WO2020133570A1 - 一种具有压电效应的透明导电膜及其制备方法 - Google Patents

一种具有压电效应的透明导电膜及其制备方法 Download PDF

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WO2020133570A1
WO2020133570A1 PCT/CN2019/070626 CN2019070626W WO2020133570A1 WO 2020133570 A1 WO2020133570 A1 WO 2020133570A1 CN 2019070626 W CN2019070626 W CN 2019070626W WO 2020133570 A1 WO2020133570 A1 WO 2020133570A1
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conductive film
transparent conductive
piezoelectric effect
coating
parts
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PCT/CN2019/070626
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English (en)
French (fr)
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陆华俊
曾西平
靳世东
李晓明
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深圳市华科创智技术有限公司
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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
    • 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

Definitions

  • the invention relates to the field of conductive materials, in particular to a transparent conductive film with piezoelectric effect and a preparation method thereof.
  • Piezoelectric effect means that when some dielectric is deformed by external force in a certain direction, polarization will occur inside it, and positive and negative charges will appear on its two opposite surfaces. When the external force is removed, it will return to the uncharged state. This phenomenon is called the positive piezoelectric effect. When the direction of the applied force changes, the polarity of the charge changes accordingly. Conversely, when an electric field is applied in the polarization direction of the dielectric, these dielectrics also deform. After the electric field is removed, the deformation of the dielectric disappears. This phenomenon is called the inverse piezoelectric effect. A type of sensor developed based on the dielectric piezoelectric effect is called a piezoelectric sensor.
  • piezoelectric film when you stretch or bend a piece of piezoelectric polyvinylidene fluoride PVDF (Poly (vinylidene fluoride)) polymer film (piezo film), a film will be produced between the upper and lower electrode surfaces of the film Electrical signal (charge or voltage), and proportional to the stretched or bent shape.
  • PVDF Poly (vinylidene fluoride)
  • General piezoelectric materials are sensitive to pressure, but for a piezoelectric film, when a small force is applied in the longitudinal direction, a large stress will be generated in the lateral direction, and if the same force is applied to a large area of the film, it will produce The stress will be much smaller.
  • the existing piezoelectric film is mostly made of polyvinylidene fluoride (PVDF), which has high resistance and is not resistant to bending, which limits its application range.
  • the present invention provides a transparent conductive film with a piezoelectric effect and a preparation method thereof.
  • the silver nanowire is used as a main raw material in combination with an ultra-thin base film material to prepare a bend resistant, low resistance value, having Transparent conductive film with piezoelectric effect.
  • a transparent conductive film having a piezoelectric effect includes a base film, a nano silver conductive layer and an OC (OVER COATING) protective layer which are sequentially coated on the surface of the base film; nano silver
  • the raw materials of the conductive layer include: silver nanowires, adhesives, leveling agents, surfactants, antioxidants, ultrapure water; the raw materials of the OC protective layer include: acrylic resin, photoinitiator, leveling agent, SiO 2 nano Particles, organic solvents.
  • the raw materials of the nano silver conductive layer include: silver nano wire 0.1-0.5wt%, adhesive 0.5-1.0wt%, leveling agent 0.1-0.5wt%, surfactant 0.05-0.1wt%, antioxidant 0.001 -0.005wt%, the balance is ultrapure water;
  • OC protective layer includes the following parts by weight of raw materials: acrylic resin 1-5 parts, photoinitiator 0.5-2 parts, leveling agent 0.1-0.5 parts, SiO 2 nanoparticles 0.01 -0.05 parts, 80-90 parts of organic solvent.
  • the diameter of the silver nanowire is 10-30 nm, and the aspect ratio is ⁇ 1000.
  • the thickness of the nano silver conductive layer is 20-35 ⁇ m, and the thickness of the OC protective layer is 5-12 ⁇ m.
  • the adhesive agent is one or more of cellulose acetate, cellulose propionate, cellulose acetate propionate, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose;
  • the leveling agent is Water-based leveling agent;
  • surfactant is one or more of polyvinylpyrrolidone, sodium benzenesulfonate and fluorosurfactant;
  • antioxidant is compound of phosphite antioxidant and phenolic antioxidant; acrylic acid
  • the resin is one or more of epoxy acrylic resin, polyurethane acrylic resin, polyester acrylic resin; photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2- Methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-acetone, 1-hydroxycyclohexylphenyl ketone, 2,4,6 (trimethyl One or more of benzoyl)diphenylphosphine oxide.
  • the transparent conductive film of the present invention uses silver nanowires as raw materials to prepare a conductive layer.
  • the silver nanowires can reduce the conductive resistance of the conductive film, improve wear resistance and bending properties; at the same time, an OC protective layer is coated on the conductive layer.
  • the conductive film of the present invention has a piezoelectric effect, and has strong bending resistance, and can withstand more than 200,000 bending times and 90° bending at a bending angle of 180°
  • the number of bending times is more than 5 million times under the folding angle, and the square resistance is low, the service life is long, and the application range of the conductive film with piezoelectric effect is improved.
