WO2022020975A1 - Film composite conducteur transparent résistant à la flexion et son procédé de fabrication - Google Patents

Film composite conducteur transparent résistant à la flexion et son procédé de fabrication Download PDF

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Publication number
WO2022020975A1
WO2022020975A1 PCT/CN2020/000179 CN2020000179W WO2022020975A1 WO 2022020975 A1 WO2022020975 A1 WO 2022020975A1 CN 2020000179 W CN2020000179 W CN 2020000179W WO 2022020975 A1 WO2022020975 A1 WO 2022020975A1
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WO
WIPO (PCT)
Prior art keywords
transparent conductive
film
bending
mound
polymer layer
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Application number
PCT/CN2020/000179
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English (en)
Chinese (zh)
Inventor
张汉焱
沈奕
冯兆昌
郑丹旭
吕岳敏
欧建平
Original Assignee
汕头超声显示器技术有限公司
汕头超声显示器（二厂）有限公司
汕头超声显示器有限公司
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Application filed by 汕头超声显示器技术有限公司, 汕头超声显示器（二厂）有限公司, 汕头超声显示器有限公司 filed Critical 汕头超声显示器技术有限公司
Publication of WO2022020975A1 publication Critical patent/WO2022020975A1/fr

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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
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • 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

Definitions

  • the invention relates to a transparent conductive composite film, in particular to a bending-resistant transparent conductive composite film and a manufacturing method thereof.
  • Transparent conductive films are generally used as transparent electrodes on touch displays (such as touch screens, displays).
  • touch displays such as touch screens, displays.
  • touch display can also be made flexible, and thus the transparent conductive film as its transparent electrode is required to have bending resistance.
  • the traditional transparent conductive films are mostly transparent conductive oxide films such as indium tin oxide (ITO) and zinc aluminum oxide (AZO).
  • ITO indium tin oxide
  • AZO zinc aluminum oxide
  • ITO indium tin oxide
  • ITO indium tin oxide
  • AZO zinc aluminum oxide
  • non-transparent conductive oxide films such as metal mesh and nano-silver wire film as a bending-resistant transparent conductive film, which generally has good bending resistance.
  • these non-transparent conductive oxide films The transparency, conductivity or uniformity of oxide films are generally poor, and when they are applied to touch displays, the performance of the touch displays is often degraded.
  • the technical problem to be solved by the present invention is to provide a bending-resistant transparent conductive composite film and a manufacturing method thereof.
  • the transparent conductive composite film has good bending resistance and can also maintain good transparency, conductivity and uniformity.
  • the bending-resistant transparent conductive composite film includes a transparent conductive film arranged on a flexible support film, the transparent conductive film is a transparent conductive oxide film plated on the flexible support film, and is characterized in that: it also includes a polymer layer; the The transparent conductive film includes a film base and a large number of mound-shaped protrusions evenly distributed on the film base; the polymer layer is arranged on the transparent conductive film, and the polymer layer includes a large number of polymer chains, and at least part of the polymer chains surround the The mound-shaped bulge forms the binding structure of the mound-shaped bulge.
  • the mound-shaped protrusions are evenly distributed on the film substrate, and the mound-shaped protrusions are surrounded by a large number of polymer chains to form a confinement structure of the mound-shaped protrusions; using this structure makes the transparent conductive composite film.
  • the confinement structure of the mound-shaped protrusions can play a supporting and tightening role, tightening the transparent conductive composite film, avoiding the rupture of the transparent conductive composite film, and effectively maintaining the conductivity of the transparent conductive composite film.
  • the flexible support film usually adopts glass sheet, plastic film, polyimide plastic film or colorless polyimide plastic film.
  • the glass sheet is usually a sheet with a thickness of less than 0.2mm.
  • the polyimide plastic film has good high temperature resistance (high temperature facilitates the film formation and crystallization of the transparent conductive film), and the colorless polyimide plastic film can ensure transparency.
  • the transparent conductive film is a thin film made of indium tin oxide (ITO), zinc aluminum oxide (AZO), indium gallium zinc oxide (IGZO) or other transparent conductive oxides.
  • the thickness of the transparent conductive film is 10-100 nm, and in a specific solution, the thickness of the transparent conductive film is 20-60 nm. The use of such a thickness of the transparent conductive film can reduce the internal stress of the film when it is subjected to bending under the condition of ensuring the conductive performance of the film.
  • the mound-shaped protrusions when the mound-shaped protrusions are coated, the mound-shaped protrusions are naturally generated on the surface of the transparent conductive film through the control of coating parameters.
  • the mound-shaped protrusions are the outwardly extending parts of the columnar crystals embedded in the film substrate.
  • a magnetron sputtering deposition process can be used to form the transparent conductive film, based on magnetron sputtering.
  • the film formation mechanism of the sputtered island crystal growth makes the transparent conductive film a polycrystalline structure composed of columnar crystals, and the consistency of the growth rate of each columnar crystal is reduced by increasing the sputtering power, so that the final growth rate is higher.
