of the combination fixes the nano silver wire to the PET surface, and the adhesion of the prepared nano silver wire transparent conductive film is greatly improved.
  • the transparent conductive film of the invention has strong adhesion and high flex resistance, and has mild conditions and simple operation, and has high application value in the field of flexible electronics.
  • Step 1) Decontamination of the surface of the PET substrate Wash the 50 um optical grade double-sided hardened PET substrate with a protective film with a mixed solvent of absolute ethanol/acetone volume ratio of 1, and then rinse the surface of the PET substrate with distilled water. a mixed solvent, vacuum dried at 80 ° C to obtain a surface clean PET substrate;
  • Step 2) Preparation of nano silver wire mixture: 0.5 g of silane coupling agent KH-590 was added to a solution of 0.08 mg/ml nano silver wire ethanol, and the obtained coupling agent-nano silver wire ethanol solution was subjected to magnetic force at 60 ° C. Stir After 90 min, a nano silver wire mixture is prepared;
  • Step 3) Preparation of the transparent conductive film: the surface clean PET substrate obtained in the step 1) is immersed in the nano silver wire mixture prepared in the step 2), and after repeatedly reacting for 150 minutes at a temperature of 40 ° C, the PET base is repeatedly washed with distilled water. The un-grafted polymer on the surface of the material was baked at 100 ° C for 60 min to obtain a PET/nano-silver transparent conductive film with a thickness of 50 nm.
  • Step 1) Decontamination of the surface of the PET substrate Wash the 50 um optical grade double-sided hardened PET substrate with a protective film with a mixed solvent of absolute ethanol/acetone volume ratio of 1, and then rinse the surface of the PET substrate with distilled water. a mixed solvent, vacuum dried at 80 ° C to obtain a surface clean PET substrate;
  • Step 2) Preparation of the nano silver wire mixture: 1 g of the silane coupling agent KH-590 is added to a 0.3 mg/ml nano silver wire ethanol solution, and after magnetic stirring at 90 ° C for 60 min, a nano silver wire mixture is prepared;
  • Step 3) Preparation of the transparent conductive film: the surface clean PET substrate obtained in the step 1) is immersed in the nano silver wire mixture prepared in the step 2), and the PET base is repeatedly washed by distilled water at a temperature of 60 ° C for 120 minutes. The un-grafted polymer on the surface of the material was baked at 100 ° C for 60 min to obtain a PET/nano-silver transparent conductive film with a thickness of 50 nm.
  • Step 1) Decontamination of the surface of the PET substrate 100 ⁇ m optical grade double-sided hardened PET substrate with a protective film was washed with a mixed solvent of absolute ethanol/acetone volume ratio of 1, and then the surface of the PET substrate was rinsed with distilled water. a mixed solvent, vacuum dried at 80 ° C to obtain a surface clean PET substrate;
  • Step 2) Preparation of nano silver wire mixture: 0.5 g of silane coupling agent KH-590 was added to 0.08 mg/ml nano silver wire ethanol solution, and magnetic stirring was carried out at 60 ° C for 90 min to prepare a nano silver wire mixture. ;
  • Step 3) Preparation of the transparent conductive film: the surface clean PET substrate obtained in the step 1) is immersed in the nano silver wire mixture prepared in the step 2), and after repeatedly reacting for 150 minutes at a temperature of 40 ° C, the PET base is repeatedly washed with distilled water. The ungrafted polymer on the surface of the material is baked at 100 ° C for 60 min. A PET/nano-silver transparent conductive film having a thickness of 50 nm.
  • Step 1) Decontamination of the surface of the PET substrate 100 ⁇ m optical grade double-sided hardened PET substrate with a protective film was washed with a mixed solvent of absolute ethanol/acetone volume ratio of 1, and then the surface of the PET substrate was rinsed with distilled water. a mixed solvent, vacuum dried at 80 ° C to obtain a surface clean PET substrate;
  • Step 2) Preparation of the nano silver wire mixture: 1 g of the silane coupling agent KH-590 is added to a 0.3 mg/ml nano silver wire ethanol solution, and after magnetic stirring at 90 ° C for 60 min, a nano silver wire mixture is prepared;
  • Step 3) Preparation of the transparent conductive film: the surface clean PET substrate obtained in the step 1) is immersed in the nano silver wire mixture prepared in the step 2), and the PET base is repeatedly washed by distilled water at a temperature of 60 ° C for 120 minutes. The un-grafted polymer on the surface of the material was baked at 100 ° C for 60 min to obtain a PET/nano-silver transparent conductive film with a thickness of 50 nm.
