WO2013047493A1 - Substrat doté d'une couche électroconductrice transparente et son procédé de fabrication - Google Patents

Substrat doté d'une couche électroconductrice transparente et son procédé de fabrication Download PDF

Info

Publication number
WO2013047493A1
WO2013047493A1 PCT/JP2012/074507 JP2012074507W WO2013047493A1 WO 2013047493 A1 WO2013047493 A1 WO 2013047493A1 JP 2012074507 W JP2012074507 W JP 2012074507W WO 2013047493 A1 WO2013047493 A1 WO 2013047493A1
Authority
WO
WIPO (PCT)
Prior art keywords
substrate
layer
conductive layer
transparent conductive
transparent
Prior art date
Application number
PCT/JP2012/074507
Other languages
English (en)
Japanese (ja)
Inventor
宮本　雅史
嘉一 山崎
Original Assignee
Dic株式会社
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 Dic株式会社 filed Critical Dic株式会社
Priority to JP2013505224A priority Critical patent/JP5282991B1/ja
Publication of WO2013047493A1 publication Critical patent/WO2013047493A1/fr

Links

Images

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
    • C08J7/042—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
    • 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

Definitions

  • the present invention relates to a substrate with a transparent conductive layer having a transparent conductive layer containing metal nanowires and a method for producing the same.
  • a substrate with a transparent conductive layer in which a transparent conductive layer is formed on a transparent substrate is used in many cases as an important functional member in a display element or the like using light emitting and light receiving functions.
  • a transparent conductive layer into a pattern, a transparent conductive sheet in which a large number of conductive regions are arranged on a sheet-like transparent substrate and have a function such as an electrode or a switch is made thin and small in size. It is an indispensable member for high functionality.
  • the pattern of the transparent conductive layer is a method of forming an ITO layer or a zinc oxide layer on a transparent substrate by vapor deposition or sputtering, and then patterning by dry etching such as plasma, or using a positive / negative resist in combination. Is adopted.
  • vapor deposition and sputtering require a large amount of equipment and energy, and when a plastic film is used as a transparent substrate in order to provide flexibility, which is one of advanced functions, the heat during vapor deposition and sputtering. This sometimes causes problems such as distortion of the plastic film. Therefore, there is a need for a transparent conductive sheet that does not require much heat energy, has a simple manufacturing apparatus, and has high productivity.
  • a method of obtaining a transparent conductive layer by applying a coating solution of conductive nanowires such as metal and carbon to a substrate has been studied.
  • metal nanowires are attracting attention as a material that has a small specific resistance and can form a transparent electrode having a lower surface resistance (see, for example, Patent Document 1).
  • the metal nanowire is a metal having an aspect ratio, the light that enters and passes through the transparent conductive layer becomes a diffuse reflection unique to the metal nanowire, not a simple metal reflection, and a yellowish color is perceived. was there. This is not suitable for an electrode that requires accurate color reproducibility such as a display element, and its application is limited.
  • a method for suppressing irregular reflection of the metal nanowires for example, a method of forming a transparent conductive member containing conductive particles and a colored resin binder on a transparent primer (see, for example, Patent Document 2), or blackening the surface A transparent conductive member using a metal nanowire that has been made is known (for example, see Patent Document 3).
  • Patent Document 2 since the colored resin binder inhibits the contact of the metal nanowires, there is a risk that the electric resistance value of the obtained conductive layer may increase or the reliability may decrease.
  • the method of patent document 3 also processed metal nanowire itself, there existed a possibility that the electrical resistance value of a conductive layer might go up, and there existed a possibility that reliability might fall.
  • a color correction sheet has also been proposed for the purpose of correcting the color of the ITO transparent electrode of the touch panel.
  • This is a method of providing a sheet having a color complementary to the color of ITO, which is a uniform metal film obtained by sputtering.
  • the knowledge about the metal irregular reflection of the metal nanowire is not described, and the knowledge about the color material which is a complementary color is not described.
  • An object of the present invention is to provide a substrate with a transparent conductive layer that exhibits a good electrical resistance value and is transparent and excellent in color reproducibility.
  • the inventors of the present invention have an absorbance of 0.001 to 0.00 nm as the anchor coat layer between the transparent substrate and the transparent conductive layer containing metal nanowires, each independently having a wavelength of 450 nm, a wavelength of 550 nm, and a wavelength of 650 nm.
  • the above-mentioned problem was solved by providing a colored transparent layer having a haze value in the range of 1 and a range of 0.1 to 2%.
  • a layer containing a ⁇ -conjugated compound is preferable because visibility can be improved while maintaining good conductivity.
  • the absorbance at a wavelength of 450 nm, a wavelength of 550 nm, and a wavelength of 650 nm is independently in the range of 0.001 to 0.1 on the transparent substrate, and the haze value is in the range of 0.1 to 2%.
  • the present invention is also a method for producing a substrate with a transparent conductive layer as described above, A colored transparent layer having absorbances at wavelengths of 450 nm, 550 nm, and 650 nm independently in the range of 0.001 to 0.1 and a haze value in the range of 0.1 to 2% on the substrate
  • Step 5 of forming a pattern of the transparent conductive layer (2) on the substrate, Applying a protective layer coating to
  • the present invention it is possible to provide a substrate with a transparent conductive layer which exhibits a good electric resistance value, can suppress yellowness, is transparent and has excellent color reproducibility.
  • the method for producing a substrate with a transparent conductive layer of the present invention can be formed entirely by a coating process, and the transparent conductive layer can be patterned without performing a wet process such as etching. The layer can be fixed well without being sintered or fired.
  • the absorbance at a wavelength of 450 nm, a wavelength of 550 nm, and a wavelength of 650 nm is independently in the range of 0.001 to 0.1, and the haze value is 0.1. If it is in the range of ⁇ 2%, there is no particular limitation.
  • the absorbance is measured by a method based on JIS K-0115, and specifically indicates a value measured by the following method.
  • the absorbance of the colored transparent layer (1) used in the present invention is in the range of 0.001 to 0.1 in the wavelength range of 450 nm, wavelength 550 nm, and wavelength 650 nm so that both transmittance and visibility can be achieved. In terms of this point, it is preferably in the range of 0.001 to 0.02, more preferably in the range of 0.001 to 0.01.
  • the absorbance at each wavelength may be the same or different. When the absorbance is less than 0.001, a sufficient light absorption effect cannot be obtained, and the irregularly reflected light of the metal nanowire tends to be visually recognized. On the other hand, if the absorbance exceeds 0.1, the light absorption effect becomes too high, and the total light transmittance may be lowered.
  • the absorbance when used as a transparent electrode layer for a touch panel, since higher transparency is required, the absorbance is preferably in the range of 0.001 to 0.1. On the other hand, when used as a transparent electrode layer for a solar cell, the transparency for the touch panel is not required, so the absorbance may be about 0.001 to 0.2.
  • the haze value is measured by a method based on JIS K-7136.
  • the total light transmittance is measured by a method based on JIS K-7361, and specifically shows a value measured by the following method.
  • the range of the haze value of the colored transparent layer (1) used in the present invention is preferably from 0.1 to 2%, more preferably from 0.1 to 1%, and from 0.1 to 0.5%. Further preferred.
  • the haze value is less than 0.1%, it means that the thickness of the transparent layer is too thin, and the light absorption effect is too low, so that irregularly reflected light of the metal nanowires may be easily visible.
  • the haze value exceeds 2%, it means that the thickness of the transparent layer is too thick, the light absorption effect becomes too high, and the total light transmittance may be lowered.
  • the resulting substrate with a transparent conductive layer preferably has a haze value in the range of 0.1 to 2%.
