WO2024258130A1 - Élément chauffant plan, article le comprenant et procédé de fabrication d'élément chauffant plan - Google Patents

Élément chauffant plan, article le comprenant et procédé de fabrication d'élément chauffant plan Download PDF

Info

Publication number
WO2024258130A1
WO2024258130A1 PCT/KR2024/007890 KR2024007890W WO2024258130A1 WO 2024258130 A1 WO2024258130 A1 WO 2024258130A1 KR 2024007890 W KR2024007890 W KR 2024007890W WO 2024258130 A1 WO2024258130 A1 WO 2024258130A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
heating element
conductive oxide
hard coating
oxide layer
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.)
Ceased
Application number
PCT/KR2024/007890
Other languages
English (en)
Korean (ko)
Inventor
방금혁
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.)
Toray Advanced Materials Korea Inc
Original Assignee
Toray Advanced Materials Korea Inc
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 Toray Advanced Materials Korea Inc filed Critical Toray Advanced Materials Korea Inc
Publication of WO2024258130A1 publication Critical patent/WO2024258130A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional [2D] plane, e.g. plate-heater
    • H05B3/22—Heating elements having extended surface area substantially in a two-dimensional [2D] plane, e.g. plate-heater non-flexible
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • 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
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/02—Details
    • H05B3/03—Electrodes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/146—Conductive polymers, e.g. polyethylene, thermoplastics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/013—Heaters using resistive films or coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/017—Manufacturing methods or apparatus for heaters

