EP4225837A1 - Film conducteur transparent et son utilisation - Google Patents

Film conducteur transparent et son utilisation

Info

Publication number
EP4225837A1
EP4225837A1 EP21782636.1A EP21782636A EP4225837A1 EP 4225837 A1 EP4225837 A1 EP 4225837A1 EP 21782636 A EP21782636 A EP 21782636A EP 4225837 A1 EP4225837 A1 EP 4225837A1
Authority
EP
European Patent Office
Prior art keywords
transparent
conductive film
layer
conductive
full
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21782636.1A
Other languages
German (de)
English (en)
Inventor
Christoph HUNGER
Kerstin GOTTSCHLING
Daniel Lenssen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Giesecke and Devrient Currency Technology GmbH
Original Assignee
Giesecke and Devrient Currency Technology GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Giesecke and Devrient Currency Technology GmbH filed Critical Giesecke and Devrient Currency Technology GmbH
Publication of EP4225837A1 publication Critical patent/EP4225837A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the invention relates to a transparent, conductive film and uses thereof.
  • Transparent, conductive films that are suitable, for example, for equipping the windshield of a vehicle have been described in the prior art, see, for example, EP 2764996 B1, EP 2284134 B1 and WO 2016/192858 A1.
  • a transparent, conductive film is produced on the basis of a multi-stage process in which a washable coating is first applied to a transparent carrier substrate and, when it dries, forms numerous cracks in the form of a dense, cohesive network. This is followed by metal sputtering, followed by removal of the cracked, washable coating in a washing step.
  • the product obtained is such that it has a transparent, conductive metallization in the form of a densely meshed, coherent network above the carrier substrate.
  • Transparent, conductive film comprising a transparent substrate, on the main surface of which a conductive metallization in the form of a densely meshed, coherent network with a large number of openings of different geometric shape is formed, the transparent, conductive film additionally having is provided with a full-surface, transparent, IR-radiation reflecting layer.
  • Transparent, conductive film according to paragraph 1 wherein the full-area, transparent, IR radiation-reflecting layer is arranged between the transparent substrate and the conductive metallization in the form of a densely meshed, coherent network.
  • Transparent, conductive film according to paragraph 1 wherein the full-area, transparent, IR-radiation-reflecting layer is arranged on the side of the transparent substrate opposite the conductive metallization in the form of a dense-meshed, cohesive net.
  • ITO indium tin oxide
  • AZO aluminum-doped zinc oxide
  • GZO Gallium-doped zinc oxide
  • Transparent, conductive film according to one of paragraphs 1 to 10, wherein the transparent, conductive film has two separate, full-surface, transparent, IR radiation-reflecting layers, each on the top and on the bottom of the conductive Metallization are arranged in the form of a dense, cohesive network.
  • the present invention is based on the technology known from WO 2016/192858 A1 for the fine structuring of metallizations, on the basis of which electrical devices, e.g. films for use in the windshield of a vehicle, can be provided.
  • the technology includes the use of a crack-forming coating, preferably a dispersion or solution of a polymer.
  • the crack-forming coating is applied to the transparent substrate, e.g. by means of printing, so that a thin film is produced which forms cracks in the form of a dense-meshed, coherent network during drying. This is followed by metal sputtering, followed by removal of the cracked, washable coating in a washing step.
  • the product obtained is such that it has, above the transparent substrate, a transparent, conductive metallization in the form of a close-meshed, coherent network.
  • the present invention is based on the finding that an IR-reflecting function of a transparent, conductive film based on a metal network can be achieved by additionally providing the film with a full-area, transparent, IR-radiation-reflecting layer. This is done in particular by means of a thin vapor-deposited and therefore optically transparent metal layer, by optically transparent metal oxides such as indium tin oxide (ITO), aluminum-doped zinc oxide (AZO) or gallium-doped zinc oxide (GZO), or by a combination of a thin metal layer and metal oxide layer.
  • ITO indium tin oxide
  • AZO aluminum-doped zinc oxide
  • GZO gallium-doped zinc oxide
  • a transparent, conductive film based on a metal network is provided with an electrically conductive, full-area, transparent layer that reflects IR radiation, a particularly advantageous electrical conductivity of the metal network can be achieved.
  • the electrically conductive, full-surface, transparent layer ensures full-surface conductivity, while the metal network as the backbone ensures low surface resistance.
  • Such a film is of particular advantage for various applications, for example with regard to the provision of transparent, conductive electrodes for organic photovoltaics and light-emitting diodes, as well as smart windows based on electrochromic and liquid-crystalline materials.
  • a uniform substrate is advantageous in order to ensure that crack formation is always the same.
  • An electrically conductive, full-surface, transparent layer offers just such a uniform substrate, because crack formation is not always the same when different substrates are used, so that the formulation of the crack template would have to be adapted for the respective specific substrate.
  • An additional advantage can be achieved in that, in the case of special, full-area, transparent layers, a neutral color impression with low reflection can be brought about. In this way, the visually disturbing, reddish color impression of the metal can be avoided, particularly in the case of copper-based metal networks.
  • the production of the products according to the invention can be carried out in a technically simple manner because the additional layers can be applied over the entire area above and/or below the metal network.