  • a range of 1 to 0.5% is more preferable.
  • the colored transparent layer (1) used in the present invention is not particularly limited as long as it is a transparent layer having the above-described absorbance and haze, but is a colored transparent layer (1) composed of a transparent resin film containing a coloring material. It is preferable because it is easy to form.
  • the transparent resin film containing the coloring material can be easily formed by applying a coating composition containing at least a colorant and a binder resin, followed by drying and / or curing.
  • the colorant used for the colored transparent layer (1) it is preferable to use a ⁇ -conjugated compound because it is easy to adjust the absorbance and haze value within suitable ranges.
  • the ⁇ -conjugated compound used in the present invention may have any structure as long as it has an aromatic hydrocarbon ring or aromatic heterocycle.
  • aromatic hydrocarbon ring or aromatic heterocycle For example, “Organic Field-Effect Transistors” (2007, CRC Press) 159-228.
  • Examples of the organic semiconductor molecules include those described on the page and other known organic semiconductor molecules.
  • an aromatic hydrocarbon ring or aromatic such as benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, furan ring, thiophene ring It is a structure having a hetero ring, and more preferably, two or more of these aromatic hydrocarbon rings or aromatic hetero rings are condensed and / or covalently linked, and the aromatic ring It is preferable that the ⁇ electron which each hydrocarbon ring or aromatic hetero ring has is widely delocalized.
  • the number of condensed aromatic rings and / or covalently linked aromatic hydrocarbon rings or aromatic heterocycles is preferably 1-20, and more preferably 2-12.
  • ⁇ -conjugated compounds include phthalocyanines, porphyrins, anthracene, tetracene, pentacene, triphenylene, hexabenzocoronene, fullerene, polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines. , Polyacenes, polythiophene vinylenes, and copolymers thereof.
  • phthalocyanines used as pigments polypyrroles used as antistatic agents, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, etc.
  • the high molecular weight polymer is preferable because it is excellent in transparency and can be easily formed into a coating film.
  • the conductive polymer functions as an antistatic film, electrostatic breakdown of the silver nanowire coating film due to electrostatic discharge can be prevented.
  • a blue pigment is preferable because the yellowness of the obtained substrate with a transparent conductive layer is particularly easy to reduce.
  • a polythiophene-based colorant and commercially available products such as PEDOT (manufactured by SIGMA-ALDRICH) and Alacoat AS601 (manufactured by Arakawa Chemical Industries) containing a polythiophene-based colorant can be used.
  • the conjugated compound is used as the colored transparent layer (1)
  • a resin serving as a binder or various solvents it is possible to mix a resin serving as a binder or various solvents and use it as a coating solution from the viewpoint of workability and adhesion to a substrate.
  • the resin to be mixed include polyester resins, polyurethane resins, polyester urethane resins, acrylic resins, melamine resins, vinyl chloride resins, styrene resins, polycarbonate resins, and cycloolefin resins. Of these, polyester resins and acrylic resins are preferred because of their high transparency. Moreover, you may use various additives in the range which does not impair the effect of this invention.
  • a resin such as the polyester resin may be mixed in order to improve the adhesion to the transparent substrate.
  • the transparent substrate is a resin sheet made of plastic or the like
  • the adhesion can be further enhanced by selecting a resin having a structure similar to the resin structure of the transparent substrate.
  • the concentration of the coating solution of the conjugated compound may be appropriately adjusted according to the conjugated compound to be used so as to maintain the absorbance and haze, and is not particularly limited.
  • the thickness of the colored transparent layer (1) is not particularly limited as long as the absorbance and haze can be maintained.
  • the film thickness is preferably such that it does not peel off together with the transparent conductive layer. Specifically, it is preferably in the range of 0.1 ⁇ m to 1.0 ⁇ m.
  • a coating method is preferable.
  • a coating method a known coating method such as spray coating, bar coating, roll coating, die coating, inkjet coating, screen coating, dip coating, or the like can be used.
  • spray coating bar coating, roll coating, die coating, inkjet coating, screen coating, dip coating, or the like
  • it can provide by the in-line coating system which provides an application layer in the manufacturing process of a film, and the offline coating system which provides an application layer after film manufacture.
  • the transparent substrate used as the support of the substrate with a transparent conductive layer of the present invention is not particularly limited as long as it has sufficient physical strength and light transmittance as a support, but a sheet-like transparent substrate is handled. This is preferable because the property is improved.
  • a sheet or film of transparent or translucent resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic, polypropylene, polycarbonate, cycloolefin, etc. preferable.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • acrylic polypropylene
  • polycarbonate polycarbonate
  • cycloolefin etc.
  • These may be single layers or multilayers, and may be surface-treated by a known method such as plasma for the purpose of improving adhesion, or coated with a surface coating material for the purpose of obtaining surface hardness. Also good.
  • a PET film or a PEN film is particularly preferable from the viewpoint of mechanical strength.
  • the range of 5 ⁇ m to 300 ⁇ m is preferable because of good handling and excellent transmittance. More preferably, it is in the range of 10 ⁇ m to 250 ⁇ m, and more preferably 25 ⁇ m to 200 ⁇ m.
  • the total light transmittance of the transparent substrate is preferably 90% or more, and particularly preferably 95% or more.
  • the transparent substrate is preferably a transparent substrate that is not colored. By using the transparent substrate, it is easy to obtain a substrate with a transparent conductive layer having high transparency.
  • the metal nanowire is a thin rod having a straight or curved shape
  • the material is a metal
  • the thickness is a fine nanometer size.
  • fine conductive materials are in the form of fibers, preferably wires, they are entangled with each other to form a mesh, thereby forming a good electrical conduction path even with a small amount of conductive materials. This is preferable because the resistance value of the conductive layer can be further reduced.
  • a mesh-like shape since the opening of the gap portion of the mesh is large, even if the fibrous conductive material itself is not transparent, it achieves good transparency as a coating film. Is possible.
  • metal of the metal nanowire include iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, cadmium, osmium, iridium, platinum, and gold. From the viewpoint of conductivity, copper, silver Platinum, gold are preferable.
  • the maximum diameter of the cross section is preferably less than 500 nm, more preferably less than 200 nm, and even more preferably less than 100 nm.
  • the metal nanowire preferably has an aspect ratio exceeding 10. The aspect ratio is more preferably more than 50 and still more preferably has an aspect ratio exceeding 100. The shape and size of the metal nanowire can be confirmed with a scanning electron microscope or a transmission electron microscope.
  • Metal nanowires can be prepared and prepared by methods known in the art. For example, a method of reducing silver nitrate in a solution, a method in which an applied voltage or current is applied to the precursor surface from the tip of the probe, a metal nanowire is drawn at the probe tip, and the metal nanowire is continuously formed, etc. (Japanese Patent Laid-Open No. 2004-223893).
  • a method for reducing silver nitrate in a solution more specifically, silver nanowires are synthesized by liquid phase reduction of silver salts such as silver nitrate in the presence of polyols such as ethylene glycol and polyvinylpyrrolidone. Is possible. For example, Xia, Y. et al. etal.
  • Such a conductive metal nanowire has a state in which the metal nanowires are entangled with each other while maintaining an appropriate interval on the transparent substrate, and a substantially transparent conductive network is possible by forming a conductive network.
  • Specific metal types, shaft lengths, aspect ratios, and the like may be appropriately determined according to the purpose of use.
  • the method for forming the transparent conductive layer (2) containing the metal nanowire is not particularly limited as long as the metal nanowire is a transparent conductive layer in which a conductive network is formed in a state where the metal nanowire is entangled with each other on the transparent substrate. It can be easily formed by applying a dispersion liquid in which is dispersed in a dispersion medium and drying and / or curing.
