CN110797139A - Transparent conductive laminate and method for producing transparent conductive laminate - Google Patents
Transparent conductive laminate and method for producing transparent conductive laminate Download PDFInfo
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- CN110797139A CN110797139A CN201910692566.8A CN201910692566A CN110797139A CN 110797139 A CN110797139 A CN 110797139A CN 201910692566 A CN201910692566 A CN 201910692566A CN 110797139 A CN110797139 A CN 110797139A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
Abstract
[ problem ] to]The invention provides a transparent conductive laminate having high conductivity and transparency, and a method for producing the conductive laminate. [ solution means ] to]A transparent conductive laminate having a substrate and a surface resistivity of 1 x 10, the substrate comprising a carbon material2Ω/sq～1×1011A transparent conductive laminate of an omega/sq conductive layer,the carbon material having a major axis of 10 μm or more and a minor axis of 2 μm or more is contained in an amount of 10 particles/cm2The following.
Description
Technical Field
The present invention relates to a transparent conductive laminate and a method for producing a transparent conductive laminate.
Background
Carbon materials are known to exhibit high chemical stability in addition to excellent electrical and thermal conductivity, and are expected as excellent electrically conductive materials in the fields of optical applications and the like. However, carbon materials have a large aspect ratio and a coordinately unsaturated structure, and therefore have a strong intermolecular interaction and a property of being easily aggregated. The carbon material cannot sufficiently exhibit properties such as conductivity and transparency in an aggregated state, and thus it is required to improve dispersibility of the carbon material in the conductive paint. In order to improve the dispersibility of the carbon material, for example, it is known to perform a dispersion treatment using ultrasonic waves.
However, the above dispersion treatment is insufficient for the recent market demand for high transparency. In order to meet the demand for high transparency, a method of reducing a carbon material to achieve high conductivity has been proposed (patent document 1); only the method of separating and using a carbon nanomaterial having high conductivity (patent document 2) has been known, but these methods require special equipment and steps, and thus there remains a problem in commercial production.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-
Patent document 2: japanese patent No. 6237967
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a transparent conductive laminate having high conductivity and transparency.
Means for solving the problems
The present inventors have found that the number of carbon materials having a specific size (in the present specification, as described later, including the case of aggregates containing a carbon material) per unit area has a large influence on the electrical conductivity and transparency, and have newly found that a transparent conductive laminate having a substrate containing a carbon material and having a surface resistivity of 1 × 10 can obtain high electrical conductivity and transparency, and have completed the present invention2Ω/sq～1×1011A transparent conductive laminate of an omega/sq conductive layer, characterized in that the carbon material having a major axis of 10 μm or more and a minor axis of 2 μm or more is 10 particles/cm2The following.
Namely, the present invention relates to the following:
[1]a transparent conductive laminate having a substrate and a surface resistivity of 1 x 10, the substrate comprising a carbon material2Ω/sq～1×1011A transparent conductive laminate of an omega/sq conductive layer,
the carbon material having a major axis of 10 μm or more and a minor axis of 2 μm or more is contained in an amount of 10 particles/cm2The following.
[2] The transparent conductive laminate according to [1], wherein the haze value of the transparent conductive laminate is 3% or less.
[3] The transparent conductive laminate according to [1] or [2], wherein the carbon material is at least one selected from the group consisting of graphene, fullerene and carbon nanotube.
[4]Such as [1]]～[3]The transparent conductive laminate according to any one of the above, wherein the content of the carbon material in the conductive layer is 50mg/m2The following.
[5] A conductive coating material for forming a conductive layer in the transparent conductive laminate according to any one of [1] to [4 ].
[6] A display device comprising the transparent conductive laminate according to any one of [1] to [4 ].
[7] A light control device comprising the transparent conductive laminate according to any one of [1] to [4 ].
[8] The method for producing a transparent conductive laminate according to any one of [1] to [4], which comprises a step of forming a conductive layer on a substrate using a conductive coating material containing a carbon material.
[9] The method for producing a transparent conductive laminate according to [8], wherein the step of forming the conductive layer comprises a step of filtering a conductive paint containing a carbon material with a filter having a pore size of 1 to 20 μm.