  • Step 1) Decontamination of the surface of the PET substrate Wash the 125um optical grade double-sided hardened PET substrate with a protective film with a mixed solvent of absolute ethanol/acetone volume ratio of 1, and then rinse the surface of the PET substrate with distilled water. a mixed solvent, vacuum dried at 80 ° C to obtain a surface clean PET substrate;
  • Step 2) Preparation of nano silver wire mixture: 0.5 g of silane coupling agent KH-590 was added to 0.08 mg/ml nano silver wire ethanol solution, and magnetic stirring was carried out at 60 ° C for 90 min to prepare a nano silver wire mixture. ;
  • Step 3) Preparation of the transparent conductive film: the surface clean PET substrate obtained in the step 1) is immersed in the nano silver wire mixture prepared in the step 2), and after repeatedly reacting for 150 minutes at a temperature of 40 ° C, the PET base is repeatedly washed with distilled water. The un-grafted polymer on the surface of the material was baked at 100 ° C for 60 min to obtain a PET/nano-silver transparent conductive film with a thickness of 50 nm.
  • Step 1) Removing the surface of the PET substrate: Wash the 125um optical grade double-sided hardened PET substrate with a protective film with a mixed solvent of absolute ethanol/acetone volume ratio of 1, and then rinse the PET substrate with distilled water. a mixed solvent remaining on the surface, vacuum dried at 80 ° C to obtain a surface clean PET substrate;
  • Step 2) Preparation of the nano silver wire mixture: 3 g of the silane coupling agent KH-590 is added to the 2 mg/ml nano silver wire ethanol solution, and after magnetic stirring at 90 ° C for 60 min, a nano silver wire mixture is prepared;
  • Step 3) Preparation of transparent conductive film:
  • the surface clean PET substrate obtained in the step 1) is immersed in the nano silver wire mixture prepared in the step 2), and the PET base is repeatedly washed by distilled water at a temperature of 90 ° C for 120 minutes.
  • the un-grafted polymer on the surface of the material was baked at 90 ° C for 100 min to obtain a PET/nano-silver transparent conductive film with a thickness of 50 nm.
  • Step 1) Decontamination of the surface of the PET substrate Wash the 50 um optical grade double-sided hardened PET substrate with a protective film with a mixed solvent of absolute ethanol/acetone volume ratio of 1, and then rinse the surface of the PET substrate with distilled water. a mixed solvent, vacuum dried at 80 ° C to obtain a surface clean PET substrate;
  • Step 2) Preparation of nano silver wire transparent conductive film: directly immerse the surface clean PET substrate obtained in step 1) into a 0.3 mg/ml nano silver wire ethanol solution, immerse at 60 ° C for 180 min, rinse with distilled water and pass through the oven. The film was baked at a temperature of 100 ° C for 60 minutes to obtain a nano silver wire transparent conductive film having a thickness of 40 nm.
  • Step 1) Decontamination of the surface of the PET substrate 100 ⁇ m optical grade double-sided hardened PET substrate with a protective film was washed with a mixed solvent of absolute ethanol/acetone volume ratio of 1, and then the surface of the PET substrate was rinsed with distilled water. a mixed solvent, vacuum dried at 80 ° C to obtain a surface clean PET substrate;
  • Step 2) Preparation of nano silver wire transparent conductive film: directly immerse the surface clean PET substrate obtained in step 1) into a 0.3 mg/ml nano silver wire ethanol solution, immerse at 60 ° C for 180 min, rinse with distilled water and pass through the oven. The film was baked at a temperature of 100 ° C for 60 minutes to obtain a nano silver wire transparent conductive film having a thickness of 40 nm.