  • the liquid that is a dispersion medium for obtaining the dispersion liquid of the metal nanowires is not particularly limited, and various known dispersion media can be used.
  • saturated hydrocarbons such as hexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, propanol, and butanol, ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and diisobutyl ketone
  • Esters such as ethyl acetate and butyl acetate
  • ethers such as tetrahydrofuran, dioxane and diethyl ether
  • amides such as N, N-dimethylformamide, N-methylpyrrolidone (NMP) and N, N-dimethylacetamide, ethylene chloride
  • halogenated hydrocarbons such as chlorobenzene.
  • a dispersing agent can also be used according to the kind of dispersion medium.
  • these dispersion media polar dispersion media are preferable, and those having an affinity for water such as alcohols such as methanol and ethanol and amides such as NMP can be dispersed without using a dispersant. Is favorable and suitable. These liquids can be used singly or as a mixture of two or more.
  • water can be used as a dispersion medium, but in the case of water, when the colored transparent layer (1) is hydrophobic, it is easy to repel water and it is difficult to obtain a uniform film. In such a case, it is possible to obtain a uniform film by mixing and adding an alcohol to water or a surfactant that improves the wettability to a hydrophobic transparent substrate. is there.
  • the amount of the liquid as a dispersion medium to be used is not particularly limited, and the metal nanowire dispersion may have a viscosity suitable for coating.
  • the metal nanowire dispersion may have a viscosity suitable for coating.
  • it can be set in a wide range of about 100 to 100,000 parts by weight of the liquid with respect to 100 parts by weight of the metal nanowires, depending on the types of the metal nanowires and the dispersion medium, the stirring used, and the dispersing device. It can be selected appropriately.
  • the dispersion of the metal nanowires in the dispersion medium can be performed by applying a known dispersion method to the mixture of the metal nanowires and the liquid that is the dispersion medium as necessary.
  • a known dispersion method to form a transparent conductive layer having good transparency and conductivity.
  • selection of a dispersion method that does not destroy the shape of the metal nanowires is important.
  • the dispersion of the metal nanowires preferably does not contain a binder resin in terms of improving the conductive performance.
  • the contact between the metal nanowires is not inhibited unless a binder resin is used. Therefore, the electrical conductivity between metal nanowires is ensured and the electric resistance value of the obtained conductive layer can be kept lower.
  • the transparent conductive coating film when the substrate with a transparent conductive layer of the present invention is prepared by the lift-off method described later, when the transparent conductive coating film is formed on the substrate by eliminating the binder resin from the dispersion of metal nanowires Furthermore, it is also preferable in that the transparent conductive coating film can be easily peeled from the transparent substrate in the next step. Further, when the patterned transparent conductive layer is fixed on the substrate with the protective layer coating, the transparent conductive layer is impregnated in the conductive layer and reaches the substrate.
  • the fact that the dispersion liquid of the active substance does not contain the binder resin means that the transparent conductive layer contains more gaps, which is preferable in that the fixation by impregnation of the protective layer coating is not hindered.
  • the amount is such that the conductivity of the coating film on the substrate and the peeling property of the coating film from the substrate are not deteriorated and the fixing step of the conductive layer by the resin in the coating material for the protective layer is not impaired.
  • the type and amount thereof can be appropriately selected within the range in which the above characteristics are obtained.
  • the dispersion of metal nanowires may contain the resin and other additives in order to control viscosity, prevent corrosion, improve adhesion to the substrate, and disperse the conductive material.
  • suitable additives and binders include carboxymethylcellulose (CMC), 2-hydroxyethylcellulose (HEC), hydroxypropylmethylcellulose (HPMC), methylcellulose (MC), polyvinyl alcohol (PVA), tripropylene glycol (TPG), And xanthan gum (XG), and surfactants such as ethoxylates, alkoxylates, ethylene oxide, and propylene oxide, and copolymers thereof, sulfonates, sulfates, disulfonates, sulfosuccinates, phosphate esters , And fluorosurfactants, but are not limited thereto.
  • metal nanowire when metal nanowire is manufactured by an aqueous system, various water-soluble resins, such as a polyvinyl alcohol-type resin, a vinyl pyrrolidone type polymer, a cellulose derivative, can be used. Further, non-polymeric organic compounds such as 2-alkoxyethanol, ⁇ -diketone and alkyl acetate can also be used as a film forming agent.
  • various water-soluble resins such as a polyvinyl alcohol-type resin, a vinyl pyrrolidone type polymer, a cellulose derivative
  • non-polymeric organic compounds such as 2-alkoxyethanol, ⁇ -diketone and alkyl acetate can also be used as a film forming agent.
  • the desired properties of the transparent conductive layer (2) vary depending on the application.
  • the surface resistivity is preferably 0.01 ⁇ / ⁇ to 1000 ⁇ / ⁇ , and preferably has high transparency in the visible light region.
  • a coating method is preferable. Specifically, the dispersion liquid of the metal nanowires is applied on the colored transparent layer (1) and then dried.
  • a coating method a known coating method such as spray coating, bar coating, roll coating, die coating, inkjet coating, screen coating, dip coating, or the like can be used.
  • spray coating bar coating, roll coating, die coating, inkjet coating, screen coating, dip coating, or the like.
  • it can provide by the in-line coating system which provides an application layer in the manufacturing process of a film, and the offline coating system which provides an application layer after film manufacture.
  • the film thickness of the transparent conductive layer (2) can be appropriately adjusted depending on the application, but the conductivity tends to decrease as the thickness becomes thinner. On the other hand, if it is too thick, the haze value increases, the total light transmittance decreases, etc. The transparency tends to decrease. For these reasons, for example, when used as a transparent electrode layer for a touch panel, adjustment is often made appropriately between 10 nm and 10 ⁇ m. In particular, since metal nanowires themselves are not transparent, the transparency tends to decrease with an increase in film thickness, so a conductive layer having a thinner film thickness is often formed.
  • the conductive layer has an extremely large number of openings, but when measured with a contact-type film thickness meter, the average film thickness is preferably 10 nm to 500 nm, more preferably 30 nm to 300 nm, and more preferably 50 nm to 150 nm. Is most preferred.
  • the transparent conductive layer (2) contains metal nanowires or metal nanowires and a resin and the other additives described above.
  • the amount added when using the resin is determined in consideration of the conductivity of the conductive coating film, the peelability, the ease of immersion of the protective layer paint, etc., but the metal nanowires in the transparent conductive layer are attached to the substrate.
  • the resin tends to concentrate on the substrate side of the transparent conductive layer, and the metal nanowire tends to be easily fixed to the substrate. Tends to be exposed without being covered with resin and to have a gap between the conductive materials.
  • the said transparent conductive layer (2) increases the contact area and increases the contact area while increasing the contact point in the intersection part of metal nanowires in the transparent conductive layer (2) after application
  • the step of pressurizing the intersecting portion of the conductive substance is specifically a step of pressurizing the surface of the transparent conductive layer, and the pressure is applied to the transparent conductive layer of the metal nanowires dispersed in a mesh form from directly above.
  • This step is not particularly limited as long as it is a publicly known method for pressurizing the coating surface, but the layer obtained by coating is, for example, a transparent conductive layer disposed between two flat plates that can be pressurized, and fixed.
  • the layer obtained by coating is, for example, a transparent conductive layer disposed between two flat plates that can be pressurized, and fixed. Examples thereof include a flat plate pressing method in which pressure is applied for a period of time, a calendering method in which a transparent conductive layer is sandwiched between two pressurizable rolls, linearly pressed, and the entire surface is pressed by rotating the roll.