[10] The method for producing a transparent conductive laminate according to [9], wherein the filter is made of polyolefin.
[11] A method for producing an electrically conductive coating material comprising a carbon material,
according to the content of the carbon material of 50mg/m2In the case of forming the conductive layer by applying the conductive coating material to a substrate, the conductive layer satisfies the following conditions (a) to (c):
(a) surface resistivity of 102Ω/sq～1011Ω/sq；
(b) A haze value of 3% or less; and
(c) the carbon material having a major axis of 10 μm or more and a minor axis of 2 μm or more is contained in an amount of 10 particles/cm2The following.
[12] The method for producing a conductive paint according to [11], wherein the carbon material is at least one selected from the group consisting of graphene, fullerene and carbon nanotube.
[13] The method for producing a conductive paint according to [11] or [12], which comprises a step of filtering the conductive paint by using a filter having a pore size of 1 μm to 20 μm.
[14] The method for producing a conductive paint according to [13], wherein the filter is made of polyolefin.
[15] The method for producing a conductive paint according to any one of [11] to [14], which comprises a step of dispersing a carbon material under a condition exceeding a surface resistivity minimum point.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a transparent conductive laminate having high conductivity and transparency can be obtained.
Detailed Description
< transparent conductive laminate >
First, the transparent conductive laminate of the present invention will be explained.
The transparent conductive laminate of the present invention is characterized in that it comprises a substrate and a carbon-containing material and has a surface resistivity of 1X 102Ω/sq～1×1011Omega/sq, and a carbon material having a major diameter of 10 μm or more and a minor diameter of 2 μm or more, in an amount of 10 particles/cm2The following.
< substrate >
The material of the substrate is not particularly limited, and may be any of an inorganic substrate and an organic substrate. Among these, inorganic substrates are preferable because they are less susceptible to the solvent contained in the conductive coating material and any solvent can be used. The inorganic substrate is preferably alkali-free glass, borosilicate glass, aluminosilicate glass, or the like, and more preferably alkali-free glass. Examples of the organic base material include a polyester resin such as cycloolefin polymer (COP), acrylic resin, polyethylene terephthalate (PET), amorphous PET, polyethylene naphthalate (pen), and modified polyester, a polyolefin resin such as polyethylene resin (PE), polypropylene resin (PP), polystyrene resin, and cycloolefin resin, a vinyl resin such as polyvinyl chloride and polyvinylidene chloride, a polyether ether ketone resin (PEEK), a polysulfone resin (PSF), a polyether sulfone resin (PEs), a polycarbonate resin (PC), a polyamide resin, a polyimide resin, an acrylic resin, and a triacetyl cellulose resin (TAC). Among these, cycloolefin polymer (COP), acrylic resin, polyethylene terephthalate (PET), polyvinyl alcohol resin, triacetyl cellulose resin (TAC), and the like are preferably used. These may be used alone or in combination of two or more.
For the purpose of facilitating adhesion, improving wettability, and the like, various surface treatments such as corona treatment, plasma treatment, alkali treatment, excimer treatment, primer coating, degreasing treatment, surface roughening treatment, and the like may be applied to the surface of the base material. In particular, inorganic substrates are preferably subjected to etching or a cleaning step with an alkaline solution in order to reduce the thickness and weight of the inorganic substrate and to improve the wettability of the conductive coating material to the substrate.
In the case of the inorganic base material, the thickness of the base material is not particularly limited, but is preferably 10mm or less, more preferably 0.01mm to 50mm, and further preferably 0.01mm to 1 mm.
In the case of an organic substrate, the shape thereof may be, for example, a film shape or a sheet shape. In the case of the film shape, the thickness is not particularly limited, and is, for example, preferably 10 to 200 μm, more preferably 50 to 150 μm. In the case of the sheet shape, the thickness is not particularly limited, and is, for example, preferably 0.1mm to 5mm, more preferably 0.2mm to 1 mm.
< conductive layer >
The conductive layer in the transparent conductive laminate of the present invention contains a carbon material and has a surface resistivity of 1X 102Ω/sq～1×1011Omega/sq. By providing such a conductive layer, a transparent conductive laminate having excellent conductivity can be provided.