  • Step 1) Decontamination of the surface of the PET substrate Wash the 125um optical grade double-sided hardened PET substrate with a protective film with a mixed solvent of absolute ethanol/acetone volume ratio of 1, and then rinse the surface of the PET substrate with distilled water. a mixed solvent, vacuum dried at 80 ° C to obtain a surface clean PET substrate;
  • Step 2) Preparation of nano silver wire transparent conductive film: directly immerse the surface clean PET substrate obtained in step 1) into a 0.3 mg/ml nano silver wire ethanol solution, immerse at 60 ° C for 180 min, rinse with distilled water and pass through the oven. The film was baked at a temperature of 100 ° C for 60 minutes to obtain a nano silver wire transparent conductive film having a thickness of 40 nm.
  • Table 1 shows the performance indexes of the PET nano silver wire transparent conductive film modified by chemical grafting in each example:
  • the chemically graft modified PET nano silver wire transparent conductive film of the invention has strong adhesion and flex resistance, and has mild conditions and simple operation, and has high application value for the flexible electronic field.

Abstract

一种化学接枝改性的PET/纳米银线透明导电膜的制备方法，涉及柔性透明导电薄膜技术领域，该制备方法包括：PET基材选用经过双面硬化层处理的光学级镀膜PET，并采用丙酮与乙醇混合溶剂对PET基材进行处理、清洗、干燥备用；将0.1-10g偶联剂加入到浓度为0.01-10mg/ml的纳米银线乙醇溶液中，升温至30-150℃搅拌30-240min得到纳米银线混合液；将经表面除杂后的PET基材浸入到纳米银线混合液中，反应温度控制在30-120℃，时间30-180min，反应结束后，经蒸馏水反复冲洗，再在60-180℃烤箱烘烤30-240min，制备得到透明导电薄膜。该方法制备得到的PET/纳米银线透明导电薄膜附着力强，耐挠曲性得到提高，同时制备条件温和，操作简单，对于柔性电子领域具有很高的应用价值。

Description

一种化学接枝改性的PET/纳米银线透明导电膜的制备 技术领域
本发明涉及柔性透明导电薄膜技术领域，具体涉及一种化学接枝改性的PET/纳米银线透明导电膜的制备。
背景技术