  • the roll linear pressure for pressing the transparent conductive layer (2) is 1 kN / m to 500 kN / m, preferably 5 kN / m to 300 kN / m, more preferably 10 kN / m to 100 kN / m. is there.
  • the substrate with a transparent conductive layer of the present invention is a substrate with a transparent conductive layer having, in this order, a colored transparent layer (1) and a transparent conductive layer (2) on the transparent substrate. Since the substrate with a transparent conductive layer of the present invention has such a configuration, it can reduce yellowness due to irregular reflection of metal nanowires without performing coating of metal nanowires, etc., and thus has a good electrical resistance value, and Transparent and excellent in color reproducibility.
  • the substrate with a transparent conductive layer of the present invention preferably has a haze value of 5% or less, more preferably 3% or less, more preferably 2% or less, and more preferably 1% or less. Particularly preferred. Particularly when used as a transparent electrode layer for a touch panel, the content is preferably in the range of 0.1 to 2%, and more preferably in the range of 0.1 to 0.5%. Further, the total light transmittance is preferably 80% or more, more preferably 85% or more, and further preferably 88% or more. By setting it as the said range, it can be used conveniently as a transparent electrode used for the portable electronic device by which a thin and high-density mounting is calculated
  • the surface resistance value of the substrate with a transparent conductive layer is preferably 0.01 to 1000 ⁇ / ⁇ , more preferably 1 to 500 ⁇ / ⁇ , and further preferably 10 to 300 ⁇ / ⁇ . By setting it as the said range, it can be conveniently used as a transparent electrode used for a portable electronic device, especially as a transparent electrode for touch panels.
  • a known patterning method can be selected. For example, (A) Using various printing methods such as screen printing, etc., fix the silver nanowires in a pattern using a binder resin, etc., and then wash or brush the non-immobilized area with an appropriate solvent, or adhere Forming a transparent conductive pattern by removing with a conductive roller. (B) After forming a transparent conductive layer of silver nanowires on a substrate, a resist paint that can be cured by light or heat is applied to the entire surface of the conductive layer, and light or heat is supplied only to the portion to be left as a pattern.
  • C After forming a transparent conductive layer of silver nanowires on a substrate, a sheet having a layer having a negative patterned adhesive region prepared separately is attached to the transparent electrode layer, and then peeled off. A method for forming a pattern of a transparent conductive layer thereon.
  • D After forming a transparent conductive layer of silver nanowires on the substrate, the liquid containing the silver nanowire remover is pattern-printed on the portions that are not necessary for forming the pattern electrode, and then the above (A) A method for forming a transparent conductive pattern by removing unnecessary portions using the same method as described above. Etc.
  • the method (B) or (C) is preferable because a transparent conductive layer pattern free of disconnection and short circuit patterned with high definition can be easily formed at low cost.
  • a resist paint that can be cured by light or heat in the method (B) a resist paint that is usually used for etching a transparent conductive layer such as indium oxide, zinc oxide, or tin oxide is used.
  • a pattern can be formed by exposure, it is preferable to use a resist paint for photolithography.
  • the exposure conditions for exposing the pattern are preferably performed under the exposure conditions suitable for the resist paint.
  • nitric acid, ammonium persulfate, and the like, or an oxidizing agent such as potassium permanganate can be used as a developer used for development.
  • Step 1 Colors having absorbances at wavelengths of 450 nm, 550 nm, and 650 nm independently in the range of 0.001 to 0.1 and haze values in the range of 0.1 to 2% on the substrate.
  • the transparent layer (1) is formed by coating.
  • Step 2 A peelable transparent conductive layer (2) containing metal nanowires is formed on the transparent layer (1) by coating.
  • Step 3 A layer having a negative patterned adhesion region is formed on the support.
  • Step 4 The substrate and the support are bonded together so that the transparent conductive layer (2) and the adhesion region of the layer having the adhesion region are in close contact with each other.
  • Step 5 The support is peeled from the substrate, and the portion of the transparent conductive layer (2) in close contact with the adhesion region of the layer having the adhesion region is transferred onto the adhesion region of the layer having the adhesion region. By doing so, a pattern of the transparent conductive layer (2) is formed on the substrate.
  • Step 6 A protective layer coating is applied to the entire surface of the substrate on which the pattern of the transparent conductive layer (2) is formed, and the transparent conductive layer (2) is fixed on the substrate.
  • the negative pattern represents a pattern of a transparent conductive layer (positive pattern) to be formed on a substrate and a pattern of the same scale which is the reverse of negative and positive.
  • Steps 1 and 2 are as described above.
  • the “layer having a negative patterned adhesive region formed on the support” is, It is a release material for partially peeling the transparent conductive layer formed on the transparent layer (1).
  • the “release material having a heat-sensitive adhesive layer that has been negatively patterned in advance on the support” may be simply referred to as “release material”.
  • the release material can be widely used as long as a layer having a negative patterned adhesive region for partially peeling the transparent conductive layer is formed on a sheet-like support.
  • a release material As a method for producing such a release material, after uniformly forming a functional coating film that has an adhesive function or can be expressed on a support, the adhesive function is obtained by partially patterning with light or the like. Expression or inactivation can be performed. Alternatively, a release material may be produced by printing a negative pattern directly on a support using an adhesive from the beginning.
  • a photocurable composition having adhesiveness is applied on a support to form a uniform coating film, and light irradiation is performed while masking the negative pattern to form a negative pattern. It can be carried out by curing the coating film part other than the above, losing the adhesiveness of the part, and producing a negative pattern adhesive region.
  • a photocurable composition having adhesiveness that can be used for producing a release material for example, a polymerizable polymer in which a photopolymerizable unsaturated bond is introduced into a polymer such as an alkyl acrylate ester or an alkyl methacrylate ester,
  • a photopolymerizable polyfunctional oligomer such as tetramethylol methane tetraacrylate or pentaerythritol triacrylate may be added, and a material utilizing curing shrinkage and a decrease in elastic modulus due to light irradiation may be used.
  • Partial peeling of the transparent conductive layer can be performed.
  • the surface of the transparent conductive layer is exposed to light through masking to partially develop adhesiveness or lose adhesiveness. Exfoliation can also be performed.
  • the release material used in the present invention has a negative-patterned heat-sensitive adhesive layer on the support.
  • the release material apply a heat-sensitive adhesive layer coating containing a heat-sensitive adhesive and a solvent on the support in a negative pattern opposite to the desired conductive pattern to be formed on the substrate. Can be formed.
  • the thermosensitive adhesive does not exhibit any tackiness at room temperature, but develops tackiness when heated.
  • the heat-sensitive adhesive of the heat-sensitive adhesive layer formed on the support has an affinity for both the transparent conductive layer (2) formed on the transparent substrate and the support, and strongly bonds them together. Any known heat-sensitive adhesive can be used without particular limitation as long as the heat-sensitive adhesive can be used.
  • the transparent substrate is a thermoplastic
  • the temperature at which the stickiness is developed is preferably such that the stickiness is exhibited at a temperature that does not greatly exceed the glass transition temperature of the thermoplastic plastic.
  • it is preferable that when heated to that temperature it penetrates into the gap between the metal nanowires of the transparent conductive layer (2) and adheres well. Further, after the heating, when the support is peeled off at about room temperature, it is preferable to show strong adhesion to both the metal nanowires and the support.