The conductive layer can be formed, for example, by applying a conductive coating material containing a carbon material to a substrate and then performing heat treatment. The conductive coating material may be applied directly to at least one surface of the substrate, or may be applied to another functional layer such as an undercoat layer provided on the substrate in advance.
Examples of the resin used for the functional layer include polyurethane resin, polyester resin, acrylic resin, epoxy resin, and other general-purpose resins.
(carbon Material)
Examples of the carbon material include carbon nanotubes, graphene, and fullerene. These may be used alone or in combination of two or more.
The carbon nanotube is not particularly limited, and a carbon nanotube produced by an arc discharge method, a laser evaporation method, a chemical vapor deposition method (CVD method), or the like can be used, and more specifically, any of a single-walled carbon nanotube, a double-walled carbon nanotube, a multi-walled carbon nanotube, and a mixture thereof can be used. In view of excellent conductivity, it is preferable to include at least a single-walled carbon nanotube.
The length of the carbon nanotube is preferably 1 to 2000. mu.m, more preferably 5 to 1000. mu.m, and still more preferably 5 to 500. mu.m. When the length of the carbon nanotube is within the above range, the conductive layer is excellent in conductivity and transparency.
In the case of single-walled carbon nanotubes, the diameter of the carbon nanotubes is preferably 0.5nm to 20nm, more preferably 1nm to 10 nm. When the diameter of the carbon nanotube is within the above range, the conductive layer is excellent in conductivity and transparency.
The content of the carbon material in the conductive coating material is not particularly limited, and is preferably 0.1 to 40 parts by weight, more preferably 0.5 to 30 parts by weight, and further preferably 1 to 20 parts by weight, based on 100 parts by weight of the solid content of the conductive coating material. When the content of the carbon nanotube is within the above range, the conductive layer can be preferably formed to have both conductivity and transparency.
(dispersing agent)
The carbon material may be previously subjected to a dispersion treatment in water or the like using a dispersant. Examples of the dispersant include cationic dispersants, anionic dispersants, zwitterionic dispersants, nonionic dispersants, and polymeric dispersants. These may be used alone or in combination of two or more. The dispersant is preferably a dispersant having an HLB value of 12 or more, and more preferably a dispersant having an HLB value of 14 or more. The HLB value in the present specification can be calculated by the following numerical expression.
Griffin method: HLB value ═ molecular weight of hydrophilic moiety ÷ (molecular weight of the whole) ] × 20
Examples of the cationic dispersant include alkylamine salts having an alkyl group having 8 to 22 carbon atoms such as stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride and cetyltrimethylammonium bromide.
Examples of the anionic dispersant include sodium alkylsulfates having 8 to 18 carbon atoms such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate salts having 8 to 18 carbon atoms such as sodium polyoxyethylene lauryl ether sulfate, alkylbenzene sulfonates having 8 to 18 carbon atoms such as sodium deoxycholate and sodium dodecylbenzenesulfonate, fatty acid salts, and naphthalene sulfonic acid formaldehyde condensates such as sodium salts of β -naphthalene sulfonic acid formaldehyde condensates.
Examples of the zwitterionic dispersant include alkylbetaines having an alkyl group having 8 to 22 carbon atoms, and alkylamine oxides having an alkyl group having 8 to 18 carbon atoms.
Examples of the nonionic dispersant include polyoxyethylene alkyl ethers having an alkyl group having 1 to 20 carbon atoms, block copolymers composed of ethylene oxide and propylene oxide, alkylphenol polyglycol ethers having an alkyl group having 1 to 20 carbon atoms, polyoxyalkylene derivatives such as polycarboxylate ethers having an alkylene group having 2 to 4 carbon atoms, and sorbitan fatty acid esters such as sorbitan tristearate.
Examples of the polymer-based dispersing agent include polyvinylpyrrolidone, polyvinyl alcohol, hydroxycellulose, hydroxyalkyl cellulose having an alkyl group having 1 to 8 carbon atoms, cellulose derivatives such as carboxymethyl cellulose and carboxypropyl cellulose, and polymer-based dispersing agents such as starch, gelatin, acrylic copolymers, polycarboxylic acids or derivatives thereof, polystyrene sulfonic acid or salts thereof.