  • Some columnar crystals form hill-like protrusions on the surface of the transparent conductive film.
  • the mound-shaped protrusion is the outward extension of the columnar crystal embedded in the film matrix, that is to say, the mound-shaped protrusion has a root embedded in the film matrix, and the combination with the film matrix is tighter.
  • the force of the polymer chains can be effectively transferred into the film matrix, which makes the transparent conductive composite film more tough.
  • the mound-shaped protrusions are formed by roughening a process after the transparent conductive film is formed.
  • the mound-shaped protrusions are formed by etching the surface of the transparent conductive film with an etching solution after the transparent conductive film is fabricated. Since the crystallinity of different regions of the transparent conductive film (such as the center and edge of the crystal grains that constitute the polycrystalline film) is inconsistent, the etching speed is also inconsistent, and the position where the etching is slower (such as the center of the crystal grain) forms a mound-shaped protrusion. In other words, the mound-shaped protrusions formed by etching can also form a structure in which the roots are embedded in the film substrate.
  • the above-mentioned etching solution can be diluted aqua regia or the like.
  • the height of the mound-shaped protrusion is 20%-50% of the substrate of the transparent conductive film.
  • the height of the mound-shaped protrusion can be controlled by process adjustment (such as coating power, etching time).
  • the height of the mound-shaped protrusion is 20%-50% of the transparent conductive film substrate, so that the polymer chain can The protrusions form a restraining structure.
  • the polymer layer is a polymer coating, and the polymer layer is formed by polymerizing or cross-linking monomer molecules on the surface of the transparent conductive film.
  • the polymer coating is made of materials with good elasticity and toughness (such as polyethylene, polypropylene, polyamide, polyimide, etc.), and the polymer coating generally contains a large number of polymer chains;
  • the monomer molecules used to form the polymer chain can be placed on the surface of the transparent conductive film by means of evaporation, solution coating, etc., and then the polymerization reaction is initiated to form the polymer layer.
  • the permeability is good, and it easily penetrates into the gaps between the mound-shaped protrusions, and then polymerization can effectively form a polymer chain that binds the mound-shaped protrusions.
  • the polymer layer has a preset tensile stress.
  • the polymer layer maintains a certain tension state between the mound-shaped protrusions, so that when the composite film is subjected to bending, the polymer layer can adapt to the bending change of the composite film more quickly, so as to maintain the toughness of the composite film during the bending process. Avoid cracking of the transparent conductive film.
  • the polymer chain is formed by light-initiated polymerization or cross-linking reaction, and the light-initiated polymerization or cross-linking reaction can generally make the formed polymer chain in a tensioned state, and finally in the polymer layer.
  • a preset tensile stress is formed.
  • the polymer layer is a polyacrylic acid film formed by photo-initiated polymerization or cross-linking reaction. Polyacrylic films are capable of forming significant tensile stress.
  • the polymer chain length of the polymer layer is increased by optimizing the components and/or the polymerization process, so that in the polymer layer, at least part of the polymer chain length is increased.
  • the polymer chains together form a binding structure around two adjacent mound-like protrusions.
  • the polymer chains together form an "8"-shaped binding structure around two adjacent hill-shaped projections.
  • the above structure can bind the adjacent mound-shaped protrusions, improve the overall toughness of the composite film, and further increase its bending resistance.
  • the thickness of the polymer layer only needs to be made equal to the height of the mound-shaped protrusions, so that the toughness and bending resistance of the transparent conductive composite film can be improved.
  • the polymer layer can also be made thicker, such as a thick coating of 1 ⁇ m to 10 ⁇ m, the bottom of which is in contact with the transparent conductive film also has the above-mentioned polymer chains surrounding the hill-shaped protrusions to form a bond. structure.
  • a manufacturing method of a bending-resistant transparent conductive composite film characterized in that it comprises the following steps:
  • Step (1) disposing a transparent conductive oxide film on the flexible support film, and distributing a large number of mound-shaped protrusions on the surface of the transparent conductive oxide film;
  • step (2) a polymer layer is arranged on the transparent conductive oxide film, and at least part of the polymer chain of the polymer layer is formed around the mound-shaped protrusion to form a binding structure.
  • the mound-shaped protrusions are the outwardly extending parts of the columnar crystals embedded in the film substrate.
  • a magnetron sputtering deposition process can be used to form the transparent conductive Film, based on the film-forming mechanism of magnetron sputtering island crystal growth, the transparent conductive film is finally a polycrystalline structure composed of columnar crystals, and the consistency of the growth rate of each columnar crystal is reduced by increasing the sputtering power, so that the Finally, some columnar crystals with higher growth rate form hill-shaped protrusions on the surface of the transparent conductive film.
  • the mound-shaped protrusions are formed by etching the surface of the transparent conductive film with an etching solution after the transparent conductive film is fabricated.
  • the etching solution can be diluted aqua regia.