  • heat-sensitive adhesives examples include polyurethane adhesives, polyester adhesives, vinyl acetate (vinyl chloride / vinyl acetate copolymer) adhesives, acrylic adhesives, and the like.
  • a heat-sensitive adhesive having a glass transition temperature Tg of room temperature or higher, an acid group such as a carboxylic acid group or a sulfonic acid group, and mainly composed of an amorphous polyester resin or a polyester polyurethane resin is preferable. Is preferably in the range of 20 to 100 ° C. Further, for the purpose of manipulating the heat sensitive temperature, an appropriate amount of a resin having compatibility with the main agent and having a different glass transition temperature Tg may be blended.
  • polyolefin resin particles can be added to the heat-sensitive adhesive as an anti-blocking agent.
  • addition of polyethylene resin particles or polypropylene resin particles is preferable, and more specifically, high density polyethylene resin particles, low density polyethylene resin particles, modified polyethylene resin particles, decomposable low density polyethylene resin particles, decomposable polypropylene. Addition of resin particles is preferred.
  • the polyethylene resin particles, degradable polyethylene resin particles, polypropylene resin particles, and decomposable polypropylene resin particles have a weight average particle diameter of 0.1 to 25 ⁇ m.
  • the long axis is preferably in the range of 3 to 25 ⁇ m, the molecular weight is preferably in the range of 1,000 to 29,000, and the melting point is preferably in the range of 100 to 150 ° C.
  • any non-corrosive solvent can be used as the solvent for the heat-sensitive adhesive layer coating as long as the binder resin used for the heat-sensitive adhesive is dissolved or dispersed well.
  • suitable solvents include water, alcohols and ketones, cyclic ether compounds such as tetrahydrofuran, hydrocarbons such as cyclohexane, and aromatic solvents such as benzene, toluene and xylene.
  • the solvent is volatile and preferably has a boiling point of 200 ° C. or lower, more preferably below 150 ° C., and further preferably has a boiling point of 100 ° C. or lower.
  • the support used for the release material mainly includes polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene, polypropylene, polystyrene and EVA, vinyl resins such as polyvinyl chloride and polyvinylidene chloride, A sheet made of plastic such as polysulfone, polyethersulfone, polycarbonate, polyamide, polyimide, or acrylic resin can be used. Among these, those that do not cause thermal deformation in the step of bringing the transparent conductive layer and the heat-sensitive adhesive layer into close contact with each other and heat bonding are preferable.
  • the support may be colored to the extent that the object of the present invention is not hindered, and can be used as a single layer, but may be used as a multilayer film in which two or more layers are combined. Of these, a polyethylene terephthalate film is most suitable in terms of transparency, heat resistance, ease of handling, and cost.
  • the thickness of the support is preferably 5 ⁇ m to 100 ⁇ m because the heat resistance is poor if it is thin, and if it is thick, the heat capacity becomes large and a long heating time is required to develop tackiness by heating the heat-sensitive adhesive. More preferably, the thickness is 10 ⁇ m to 50 ⁇ m, and more preferably 15 ⁇ m to 30 ⁇ m.
  • the heat-sensitive adhesive layer on the support is formed in a so-called negative pattern in which a desired transparent conductive pattern to be obtained on the substrate is inverted.
  • a method for forming a negative pattern of adhesive a known printing method can be used. Sufficient heat sensitivity for the heat-sensitive adhesive layer exhibiting tackiness by heating to adhere well to the transparent conductive layer on the substrate in the next step.
  • a known method can be used.
  • a gravure printing method, an offset printing method, a gravure offset printing method, a screen printing method, an ink jet printing method and the like can be used.
  • the thickness of the heat-sensitive adhesive layer is preferably 0.05 ⁇ m to 5.0 ⁇ m, more preferably 0.1 ⁇ m to 2.0 ⁇ m, and still more preferably 0.2 ⁇ m to 1.0 ⁇ m.
  • the release material can be continuously formed on a roll-like support by applying or printing a heat-sensitive adhesive layer coating, and this can be used as it is in the next release step.
  • the patterning step of the transparent conductive layer (2) includes the step 4, that is, the step of bonding the substrate and the support so that the transparent conductive layer (2) and the heat-sensitive adhesive layer are in close contact with each other; That is, by peeling the support from the substrate and transferring the transparent conductive layer (2) in close contact with the heat-sensitive adhesive layer onto the heat-sensitive adhesive layer, a desired transparent conductive layer is formed on the substrate. (2) and forming a pattern.
  • the bonding step the substrate provided with the transparent conductive layer (2) and the release material are bonded and heated and heated so that the transparent conductive layer (2) and the heat-sensitive adhesive layer are in close contact with each other. Press.
  • the heat-sensitive adhesive is softened by heating and pressurizing the heat-sensitive adhesive layer, and the metal of the transparent conductive layer (2).
  • the heat-sensitive adhesive and the metal nanowires in the transparent conductive layer (2) adhere to each other through the gap between the nanowires or the network of the fibrous conductive material.
  • the release material is peeled off from the substrate, and the transparent conductive layer (2) bonded to the heat-sensitive adhesive layer is negative on the support.
  • the bonding method in the production method of the present invention is not particularly limited as long as it does not cause thermal deformation of the substrate due to heating and pressurization at the time of bonding.
  • a flat plate that is heated and pressed for a certain period of time by placing a substrate having the transparent conductive layer (2) and a heat-sensitive adhesive layer on a support in the release material between two flat plates that can be heated and pressed.
  • the roll laminate type roll may be a roll in which either one or both can be heated.
  • the material of the roll is not particularly limited as long as the transparent conductive layer (2) and the heat-sensitive adhesive layer can be favorably thermally bonded without causing thermal deformation of the transparent substrate or support used.
  • a combination of a rigid roll mainly made of a metal roll and an elastic roll mainly made of heat-resistant rubber is preferable, and any combination of metal / metal, metal / elasticity, and elasticity / elasticity can be used.
  • an elastic / elastic and elastic / metal roll pair having a wide nip width and a long heating time is preferable in order to develop the tackiness of the heat-sensitive adhesive between the nips of the roll pair.
  • the temperature and pressure conditions for appropriately expressing the adhesiveness of the heat-sensitive adhesive to the transparent conductive layer without causing thermal deformation of the transparent substrate are appropriately selected.
  • the treatment temperature is preferably 70 ° C. to 150 ° C., more preferably 80 ° C. to 130 ° C., and further preferably 90 ° C. to 120 ° C.
  • the pressure may be a roll linear pressure, and a minimum linear pressure that provides a good transfer state in a range of 10 kN / m to 60 kN / m may be selected.
  • you may preheat a heat-sensitive adhesive layer part before bonding as needed.
  • the bonded substrate with the transparent conductive layer (2) and the release material are cooled to about room temperature, and the release material is released from the substrate.
  • the transparent conductive layer (2) bonded to the heat-sensitive adhesive layer in the peeling process is peeled from the substrate together with the heat-sensitive adhesive layer.
  • the transparent conductive layer (2) that does not correspond to the portion where the heat-sensitive adhesive is formed remains as a positive pattern of the transparent conductive layer (2) on the substrate, and the pattern of the transparent conductive layer (2) is completed on the substrate.
  • taking cooling means such as blowing cooling air before peeling is effective for the purpose of good peeling and preventing patterning defects such as the occurrence of unpeeled portions.
  • a transparent pattern is formed uniformly on a colored transparent layer provided on a substrate by forming a negative pattern with a heat-sensitive adhesive on a release material. Unnecessary portions are peeled off from the layer (2).