  • Another aspect of the present invention provides a method for preparing a transparent conductive film having a piezoelectric effect, including the following steps: (1) silver nanowire 0.1-0.5wt%, adhesive 0.5-1.0wt%, leveling Agent 0.1-0.5wt%, surfactant 0.05-0.1wt%, antioxidant 0.001-0.005wt% and ultrapure water are added to the mixer to defoam and mix evenly to obtain the first mixture; (2) Acrylic resin 1- 5 parts, 0.5-2 parts of photoinitiator, 0.1-0.5 parts of leveling agent, 0.01-0.05 parts of SiO 2 nanoparticles, 80-90 parts of organic solvent, stirring and mixing to obtain the second mixture; (3) coating on the base film The first mixture is laid and baked and cured to obtain a nano-silver conductive layer; (4) The second mixture is coated on the nano-silver conductive layer and baked and cured to obtain a transparent conductive film.
  • the coating speed in step (3) is 8-12 m/min
  • the curing temperature is 100-150° C.
  • the curing time is 80-120 s.
  • the coating speed in step (4) is 2-6 m/min
  • the curing temperature is 100-150° C.
  • the curing time is 200-300 s.
  • UV (ultraviolet) curing is also included.
  • the ultraviolet light energy of UV curing is 4.0mW/cm 2 -6.0mW/cm 2
  • the curing time is 1-3s.
  • the raw materials of the conductive layer and the protective layer are mixed and coated on the surface of the base film in sequence, and a transparent conductive film with piezoelectric effect and bending resistance is obtained after curing.
  • the preparation method of the invention is simple, the film-forming process flow is simple, the equipment requirements are low, the film-forming efficiency is high, and it is favorable for large-area production.
  • the transparent conductive film includes a base film and a nano silver conductive layer and an OC protective layer coated on the surface of the base film in sequence; raw materials of the nano silver conductive layer include: silver nanowires, adhesion Agent, leveling agent, surfactant, antioxidant, ultrapure water; OC protective layer includes the following raw materials: acrylic resin, photoinitiator, leveling agent, SiO 2 nanoparticles, organic solvent.
  • the transparent conductive film of the present invention uses silver nanowires as raw materials to prepare a conductive layer.
  • the silver nanowires can reduce the conductive resistance of the conductive film, improve wear resistance and bending properties; at the same time, an OC protective layer is coated on the conductive layer.
  • the conductive film of the present invention has a piezoelectric effect, strong bending resistance, low square resistance, and long service life, and improves the application of the conductive film with piezoelectric effect range.
  • the raw material of the nano silver conductive layer includes: silver nanowire 0.1-0.5wt%, adhesive 0.5-1.0wt%, leveling agent 0.1-0.5wt%, surfactant 0.05-0.1 wt%, antioxidant 0.001-0.005wt%, the balance is ultrapure water;
  • OC protective layer includes the following parts by weight of raw materials: acrylic resin 1-5 parts, photoinitiator 0.5-2 parts, leveling agent 0.1-0.5 parts , SiO 2 nanoparticles 0.01-0.05 parts, organic solvent 80-90 parts.
  • the diameter of the silver nanowire is 10-30 nm, and the aspect ratio is ⁇ 1000.
  • the transparent conductive film based on silver nanowires has the characteristics of high transparency, high conductivity, low haze, low yellowness, and good bending resistance.
  • the thickness of the nano silver conductive layer is 20-35 ⁇ m, preferably, the thickness of the conductive layer is 25 ⁇ m; the thickness of the OC protective layer is 5-12 ⁇ m, preferably, the thickness of the protective layer is 9 ⁇ m.
  • the SiO 2 nanoparticles in the raw material of the OC protective layer are used as piezoelectric materials, so that the transparent conductive film of the present invention has the characteristics of a piezoelectric thin film, which replaces the conventional polyvinylidene fluoride piezoelectric film and is combined with silver nanowires to improve It overcomes the shortcomings of conventional piezoelectric film products, such as high resistance and resistance to bending, and improves the bending resistance of the conductive film.
  • the OC protective layer is coated on the nano-silver conductive layer to protect the conductive layer, and the piezoelectric material is evenly mixed in the raw material of the protective layer, so that the cured protective layer has pressure everywhere Electrical effect.
  • the adhesion agent is cellulose acetate, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate, methyl cellulose, hydroxyethyl cellulose, Ethyl cellulose, ethyl methyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, polyvinyl alcohol, polyurethane, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl One or more of cellulose and xanthan gum.
  • the addition of the adhesive improves the adhesion ability of the nano silver conductive layer to the surface of the base film.
  • the leveling agent is an aqueous leveling agent; preferably, the model of the leveling agent is BYK-333, BYK-371, BYK-349 of German BYK Company.
  • the leveling agent is added to make the film formation more uniform and natural when the conductive film is coated on the surface of the base film.
  • the surfactant is one or more of polyvinylpyrrolidone, sodium benzenesulfonate, and fluorosurfactant.
  • the addition of surfactant helps to improve the dispersibility of silver nanowires.
  • the antioxidant is a compound of phosphite antioxidant and phenolic antioxidant; preferably, the antioxidant is antioxidant 168 (tri [2.4-di-tert-butylphenyl] sulfoxide Phosphate esters) and phenolic antioxidants 1790 are compounded in a mass ratio of 1:3.
  • Antioxidant 168 is a phosphite antioxidant with excellent performance. It has strong extraction resistance, is stable to hydrolysis, and can significantly improve the light stability of the product. It can be fully used with phenolic oxidant 1790.