  • the full-area, transparent, IR-radiation-reflecting layer is arranged between the transparent substrate and the conductive metallization in the form of a close-meshed, cohesive network.
  • the conductive metallization is arranged in the form of a close-meshed, cohesive network between the transparent substrate and the full-area, transparent, IR-radiation-reflecting layer.
  • the full-area, transparent, IR-radiation-reflecting layer is arranged on the side of the transparent substrate opposite the conductive metallization in the form of a densely meshed, cohesive net.
  • the full-area, transparent, IR-radiation-reflecting layer is electrically conductive
  • a transparent, conductive film with particularly high electrical conductivity can be achieved in that the conductive metallization in the form of a dense, cohesive network and the electrically conductive, full-area , transparent, IR radiation-reflecting layer are electrically conductively connected to each other.
  • the conductive metallization is embedded in an electrically insulating filling material in the form of a densely meshed, coherent network.
  • a metal layer or a metal oxide layer in particular indium tin oxide (ITO) or aluminum-doped zinc oxide (AZO) or gallium-doped zinc oxide (GZO), or a combination of a metal layer and a metal oxide layer.
  • ITO indium tin oxide
  • AZO aluminum-doped zinc oxide
  • GZO gallium-doped zinc oxide
  • the metal is preferably selected from the group consisting of aluminum, chromium, silver and an alloy comprising one or more of the above elements.
  • a material selected from the group consisting of a metal or an alloy, preferably chromium, aluminum, nickel, iron, silicon, titanium or a combination of two or more, is particularly suitable for achieving the advantageous effect of reducing the visual perceptibility of the metallic network of the above-mentioned elements, a metal oxide layer, preferably chromium oxide or a metal oxide layer based on copper oxide or a substoichiometric aluminum oxide, an antireflective thin-layer structure with in particular the layer sequence metal/dielectric/metal (e.g. a Cu/SiCb/Cr structure) or the layer sequence
  • dielectric/ metal/ dielectric/ metal e.g. a SiCh/Cr/SiCh/ Al structure, a SiCL/ Cr/SiCb/ Cu structure or a SiCb/ Al/SiCL/ Cu structure
  • black chrome ie black passivated chrome
  • black nickel ie black passivated nickel
  • a metal sulfide layer an overprint based on a colored lacquer or a pigmented lacquer, an overprint formed by a nanostructuring or moth's eye structure antireflection layer and a combination of two or more of the above elements.
  • Antireflective thin film structures are known in the art, see for example Sang-Hwan Cho et al., Journal of the Korean Physical Society, Vol. 2 Aug 2009, 501-507.
  • Thin-film elements with a multi-layer structure with a dark-appearing nanostructured area (so-called
  • An antireflection layer formed by nanostructuring is based in particular on a metal, e.g. Cu, a metal oxide, a nitride, a polymer or on a dielectric.
  • the structure according to the invention can also be provided with a transparent coating that levels the layer structure, e.g. a UV-curing or heat-curing primer lacquer.
  • the product thus obtained can then be provided with an adhesive layer, which is arranged, for example, on the side of the transparent substrate opposite the layer structure.
  • the adhesive layer can alternatively be placed over the transparent leveling coating.
  • a heat-seal lacquer for example, is suitable as an adhesive layer.
  • the adhesive layer used e.g. a heat-sealing lacquer, can be identical to the transparent coating used for leveling the layer structure.
  • the transparent substrate is in particular a glass substrate or a plastic film, eg a polyethylene terephthalate (PET) film.
  • PET polyethylene terephthalate
  • the conductive metallization is preferably chosen from a copper, gold, aluminum or silver layer.
  • the production of the products according to the invention is based on the production described in WO 2016/192858 A1.
  • a dispersion more preferably a colloidal dispersion, is preferably used as the crack-forming coating.
  • Particularly suitable are e.g conducting electrode based on highly interconnected Cu wire network", J. Mater. Chem. C, 2014, Volume 2, pages 2089-2094. See also the document US 10626279 B2.
  • the crack-forming coating on a solution present The polymer solution is applied to the substrate, e.g. by printing, so that a thin polymer film is produced. The thin polymer film forms cracks during drying.
  • the line widths that can be achieved at the end of the manufacturing process are in the range from 0.5 ⁇ m to 50 ⁇ m, with the lines usually being so fine that they can only be recognized as lines when a magnifying glass is used.
  • the human eye does not resolve the individual lines on the surface, but you can see one in reflected light (or reflection) as well as in transmitted light (or transmission). Difference compared to the untreated or bare film. Because the fine lines form an irregular, connected network, unwanted diffraction effects can be minimized.
  • the reflectance or the light transmittance can be adjusted in a suitable manner.
  • the method of removing the cracked coating is advantageously by dissolving with a suitable solvent.
  • the solvent is expediently selected in coordination with the coating.
  • the following solvents can be used: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methoxypropyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methylene chloride, chloroform, toluene, xylene, methanol, ethanol, 2-propanol.
  • acetals or mixtures of the aforementioned solvents can be used.
  • the crack-forming coating can also be detached by infiltration.
  • aqueous solutions mixtures of solvents and water, optionally with surfactants, optionally with defoamers and other additives.
  • the detachment or dissolution of the cracked coating can also be assisted by spray nozzles or else mechanically by brushes, rollers or by felts.
  • the metallization according to the invention in the form of a densely-meshed, cohesive network exhibits an electrical conductivity and an optical transmission which is comparable to a full-area ITO layer.