  • the patterning of the transparent conductive layer (2) with the release material is determined only by the presence or absence of the heat-sensitive adhesive applied on the support of the release material, and the pattern of the release material corresponding to the unpeeled portion of the transparent conductive layer (2). No heat sensitive adhesive is applied to the part. For this reason, the transparent conductive layer (2) can be reliably left on the colored transparent layer (1), and unnecessary heat-sensitive adhesive remains on the transparent conductive layer (2), and the light of the transparent conductive layer (2) There is no risk of lowering the transmittance.
  • the transparent conductive layer (2) is formed by coating.
  • the transparent conductive layer (2) on the substrate formed by the step is partially left as it is.
  • the heat-sensitive adhesive layer is not formed adjacent to the transparent conductive layer (2) as in the case of using the peeled portion in the peeling step using the positive pattern.
  • the portion of the conductive layer that is in contact with the substrate becomes the uppermost layer after pattern formation.
  • the resin When resin is used to form the conductive layer, the resin concentrates on this part, the surface resistivity is high, and the resin interferes with soaking the protective layer paint in the conductive layer in a later step. It becomes difficult.
  • the conductive layer is peeled off in the peeling step using a negative pattern, the remaining transparent conductive layer is concentrated on the side closer to the substrate as in the case where it is formed, The metal nanowire and the base are fixed and the side away from the base is in a state where the metal nanowire is exposed from the resin. For this reason, the coating material for protective layers in the next step is immersed well in the conductive layer, and the metal nanowires in the conductive layer are well fixed to the substrate.
  • the surface of the conductive layer is basically exposed with metal nanowires and has a low surface resistivity and good conductivity. It can be immersed in the layer to achieve a surface resistivity that matches the intended use. Furthermore, by applying a coating for the protective layer and forming a pattern before fixing the transparent conductive layer, the adhesive comes into contact with the heat-sensitive adhesive in the metal nanowires in the conductive layer. The conductive layer can be easily peeled from the substrate.
  • the substrate with a transparent conductive layer of the present invention is preferably provided with a protective layer for the purpose of protecting the transparent conductive layer (2).
  • the protective layer is formed on the substrate and the entire surface of the transparent conductive layer formed on the substrate after forming the desired pattern. It can be obtained by coating.
  • the coating process for the protective layer coating is performed by applying the coating for the protective layer to the entire surface of the colored transparent layer partially covered with the formed transparent conductive layer pattern by the bonding process and the peeling process described above. It is carried out by drying the components and curing the resin components contained as necessary to form a protective layer.
  • the surface of the transparent conductive layer is covered and protected, and the protective layer coating is composed of gaps between the conductive fine particles in the transparent conductive layer and mesh gaps formed by the fibrous, preferably wire-like conductive substance.
  • the transparent conductive layer as a whole is firmly fixed on the substrate when it reaches the substrate while being filled and cured, thereby forming a substrate with a transparent conductive layer.
  • the coating material for the protective layer is not limited to those that can be cured and formed through polymerization and crosslinking processes, but from the viewpoint of the durability and scratch resistance of the coating film, the monomer by visible light or ultraviolet light, electron beam, heating, etc. It is preferably fixed through polymerization of the polymer or by crosslinking of the polymer compound with a crosslinking agent. Specifically, a paint containing a binder resin and a reactive monomer or a reactive oligomer, a paint made of a reactive monomer or a reactive oligomer, and the like can be given.
  • the organic polymer used for forming the solid polymer matrix as the binder resin preferably has a polar functional group bonded to the carbon skeleton.
  • the polar functional group include a carboxyl group, an ester group, a ketone group, a nitrile group, an amino group, a phosphoric acid group, a sulfonyl group, a sulfonic acid group, a polyalkylene glycol group, and an alcoholic hydroxyl group.
  • polymers useful as binders include acrylic resins, alkyd resins, polyurethanes, acrylic urethanes, polycarbonates, polyesters, polystyrenes, polyacetals, polyamides, polyvinyl alcohol, polyvinyl acetate, and cellulose.
  • An example of the inorganic polymer is a siloxane polymer produced by hydrolysis / condensation of tetraalkoxysilane.
  • examples of polymerizable organic monomers or oligomers that are monomers include methyl acrylate, methyl methacrylate, methoxypolyethylene glycol methacrylate, glycidyl acrylate, ethylene oxide.
  • Acrylate and methacrylate type monomers and oligomers represented by modified phosphoric acid acrylate, urethane acrylate, polyethylene glycol methacrylate, polybutadiene acrylate, polyester acrylate, etc .; mono (2-methacryloyloxyethyl) acid phosphate, acrylic acid, methacrylic acid, itacon Other vinyl monomers such as acid, acrylonitrile, methacrylonitrile, styrene, vinyltoluene; Epoxide compounds such as Nord A diglycidyl ether, and the like.
  • examples of polymerizable inorganic monomers that are monomers include Si, Ti, Zr, Al, Sn, Fe, Co, Ni, Cu, Zn, and Pb. , Ag, In, Sb, Pt, Au and other metal mineral salts, organic acid salts, alkoxides, and complexes (chelates). These are polymerized through hydrolysis or thermal decomposition and finally become inorganic substances (metal oxides, hydroxides, carbides, metals, etc.), and therefore are treated as inorganic monomers in the present invention. These inorganic monomers can also be used in the state of the partial hydrolyzate. Next, although the specific example of each metal compound is illustrated, it is not limited to these.
  • the above-mentioned polymer binder (organic polymer, inorganic polymer) resin, or one or more of organic or inorganic monomers or oligomers forming the polymer binder are dissolved or diluted with an organic solvent as necessary, and the viscosity is 25 cps.
  • a liquid of preferably 10 cps or less is prepared and used for impregnation of the coating film formed in the first step.
  • the viscosity of this liquid is higher than 25 cps, the liquid does not sufficiently penetrate into the coating film so as to reach the substrate when impregnated with the coating film, and the intended effect of improving the adhesion and film strength cannot be obtained.
  • the organic solvent used for dissolution or dilution is not particularly limited, and a liquid organic compound and water can be used as the solvent as long as the binder or the monomer forming the binder can be dissolved.
  • the coating material for the protective layer used as the impregnating liquid includes a curing catalyst (in the case of heat curing), a photopolymerization initiator (in the case of ultraviolet curing), a crosslinking agent, a hydrolysis catalyst (eg, acid), Polymerization initiators, stabilizers (for example, antioxidants and UV stabilizers for prolonging product life, and polymerization inhibitors for improving the shelf life) surfactants, pH adjusting agents, and the like can be added. Furthermore, you may further contain the corrosion inhibitor which prevents the corrosion of metal nanowire.
  • solvents examples include water, alcohols, ketones, cyclic ether compounds (such as tetrahydrofuran), hydrocarbons (eg, cyclohexane), or aromatic solvents (such as benzene, toluene, xylene). More preferably, the solvent is volatile and has a boiling point of 200 ° C. or lower, 150 ° C. or lower, or 100 ° C. or lower.
  • the method for forming the protective layer is not particularly limited as long as it is a known wet coating method. Specifically, spray coating, bar coating, roll coating, die coating, ink jet coating, screen coating, dip coating and the like can be mentioned.
  • the protective layer When the protective layer is formed while the transparent conductive layer is impregnated with the protective layer coating, if the protective layer after coating and drying is too thin relative to the transparent conductive layer before the coating for the protective layer is applied, it is scratch resistant. In addition, the function as a protective layer such as wear resistance and weather resistance is lowered, and if it is too thick, the contact resistance as a conductor increases.
  • the coating thickness of the transparent conductive layer is preferably 30 to 150 nm after coating and drying.
  • the surface resistivity, haze, etc. can be adjusted so as to achieve predetermined values. 40 to 175 nm is more preferable, and 50 to 150 nm is most preferable.