Definitions

  • the present disclosure relates to a surface heating element, an article including the same, and a method for manufacturing the surface heating element.
  • Surface heating elements are structures that generate radiant heat by voltage.
  • Surface heating elements are not only pollution-free and energy-efficient, but also operate with low noise, and are used in various fields such as automobile windshields, refrigerator front display cases, smart glass, bathroom mirrors, and industrial heating.
  • a planar heater is manufactured by forming a layer by applying a conductive material to one side of an insulating substrate, and operates by applying voltage to generate heat.
  • conductive materials used include graphene, Ag nanowires, metal mesh, and ITO (indium tin oxide).
  • ITO indium tin oxide
  • One aspect is to provide a novel structural planar heating element that satisfies all of the characteristics of improved transmittance, excellent heat generation efficiency even under low voltage, stable corrosion resistance even under high temperature and humid environments, low curl height, and no thermal wrinkle generation.
  • Another aspect is to provide an article comprising the above surface heating element.
  • Another aspect is to provide a method for manufacturing the above-mentioned surface heating element.
  • a hard coating layer positioned on the upper part of the above substrate
  • a first conductive oxide layer positioned on top of the hard coating layer
  • a metal layer positioned on top of the first conductive oxide layer
  • a surface heating element comprising: an electrode layer arranged to be in contact with the substrate, the hard coating layer, the first conductive oxide layer, the metal layer, and the second conductive oxide layer.
  • the above hard coating layer may include at least one resin selected from an acrylate-based resin, a thiol-based resin, a urethane-based resin, and an epoxy-based resin.
  • the thickness of the above hard coating layer may be 0.1 ⁇ m to 5 ⁇ m.
  • the above metal layer can be a metal selected from Ag, Au, Pt, Al, Cu, Cr, V, Mg, Ti, Sn, Pb, Pd, W or an alloy thereof.
  • the first conductive oxide layer and the second conductive oxide layer may be oxides selected from zinc tin oxide (ZTO), indium gallium zinc oxide (IGZO), zinc aluminum oxide (ZAO), indium zinc oxide (IZO), zinc oxide (ZnO), and combinations thereof.
  • ZTO zinc tin oxide
  • IGZO indium gallium zinc oxide
  • ZAO zinc aluminum oxide
  • IZO indium zinc oxide
  • ZnO zinc oxide
  • the thicknesses of the first conductive oxide layer and the second conductive oxide layer may each be less than 30 nm to 100 nm.
  • the above substrate is a transparent substrate and may have a thickness of 50 ⁇ m to 200 ⁇ m.
  • the surface resistance at room temperature can be less than 20 ⁇ / ⁇ .
  • A is the surface resistance ( ⁇ / ⁇ ) before being left for 360 hours at 85°C and 85% relative humidity
  • B is the surface resistance ( ⁇ / ⁇ ) after being left at 85°C and 85% relative humidity for 360 hours.
  • the visible light transmittance may be greater than 60% and the haze may be less than 1.1.
  • a method for manufacturing a surface heating element comprising: a step of arranging an electrode layer so as to be in contact with the substrate, the hard coating layer, the first conductive oxide layer, the metal layer, and the second conductive oxide layer.
  • a planar heater according to one aspect has corrosion resistance with no change in surface resistance even under a high temperature and high humidity environment, including a hard coating layer between a substrate and a first conductive oxide layer.
  • the planar heater has excellent heat generation efficiency even under a low voltage, including a metal layer between the first conductive oxide layer and the second conductive oxide layer .
  • the planar heater has high visible light transmittance, low haze, low average curl height, and no thermal wrinkles. Therefore, articles including the planar heater can be widely used in various fields.
  • Figure 1 is a cross-sectional schematic diagram of a structure included in a surface heating element according to one embodiment.
  • Figure 2 is a cross-sectional schematic diagram of a surface heating element according to one embodiment.
  • a method of forming a metal layer by directly sputtering a metal such as Ag onto one surface of a substrate uses a substrate with high roughness, a metal such as Ag is grown as is on the substrate with high roughness to form a metal layer with high roughness.
  • the conductive oxide layer laminated on the metal layer with high roughness has a reduced film quality and fails to perform the role of a corrosion-preventive film, so that the metal layer can easily corrode when used at high temperatures for a long time.
  • there is a method of changing the type of material of the conductive oxide layer laminated on the metal layer is changed. However, even if the type of material of the conductive oxide layer is changed, it is difficult to improve the performance of the corrosion-preventive film due to the high roughness of the conductive oxide layer.
  • the inventors of the present invention propose a novel surface heating element having a structure, an article including the same, and a method for manufacturing the surface heating element.
  • a planar heater includes: a substrate; a hard coating layer positioned on an upper portion of the substrate; a first conductive oxide layer positioned on an upper portion of the hard coating layer; a metal layer positioned on an upper portion of the first conductive oxide layer; a second conductive oxide layer positioned on an upper portion of the metal layer; and an electrode layer positioned to be in contact with the substrate, the hard coating layer, the first conductive oxide layer, the metal layer, and the second conductive oxide layer.
  • the planar heater has the hard coating layer positioned between the substrate and the first conductive oxide layer, the first conductive oxide layer, the metal layer, and the second conductive oxide layer can be planarized, thereby providing stable corrosion resistance even when used for a long time in a high-temperature and high-humidity environment. Since the planar heater has the metal layer positioned between the first conductive oxide layer and the second conductive oxide layer, the planar heater can have excellent heat generation efficiency even under improved transmittance and low voltage. At the same time, the planar heater structure has the characteristics of low curl height and no thermal wrinkles.
  • Fig. 1 is a cross-sectional schematic diagram of a structure included in a surface heating element according to one embodiment.