  • the fine metallic lines can be used in combination with conventional embossing lacquers, conventional primer compositions and conventional heat-sealing lacquers and act as a reflector.
  • Another aspect of the present invention is the use of the transparent, conductive film, e.g. as a heating film, in particular in the windshield of a vehicle, in other windows or in the glazing of buildings, and for coupling in electricity without visible leads, e.g. for use in EED films, in Solar cells, in smart glass applications, in OEEDs or in touch panels.
  • FIG. 1 shows a transparent, conductive film according to a first exemplary embodiment in plan view
  • FIG. 2 shows the transparent, conductive film according to the first exemplary embodiment in a cross-sectional view
  • FIG. 3 shows a transparent, conductive film according to a second exemplary embodiment in a cross-sectional view
  • FIG. 4 shows a transparent, conductive film according to a third exemplary embodiment in a cross-sectional view
  • FIG. 5 shows a transparent, conductive film according to a fourth exemplary embodiment in a cross-sectional view
  • FIG. 6 shows a transparent, conductive film according to a fifth exemplary embodiment in a cross-sectional view
  • FIG. 7 shows a transparent, conductive film according to a sixth exemplary embodiment in a cross-sectional view
  • FIG. 8 shows a transparent, conductive film according to a seventh exemplary embodiment in a cross-sectional view
  • FIG. 9 shows a transparent, conductive film according to an eighth exemplary embodiment in a cross-sectional view.
  • FIG. 1 illustrates a transparent, conductive film 1 according to a first exemplary embodiment in a plan view.
  • a transparent, conductive, copper-based metallization can be seen in the form of a densely meshed, coherent network.
  • FIG. 2 shows the transparent conductive film 1 according to the first embodiment in a cross-sectional view (along the dashed line A-A′ shown in FIG. 1).
  • the film 1 is based on a transparent substrate 2, in the present case a polyethylene terephthalate (PET) film, which is provided with a full-surface, IR-reflecting layer 3 made of indium tin oxide (ITO) with a thickness in a range from 50 nm to 300 nm .
  • ITO indium tin oxide
  • Above the full-area, IR-reflecting layer is a copper-based metallization 4 in the form of a dense, cohesive network.
  • the metallization 4 is produced in accordance with WO 2016/192858 A1 known methods.
  • the IR-reflecting layer 3 is first provided with a crack-forming coating, which is based, for example, on dispersions of SiCh nanoparticles or of acrylic resin nanoparticles.
  • the crack-forming coating is preferably applied by printing, for example by means of gravure printing, flexographic printing or by means of an inkjet process. When drying, the crack-forming coating develops numerous cracks in the form of a dense, coherent network.
  • a conductive Cu layer is vapor-deposited, which is deposited both above the cracked coating and within the cracks in the coating.
  • the cracked coating, including the Cu layers above the coating is then removed in a washing step. Washing is done by dissolving with a suitable solvent, eg methyl acetate.
  • the transparent, conductive film 1 is particularly advantageous as a result of its IR-reflecting function and is suitable, for example, for use in window glass in the automotive sector, in order to prevent the vehicle interior from heating up.
  • FIG. 3 shows a transparent, conductive film 5 according to a second exemplary embodiment in a cross-sectional view.
  • the transparent substrate 2 ie the polyethylene terephthalate (PET) film
  • PET polyethylene terephthalate
  • the IR-reflecting layer 3 is a thin Ag layer with a thickness ⁇ m Range from 1 nm to 20 nm, which, in addition to its IR-reflecting function, also ensures full-surface conductivity.
  • the metal network 4 has a low sheet resistance.
  • the transparent, conductive film 5 is advantageous if an IR-reflecting function is desired, but no direct contact of the IR-reflecting layer with the dense, cohesive network.
  • FIG. 4 shows a transparent, conductive film 6 according to a third exemplary embodiment in a cross-sectional view.
  • the transparent substrate 2 i.e. the polyethylene terephthalate (PET) film
  • PET polyethylene terephthalate
  • the IR-reflecting layer 3 is a thin Ag layer which, in addition to its IR-reflecting function, also ensures full-area conductivity and is also in electrically conductive contact with the metal network 4 .
  • FIG. 5 shows a transparent, conductive film 7 according to a fourth exemplary embodiment in a cross-sectional view.
  • the transparent substrate 2 ie the polyethylene terephthalate (PET) film
  • PET polyethylene terephthalate
  • the IR-reflecting layer 3 is a thin Ag layer which, in addition to its IR-reflecting function, also ensures full-area conductivity.
  • the transparent, conductive film 7 is therefore particularly advantageous for special electronic applications in addition to its IR-reflecting function.
  • Figures 6 to 9 each illustrate a fifth, sixth, seventh and eighth embodiment, in which the transparent, conductive film 9, 12, 13 and 14 each have a first transparent substrate 2, on whose main surface a conductive metallization 4 in the form a densely meshed, cohesive network with a large number of openings of different geometric shapes, and has a second transparent substrate 10, the main surface of which is provided with a full-surface, transparent, IR radiation-reflecting layer 3, the first substrate 2 and the second substrate 10 are connected to one another by means of an adhesive layer 11 .
  • the production of the transparent, conductive film 9, 12, 13, 14 starting from two separate film elements by means of gluing simplifies the manufacturing process and allows the manufacturer freedom of design.
  • the transparent, conductive film 9, 12, 13, 14 in the respective fifth, sixth, seventh and eighth exemplary embodiment is based on the first, second, third and fourth exemplary embodiments described above with regard to the material selection of the components 2, 3 and 4.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