透明导电薄膜是一种既具有导电性，又具有高透光性的薄膜，广泛应用于液晶显示、触控面板和太阳能电池等电子元器件领域。未来移动终端、可穿戴设备、智能家电等产品，对触摸面板有着强劲需求，同时随着触控面板大尺寸化、低价化，以及传统ITO薄膜不能应用于可弯曲面，导电性及透光率等本质问题不易克服等因素，众厂商纷纷开始研究ITO的替代品，包括纳米银线、金属网格、碳纳米管以及石墨烯等材料。从市场反应上来看，应用新材料技术生产的薄膜产品所占的比重在逐年提高。目前，石墨烯仍处于研发阶段，离量产还有很远的距离。碳纳米管工业化量产技术尚未完善，其制成的薄膜产品导电性还不能达到普通ITO薄膜的水平。金属网格技术制作的产品有不可克服的莫瑞干涉问题，应用受到限制。若要降低金属网格中金属的线宽，则需要更改制成工艺，成本会随之增加，而且会有易断线等问题。而纳米银线技术则是最有可能接近量产的新型材料。
纳米银线技术因制程工艺简单，可采用印刷制程快速生产大面积的触控面板，同时具有较小的弯曲半径，且在弯曲时电阻变化率较小，应用在具有柔性曲面显示的设备。现有的柔性曲面设备中用到的衬底材料多为聚对苯二甲酸乙二醇酯(PET)薄膜，PET大分子链结构规整，结晶度较高，且分子中无强极性基团，故其表面亲和性较差。目前主要采用的方法有表面涂覆法、表面氧化法、等离子体法、高能辐射、紫外光辐射等，但这均影响了PET的本体性能或无法达 到长期改性效果。可见，现有技术仍存在较大的缺陷。
发明内容
有鉴于此，有必要针对上述问题，提供一种既可以达到表面改性提高附着力的目的，又不会损坏基材的本体性能的化学接枝改性的PET/纳米银线透明导电膜的制备方法。
为实现上述目的，本发明采取以下技术方案：
本发明的化学接枝改性的PET/纳米银线透明导电膜的制备，包括：PET基材表面除杂、纳米银线混合液制备以及透明导电膜的制备；
所述PET基材表面除杂包括：PET基材选用经过双面硬化层处理的光学级镀膜PET，并采用丙酮与乙醇混合溶剂对PET基材进行处理、清洗、干燥备用；
所述纳米银线混合液制备包括：将0.1-10g偶联剂加入到浓度为0.01-10mg/ml的纳米银线乙醇溶液中，得到的偶联剂-纳米银线乙醇溶液升温至30-150℃搅拌30-240min得到纳米银线混合液；
透明导电膜的制备包括：将经表面除杂后的PET基材浸入到纳米银线混合液中，反应温度控制在30-120℃，时间30-180min，反应结束后，经蒸馏水反复冲洗，再在60-180℃烤箱烘烤30-240min，制备得到透明导电薄膜。
作为优选的，所述偶联剂加入量为0.1-5g，纳米银线乙醇溶液的浓度为0.01-5mg/ml。
作为优选的，所述偶联剂-纳米银线乙醇溶液升温至30-120℃搅拌30-150min。
作为优选的，所述透明导电膜的制备中，反应温度控制在30-100℃，时间30-150min；所述烤箱烘烤温度为60-120℃，时间为30-150min。
作为优选的，所述PET基材厚度为50um、100um、125um，并自带保护膜。
作为优选的，所述无水乙醇与丙酮体积比为1。
作为优选的，所述偶联剂为巯基硅烷偶联剂KH-580或巯基硅烷偶联剂 KH-590。
进一步的，所述偶联剂为巯基硅烷偶联剂KH-590。
本发明制备得到的透明导电薄膜厚度为50-600nm，优选为50-300nm。
与现有纳米银线透明导电薄膜技术相比，本发明的有益效果为：
本发明采用纳米银线取代纳米银颗粒作为薄膜导电材料分散于乙醇中，通过银线之间相互接触达到导电目的；
通过硅烷偶联剂一端的巯基与纳米银的配位作用使纳米银线表面化学修饰上偶联剂，同时偶联剂另一端的硅氧烷基与PET表面上的硬化层相结合，以化学键合的形式将纳米银线固定附着于PET表面，使制备的纳米银线透明导电薄膜的附着力得到大幅提高。
本发明的透明导电薄膜附着力强，耐挠曲性得到提高，同时条件温和，操作简单，对于柔性电子领域具有很高的应用价值。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明的技术方案作进一步清楚、完整地描述。需要说明的是，所描述的实施例仅仅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。
实施例1
步骤1)PET基材表面除杂：将带有保护膜的50um光学级双面硬化PET基材用无水乙醇/丙酮体积比为1的混合溶剂清洗后，再用蒸馏水冲洗PET基材表面残留的混合溶剂，80℃真空干燥后得到表面洁净的PET基材；
步骤2)纳米银线混合液的制备：将0.5g硅烷偶联剂KH-590加入到0.08mg/ml的纳米银线乙醇溶液中，得到的偶联剂-纳米银线乙醇溶液经60℃磁力搅拌 90min后，制备得到纳米银线混合液；