  • Fig. 2 is a cross-sectional schematic diagram of a surface heating element according to one embodiment.
  • a structure (100) included in a surface heating element is a structure in which a substrate (11), a hard coating layer (21), a first conductive oxide layer (31), a metal layer (41), and a second conductive oxide layer (51) are sequentially laminated.
  • a surface heating element (100') according to one embodiment shows an electrode layer (61) formed by connecting upper and lower ends of both ends so as to be in contact with each layer of the structure of FIG. 1.
  • the substrate (11) may be a film or a sheet.
  • the substrate (11) may be a film.
  • the substrate (11) may use a film with excellent heat resistance that can withstand high temperatures.
  • the substrate (11) may use a transparent substrate.
  • the substrate (11) may be a transparent polymer film.
  • Examples of the substrate (11) may include, but are not limited to, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyarylate, polycarbonate, polyetherimide, polyamideimide, polyimide, or polybenzoxazole.
  • the substrate (11) may be a single layer. Alternatively, the substrate (11) may be a multilayer structure of two or more layers. When the substrate (11) is a multilayer structure of two or more layers, the polymer materials constituting each layer may be the same or different materials.
  • the thickness of the substrate (11) may be 50 ⁇ m to 200 ⁇ m. If the thickness of the substrate (11) is less than 50 ⁇ m, thermal wrinkles may occur during the sputtering process, which may deteriorate the bonding properties. If the thickness of the substrate (11) is more than 200 ⁇ m, the bonding properties may deteriorate due to high stiffness during bonding.
  • the stiffness of the substrate (11) may be 5 N/mm to 81 N/mm.
  • the substrate (11) may undergo surface treatment such as plasma treatment or corona treatment to improve adhesion with the hard coating layer (21).
  • the hard coating layer (21) serves to planarize the first conductive oxide layer (31), the metal layer (41), and the second conductive oxide layer (51).
  • the hard coating layer (21) may include one or more types of resin selected from acrylate-based resins, thiol-based resins, urethane-based resins, and epoxy-based resins.
  • Acrylate resins include (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, silicone (meth)acrylate, etc., either singly or in combination of two or more.
  • polyfunctional (meth)acrylates include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerol tri(meth)acrylate, and triallyl (meth)acrylate.
  • the polyfunctional (meth)acrylate may contain an ethylene oxide (EO) or propylene oxide (PO) addition type polyfunctional (meth)acrylate.
  • the addition type polyfunctional (meth)acrylate is a compound obtained by esterifying an ethylene oxide (EO) or propylene oxide (PO) addition type polyhydric alcohol with acrylic acid. Examples thereof include EO or PO modified glycerol triacrylate, EO or PO modified trimethylolpropane acrylate, EO or PO modified pentaerythritol tetraacrylate, EO or PO modified dipentaerythritol hexaacrylate, and the like.
  • the content of adding EO or PO is in the range of 5 to 20 mol per 1 mol of the polyfunctional (meth)acrylate, appropriate flexibility can be imparted to the hard coating layer (21).
  • the thiol resin may be, for example, a polyfunctional thio(meth)acrylate resin.
  • the polyfunctional thio(meth)acrylate resin can be obtained by adding a polyfunctional thiol compound, a hydroxy-containing ethylenically unsaturated compound, and an isocyanate group-containing (meth)acrylate compound.
  • the polyfunctional thiol compound is not limited as long as it is a compound containing two or more thiol groups (-SH) at the terminal.
  • hydroxy-containing ethylenically unsaturated compounds examples of which may be used alone or in combination of two or more include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, polyethylene glycol-propylene glycol mono (meth)acrylate, polyethylene glycol-tetramethylene glycol mono (meth)acrylate, polypropylene glycol-polybutylene glycol mono (meth)acrylate, polycaprolactone mono (meth)acrylate, hydroxyethyl vinyl ether, and diethylene glycol monovinyl ether, but are not limited thereto.
  • (meth)acrylate compounds containing an isocyanate group include, but are not limited to, 2-isocyanateethyl (meth)acrylate, 3-isocyanatepropyl (meth)acrylate, etc.
  • the urethane-based resin may be urethane (meth)acrylate.
  • the urethane (meth)acrylate may be a multifunctional urethane (meth)acrylate.
  • the multifunctional urethane (meth)acrylate may be a multifunctional urethane (meth)acrylate containing a cyclohexyl group.
  • the multifunctional urethane (meth)acrylate containing a cyclohexyl group may be prepared by a condensation reaction of a diisocyanate containing a cyclohexyl group and a multifunctional (meth)acrylate containing a hydroxy group.
  • the diisocyanate containing a cyclohexyl group may be, but is not limited to, 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, or 4,4-dicyclohexylmethane diisocyanate, either singly or in combination of two or more thereof.
  • the polyfunctional (meth)acrylate containing a hydroxy group may be used alone or in combination of two or more of trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, or dipentaerythritol penta(meth)acrylate, but is not limited thereto.
  • the epoxy resin may include, but is not limited to, epoxy acrylate, siloxane resin having an alicyclic epoxy group, etc.
  • the thickness of the hard coating layer (21) may be 0.1 ⁇ m to 5 ⁇ m.
  • the thickness of the hard coating layer (21) may be 0.1 ⁇ m to 5 ⁇ m, or may be 0.1 ⁇ m to 4 ⁇ m, or may be 0.1 ⁇ m to 3 ⁇ m, or may be 0.5 ⁇ m to 5 ⁇ m, or may be 0.5 ⁇ m to 4 ⁇ m, or may be 0.5 ⁇ m to 3 ⁇ m, or may be 1 ⁇ m to 5 ⁇ m, or may be 1 ⁇ m to 4 ⁇ m, or may be 1 ⁇ m to 3 ⁇ m.
  • the thickness of the hard coating layer (21) is less than 0.1 ⁇ m, a flat layer is not formed, and thus crystals may occur.
  • the thickness of the hard coating layer (21) is more than 5 ⁇ m, the height of the curl may increase, thereby reducing the cohesion of the planar heating element (100') .
  • the first conductive oxide layer (31) and the second conductive oxide layer (51) may be transparent conductive oxide layers.
  • the first conductive oxide layer (31) and the second conductive oxide layer (51) may be oxides selected from zinc tin oxide (ZTO), indium gallium zinc oxide (IGZO), zinc aluminum oxide (ZAO), indium zinc oxide (IZO), zinc oxide (ZnO), and combinations thereof.
  • the first conductive oxide layer (31) and the second conductive oxide layer (51) may be zinc tin oxide (ZTO).