  • the film thickness after drying of the coating for the protective layer depends on the film thickness of the transparent conductive layer, if the film thickness is 30 nm or more, the metal nanowires are not exposed to the surface of the protective layer and the protective function by the protective layer is more When the film thickness is 150 nm or less, an excessively thick film is not formed on the surface of the transparent conductive material, and better conductive performance tends to be ensured. Covering the entire surface of the substrate while the coating for the protective layer is immersed in the transparent conductive layer portion by coating the entire surface of the substrate with the coating for the protective layer coated on the patterned transparent conductive layer. become.
  • the surface of the patterned transparent conductive film becomes smoother than when the conductive layer is fixed with the protective layer coating and then the conductive pattern is formed.
  • an optically uniform patterned transparent conductive film can be formed by the penetration of the protective layer coating material into the conductive layer by immersion.
  • a colored transparent layer coating for forming a colored transparent layer was prepared with the blending amounts described in the following adjustment examples.
  • Adjustment example of paint for colored transparent layer (1-1) Water 24 parts by mass Isopropyl alcohol 24 parts by mass Antistatic agent “ARACOAT UR-AS601-A” 7 parts by mass [Antistatic component: conductive polymer, solid content: 5%, manufactured by Arakawa Chemical Industries, Ltd.] Hardener “Aracote UR-AS601-B” 1 part by mass [solid content: 5%, manufactured by Arakawa Chemical Industries, Ltd.]
  • the colored transparent layers (1-1) to (1-10), (1-H) and (1-I) are coated with a highly transparent PET film having a thickness of 125 ⁇ m (manufactured by Teijin DuPont Films Ltd.) It was coated on a substrate of HF1C22-125) so as to have a wet thickness of 20 ⁇ m and dried.
  • the PET film used here has a haze value of 0.28 measured by the method described later, the absorbance at a wavelength of 450 nm is 0.0458, the absorbance at a wavelength of 550 nm is 0.0420, and the absorbance at a wavelength of 650 nm is 0.0380. is there.
  • haze value and absorbance were as follows.
  • the haze value and absorbance in the table are values obtained by subtracting the haze value and absorbance of the PET film itself from the haze value and absorbance of the film obtained by coating a colored transparent layer on PET.
  • Silver nanowires are Sun, B.M. Gates, B.B. Mayers, & Y. Xia, “Crystalline silver nanobe by soft solution processing”, Nano letters, (2002), 2 (2) 165-168, followed by a method using polyols in the presence of polyvinyl pyrrolidone (PVP). It is a nanowire synthesized by dissolving silver sulfate and reducing it. That is, in the present invention, nanowires synthesized by the modified polyol method described in Cambrios Technologies Corporation US Provisional Application No. 60 / 815,627 were used.
  • PVP polyvinyl pyrrolidone
  • a silver nanowire synthesized by the above method and having a minor axis diameter of about 70 nm to 80 nm and an aspect ratio of 100 or more is contained in an aqueous medium in an amount of 0.1% w / v.
  • An aqueous dispersion (ClearOmTM, Ink-A AQ, manufactured by Cambrios Technologies Corporation) was applied to the colored transparent layer (1) to a wet thickness of 20 ⁇ m using a two reverse roll coater, dried, and rolled.
  • a substrate on which a transparent conductive layer was formed was obtained as a coated product. This is referred to as a substrate with a transparent conductive layer (PN).
  • thermosensitive adhesive solution was subjected to pattern printing on a 23 ⁇ m thick PET film (Teijin Tetron Film G2 manufactured by Teijin DuPont Films) as a support.
  • the conductive layer pattern formed on the substrate was a diamond pattern for a capacitive projection touch panel.
  • the diamond pattern is a linear pattern (Y pattern) in which a diamond-shaped electrostatic element pattern having a side length of 4 mm and an inner angle of 90 degrees and a thin line pattern having a line width of 600 ⁇ m are alternately arranged
  • the flow of the original fabric is a linear pattern (X pattern) in which a pattern of diamond-shaped electrostatic elements with a side length of 4 mm and an inner angle of 90 degrees and a thin line pattern with a line width of 400 ⁇ m are alternately arranged. It was set as the pattern arrange
  • the transparent conductive layer and the heat-sensitive adhesive layer are brought into contact with each other while running the substrate on which the transparent conductive layer formed as the roll-shaped coating is formed and the peeling substrate having the negative-patterned heat-sensitive adhesive layer. Stacked face to face, heated with metal heating roll and heat resistant silicon roll, using laminator with pressure nip, heating roll temperature 115 ° C, roll nip pressure (linear pressure) 30kN / m, speed 3m / min Then, the lamination was performed continuously. While the bonded material is running, when the temperature of the bonded portion is lowered to about room temperature, the support is continuously peeled from the substrate, and the transparent conductive layer (2) remains in a desired pattern on the substrate. A roll-shaped film substrate having a patterned transparent conductive layer (2) was obtained. This is referred to as a patterned substrate (P) with a transparent conductive layer.
  • P patterned substrate
  • Example 1 Production of substrate with transparent conductive layer (PN-1) and substrate with transparent conductive layer with pattern (P-1))
  • a colored transparent layer (1-1) having a thickness of 0.1 ⁇ m was formed using the paint for the colored transparent layer (1-1), and a transparent conductive layer (2) was formed thereon. This was provided with a protective layer to obtain a substrate with a transparent conductive layer (PN-1).
  • a transparent conductive layer (2) was formed thereon, followed by patterning.
  • a protective layer was provided on the transparent conductive layer (2) to obtain a substrate (P-1) with a patterned transparent conductive layer.
  • Example 2 A substrate with a transparent conductive layer (PN-1) and a transparent conductive layer with a pattern were formed in the same manner as in Example 1 except that the colored transparent layer (1-2) was used instead of the colored transparent layer (1-1). A layered substrate (P-1) was obtained.
  • Example 3 A substrate with a transparent conductive layer (PN-1) and a transparent conductive layer with a pattern are formed in the same manner as in Example 1 except that the colored transparent layer (1-3) is used instead of the colored transparent layer (1-1). A layered substrate (P-1) was obtained.
  • Example 4 A substrate with a transparent conductive layer (PN-1) and a transparent conductive layer with a pattern were formed in the same manner as in Example 1 except that the colored transparent layer (1-4) was used instead of the colored transparent layer (1-1). A layered substrate (P-1) was obtained.
  • Example 5 A substrate with a transparent conductive layer (PN-1) and a transparent conductive layer with a pattern were produced in the same manner as in Example 1 except that the colored transparent layer (1-5) was used instead of the colored transparent layer (1-1). A layered substrate (P-1) was obtained.
  • Example 6 A substrate with a transparent conductive layer (PN-1) and a transparent conductive layer with a pattern were formed in the same manner as in Example 1 except that the colored transparent layer (1-6) was used instead of the colored transparent layer (1-1). A layered substrate (P-1) was obtained.
  • Example 7 A substrate with a transparent conductive layer (PN-1) and a transparent conductive layer with a pattern, in the same manner as in Example 1, except that the colored transparent layer (1-7) was used instead of the colored transparent layer (1-1).
  • a layered substrate (P-1) was obtained.
  • Example 8 A substrate with a transparent conductive layer (PN-1) and a transparent conductive layer with a pattern were formed in the same manner as in Example 1 except that the colored transparent layer (1-8) was used instead of the colored transparent layer (1-1). A layered substrate (P-1) was obtained.
  • Example 9 A substrate with a transparent conductive layer (PN-1) and a transparent conductive layer with a pattern were formed in the same manner as in Example 1 except that the colored transparent layer (1-9) was used instead of the colored transparent layer (1-1). A layered substrate (P-1) was obtained.
  • Example 10 A substrate with a transparent conductive layer (PN-1) and a transparent conductive layer with a pattern are formed in the same manner as in Example 1 except that the colored transparent layer (1-10) is used instead of the colored transparent layer (1-1).
  • a layered substrate (P-1) was obtained.
  • Example 1 Except not forming a colored transparent layer, it carried out similarly to Example 1, and obtained the base
  • Example 2 Substrate with a transparent conductive layer (PN-1) and patterned transparent conductive material in the same manner as in Example 1 except that the colored transparent layer (1-H) was used instead of the colored transparent layer (1-1). A layered substrate (P-1) was obtained.