Among these, polyvinylpyrrolidone, polyoxyalkylene derivative, polystyrene sulfonic acid, cellulose derivative, polycarboxylic acid, acrylic copolymer, and alkylbenzene sulfonate are preferable, and polyvinylpyrrolidone, polyoxyalkylene derivative, polycarboxylic acid, and acrylic copolymer are preferable for better dispersibility of the carbon material. Further, a dispersant having 1 or more branches and a molecular weight of 15 or more is preferable because the molecular chain of the dispersant is extended in all directions and the dispersibility of the carbon material is further improved.
From the viewpoint of achieving both dispersibility and transparency, the amount of the dispersant to be added is preferably 0.01 to 100 parts by weight, more preferably 0.2 to 40 parts by weight, and still more preferably 0.5 to 10 parts by weight, based on 1 part by weight of the carbon material.
By dispersing the carbon material in water in the presence of the dispersant, the carbon material and the dispersant are made to interact with each other, and a conductive coating material in which the carbon material is well dispersed in water can be obtained.
< Binder resin >
In order to improve strength when the conductive layer is formed, the conductive paint may include a binder resin. The binder resin is not particularly limited, and examples thereof include acrylic resins, polyester resins, urethane resins, melamine resins, silicate resins, titanate resins, and aluminate resins. These may be used alone or in combination of two or more. In particular, from the viewpoint of strength, transparency and durability, it is preferable to contain at least a silicate resin or a melamine resin.
The acrylic resin is not particularly limited as long as it is a polymer containing, as a constituent monomer, a polymerizable monomer having an acid group such as a carboxyl group, an acid anhydride group, a sulfonic acid group, or a phosphoric acid group, and examples thereof include a homopolymer or a copolymer of a polymerizable monomer having an acid group, a copolymer of a polymerizable monomer having an acid group and a copolymerizable monomer, and more specifically, a (meth) acrylic resin, and the like.
The (meth) acrylic resin may contain a (meth) acrylic monomer as a main constituent monomer (for example, 50 mol% or more), and may be polymerized with a copolymerizable monomer, in which case at least one of the (meth) acrylic monomer and the copolymerizable monomer may have an acid group.
Examples of the (meth) acrylic resin include: (meth) acrylic monomers having an acid group [ e.g., [ (meth) acrylic acid, sulfoalkyl (meth) acrylate, sulfonic acid group-containing (meth) acrylamide ], or copolymers thereof, copolymers of (meth) acrylic monomers having or not having an acid group with other polymerizable monomers having an acid group [ e.g., other polymerizable carboxylic acids, polymerizable polycarboxylic acids or anhydrides, vinyl aromatic sulfonic acids ], and/or copolymerizable monomers [ e.g., alkyl (meth) acrylates, glycidyl (meth) acrylates, (meth) acrylonitrile, aromatic vinyl monomers ], copolymers of other polymer monomers having an acid group with (meth) acrylic copolymerizable monomers [ e.g., alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, glycidyl (meth) acrylates, meth) acrylonitrile, etc. ], copolymers of the (meth) acrylic copolymerizable monomers with an acid group, copolymers of the (meth) acrylic monomers with an acid group, and the like, Rosin-modified urethane acrylate, special modified acrylic resin, urethane acrylate, epoxy acrylate, urethane acrylate emulsion, and the like.
Among these (meth) acrylic resins, preferred are (meth) acrylic acid- (meth) acrylate polymers (such as acrylic acid-methyl methacrylate copolymers), and (meth) acrylic acid- (meth) acrylate-styrene copolymers (such as acrylic acid-methyl methacrylate-styrene copolymers).
The polyester resin is not particularly limited as long as it is a polymer compound obtained by polycondensing a compound having 2 or more carboxyl groups in the molecule and a compound having 2 or more hydroxyl groups, and examples thereof include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and the like.