  • the phosphite in the component is an auxiliary antioxidant, which can not play a long-term stabilizing role, but after compounding with hindered phenol, a good compounding effect is obtained, which can be used in a variety of polymers.
  • the acrylic resin is one or more of epoxy acrylic resin, polyurethane acrylic resin, and polyester acrylic resin.
  • the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-methyl-2-(4-morpholinyl)-1-[4 -One or more of (methylthio) phenyl]-1-acetone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide.
  • the base film material includes polyethylene terephthalate, polyethylene naphthalate, cellulose ester, polyethylene acetal, acrylic, polycarbonate, and polybenzene Ethylene; preferably, the base film is an ultra-thin PET (polyethylene terephthalate) base film, which has an excellent optical index and temperature and weather resistance.
  • the organic solvent is an alcohol solvent, a ketone solvent, an ester solvent, and an ether solvent in a mass ratio of 1:1:1:1.
  • the alcohol solvent may be methanol, ethanol, propanol, butanol, etc.
  • the ketone solvent may be acetone, methyl ethyl ketone, methylpentanone, methyl isobutyl ketone, cyclohexanone, etc.
  • the ester solvent may be Ethyl acetate, butyl acetate, isopropyl acetate, etc.
  • ether solvents can be diethylene glycol monomethyl ether, propylene glycol methyl ether, dipropylene glycol dimethyl ether, diethylene glycol butyl ether, propylene glycol butyl ether, etc.
  • the invention also provides a method for preparing a transparent conductive film with piezoelectric effect, including the following steps:
  • Silver nanowire 0.1-0.5wt%, adhesive 0.5-1.0wt%, leveling agent 0.1-0.5wt%, surfactant 0.05-0.1wt%, antioxidant 0.001-0.005wt% and ultra-pure Add water to the mixer to defoam and mix evenly to obtain the first mixture;
  • the coating speed is 8-12 m/min
  • the curing temperature is 100-150° C.
  • the curing time is 80-120 s.
  • the coating speed is 10 m/min
  • the curing temperature is 120° C.
  • the curing time is 90 s.
  • the second mixture is coated on the nano silver conductive layer, and baked and cured to obtain a transparent conductive film.
  • the coating speed is 2-6 m/min
  • the curing temperature is 100-150° C.
  • the curing time is 200-300 s.
  • the coating speed is 4 m/min
  • the curing temperature is 120° C.
  • the curing time is 240 s.
  • UV curing is also included.
  • the UV light energy of UV curing is 4.0 mW/cm 2 -6.0 mW/cm 2
  • the curing time is 1-3 s.
  • the UV light energy of UV curing is 5mW/cm 2 and the curing time is 2s.
  • methods for coating the first mixture on the base film and coating the second mixture on the nano silver conductive layer include wire bar coating, dip coating, blade coating, curtain coating, slope Any one of flow coating, roll-to-roll slit coating, roll coating, micro concave coating, and micro convex coating.
  • the roll-to-roll slit coating method is adopted, which has the advantages of high coating precision, fast speed, easy control, and wide viscosity adaptability range.
  • the raw materials of the conductive layer and the protective layer are mixed and coated on the surface of the base film in sequence, and the transparent conductive film with piezoelectric effect and bending resistance is obtained by baking and curing.
  • the preparation method of the invention is simple, the film-forming process flow is simple, the equipment requirements are low, the film-forming efficiency is high, and it is favorable for large-area production.
  • the second mixture is coated on the nano silver conductive layer at a coating speed of 4m/min, and is baked and cured at a curing temperature of 120°C and a curing time of 220s, and then subjected to UV curing. /cm 2 , curing time 2s, to obtain a transparent conductive film.
  • the second mixture is coated on the nano silver conductive layer at a coating speed of 3m/min, and baked and cured at a curing temperature of 100°C and a curing time of 200s, and then subjected to UV curing, and the UV energy of UV curing is 6.0 mW/cm 2 , curing time 1s, to obtain a transparent conductive film.
  • the second mixture is coated on the nano silver conductive layer at a coating speed of 6 m/min, and baked and cured at a curing temperature of 150° C. and a curing time of 300 s to obtain a transparent conductive film.
  • Example 1-4 The transparent conductive film obtained in Example 1-4 and the piezoelectric thin film in Comparative Example 1-2 were tested for square resistance, transmittance, haze, and piezoelectric performance. The test results are shown in Table 1.
  • the repetitive bending machine model XHS-ZW-03A produced by Shenzhen Xinhengsen Instrument Equipment Co., Ltd. was used to test the touch modules prepared in the examples and comparative examples.
  • the test conditions were: the module to be tested One end of the group is clamped by a splint. One end of the splint is a semi-circular corner with a radius of 1mm, and the other end is clamped on the crankshaft. Under the drive of the motor, the module is repeatedly bent, the bending frequency is once per second, and the bending angles are respectively 90° and 180°, record the bending times and resistance change rate of different modules. The results are shown in Table 2 and Table 3.
  • the transparent conductive film with piezoelectric effect of the present invention has the advantages of low square resistance, high transmittance, and low haze, and its piezoelectric strain constant can reach that of existing piezoelectric films Piezoelectric strain constant value can replace the existing piezoelectric film materials; at the same time, it can withstand more than 200,000 bending times at 180° bending angle and more than 5 million bending times at 90° bending angle, It has good bending resistance and can effectively replace the existing polyvinylidene fluoride piezoelectric film.