Abstract

La présente invention concerne un substrat doté d'une couche électroconductrice transparente, un substrat transparent possédant sur celui-ci, dans l'ordre suivant : une couche transparente colorée (1) possédant un facteur d'absorption à une longueur d'onde de 450 nm, une longueur d'onde de 550 nm et une longueur d'onde de 650 nm, indépendamment les unes des autres, dans la plage de 0,001 à 0,1, et une valeur de Hayes dans la plage de 0,1 à 2 % ; et une couche électroconductrice transparente (2) comprenant un nanofil métallique. L'invention concerne également un procédé de fabrication du substrat doté d'une couche électroconductrice transparente comprenant : la formation de la couche transparente colorée (1) et de la couche électroconductrice transparente (2) par revêtement sur le substrat transparent ; la liaison puis la séparation du substrat et d'un corps de support possédant une couche de région adhésive soumise à une formation de motif négatif ; le transfert de la couche électroconductrice transparente (2) sur des parties en contact étroit avec la région adhésive sur la région adhésive, et la formation d'un motif de la couche électroconductrice transparente (2) sur le substrat ; puis l'application d'un revêtement de couche protectrice et la fixation de la couche électroconductrice transparente (2) sur le substrat.
PCT/JP2012/074507 2011-09-26 2012-09-25 Substrat doté d'une couche électroconductrice transparente et son procédé de fabrication WO2013047493A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2013505224A JP5282991B1 (ja) 2011-09-26 2012-09-25 透明導電層付き基体及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-209178 2011-09-26
JP2011209178 2011-09-26

Publications (1)

Publication Number Publication Date
WO2013047493A1 true WO2013047493A1 (fr) 2013-04-04

Family

ID=47995525

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/074507 WO2013047493A1 (fr) 2011-09-26 2012-09-25 Substrat doté d'une couche électroconductrice transparente et son procédé de fabrication

Country Status (3)

Country Link
JP (1) JP5282991B1 (fr)
TW (1) TW201324546A (fr)
WO (1) WO2013047493A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3021374A3 (fr) * 2014-10-20 2016-08-24 Samsung Display Co., Ltd. Dispositifs d'affichage transparents et leurs procédés de fabrication
JP2017539047A (ja) * 2014-10-17 2017-12-28 シー３ナノ・インコーポレイテッドＣ３Ｎａｎｏ Ｉｎｃ． ナノスケール着色剤を使用して明るい色相が制御される透明フィルム
CN109976596A (zh) * 2014-06-27 2019-07-05 宸盛光电有限公司 触控感应单元
JPWO2020137797A1 (ja) * 2018-12-27 2021-11-11 富士フイルム株式会社 導電性転写材料、パターンつき基板の製造方法、積層体、及びタッチパネル

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102080862B1 (ko) * 2013-08-30 2020-02-25 동우 화인켐 주식회사 투명 도전체

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010044364A1 (fr) * 2008-10-15 2010-04-22 コニカミノルタホールディングス株式会社 Élément de conversion photoélectrique organique et procédé de fabrication d'élément de conversion photoélectrique organique
JP2011086413A (ja) * 2009-10-13 2011-04-28 Nissha Printing Co Ltd ディスプレイ電極用透明導電膜

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5487787B2 (ja) * 2009-08-04 2014-05-07 大日本印刷株式会社 透明導電部材

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010044364A1 (fr) * 2008-10-15 2010-04-22 コニカミノルタホールディングス株式会社 Élément de conversion photoélectrique organique et procédé de fabrication d'élément de conversion photoélectrique organique
JP2011086413A (ja) * 2009-10-13 2011-04-28 Nissha Printing Co Ltd ディスプレイ電極用透明導電膜

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109976596A (zh) * 2014-06-27 2019-07-05 宸盛光电有限公司 触控感应单元
JP2017539047A (ja) * 2014-10-17 2017-12-28 シー３ナノ・インコーポレイテッドＣ３Ｎａｎｏ Ｉｎｃ． ナノスケール着色剤を使用して明るい色相が制御される透明フィルム
EP3021374A3 (fr) * 2014-10-20 2016-08-24 Samsung Display Co., Ltd. Dispositifs d'affichage transparents et leurs procédés de fabrication
CN106200062A (zh) * 2014-10-20 2016-12-07 三星显示有限公司 透明显示装置及其制造方法
US9564605B2 (en) 2014-10-20 2017-02-07 Samsung Display Co., Ltd. Transparent display devices including a polymer substrate comprising colored particles with improved flexible and mechanical properties
CN106200062B (zh) * 2014-10-20 2020-10-27 三星显示有限公司 透明显示装置及其制造方法
JPWO2020137797A1 (ja) * 2018-12-27 2021-11-11 富士フイルム株式会社 導電性転写材料、パターンつき基板の製造方法、積層体、及びタッチパネル

Also Published As

Publication number Publication date
JPWO2013047493A1 (ja) 2015-03-26
TW201324546A (zh) 2013-06-16
JP5282991B1 (ja) 2013-09-04

Similar Documents

Publication Publication Date Title
JP4737348B2 (ja) 透明導電層パターンの形成方法
US9236162B2 (en) Transparent conductive ink and transparent conductive pattern forming method
JP5533530B2 (ja) 両面粘着シートを用いた透明導電膜積層体およびタッチパネル装置
US8664533B2 (en) Substrate having transparent conductive layer, method for producing same, transparent conductive film laminate for touch panel, and touch panel
US8795462B2 (en) Transparent conductive coating with filler material
KR102254683B1 (ko) 패턴화된 나노와이어 투명 전도체들에 대한 전자 컴포넌트들의 본딩
JP2014191894A (ja) 透明導電フィルム及びタッチパネル
Park et al. High-resolution and large-area patterning of highly conductive silver nanowire electrodes by reverse offset printing and intense pulsed light irradiation
JP5282991B1 (ja) 透明導電層付き基体及びその製造方法
JP2012151095A (ja) 透明導電性フィルム、静電容量式タッチパネルの透明電極及びタッチパネル
JP2010244746A (ja) 透明電極、透明電極の製造方法及び有機エレクトロルミネッセンス素子
EP3053012B1 (fr) Revêtement de protection pour motif conducteur imprimé sur conducteurs transparents texturés à base de nanofils
JP5516147B2 (ja) 両面粘着シートを用いた透明導電膜積層体およびタッチパネル装置
KR20160094621A (ko) 수전사용 전도성 전사필름, 이를 이용한 코팅 방법
JP2013202911A (ja) 透明導電層付き基体の製造方法
JP2014116103A (ja) 導電性基体の製造方法、導電性基体及び接着剤層付き支持体
JP2013206804A (ja) 透明導電層付き基体、その製造方法、及びそれを用いたタッチパネル
JP7172712B2 (ja) 導電体及び導電体の製造方法
KR20230142601A (ko) 투명 도전성 필름
KR20230142602A (ko) 투명 도전성 필름
JP2014099294A (ja) 基材の製造方法、基材、および基材を用いた成形体

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2013505224

Country of ref document: JP

Kind code of ref document: A

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

Ref document number: 12836369

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: 12836369

Country of ref document: EP

Kind code of ref document: A1