步骤3)透明导电膜的制备：将步骤1)得到的表面洁净的PET基材浸入到步骤2)制备的纳米银线混合液中，在温度40℃、反应150min后，经蒸馏水反复冲洗PET基材表面未接枝的聚合物，再经烤箱温度100℃下烘烤60min，得到厚度为50nm的PET/纳米银线透明导电薄膜。
实施例2
步骤1)PET基材表面除杂：将带有保护膜的50um光学级双面硬化PET基材用无水乙醇/丙酮体积比为1的混合溶剂清洗后，再用蒸馏水冲洗PET基材表面残留的混合溶剂，80℃真空干燥后得到表面洁净的PET基材；
步骤2)纳米银线混合液的制备：将1g硅烷偶联剂KH-590加入到0.3mg/ml的纳米银线乙醇溶液中，经90℃磁力搅拌60min后，制备得到纳米银线混合液；
步骤3)透明导电膜的制备：将步骤1)得到的表面洁净的PET基材浸入到步骤2)制备的纳米银线混合液中，在温度60℃、反应120min后，经蒸馏水反复冲洗PET基材表面未接枝的聚合物，再经烤箱温度100℃烘烤下60min，得到厚度为50nm的PET/纳米银线透明导电薄膜。
实施例3
步骤1)PET基材表面除杂：将带有保护膜的100um光学级双面硬化PET基材用无水乙醇/丙酮体积比为1的混合溶剂清洗后，再用蒸馏水冲洗PET基材表面残留的混合溶剂，80℃真空干燥后得到表面洁净的PET基材；
步骤2)纳米银线混合液的制备：将0.5g硅烷偶联剂KH-590加入到0.08mg/ml的纳米银线乙醇溶液中，经60℃磁力搅拌90min后，制备得到纳米银线混合液；
步骤3)透明导电膜的制备：将步骤1)得到的表面洁净的PET基材浸入到步骤2)制备的纳米银线混合液中，在温度40℃、反应150min后，经蒸馏水反复冲洗PET基材表面未接枝的聚合物，再经烤箱温度100℃下烘烤60min，得到 厚度为50nm的PET/纳米银线透明导电薄膜。
实施例4
步骤1)PET基材表面除杂：将带有保护膜的100um光学级双面硬化PET基材用无水乙醇/丙酮体积比为1的混合溶剂清洗后，再用蒸馏水冲洗PET基材表面残留的混合溶剂，80℃真空干燥后得到表面洁净的PET基材；
步骤2)纳米银线混合液的制备：将1g硅烷偶联剂KH-590加入到0.3mg/ml的纳米银线乙醇溶液中，经90℃磁力搅拌60min后，制备得到纳米银线混合液；
步骤3)透明导电膜的制备：将步骤1)得到的表面洁净的PET基材浸入到步骤2)制备的纳米银线混合液中，在温度60℃、反应120min后，经蒸馏水反复冲洗PET基材表面未接枝的聚合物，再经烤箱温度100℃烘烤下60min，得到厚度为50nm的PET/纳米银线透明导电薄膜。
实施例5
步骤1)PET基材表面除杂：将带有保护膜的125um光学级双面硬化PET基材用无水乙醇/丙酮体积比为1的混合溶剂清洗后，再用蒸馏水冲洗PET基材表面残留的混合溶剂，80℃真空干燥后得到表面洁净的PET基材；
步骤2)纳米银线混合液的制备：将0.5g硅烷偶联剂KH-590加入到0.08mg/ml的纳米银线乙醇溶液中，经60℃磁力搅拌90min后，制备得到纳米银线混合液；
步骤3)透明导电膜的制备：将步骤1)得到的表面洁净的PET基材浸入到步骤2)制备的纳米银线混合液中，在温度40℃、反应150min后，经蒸馏水反复冲洗PET基材表面未接枝的聚合物，再经烤箱温度100℃烘烤下60min，得到厚度为50nm的PET/纳米银线透明导电薄膜。
实施例6
步骤1)PET基材表面除杂：将带有保护膜的125um光学级双面硬化PET基材用无水乙醇/丙酮体积比为1的混合溶剂清洗后，再用蒸馏水冲洗PET基材 表面残留的混合溶剂，80℃真空干燥后得到表面洁净的PET基材；
步骤2)纳米银线混合液的制备：将3g硅烷偶联剂KH-590加入到2mg/ml的纳米银线乙醇溶液中，经90℃磁力搅拌60min后，制备得到纳米银线混合液；
步骤3)透明导电膜的制备：将步骤1)得到的表面洁净的PET基材浸入到步骤2)制备的纳米银线混合液中，在温度90℃、反应120min后，经蒸馏水反复冲洗PET基材表面未接枝的聚合物，再经烤箱温度90℃烘烤下100min，得到厚度为50nm的PET/纳米银线透明导电薄膜。
对比实施例1
步骤1)PET基材表面除杂：将带有保护膜的50um光学级双面硬化PET基材用无水乙醇/丙酮体积比为1的混合溶剂清洗后，再用蒸馏水冲洗PET基材表面残留的混合溶剂，80℃真空干燥后得到表面洁净的PET基材；