  • the method for forming the polymer chain surrounding the mound-shaped protrusion is to use monomer molecules on the surface of the transparent conductive film by photo-induced polymerization or cross-linking reaction to form a polymer chain.
  • the beneficial effect of the present invention is that: a large number of mound-shaped protrusions are arranged on the surface of the transparent conductive oxide thin film of the transparent conductive film, and then a polymer layer is arranged on the transparent conductive film, so that the polymer chains surround the mound-shaped protrusions When the transparent conductive composite film is bent, the polymer chains bound on the mound-shaped protrusions can tighten the transparent conductive film and prevent it from cracking. The conductivity of the transparent conductive film is effectively maintained. Therefore, this transparent conductive composite film not only has good bending resistance, but also its conductive layer is a transparent conductive oxide film, which has the good transparency, conductivity and uniformity of a general transparent conductive oxide film.
  • Example 1 is a cross-sectional view of a transparent conductive composite film in Example 1 of the present invention.
  • Example 2 is a schematic diagram of the transparent conductive film and the polymer layer of the transparent conductive composite film in Example 1 of the present invention.
  • the bending-resistant transparent conductive composite film shown in FIG. 1-2 includes a transparent conductive film 2 and a polymer layer 3 disposed on the flexible support film 1 , and the transparent conductive film 2 is a transparent conductive film plated on the flexible support film 1 .
  • the thickness of the transparent conductive film 2 was 10 nm.
  • the height of the hill-shaped protrusions 202 is 20% of the transparent conductive film substrate 201 .
  • the polymer layer 3 is a polymer coating.
  • step (1) a transparent conductive oxide film is arranged on the flexible support film 1, and a large number of mound-shaped protrusions 202 are distributed on the surface of the transparent conductive oxide film;
  • a polymer layer 3 is arranged on the transparent conductive oxide film, and part of the polymer chains 301 of the polymer layer 3 surrounds the mound-shaped protrusion 202 to form a monocyclic binding structure 302; part of the polymer chains 301 surrounds together Two adjacent mound-shaped protrusions 202 form an encircling confinement structure 303 ; part of the polymer chains 301 jointly surround the two adjacent mound-shaped protrusions 202 to form an “8”-shaped confinement structure 304 .
  • the mound-shaped protrusions 202 are the outwardly extending portions of the columnar crystals 203 embedded in the film substrate 201 , and the transparent conductive film 2 is formed by a magnetron sputtering deposition process. , based on the film-forming mechanism of the island crystal growth by magnetron sputtering, the transparent conductive film 2 is finally a polycrystalline structure composed of columnar crystals 203, and the consistency of the growth rate of each columnar crystal 203 is reduced by increasing the sputtering power , so that some columnar crystals 203 with a higher final growth rate form hill-shaped protrusions 202 on the surface of the transparent conductive film 2 .
  • the method for forming the polymer chains 301 surrounding the mound-shaped protrusions 202 is to use monomer molecules to form polymer chains on the surface of the transparent conductive film 2 by light-induced polymerization or cross-linking reaction 301.
  • the difference is that the mound-shaped protrusions are formed by etching the surface of the transparent conductive film with an etchant after the transparent conductive film is fabricated. Since the crystallinity of different regions of the transparent conductive film (such as the center and edge of the crystal grains that constitute the polycrystalline film) is inconsistent, the etching speed is also inconsistent, and the position where the etching is slower (such as the center of the crystal grain) forms a mound-shaped protrusion, which The hill-like protrusions formed by etching can also form a structure in which the roots are embedded in the film substrate.
  • the above-mentioned etching solution can be diluted aqua regia or the like.
  • the difference is that the thickness of the transparent conductive film is 100 nm.
  • the difference is that the height of the mound-shaped protrusion is 50% of the substrate of the transparent conductive film.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Non-Insulated Conductors (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un film composite conducteur transparent résistant à la flexion et son procédé de fabrication. Le film composite conducteur transparent résistant à la flexion comprend un film conducteur transparent disposé sur un film de support flexible et une couche de polymère. Le film conducteur transparent est un film mince d'oxyde conducteur transparent plaqué sur le film de support flexible ; le film conducteur transparent comprend un substrat de film mince et un grand nombre de saillies en forme de côte réparties uniformément sur le substrat de film mince ; et la couche de polymère est disposée sur le film conducteur transparent et comprend un grand nombre de chaînes de polymères, et au moins certaines des chaînes de polymère entourent les saillies en forme de côte pour former des structures de liaison de saillie en forme de côte. Le film composite conducteur transparent présente une bonne résistance à la flexion, et peut conserver une bonne transparence, une bonne conductivité et une bonne uniformité.
PCT/CN2020/000179 2020-05-25 2020-08-10 Film composite conducteur transparent résistant à la flexion et son procédé de fabrication WO2022020975A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN202010449502 2020-05-25
CN202010752092.4A CN111681806B (zh) 2020-05-25 2020-07-30 一种耐弯曲的透明导电复合膜及其制造方法
CN202010752092.4 2020-07-30