  • the thickness of the first conductive oxide layer (31) and the second conductive oxide layer (51) may be 30 nm to less than 100 nm, respectively. If the thickness of the first conductive oxide layer (31) and the second conductive oxide layer (51) is within the above range, the transmittance of the surface heating element (100') may be improved and the surface resistance may be reduced, thereby providing excellent heating efficiency.
  • the metal layer (21) positioned between the first conductive oxide layer (31) and the second conductive oxide layer (51) may be a metal selected from Ag, Au, Pt, Al, Cu, Cr, V, Mg, Ti, Sn, Pb, Pd, W or an alloy thereof.
  • the metal layer (21) may be Ag having high electrical conductivity or an alloy of Ag and the above-described metals.
  • the metal layer (21) may have improved corrosion resistance even under a high temperature and high humidity environment due to the flattening of the hard coating layer (21) on the lower surface of the first conductive oxide layer (31), thereby reducing roughness, and may have excellent heat generation efficiency even under a low voltage.
  • the thickness of the metal layer (21) may be 5 nm to 20 nm.
  • the thickness of the metal layer (21) may be 7 nm to 20 nm or may be 10 nm to 20 nm. If the thickness of the metal layer (21) is within the above range, the visible light transmittance may be high and the surface resistance may be low, thereby providing excellent heat generation efficiency even under low voltage.
  • the electrode layer (61) can be arranged to be in contact with the substrate (11), the hard coating layer (21), the first conductive oxide layer (31), the metal layer (41), and the second conductive oxide layer (51).
  • the electrode layer (61) functions as a current passage.
  • the electrode layer (61) can be formed to connect and contact the upper and lower portions of both ends of the structure (100).
  • the electrode layer (61) can be formed of a conductive material.
  • the conductive material can be a metal, a conductive metal nitride, a conductive metal oxide, or a combination thereof.
  • the conductive material can be a metal such as Cu.
  • the surface resistance of the surface heating element (100') at room temperature can be 20 ⁇ / ⁇ or less.
  • the surface heating element (100') can have a surface resistance change rate satisfying the following equation 1 before and after being left at 85°C and 85% relative humidity for 360 hours:
  • A is the surface resistance ( ⁇ / ⁇ ) before being left for 360 hours at 85°C and 85% relative humidity
  • B is the surface resistance ( ⁇ / ⁇ ) after being left at 85°C and 85% relative humidity for 360 hours.
  • the surface resistance change rate of the surface heating element (100') before and after being left at 85° C. and 85% relative humidity for 360 hours may be 2% or less, 1% or less, or 0%.
  • the surface heating element (100') may have a visible light transmittance of 60% or more and a haze of 1.1 or less.
  • Articles according to another embodiment of the present invention may include the surface heating element (100') described above.
  • Examples of the articles include automotive windshields, refrigerator front display cases, smart glasses, bathroom mirrors, industrial heating, smart farms, fish tanks, coats, medical devices, etc.
  • Another embodiment of a method for manufacturing a surface heating element may include the steps of: preparing a substrate; applying a composition for forming a hard coating layer to one surface of the substrate and photocuring the same to form a hard coating layer; depositing the hard coating layer on one surface opposite to the substrate to sequentially form a first conductive oxide layer, a metal layer, and a second conductive oxide layer; and arranging an electrode layer so as to be in contact with the substrate, the hard coating layer, the first conductive oxide layer, the metal layer, and the second conductive oxide layer.
  • composition for forming a hard coating layer is applied to one surface of the substrate and photocured to form a hard coating layer.
  • the composition for forming a hard coating layer may include the above-described resin, photoinitiator, and solvent.
  • the photoinitiator may be used without particular limitation as long as it is an initiator that can be used in the relevant technical field.
  • photoinitiators include acetophenones such as 4-phenoxydichloroacetphenone, 4-t-butyldichloroacetphenone, 4-t-butyltrichloroacetphenone, diethoxyacetphenone, 2-hydroxy-2-methyl-l-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-l-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexylphenyl ketone; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzyl dimethyl ketal; acylphosphine oxides and titanocene compounds; Benzophenones such as benzophenone, benzoylbenzoic acid,
  • the photoinitiator can be used alone or in combination of two or more.
  • the photoinitiator can be included in an amount of 0.1 to 10 wt% based on the total solid content weight of the hard coating composition. If the photoinitiator is less than 0.1 wt%, curing does not progress sufficiently, and improvement in mechanical properties and adhesion of the hard coating layer formed by the hard coating composition cannot be expected. If the amount of the photoinitiator exceeds 10 wt%, poor adhesion, breakage, and curling may occur due to curing shrinkage.
  • the solvent may include alcohols such as methanol, ethanol, isopropanol, butanol, and propylene glycol methoxy alcohol; ketones such as methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, and dipropyl ketone; acetates such as methyl acetate, ethyl acetate, butyl acetate, and propylene glycol methoxy acetate; cellosolves such as methyl cellosolve, ethyl cellosolve, and propyl cellosolve; hydrocarbons such as normal hexane, normal heptane, benzene, toluene, and xylene; and ethers such as propylene glycol monomethyl ether.
  • alcohols such as methanol, ethanol, isopropanol, butanol, and propylene glycol methoxy alcohol
  • the solvent may be 5 to 90 wt% or 20 to 70 wt% based on the total weight of the hard coating composition. If the solvent content is less than 5 wt%, the viscosity of the hard coating composition may increase, which may reduce workability. If the solvent content exceeds 90 wt%, it is difficult to control the thickness of the hard coating layer, and dry spots may occur, resulting in appearance defects.
  • the hard coating composition may additionally contain inorganic particles, leveling agents, or stabilizers.
  • Inorganic particles can be uniformly formed in a hard coating layer formed of a hard coating composition to further improve mechanical properties such as wear resistance, scratch resistance, and pencil hardness.