L'invention concerne un film conducteur transparent comprenant un substrat transparent, une métallisation conductrice étant formée sur sa surface principale sous la forme d'un réseau serré continu présentant une pluralité d'ouvertures de formes géométriques différentes, le film conducteur transparent étant en outre pourvu d'un revêtement transparent pleine surface réfléchissant le rayonnement IR.
EP21782636.1A 2020-10-06 2021-09-21 Film conducteur transparent et son utilisation Pending EP4225837A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102020006108.7A DE102020006108A1 (de) 2020-10-06 2020-10-06 Transparente, leitfähige Folie und Verwendung derselben
PCT/EP2021/025355 WO2022073632A1 (fr) 2020-10-06 2021-09-21 Film conducteur transparent et son utilisation

Publications (1)

Publication Number Publication Date
EP4225837A1 true EP4225837A1 (fr) 2023-08-16

Family

ID=77998940

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21782636.1A Pending EP4225837A1 (fr) 2020-10-06 2021-09-21 Film conducteur transparent et son utilisation

Country Status (5)

Country Link
US (1) US20230374651A1 (fr)
EP (1) EP4225837A1 (fr)
CN (1) CN116368176A (fr)
DE (1) DE102020006108A1 (fr)
WO (1) WO2022073632A1 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5021842B2 (ja) 2008-06-13 2012-09-12 エルジー・ケム・リミテッド 発熱体およびその製造方法
DE102010050895A1 (de) 2010-11-10 2012-05-10 Giesecke & Devrient Gmbh Dünnschichtelement mit Mehrschichtstruktur
JP5809117B2 (ja) 2011-10-05 2015-11-10 富士フイルム株式会社 導電シート、タッチパネル、表示装置
WO2014136039A1 (fr) 2013-03-05 2014-09-12 Jawaharlal Nehru Centre For Advanced Scientific Research Composition, substrats et procédés associés
DE102015007238B4 (de) 2015-06-05 2017-06-22 Giesecke & Devrient Gmbh Verfahren zum Herstellen einer optoelektronischen Vorrichtung

Also Published As

Publication number Publication date
CN116368176A (zh) 2023-06-30
US20230374651A1 (en) 2023-11-23
DE102020006108A1 (de) 2022-04-07
WO2022073632A1 (fr) 2022-04-14

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