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101842854A (zh) * 2007-10-31 2010-09-22 住友金属矿山株式会社 柔性透明导电膜及使用柔性透明导电膜的柔性功能性元件
CN102157223A (zh) * 2010-02-12 2011-08-17 联享光电股份有限公司 透明导电叠层体及其制造方法
JP2014092584A (ja) * 2012-10-31 2014-05-19 Dainippon Printing Co Ltd 反射防止性透明導電フィルム、タッチパネル及び画像表示装置
CN105895262A (zh) * 2016-03-30 2016-08-24 武汉光谷创元电子有限公司 透明导电薄膜及其制造方法
CN107230514A (zh) * 2016-03-23 2017-10-03 张家港康得新光电材料有限公司 柔性导电膜

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005243492A (ja) * 2004-02-27 2005-09-08 Toyobo Co Ltd イオン伝導膜
JP4653443B2 (ja) * 2004-08-20 2011-03-16 株式会社東芝 高電圧機器用樹脂組成物、絶縁材料及び絶縁構造体
CN103985434B (zh) * 2014-05-05 2016-09-21 清华大学深圳研究生院 一种透明导电膜的制造方法及透明导电膜
CN107610802B (zh) * 2016-07-11 2019-08-30 中国科学院上海高等研究院 透明导电薄膜、光电器件及其制作方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101842854A (zh) * 2007-10-31 2010-09-22 住友金属矿山株式会社 柔性透明导电膜及使用柔性透明导电膜的柔性功能性元件
CN102157223A (zh) * 2010-02-12 2011-08-17 联享光电股份有限公司 透明导电叠层体及其制造方法
JP2014092584A (ja) * 2012-10-31 2014-05-19 Dainippon Printing Co Ltd 反射防止性透明導電フィルム、タッチパネル及び画像表示装置
CN107230514A (zh) * 2016-03-23 2017-10-03 张家港康得新光电材料有限公司 柔性导电膜
CN105895262A (zh) * 2016-03-30 2016-08-24 武汉光谷创元电子有限公司 透明导电薄膜及其制造方法

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CN111681806A (zh) 2020-09-18

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