The urethane resin is not particularly limited as long as it is a polymer compound obtained by copolymerizing a compound having an isocyanate group and a compound having a hydroxyl group, and examples thereof include ester/ether polyurethanes, polyester polyurethanes, carbonate polyurethanes, and acrylic polyurethanes.
Examples of the silicate resin include alkoxysilanes (oligomers having 1 or more siloxane bonds (Si — O — Si) in 1 molecule) obtained by condensation of monomers of alkoxysilanes represented by the following general formula (I).
SiR4(1)
[ wherein R represents hydrogen, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having or not having a substituent, or a phenyl group having or not having a substituent, and at least 1 of 4R represents an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group ]
The silicate resin is preferably a product obtained by condensation of 2 or more molecules of alkoxysilane represented by the general formula (1).
The structure of the alkoxysilane oligomer is not particularly limited, and may be linear or branched.
Examples of the silicate resin include a silicon alkoxide resin such as a silicon alkoxide acrylic resin, a silicon alkoxide epoxy resin, a silicon alkoxide vinyl resin, a silicon alkoxide methacrylic resin, a silicon alkoxide thiol resin, a silicon alkoxide amino resin, a silicon alkoxide isocyanate resin, a silicon alkoxide alkyl resin, and a silicon alkoxide resin having no functional group other than a silicon alkoxide group.
The content of the binder resin is not particularly limited, and is, for example, preferably 20 to 99 parts by weight, more preferably 50 to 98 parts by weight, still more preferably 60 to 95 parts by weight, and yet more preferably 70 to 90 parts by weight, based on 100 parts by weight of the solid content of the conductive coating material. When the content of the binder resin is within the above range, the film strength and the electrical conductivity when the conductive layer is formed are good.
(leveling agent)
In order to improve the affinity to the substrate, the conductive coating material preferably contains a leveling agent. By adding the leveling agent, the occurrence of shrinkage or unevenness in the formation of the conductive layer can be suppressed. The leveling agent also contributes to improvement in dispersion stability of the conductive coating material, and the conductive layer formed from the conductive coating material containing the leveling agent is excellent in transparency and conductivity. The leveling agent having a high hydrophilicity is preferably a leveling agent having an HLB value of 10 or more, and more preferably a leveling agent having an HLB value of 12 or more, because dispersion of the carbon material is not suppressed. Further, the carbon material having higher affinity for the hydrophobic carbon material than the dispersant is preferable, and therefore, the hydrophobicity is preferably higher than the dispersant.
Specific examples of the leveling agent include a polyether leveling agent, a silicone leveling agent, a fluorine leveling agent, a polyester leveling agent, an organosilicon leveling agent, and an acrylic leveling agent. They may be used alone or in combination. Among these, polyester leveling agents having an ester bond and polyether leveling agents having an ether bond are preferable because they easily interact with the carbon material and do not inhibit dispersion of the carbon material in water-alcohol.
Examples of the polyester leveling agent include polyester-modified acryloyl group-containing polydimethylsiloxane, polyester-modified polydimethylsiloxane, and polyester polyol.
Examples of the polyether leveling agent include cellulose ether; pullulan; polyethylene glycol: silicone-modified polyethers such as polyether-modified polydimethylsiloxane, polyether-modified siloxane, polyether ester-modified hydroxyl-containing polydimethylsiloxane, polyether-modified acryl-containing polydimethylsiloxane, and the like; a polyglycerol; polyether polyol, polyoxyethylene-polyoxypropylene condensation products, alkyl ether derivatives such as polyoxyethylene alkylphenyl ether and lauryl alcohol alkoxylates, and alkyl ether sulfates.
Examples of the fluorine-based leveling agent include perfluoropolyether-modified polydimethylsiloxane, perfluoropolyester-modified polydimethylsiloxane, perfluorobutane sulfonic acid, an oligomer containing a fluorine-containing hydrophilic group and a lipophilic group, a perfluoroalkyl-containing carboxylate, a perfluoroalkyl-containing phosphate, and the like.
Examples of the silicone leveling agent include reactive polysiloxanes having reactive groups such as amino groups, epoxy groups, hydroxyl groups, and carboxyl groups introduced thereto, and non-reactive polysiloxanes having non-reactive groups such as alkyl groups, ester groups, aralkyl groups, phenyl groups, and polyether groups introduced thereto.