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Abstract

本发明涉及导电材料领域，尤其涉及一种具有压电效应的透明导电膜及其制备方法。该透明导电膜包括基膜和依次涂布在基膜表面的纳米银导电层和OC保护层，纳米银导电层的原料包括银纳米线、粘附剂、流平剂、表面活性剂、抗氧化剂、超纯水；OC保护层包括丙烯酸树脂、光引发剂、流平剂、SiO 2纳米粒子、有机溶剂。本发明以银纳米线为原料制备导电层，银纳米线可降低导电膜的导电阻值，提高耐磨性和弯折性；同时在导电层上涂布OC保护层，有助于提高导电膜的透过率，且在OC保护层中添加SiO 2纳米粒子，使其具有压电效应。本发明的导电膜，具有压电效应的同时，其耐弯折能力强，且方阻低，使用寿命长。

Description

一种具有压电效应的透明导电膜及其制备方法
本公开基于申请号为201810943686.6，申请日为2018年12月27日的中国专利申请提出，并要求该中国专利申请的优先权，该中国专利申请的全部内容在此引入本申请作为参考。
技术领域
本发明涉及导电材料领域，尤其涉及一种具有压电效应的透明导电膜及其制备方法。
背景技术
压电效应是指某些电介质在沿一定方向上受到外力的作用而变形时，其内部会产生极化现象，同时在它的两个相对表面上出现正负相反的电荷。当外力去掉后，它又会恢复到不带电的状态，这种现象称为正压电效应。当作用力的方向改变时，电荷的极性也随之改变。相反，当在电介质的极化方向上施加电场，这些电介质也会发生变形，电场去掉后，电介质的变形随之消失，这种现象称为逆压电效应。依据电介质压电效应研制的一类传感器称为压电传感器。压电薄膜作为一种动态应变传感器，当你拉伸或弯曲一片压电聚偏氟乙烯PVDF(Poly(vinylidene fluoride))高分子膜(压电薄膜)，薄膜上下电极表面之间就会产生一个电信号(电荷或电压)，并且同拉伸或弯曲的形变成比例。一般的压电材料都对压力敏感，但对于压电薄膜来说，在纵向施加一个很小的力时，横向上会产生很大的应力，而如果对薄膜大面积施加同样的力时，产生的应力会小很多。现有的压电膜的原料多为聚偏氟乙烯(PVDF)，其阻值高、不耐弯折，限制了其应用范围。
发明内容
本发明针对以上技术问题，提供一种具有压电效应的透明导电膜及其制备方法，以银纳米线为主要原料，并结合超薄基膜材料，制备得到耐弯折、低阻 值、具有压电效应的透明导电膜。
在本发明的一个方面，提供一种具有压电效应的透明导电膜，该透明导电膜包括基膜和依次涂布在基膜表面的纳米银导电层和OC(OVER COATING)保护层；纳米银导电层的原料包括：银纳米线、粘附剂、流平剂、表面活性剂、抗氧化剂、超纯水；OC保护层的原料包括：丙烯酸树脂、光引发剂、流平剂、SiO 2纳米粒子、有机溶剂。
进一步的，纳米银导电层的原料包括：银纳米线0.1-0.5wt％，粘附剂0.5-1.0wt％，流平剂0.1-0.5wt％，表面活性剂0.05-0.1wt％，抗氧化剂0.001-0.005wt％，余量为超纯水；OC保护层包括以下重量份的原料：丙烯酸树脂1-5份，光引发剂0.5-2份，流平剂0.1-0.5份，SiO 2纳米粒子0.01-0.05份，有机溶剂80-90份。
进一步的，银纳米线的直径为10-30nm，长径比≥1000。
进一步的，纳米银导电层的厚度为20-35μm，OC保护层的厚度为5-12μm。
进一步的，粘附剂为醋酸纤维素、丙酸纤维素、醋酸丙酸纤维素、甲基纤维素、羟乙基纤维素、羧甲基纤维素中的一种或多种；流平剂为水性流平剂；表面活性剂为聚乙烯吡咯烷酮、苯磺酸钠和含氟表面活性剂中的一种或多种；抗氧化剂为亚磷酸酯抗氧剂和酚类抗氧剂复配；丙烯酸树脂为环氧类丙烯酸树脂、聚氨酯类丙烯酸树脂、聚酯类丙烯酸树脂中的一种或多种；光引发剂为2-羟基-2-甲基-1-苯基-1-丙酮、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮、1-羟基环己基苯基甲酮、2,4,6(三甲基苯甲酰基)二苯基氧化膦中的一种或多种。
本发明的透明导电膜，以银纳米线为原料制备得到导电层，银纳米线可降低导电膜的导电阻值，提高耐磨性和弯折性；同时在导电层上涂布OC保护层，保护纳米银导电层增加附着力，提高导电膜的透过率，在OC保护层中添加SiO 2纳米粒子，使其具有压电效应。本发明的导电膜，相对于聚偏氟乙烯压电膜，具有压电效应的同时，其耐弯折能力强，可承受180°弯折角度下20万次以上的弯折次数以及90°弯折角度下500万次以上的弯折次数，且方阻低，使用寿命长，提高了具有压电效应的导电膜的应用范围。