步骤2)纳米银线透明导电薄膜的制备：直接将步骤1)得到的表面洁净的PET基材浸入到0.3mg/ml的纳米银线乙醇溶液中，60℃浸渍180min，用蒸馏水冲洗后经烤箱温度100℃烘烤60min，得到厚度为40nm的纳米银线透明导电薄膜。
对比实施例2
步骤1)PET基材表面除杂：将带有保护膜的100um光学级双面硬化PET基材用无水乙醇/丙酮体积比为1的混合溶剂清洗后，再用蒸馏水冲洗PET基材表面残留的混合溶剂，80℃真空干燥后得到表面洁净的PET基材；
步骤2)纳米银线透明导电薄膜的制备：直接将步骤1)得到的表面洁净的PET基材浸入到0.3mg/ml的纳米银线乙醇溶液中，60℃浸渍180min，用蒸馏水冲洗后经烤箱温度100℃烘烤60min，得到厚度为40nm的纳米银线透明导电薄膜。
对比实施例3
步骤1)PET基材表面除杂：将带有保护膜的125um光学级双面硬化PET基材用无水乙醇/丙酮体积比为1的混合溶剂清洗后，再用蒸馏水冲洗PET基材表面残留的混合溶剂，80℃真空干燥后得到表面洁净的PET基材；
步骤2)纳米银线透明导电薄膜的制备：直接将步骤1)得到的表面洁净的PET基材浸入到0.3mg/ml的纳米银线乙醇溶液中，60℃浸渍180min，用蒸馏水冲洗后经烤箱温度100℃烘烤60min，得到厚度为40nm的纳米银线透明导电薄膜。
表1中为测定各实施例经化学接枝改性的PET纳米银线透明导电薄膜的各项性能指标：
表1 上述各实施例中纳米银线透明导电薄膜的性能
Figure PCTCN2017098060-appb-000001
从上表可知，本发明的经化学接枝改性PET纳米银线透明导电薄膜附着力强，耐挠曲性得到提高，同时条件温和，操作简单，对于柔性电子领域具有很高的应用价值。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (8)

  1. 一种化学接枝改性的PET/纳米银线透明导电膜的制备，其特征在于，包括：PET基材表面除杂、纳米银线混合液制备以及透明导电膜的制备；
    所述PET基材表面除杂包括：PET基材选用经过双面硬化层处理的光学级镀膜PET，并采用丙酮与乙醇混合溶剂对PET基材进行处理、清洗、干燥备用；
    所述纳米银线混合液制备包括：将0.1-10g偶联剂加入到浓度为0.01-10mg/ml的纳米银线乙醇溶液中，得到的偶联剂-纳米银线乙醇溶液升温至30-150℃搅拌30-240min得到纳米银线混合液；
    透明导电膜的制备包括：将经表面除杂后的PET基材浸入到纳米银线混合液中，反应温度控制在30-120℃，时间30-180min，反应结束后，经蒸馏水反复冲洗，再在60-180℃烤箱烘烤30-240min，制备得到透明导电薄膜。
  2. 根据权利要求1所述的化学接枝改性的PET/纳米银线透明导电膜的制备，其特征在于，所述偶联剂加入量为0.1-5g，纳米银线乙醇溶液的浓度为0.01-5mg/ml。
  3. 根据权利要求1所述的化学接枝改性的PET/纳米银线透明导电膜的制备，其特征在于，所述偶联剂-纳米银线乙醇溶液升温至30-120℃搅拌30-150min。
  4. 根据权利要求1所述的化学接枝改性的PET/纳米银线透明导电膜的制备，其特征在于，所述透明导电膜的制备中，反应温度控制在30-100℃，时间30-150min；所述烤箱烘烤温度为60-120℃，时间为30-150min。
  5. 根据权利要求1-4任意一项所述的化学接枝改性的PET/纳米银线透明导电膜的制备，其特征在于，所述PET基材厚度为50um、100um、125um，并自带保护膜。
  6. 根据权利要求1-4任意一项所述的化学接枝改性的PET/纳米银线透明导 电膜的制备，其特征在于，所述无水乙醇与丙酮体积比为1。
  7. 根据权利要求1-4任意一项所述的化学接枝改性的PET/纳米银线透明导电膜的制备，其特征在于，所述偶联剂为巯基硅烷偶联剂KH-580或巯基硅烷偶联剂KH-590。
  8. 根据权利要求7所述的化学接枝改性的PET/纳米银线透明导电膜的制备，其特征在于，所述偶联剂为巯基硅烷偶联剂KH-590。
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