  • the inorganic particles may have an average particle diameter of 1 to 100 nm, or may have a diameter of 5 to 50 nm. If the average particle diameter of the inorganic particles is less than 1 nm, agglomeration occurs in the hard coating composition, making it impossible to form a uniform hard coating layer. In addition, if the average particle diameter of the inorganic particles exceeds 100 nm, the optical properties and mechanical properties of the hard coating layer may deteriorate.
  • the inorganic particles may be a metal oxide.
  • the inorganic particles may be Al 2 O 3 , SiO 2 , ZnO, ZrO 2 , BaTiO 3 , TiO 2 , Ta 2 O 5 , Ti 3 O 5 , ITO, IZO, ATO, ZnO-Al, Nb 2 O 3 , SnO, MgO, or a combination thereof.
  • the inorganic particles can be Al 2 O 3 , SiO 2 , ZrO 2 , or a combination thereof.
  • the inorganic particles can be present in an amount of 5 to 40 wt %, or 6 to 35 wt %, based on the total weight of the solid content of the hard coating composition.
  • the inorganic particles are present in an amount of less than 5 wt %, mechanical properties such as wear resistance, scratch resistance, and pencil hardness of the hard coating composition may not be improved. If the inorganic particles are present in an amount of more than 40 wt %, the curability of the hard coating composition may be interfered with, resulting in deteriorated mechanical properties and poor appearance of the hard coating layer. If the inorganic particles are present in an amount of more than 40 wt %, the curability of the hard coating composition may be interfered with, resulting in deteriorated mechanical properties and poor appearance of the hard coating layer.
  • a leveling agent is added to improve the smoothness and applicability of the coating film when applying the composition, and a silicone leveling agent, a fluorine-based leveling agent, an acrylic leveling agent, etc. can be used.
  • the leveling agent can be included in an amount of 3 to 5 wt% based on the total weight of the hard coating composition.
  • Stabilizers can be divided into UV stabilizers and heat stabilizers.
  • an ultraviolet stabilizer can be used to protect the surface of the coating by blocking or absorbing ultraviolet rays.
  • UV stabilizers can be classified into absorbers, quenchers, and hindered amine light stabilizers (HALS) based on their mechanism of action. In addition, they can be classified into phenyl salicylate absorbers, benzophenone absorbers, benzotriazole absorbers, nickel derivative quenchers, and radical scavengers based on their chemical structure. There is no particular limitation on the type of UV stabilizer as long as it does not significantly change the initial color of the hard coating layer formed by the hard coating composition.
  • HALS hindered amine light stabilizers
  • the heat stabilizer is a commercially applicable product, and the primary heat stabilizer is a polyphenol-based product, and the secondary heat stabilizers are a phosphite-based product and a lactone-based product, which can be used alone or in combination.
  • the UV stabilizer and the heat stabilizer can be used by appropriately adjusting the content at a level that does not affect the UV curability, and can be included in an amount of 0.1 to 3 wt% based on the total weight of the hard coating composition.
  • the method for applying the hard coating layer is not particularly limited, but examples thereof include die coaters such as fountain die and slot die, roll coaters such as gravure coaters and comma coaters, bar coaters, dip coaters, spin coaters, and spray coaters.
  • the active energy ray irradiated during photocuring examples include visible light, ultraviolet rays, infrared rays, X-rays, ⁇ -rays, ⁇ -rays, ⁇ -rays, electron rays, etc.
  • the active energy ray may be ultraviolet rays.
  • the accumulated irradiation dose of the active energy ray is, for example, approximately 50 to 10,000 mJ/cm2, and can be set according to the type and mixing amount of the photopolymerization initiator, the thickness of the hard coating layer, etc.
  • the temperature during the active energy ray irradiation can be 35°C or higher to reduce the amount of curl, and the temperature during the active energy ray irradiation can be 150°C or lower to not impair transparency due to heat.
  • heating can be performed after the active energy ray irradiation to increase the curing speed and reduce uncured material, thereby suppressing changes in the amount of curl.
  • the heating temperature can be, for example, 35°C to 180°C.
  • the heating time can be, for example, about 10 seconds to 60 minutes.
  • a first conductive oxide layer, a metal layer, and a second conductive oxide layer are sequentially formed on one side of the substrate opposite to the hard coating layer by deposition.
  • Any deposition method available in the relevant technical field can be used as the deposition method.
  • a sputtering method, a magnetron sputtering method, etc. can be used as the deposition method.
  • the electrode layer may be formed using, but is not limited to, a transparent metal such as Cu, Ag, nanowires/paste, an oxide transparent electrode such as ITO, ZnO, SnO 2 , or a non-oxide transparent electrode such as carbon nanotubes, graphene.
  • Example 1 Preparation of a surface heating element
  • PET polyethylene terephthalate
  • composition for forming the hard coating layer was applied to one surface of the substrate using a bar coater, dried at 80° C. for 1 minute, and then irradiated with a high-pressure mercury ultraviolet lamp under the condition of 300 mJ/cm 2 accumulated light dose and photocured to form a hard coating layer having a thickness of about 1 ⁇ m.
  • a structure was manufactured in which a first conductive oxide layer with a thickness of about 40 nm, a metal layer with a thickness of about 12 nm, and a second conductive oxide layer with a thickness of about 40 nm were sequentially formed on the upper surface of the hard coating layer by depositing ZTO/Ag/ZTO.
  • the magnetron sputtering process was performed as follows.
  • a surface heating element composed of a structure of substrate (about 125 ⁇ m)/hard coating layer (about 1 ⁇ m)/first conductive oxide layer (about 40 nm)/metal layer (about 12 nm)/second conductive oxide layer (about 40 nm) and an electrode layer in contact with these structures was manufactured.
  • a planar heating element composed of a structure of substrate (approximately 50 ⁇ m)/hard coating layer (approximately 1 ⁇ m)/first conductive oxide layer (approximately 40 nm)/metal layer (approximately 12 nm)/second conductive oxide layer (approximately 40 nm) and an electrode layer in contact with these structures was manufactured in the same manner as in Example 1, except that a polyethylene terephthalate (PET) transparent substrate with a thickness of approximately 50 ⁇ m was used and a hard coating layer with a thickness of approximately 3 ⁇ m was formed.