本发明的另一方面，提供一种具有压电效应的透明导电膜的制备方法，包括以下步骤：(1)将银纳米线0.1-0.5wt％、粘附剂0.5-1.0wt％、流平剂0.1-0.5wt％、 表面活性剂0.05-0.1wt％、抗氧化剂0.001-0.005wt％和超纯水加入到搅拌机中脱泡、混合均匀，得到第一混合物；(2)将丙烯酸树脂1-5份、光引发剂0.5-2份、流平剂0.1-0.5份、SiO 2纳米粒子0.01-0.05份、有机溶剂80-90份搅拌混合，得到第二混合物；(3)在基膜上涂布第一混合物，并烘烤固化，得到纳米银导电层；(4)在纳米银导电层上涂布第二混合物，并烘烤固化，得到透明导电膜。
进一步的，步骤(3)中的涂布速度为8-12m/min，固化温度100-150℃，固化时间80-120s。
进一步的，步骤(4)中的涂布速度为2-6m/min，固化温度100-150℃，固化时间200-300s。
进一步的，步骤(4)中烘烤固化后，还包括UV(ultraviolet)固化。
进一步的，UV固化的紫外光能量为4.0mW/cm 2-6.0mW/cm 2，固化时间1-3s。
本发明通过分别将导电层和保护层的原料混合、依次涂布在基膜表面，经固化得到具有压电效应的、耐弯折的透明导电膜。本发明的制备方法简单，成膜工艺流程简单、设备要求低，成膜效率高，有利于大面积生产。
具体实施方式
下面将结合具体实施例，对本发明的技术方案进行清楚、完整的描述，显然，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，本领域普通的技术人员在没有做出创造性劳动的前提下所获得的所有其它实施例，都属于本发明的保护范围。
一种具有压电效应的透明导电膜，该透明导电膜包括基膜和依次涂布在基膜表面的纳米银导电层和OC保护层；纳米银导电层的原料包括：银纳米线、粘附剂、流平剂、表面活性剂、抗氧化剂、超纯水；OC保护层包括以下原料：丙烯酸树脂、光引发剂、流平剂、SiO 2纳米粒子、有机溶剂。
本发明的透明导电膜，以银纳米线为原料制备得到导电层，银纳米线可降低导电膜的导电阻值，提高耐磨性和弯折性；同时在导电层上涂布OC保护层，保护纳米银导电层增加附着力，提高导电膜的透过率，在OC保护层中添加SiO 2纳米粒子，使其具有压电效应。本发明的导电膜，相对于聚偏氟乙烯压电膜，具有压电效应的同时，其耐弯折能力强，且方阻低，使用寿命长，提高了具有 压电效应的导电膜的应用范围。
在本发明的一些实施例中，纳米银导电层的原料包括：银纳米线0.1-0.5wt％，粘附剂0.5-1.0wt％，流平剂0.1-0.5wt％，表面活性剂0.05-0.1wt％，抗氧化剂0.001-0.005wt％，余量为超纯水；OC保护层包括以下重量份的原料：丙烯酸树脂1-5份，光引发剂0.5-2份，流平剂0.1-0.5份，SiO 2纳米粒子0.01-0.05份，有机溶剂80-90份。
在本发明的一些实施例中，银纳米线的直径为10-30nm，长径比≥1000。基于银纳米线的透明导电膜，具有透明度高、导电性高、雾度低、黄度低、耐弯曲性好等特性。
在本发明的一些实施例中，纳米银导电层的厚度为20-35μm，优选的，导电层厚度为25μm；OC保护层的厚度为5-12μm，优选的，保护层厚度为9μm。
OC保护层原料中的SiO 2纳米粒子作为压电材料，使得本发明的透明导电膜具有压电薄膜的特性，替代了常规的聚偏氟乙烯压电膜，且与银纳米线相结合，改善了常规的压电膜产品阻值高、不耐弯折的缺点，提高了导电膜的耐曲挠性。
OC保护层作为一种树脂薄膜，涂布在纳米银导电层上，起到对导电层的保护作用，且将压电材料均匀混合在保护层原料中，使得固化后的保护层各处具有压电效应。
在本发明的一些实施例中，粘附剂为醋酸纤维素、三醋酸纤维素、丙酸纤维素、醋酸丙酸纤维素、醋酸丁酸纤维素、甲基纤维素、羟乙基纤维素、乙基纤维素、乙基甲基纤维素、羟丙基纤维素、羟乙基甲基纤维素、聚乙烯醇、聚氨酯、羟丙基甲基纤维素、乙基羟乙基纤维素、羧甲基纤维素、黄原胶中的一种或多种。粘附剂的添加，提高了纳米银导电层与基膜表面的粘附能力。
在本发明的一些实施例中，流平剂为水性流平剂；优选的，流平剂的型号为德国毕克公司的BYK-333，BYK-371，BYK-349。添加流平剂，使得导电膜涂布在基膜表面时成膜更均匀、自然。
在本发明的一些实施例中，表面活性剂为聚乙烯吡咯烷酮、苯磺酸钠和含氟表面活性剂中的一种或多种。表面活性剂的添加有助于提高银纳米线的分散性。
在本发明的一些实施例中，抗氧化剂为亚磷酸酯抗氧剂和酚类抗氧剂复配；优选的，抗氧化剂为抗氧剂168(三[2.4-二叔丁基苯基]亚磷酸酯)和酚类抗氧剂1790按1:3的质量比复配得到。抗氧剂168是一种性能优异的亚磷酸酯抗氧剂，其抗萃取性强，对水解作用稳定，并能显著提高制品的光稳定性；与酚类氧化剂1790复配使用，可充分发挥协同效应，组分中的亚磷酸酯为辅助抗氧剂，不能起到长期稳定作用，但与受阻酚复配后，却获得了较好的复配效果，可用于多种聚合物中。
在本发明的一些实施例中，丙烯酸树脂为环氧类丙烯酸树脂、聚氨酯类丙烯酸树脂、聚酯类丙烯酸树脂中的一种或多种。
在本发明的一些实施例中，光引发剂为2-羟基-2-甲基-1-苯基-1-丙酮、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮、1-羟基环己基苯基甲酮、2,4,6(三甲基苯甲酰基)二苯基氧化膦中的一种或多种。
在本发明的一些实施例中，基膜材料包括聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、纤维素酯、聚乙烯乙缩醛、丙烯酸、聚碳酸酯和聚苯乙烯；优选的，基膜为超薄PET(polyethylene terephthalate，聚对苯二甲酸乙二醇酯)基膜，其具有优良的光学指数和耐温耐候性。
在本发明的一些实施例中，有机溶剂为醇类溶剂、酮类溶剂、酯类溶剂和醚类溶剂按照1:1:1:1的质量比混合而成。优选的，醇类溶剂可以为甲醇、乙醇、丙醇、丁醇等；酮类溶剂可以为丙酮、丁酮、甲戊酮、甲基异丁基酮及环己酮等；酯类溶剂可以为醋酸乙酯、醋酸丁酯及醋酸异丙酯等；醚类溶剂可以为二乙二醇单甲醚、丙二醇甲醚、二丙二醇二甲醚、二乙二醇丁醚、丙二醇丁醚等。
本发明还提供一种具有压电效应的透明导电膜的制备方法，包括以下步骤：
(1)将银纳米线0.1-0.5wt％、粘附剂0.5-1.0wt％、流平剂0.1-0.5wt％、表面活性剂0.05-0.1wt％、抗氧化剂0.001-0.005wt％和超纯水加入到搅拌机中脱泡、混合均匀，得到第一混合物；
(2)将丙烯酸树脂1-5份、光引发剂0.5-2份、流平剂0.1-0.5份、SiO 2纳米粒子0.01-0.05份、有机溶剂80-90份搅拌混合，得到第二混合物；
(3)在基膜上涂布第一混合物，并烘烤固化，得到纳米银导电层；
在本发明的一些实施例中，涂布速度为8-12m/min，固化温度100-150℃， 固化时间80-120s。优选的，涂布速度为10m/min，固化温度120℃，固化时间90s。
(4)在纳米银导电层上涂布第二混合物，并烘烤固化，得到透明导电膜。
在本发明的一些实施例中，涂布速度为2-6m/min，固化温度100-150℃，固化时间200-300s。优选的，涂布速度为4m/min，固化温度120℃，固化时间240s。
在本发明的一些实施例中，步骤(4)中烘烤固化后，还包括UV固化。在本发明的一些实施例中，UV固化的紫外光能量为4.0mW/cm 2-6.0mW/cm 2，固化时间1-3s。优选的，UV固化的紫外光能量为5mW/cm 2，固化时间2s。
在本发明的一些实施例中，在基膜上涂布第一混合物以及在纳米银导电层上涂布第二混合物的方法包括线棒式涂布、浸涂、刮刀涂布、幕涂、坡流涂布、卷对卷狭缝涂布、辊涂、微凹涂布、微凸涂布中的任意一种。优选的，采用卷对卷狭缝涂布方式，其具有涂布精度高、速度快、容易控制、粘度适应范围宽等优点。
本发明通过分别将导电层和保护层的原料混合、依次涂布在基膜表面，经烘烤固化得到具有压电效应的、耐弯折的透明导电膜。本发明的制备方法简单，成膜工艺流程简单、设备要求低，成膜效率高，有利于大面积生产。
下面将结合具体实施例对本发明的具有压电效应的透明导电膜及其制备方法作进一步描述。但这些实施例仅是描述性的，而不以任何形式限制本发明。
实施例1
一种具有压电效应的透明导电膜的制备方法，包括以下步骤：
(1)将银纳米线0.5wt％、粘附剂1.0wt％、水性流平剂BYK-333 0.5wt％、聚乙烯吡咯烷酮0.1wt％、抗氧化剂0.005wt％和超纯水97.895wt％加入到搅拌机中脱泡、混合均匀，得到第一混合物；
(2)将丙烯酸树脂5份、光引发剂1.8份、水性流平剂BYK-333 0.3份、SiO 2纳米粒子0.05份、有机溶剂90份搅拌混合，得到第二混合物；
(3)在PET基膜上涂布第一混合物，涂布速度为10m/min，并烘烤固化，固化温度120℃，固化时间100s，得到纳米银导电层；
(4)在纳米银导电层上涂布第二混合物，涂布速度为4m/min，并烘烤固化，固化温度120℃，固化时间220s，再进行UV固化，UV固化的紫外光能量为 5mW/cm 2，固化时间2s，得到透明导电膜。
实施例2
一种具有压电效应的透明导电膜的制备方法，包括以下步骤：