  • PET polyethylene terephthalate
  • a surface heating element composed of a structure of a substrate (about 125 ⁇ m)/hard coating layer (about 3 ⁇ m)/first conductive oxide layer (about 40 nm)/metal layer (about 12 nm)/second conductive oxide layer (about 40 nm) and an electrode layer in contact with these structures was manufactured in the same manner as in Example 1, except that a hard coating layer having a thickness of about 3 ⁇ m was formed.
  • a surface heating element composed of a structure of a substrate (about 200 ⁇ m)/hard coating layer (about 1 ⁇ m)/first conductive oxide layer (about 40 nm)/metal layer (about 12 nm)/second conductive oxide layer (about 40 nm) and an electrode layer in contact with these structures was manufactured in the same manner as in Example 1, except that a polyethylene terephthalate (PET) transparent substrate having a thickness of about 200 ⁇ m was used.
  • PET polyethylene terephthalate
  • a surface heating element composed of a structure of a substrate (about 125 ⁇ m)/hard coating layer (about 5 ⁇ m)/first conductive oxide layer (about 40 nm)/metal layer (about 12 nm)/second conductive oxide layer (about 40 nm) and an electrode layer in contact with these structures was manufactured in the same manner as in Example 1, except that a hard coating layer having a thickness of about 5 ⁇ m was formed.
  • a surface heating element composed of a structure of a substrate (about 125 ⁇ m)/hard coating layer (about 1 ⁇ m)/first conductive oxide layer (about 40 nm)/metal layer (about 12 nm)/second conductive oxide layer (about 70 nm) and an electrode layer in contact with these structures was manufactured in the same manner as in Example 1, except that the thickness of the second conductive oxide layer was formed to be about 70 nm.
  • a surface heating element composed of a structure of a substrate (about 125 ⁇ m)/hard coating layer (about 1 ⁇ m)/first conductive oxide layer (about 40 nm)/metal layer (about 20 nm)/second conductive oxide layer (about 40 nm) and an electrode layer in contact with these structures was manufactured in the same manner as in Example 1, except that the metal layer was formed to have a thickness of about 20 nm.
  • a surface heating element composed of a structure of a substrate (about 125 ⁇ m)/hard coating layer (about 1 ⁇ m)/first conductive oxide layer (about 40 nm)/metal layer (about 20 nm)/second conductive oxide layer (about 40 nm) and an electrode layer in contact with these structures was manufactured in the same manner as in Example 1, except that the metal layer was formed to have a thickness of about 7 nm.
  • Comparative Example 1 Manufacturing of a surface heating element
  • a surface heating element composed of a structure of a substrate (about 25 ⁇ m)/hard coating layer (about 1 ⁇ m)/first conductive oxide layer (about 40 nm)/metal layer (about 12 nm)/second conductive oxide layer (about 40 nm) and an electrode layer in contact with these structures was manufactured in the same manner as in Example 1, except that a polyethylene terephthalate (PET) transparent substrate having a thickness of about 25 ⁇ m was used.
  • PET polyethylene terephthalate
  • a surface heating element was manufactured by the same method as in Example 1, except that a hard coating layer was not formed, comprising a structure of a substrate (about 125 ⁇ m)/a first conductive oxide layer (about 40 nm)/a metal layer (about 12 nm)/a second conductive oxide layer (about 40 nm) and an electrode layer in contact with these structures.
  • a surface heating element composed of a structure of a substrate (about 125 ⁇ m)/hard coating layer (about 0.05 ⁇ m)/first conductive oxide layer (about 40 nm)/metal layer (about 12 nm)/second conductive oxide layer (about 40 nm) and an electrode layer in contact with these structures was manufactured in the same manner as in Example 1, except that a hard coating layer having a thickness of about 0.05 ⁇ m was formed.
  • a surface heating element composed of a structure of a substrate (about 125 ⁇ m)/hard coating layer (about 8 ⁇ m)/first conductive oxide layer (about 40 nm)/metal layer (about 12 nm)/second conductive oxide layer (about 40 nm) and an electrode layer in contact with these structures was manufactured in the same manner as in Example 1, except that a hard coating layer having a thickness of about 8 ⁇ m was formed.
  • a surface heating element composed of a structure of a substrate (about 125 ⁇ m)/hard coating layer (about 1 ⁇ m)/first conductive oxide layer (about 40 nm)/metal layer (about 12 nm) and an electrode layer in contact with these structures was manufactured in the same manner as in Example 1, except that the second conductive oxide layer was not formed.
  • a surface heating element composed of a structure of a substrate (about 125 ⁇ m)/hard coating layer (about 1 ⁇ m)/first conductive oxide layer (about 40 nm)/metal layer (about 12 nm)/second conductive oxide layer (about 100 nm) and an electrode layer in contact with these structures was manufactured in the same manner as in Example 1, except that the thickness of the second conductive oxide layer was formed to be about 100 nm.
  • a surface heating element composed of a structure of a substrate (about 125 ⁇ m)/hard coating layer (about 1 ⁇ m)/first conductive oxide layer (about 40 nm)/metal layer (about 12 nm)/second conductive oxide layer (about 40 nm) and an electrode layer in contact with these structures was manufactured in the same manner as in Example 1, except that the metal layer was formed to have a thickness of 30 nm.
  • Comparative Example 8 Manufacturing of a surface heating element
  • a surface heating element composed of a structure of a substrate (about 125 ⁇ m)/hard coating layer (about 1 ⁇ m)/ITO layer (about 150 nm) and an electrode layer in contact with these structures was manufactured in the same manner as in Example 1, except that the structure was formed using ITO 150 nm instead of ZTO/Ag/ZTO.
  • a surface heating element composed of a structure of a substrate (about 125 ⁇ m)/hard coating layer (about 1 ⁇ m)/first conductive oxide layer (about 40 nm)/metal layer (about 12 nm)/second conductive oxide layer (about 40 nm) and an electrode layer in contact with these structures was manufactured in the same manner as in Example 1, except that the metal layer was formed to have a thickness of 5 nm.
  • the stiffness of each planar heater was measured to evaluate the bondability of the planar heater.
  • the stiffness was measured using a bending/stiffness tester (4171S, Thwing-Albert).
  • the thickness of the hard coating layer was measured for each surface heating element.
  • the thickness of the hard coating layer was measured five times using a micrometer (Mitutoyo), and the average value was calculated to obtain the thickness.
  • the surface resistance was measured three times before and after leaving it for 360 hours at 85°C and 85% relative humidity using a temperature and humidity chamber (PR-1J, ESPEC), and the average value was calculated.
  • the surface resistance was measured using a 4-point probe (RC2175, EDTM).
  • Equation 1-1 the change rate of surface resistance for each surface heating element was obtained according to the following Equation 1-1, and the corrosion resistance of the surface heating element was evaluated:
  • A is the surface resistance ( ⁇ / ⁇ ) before being left for 360 hours at 85°C and 85% relative humidity
  • B is the surface resistance ( ⁇ / ⁇ ) after being left at 85°C and 85% relative humidity for 360 hours.
  • Each surface heating element was cut into 4 cm x 4 cm to make a sample.
  • the visible light transmittance and haze of the sample were measured.
  • the visible light transmittance and haze were measured using a haze meter (NDH-5000W, NIPPON DENSHOKU).
  • Each surface heating element was cut to a size of 10 cm x 10 cm to make a sample.
  • the sample was placed on a stone plate, and the height of the curl generated from the floor at the four corners was measured using a steel ruler, and the average value was obtained.
  • each surface heating element was observed to determine whether thermal wrinkles occurred using the following criteria.
  • Each surface heating element was cut to a size of 10 cm x 10 cm to create a sample.
  • a voltage of 8 V was applied to the electrodes of the sample using a power supply (ex-60, ODA), and the heating temperature was measured using an infrared camera (E76, FLIR).
  • the planar heaters manufactured by Examples 1 to 8 had a substrate thickness of 50 ⁇ m to 200 ⁇ m, substrate rigidity of 5.11 N/mm to 80.71 N/mm, a hard coating layer thickness of 1 ⁇ m to 5 ⁇ m, a metal layer thickness of 7 nm to 20 nm, and a second conductive oxide layer thickness of 40 nm to 70 nm.
  • planar heaters manufactured by Examples 1 to 8 had a surface resistance change rate of 0% under a high temperature and humidity environment, a heating temperature of 45 °C to 150 °C after application of 8 V voltage, a visible light transmittance of 62.1% to 85.1%, a haze of 0.69 to 1.1, an average curl height of 3.3 cm, and no thermal wrinkles occurred.
  • the planar heater manufactured by Comparative Example 1 had a substrate thickness of 25 ⁇ m, a substrate rigidity of 2.57 N/mm, and thermal wrinkles occurred on the surface.
  • the planar heaters manufactured by Comparative Examples 2 and 3 were planar heaters that did not include a hard coating layer or had a thin thickness of 0.05 ⁇ m, and thus, under a high temperature and humidity environment, their surface resistance change rates were high at 37% and 34%, respectively, which failed to prevent corrosion, and their haze increased to 1.41 and 1.37, respectively, which reduced visibility.
  • the planar heater manufactured by Comparative Example 4 was a planar heater that had a thick hard coating layer thickness of 8 ⁇ m, and thus, the average curl height increased to 19.2 cm, which reduced the lamination properties of the planar heater.
  • the planar heater manufactured by Comparative Example 5 was a planar heater that did not include a second conductive oxide layer, and under a high temperature and humidity environment, the surface resistance change rate rapidly increased to 16437%, and the visible light transmittance decreased to 59.5%. It is thought that this was because the second conductive oxide layer, which acts as a protective film to prevent corrosion and light scattering, was not present, and thus corrosion was not inhibited.
  • the planar heater manufactured by Comparative Example 6 had a thick second conductive oxide layer of 100 nm, and the visible light transmittance significantly decreased to 56.9% due to visible light absorption by the second conductive oxide layer.
  • the planar heater manufactured by Comparative Example 7 had a thick metal layer of 30 nm, and the surface resistance before and after standing decreased to 0.7 ⁇ / ⁇ , but the visible light transmittance significantly decreased to 16.3% due to visible light absorption by the metal layer.
  • the planar heater manufactured by Comparative Example 8 was a heater that used 150 nm thick ITO instead of the first conductive oxide layer/metal layer/second conductive oxide layer structure on the hard coating layer, and had high sheet resistances of 126.5 ⁇ / ⁇ and 114.5 ⁇ / ⁇ before and after standing, low heating temperature of 24.8 °C after application of 8 V voltage, and high haze of 3.6.
  • the planar heater manufactured by Comparative Example 9 had a thin metal layer of 5 nm, very high sheet resistance and sheet resistance change rate of 31.3 ⁇ / ⁇ , 817.3 ⁇ / ⁇ , and 2611% before and after standing, and low heating temperature of 32.6 °C after application of 8 V voltage, and high haze of 5.2.
  • the surface heating elements manufactured by Examples 1 to 8 satisfy all of the following characteristics: improved transmittance, excellent heating efficiency even under low voltage, stable corrosion resistance even under high temperature and humid environments, low curl height, and no occurrence of thermal wrinkles.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un élément chauffant plan, un article le comprenant, et un procédé de fabrication de l'élément chauffant plan. L'élément chauffant plan comprend : un substrat ; une couche de revêtement dur située sur la face supérieure du substrat ; une première couche d'oxyde conducteur située sur la face supérieure de la couche de revêtement dur ; une couche métallique située sur la face supérieure de la première couche d'oxyde conducteur ; une seconde couche d'oxyde conducteur située sur la face supérieure de la couche métallique ; et une couche d'électrode disposée de manière à être en contact avec le substrat, la couche de revêtement dur, la première couche d'oxyde conducteur, la couche métallique, et la seconde couche d'oxyde conducteur.
PCT/KR2024/007890 2023-03-24 2024-06-10 Élément chauffant plan, article le comprenant et procédé de fabrication d'élément chauffant plan Ceased WO2024258130A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR20230039302 2023-03-24
KR1020230075582A KR102908495B1 (ko) 2023-03-24 2023-06-13 면상 발열체, 이를 포함하는 물품, 및 상기 면상 발열체의 제조방법
KR10-2023-0075582 2023-06-13