(1)将银纳米线0.4wt％、粘附剂0.8wt％、水性流平剂BYK-333 0.4wt％、苯磺酸钠0.08wt％、抗氧化剂0.004wt％和超纯水98.316wt％加入到搅拌机中脱泡、混合均匀，得到第一混合物；
(2)将丙烯酸树脂3份、光引发剂0.5份、水性流平剂BYK-333 0.1份、SiO 2纳米粒子0.03份、有机溶剂85份搅拌混合，得到第二混合物；
(3)在PET基膜上涂布第一混合物，涂布速度为8m/min，并烘烤固化，固化温度100℃，固化时间80s，得到纳米银导电层；
(4)在纳米银导电层上涂布第二混合物，涂布速度为3m/min，并烘烤固化，固化温度100℃，固化时间200s，再进行UV固化，UV固化的紫外光能量为6.0mW/cm 2，固化时间1s，得到透明导电膜。
实施例3
一种具有压电效应的透明导电膜的制备方法，包括以下步骤：
(1)将银纳米线0.3wt％、粘附剂0.5wt％、水性流平剂BYK-371 0.2wt％、聚乙烯吡咯烷酮0.06wt％、抗氧化剂0.003wt％和超纯水98.937wt％加入到搅拌机中脱泡、混合均匀，得到第一混合物；
(2)将丙烯酸树脂1份、光引发剂2份、水性流平剂BYK-371 0.5份、SiO 2纳米粒子0.01份、有机溶剂80份搅拌混合，得到第二混合物；
(3)在PET基膜上涂布第一混合物，涂布速度为12m/min，并烘烤固化，固化温度140℃，固化时间110s，得到纳米银导电层；
(4)在纳米银导电层上涂布第二混合物，涂布速度为2m/min，并烘烤固化，固化温度130℃，固化时间260s，再进行UV固化，UV固化的紫外光能量为4mW/cm 2，固化时间3s，得到透明导电膜。
实施例4
一种具有压电效应的透明导电膜的制备方法，包括以下步骤：
(1)将银纳米线0.1wt％、粘附剂0.5wt％、水性流平剂BYK-333 0.1wt％、苯磺酸钠0.05wt％、抗氧化剂0.001wt％和超纯水99.249wt％加入到搅拌机中脱 泡、混合均匀，得到第一混合物；
(2)将丙烯酸树脂4份、光引发剂1.5份、水性流平剂BYK-333 0.4份、SiO 2纳米粒子0.04份、有机溶剂86份搅拌混合，得到第二混合物；
(3)在PET基膜上涂布第一混合物，涂布速度为9m/min，并烘烤固化，固化温度150℃，固化时间120s，得到纳米银导电层；
(4)在纳米银导电层上涂布第二混合物，涂布速度为6m/min，并烘烤固化，固化温度150℃，固化时间300s，得到透明导电膜。
对比例1
将锦州科信电子材料有限公司生产的30μm厚的PVDF压电薄膜作为对比例1。
对比例2
将南京君弘新材料有限公司生产的25μm厚的PVDF压电薄膜作为对比例2。
将实施例1-4得到的透明导电膜及对比例1-2中的压电薄膜进行方阻、透过率、雾度及压电性能测试，测试结果见表1。
表1透明导电膜性能测试结果
Figure PCTCN2019070626-appb-000001
将实施例1-4和对比例1-2中的透明导电膜进行弯折性能测试，具体试验过程如下：
采用深圳市鑫恒森仪器设备有限公司生产的型号为XHS-ZW-03A的反复弯折机对各实施例和对比例制得的触控模组进行测试，试验条件为：将待测试的模组一端用夹板夹住，夹板一端是半径为1mm的半圆角，另一端夹在曲柄轴 上，在电机带动下，模组进行反复弯折，弯折频率为每秒一次，弯折角度分别为90°和180°，记录不同模组的弯折次数以及电阻变化率。结果如表2和表3所示。
表2透明导电膜的弯折测试结果
Figure PCTCN2019070626-appb-000002
表3透明导电膜的弯折测试结果
Figure PCTCN2019070626-appb-000003
由表1至表3可知，本发明的具有压电效应的透明导电膜，具有低方阻、高透过率、低雾度的优点，且其压电应变常数可达到现有压电薄膜的压电应变常数值，即可替代现有的压电薄膜材料；同时可承受180°弯折角度下20万次以上的弯折次数以及90°弯折角度下500万次以上的弯折次数，具有良好的耐曲挠性，可有效替代现有的聚偏氟乙烯压电薄膜。
以上借助具体实施例对本发明做了进一步描述，但是应该理解的是，这里具体的描述，不应理解为对本发明的实质和范围的限定，本领域内的普通技术 人员在阅读本说明书后对上述实施例做出的各种修改，都属于本发明所保护的范围。

Claims (14)

  1. 一种具有压电效应的透明导电膜，其特征在于，所述透明导电膜包括基膜和依次涂布在所述基膜表面的纳米银导电层和OC保护层；
    所述纳米银导电层的原料包括：银纳米线、粘附剂、流平剂、表面活性剂、抗氧化剂、超纯水；
    所述OC保护层的原料包括：丙烯酸树脂、光引发剂、流平剂、SiO 2纳米粒子、有机溶剂。
  2. 根据权利要求1所述的具有压电效应的透明导电膜，其特征在于：