Publications (1)

Publication Number Publication Date
WO2024258130A1 true WO2024258130A1 (fr) 2024-12-19

Family

ID=93116771

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2024/007890 Ceased WO2024258130A1 (fr) 2023-03-24 2024-06-10 Élément chauffant plan, article le comprenant et procédé de fabrication d'élément chauffant plan

Country Status (2)

Country Link
KR (1) KR102908495B1 (fr)
WO (1) WO2024258130A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021176116A (ja) * 2018-07-24 2021-11-04 Tdk株式会社 ヒータ用透明導電フィルム及びヒータ
JP2022074708A (ja) * 2020-11-05 2022-05-18 日産自動車株式会社 透明面状ヒーター
KR20220135069A (ko) * 2021-03-29 2022-10-06 동의대학교 산학협력단 고유연성을 갖는 투명 발열체 및 이를 포함하는 발열 히터
US20230014171A1 (en) * 2019-12-19 2023-01-19 Nitto Denko Corporation Heater

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013129564A (ja) * 2011-12-21 2013-07-04 Siltronic Ag シリコン単結晶基板およびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021176116A (ja) * 2018-07-24 2021-11-04 Tdk株式会社 ヒータ用透明導電フィルム及びヒータ
US20230014171A1 (en) * 2019-12-19 2023-01-19 Nitto Denko Corporation Heater
JP2022074708A (ja) * 2020-11-05 2022-05-18 日産自動車株式会社 透明面状ヒーター
KR20220135069A (ko) * 2021-03-29 2022-10-06 동의대학교 산학협력단 고유연성을 갖는 투명 발열체 및 이를 포함하는 발열 히터

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
방금혁 등. 반응성 스퍼터링법으로 제조된 AL2O3 막을 이용한 ZNO/CU/ZNO 투명 히터의 내식성과 투과도 개선 연구. 대한금속·재료학회지. 2021: "vol. 59", NO. 3, Geumhyuck et al. Simultaneous Improvement in the Corrosion Resistance and Visible Transparency of ZnO/Cu/ZnO Transparent Heaters with Reactively Sputtered Al2O3 Layers. Korean Jornal of Metals and Materials.), pages 155 - 161, XP093250657 *

Also Published As

Publication number Publication date
KR102908495B1 (ko) 2026-01-06
KR20240143718A (ko) 2024-10-02

Similar Documents

Publication Publication Date Title
WO2014084697A1 (fr) Ecran tactile et son procédé de fabrication
KR101991545B1 (ko) 투명 도전성 필름 및 그 제조 방법
WO2015076572A1 (fr) Structure conductrice et procédé pour sa fabrication
WO2020017792A1 (fr) Film à fenêtre intelligent et son procédé de fabrication
EP2981413A1 (fr) Substrat de capot en polyimide
WO2021167377A1 (fr) Film multicouche et stratifié le comprenant
WO2015050320A1 (fr) Électrode présentant une excellente transmittance de la lumière et son procédé de fabrication, et élément électronique comprenant l'électrode
WO2012157960A2 (fr) Substrat multicouche en plastique et son procédé de fabrication
WO2013012273A2 (fr) Écran tactile
WO2017039209A1 (fr) Substrat de fenêtre de couverture et dispositif d'affichage d'image comprenant celui-ci
WO2015088295A1 (fr) Capteur tactile et son procédé de fabrication
WO2019093731A1 (fr) Composition photodurcissable et couche de revêtement comprenant le produit durci associé
WO2020085869A1 (fr) Fenêtre de couvercle de dispositif d'affichage souple et dispositif d'affichage
WO2021125695A1 (fr) Composition durcissable pour impression à jet d'encre, et dispositif d'affichage électroluminescent organique la comprenant
WO2018135865A1 (fr) Film de protection de partie inférieure de panneau delo, et appareil d'affichage électroluminescent organique le comprenant
WO2015126088A1 (fr) Fenêtre tactile et dispositif d'affichage doté de celle-ci
WO2016204488A1 (fr) Capteur tactile et son procédé de fabrication
WO2022196987A1 (fr) Composition adhésive et feuille adhésive, élément optique et appareil d'affichage produits au moyen de celle-ci
WO2024005382A1 (fr) Film de revêtement dur et fenêtre et dispositif d'affichage d'image sur lesquels est appliqué le film
WO2016204487A1 (fr) Capteur tactile et son procédé de fabrication
WO2022108053A1 (fr) Fenêtre de recouvrement pour dispositif d'affichage flexible et dispositif d'affichage flexible
WO2021167378A1 (fr) Film multicouche et stratifié le comprenant
WO2018143539A1 (fr) Composition de revêtement dur, et film de revêtement dur utilisant celle-ci
WO2020235876A1 (fr) Fenêtre de couverture de dispositif d'affichage souple et dispositif d'affichage souple
WO2012002706A2 (fr) Film protecteur

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24823650

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 24823650

Country of ref document: EP

Kind code of ref document: A1