    所述纳米银导电层的原料包括：银纳米线0.1-0.5wt％，粘附剂0.5-1.0wt％，流平剂0.1-0.5wt％，表面活性剂0.05-0.1wt％，抗氧化剂0.001-0.005wt％，余量为超纯水；
    所述OC保护层包括以下重量份的原料：丙烯酸树脂1-5份，光引发剂0.5-2份，流平剂0.1-0.5份，SiO 2纳米粒子0.01-0.05份，有机溶剂80-90份。
  3. 根据权利要求1或2所述的具有压电效应的透明导电膜，其特征在于，所述银纳米线的直径为10-30nm，长径比≥1000。
  4. 根据权利要求1-3中任一项所述的具有压电效应的透明导电膜，其特征在于，所述纳米银导电层的厚度为20-35μm，所述OC保护层的厚度为5-12μm。
  5. 根据权利要求1或2所述的具有压电效应的透明导电膜，其特征在于：
    所述粘附剂为醋酸纤维素、丙酸纤维素、醋酸丙酸纤维素、甲基纤维素、羟乙基纤维素、羧甲基纤维素中的一种或多种；
    所述流平剂为水性流平剂；
    所述表面活性剂为聚乙烯吡咯烷酮、苯磺酸钠和含氟表面活性剂中的一种或多种；
    所述抗氧化剂为亚磷酸酯抗氧剂和酚类抗氧剂复配；
    所述丙烯酸树脂为环氧类丙烯酸树脂、聚氨酯类丙烯酸树脂、聚酯类丙烯酸树脂中的一种或多种；
    所述光引发剂为2-羟基-2-甲基-1-苯基-1-丙酮、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮、1-羟基环己基苯基甲酮、2,4,6(三甲基苯甲酰基)二苯基氧化膦中的一种或多种。
  6. 根据权利要求1或2所述的具有压电效应的透明导电膜，其特征在于，所述基膜的材料为聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、纤维素酯、聚乙烯乙缩醛、丙烯酸、聚碳酸酯和聚苯乙烯中任意一种。
  7. 根据权利要求1或2所述的具有压电效应的透明导电膜，其特征在于，所述有机溶剂为醇类溶剂、酮类溶剂、酯类溶剂和醚类溶剂按照1:1:1:1的质量比混合而成。
  8. 根据权利要求7所述的具有压电效应的透明导电膜，其特征在于，所述醇类溶剂为甲醇、乙醇、丙醇、丁醇中任一种；酮类溶剂为丙酮、丁酮、甲戊酮、甲基异丁基酮及环己酮中任一种；酯类溶剂为醋酸乙酯、醋酸丁酯及醋酸异丙酯中任一种；醚类溶剂为二乙二醇单甲醚、丙二醇甲醚、二丙二醇二甲醚、二乙二醇丁醚、丙二醇丁醚中任一种。
  9. 一种如权利要求1-8中任一项所述的具有压电效应的透明导电膜的制备方法，其特征在于，包括以下步骤：
    (1)将银纳米线0.1-0.5wt％、粘附剂0.5-1.0wt％、流平剂0.1-0.5wt％、表面活性剂0.05-0.1wt％、抗氧化剂0.001-0.005wt％和超纯水加入到搅拌机中脱泡、混合均匀，得到第一混合物；
    (2)将丙烯酸树脂1-5份、光引发剂0.5-2份、流平剂0.1-0.5份、SiO 2纳米粒子0.01-0.05份、有机溶剂80-90份搅拌混合，得到第二混合物；
    (3)在所述基膜上涂布所述第一混合物，并烘烤固化，得到纳米银导电层；
    (4)在所述纳米银导电层上涂布所述第二混合物，并烘烤固化，得到OC保护层，即得透明导电膜。
  10. 根据权利要求9所述的具有压电效应的透明导电膜的制备方法，其特征在于，步骤(3)中的涂布速度为8-12m/min，固化温度100-150℃，固化时间80-120s。
  11. 根据权利要求9所述的具有压电效应的透明导电膜的制备方法，其特征在于，步骤(4)中的涂布速度为2-6m/min，固化温度100-150℃，固化时间200-300s。
  12. 根据权利要求9所述的具有压电效应的透明导电膜的制备方法，其特征在于，步骤(4)中烘烤固化后，还包括UV固化。
  13. 根据权利要求12所述的具有压电效应的透明导电膜的制备方法，其特征 在于，UV固化的紫外光能量为4.0mW/cm 2-6.0mW/cm 2，固化时间1-3s。
  14. 根据权利要求9所述的具有压电效应的透明导电膜的制备方法，其特征在于，所述第一混合物在基膜上的涂布方法和所述第二混合物在纳米银导电层上的涂布方法为线棒式涂布、浸涂、刮刀涂布、幕涂、坡流涂布、卷对卷狭缝涂布、辊涂、微凹涂布、微凸涂布中的任意一种。
PCT/CN2019/070626 2018-12-27 2019-01-07 一种具有压电效应的透明导电膜及其制备方法 WO2020133570A1 (zh)

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