Examples of the acrylic leveling agent include acrylic copolymers composed of silicone and acrylic acid.
The content of the leveling agent is not particularly limited, and is preferably 0.01 to 40 parts by weight, more preferably 0.1 to 20 parts by weight, and still more preferably 1 to 10 parts by weight, based on the total solid content of the conductive coating material. When the content of the conductive coating material is within the above range, the coatability of the substrate, the dispersion stability, and the film strength when the conductive layer is formed become good.
(solvent)
To increase the affinity for the substrate, the conductive coating may contain a solvent. The solvent is not particularly limited, and examples thereof include: alcohols such as methanol, ethanol, 2-propanol, and 1-propanol; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether; glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate; propylene glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol; propylene glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol dimethyl ether, and propylene glycol diethyl ether; propylene glycol ether acetates such as propylene glycol monomethyl ether acetate; ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; hydrocarbons such as toluene, xylene (o-xylene, m-xylene, or p-xylene), hexane, and heptane: esters such as ethyl acetate, butyl acetate, ethyl acetoacetate, methyl o-acetate, and ethyl o-formate; amide compounds such as N-methylformamide, N-dimethylformamide, gamma-butyrolactone and N-methylpyrrolidone; hydroxyl-containing compounds such as 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, catechol, cyclohexanediol, cyclohexanedimethanol, and glycerol; compounds having a sulfo group such as dimethyl sulfoxide; organic solvents such as halogens, isophorone, propylene carbonate, acetylacetone, and acetonitrile; and a mixed solvent of water and these organic solvents (water-containing organic solvent), a mixed solvent of 2 or more organic solvents, and the like.
In the case of using an inorganic base material, among the above solvents, from the viewpoint of dispersion stability of the carbon material and coatability on the base material, alcohols, ethers, acetates, ketones, mixed solvents of alcohols and ethers, mixed solvents of alcohols and acetates, mixed solvents of alcohols and ketones, and mixed solvents of water and organic solvents are preferable, and alcohols, mixed solvents of water and ethers, mixed solvents of water and acetates, mixed solvents of water and alcohols and ethers, mixed solvents of water and alcohols and acetates, mixed solvents of water and alcohols and ketones are more preferable, and alcohols, mixed solvents of water and ethers, and mixed solvents of water and acetates are even more preferable. By using these solvents, a binder resin having high hydrophobicity can be mixed in the conductive layer. In addition, it is also effective to add ethylene glycol, propylene glycol, an amide compound, or the like, in order to improve coatability.
In the case of using an organic base material, among the above solvents, from the viewpoints of dispersion stability of the carbon material, coatability on the base material, and prevention of decrease in transparency due to swelling or discoloration of the base material, a mixed solvent of water and an organic solvent is preferred, a mixed solvent of water and an alcohol is more preferred, a mixed solvent of water and an ether is more preferred, a mixed solvent of water and an acetate is more preferred, and a mixed solvent of water and an alcohol is still more preferred. The alcohol used in the mixed solvent of water and an alcohol is preferably methanol, ethanol, or 2-propanol. When water is combined with an alcohol, the alcohol ratio is preferably 20% to 99%, more preferably 30% to 97%, and still more preferably 40% to 96%. In addition, similarly to the inorganic base material, it is also effective to add ethylene glycol, propylene glycol, an amide compound, or the like, in order to improve coatability.
The content of the solvent is not particularly limited, and is preferably added so that the solid content of the conductive coating material is 3 wt% or less, and more preferably 0.1 wt% to 2 wt%. When a solvent is added to the conductive coating material, water is combined with another solvent, so that the proportion of water in the solvent contained in the conductive coating material is preferably 1 to 70 wt%, more preferably 3 to 65 wt%, and still more preferably 4 to 60 wt%.
In the present specification, a substance that completely dissolves all components of the conductive coating material (i.e., a "solvent") and a substance that disperses an insoluble component (i.e., a "dispersion medium") are not particularly distinguished and are both referred to as a "solvent".
(other Components)
The conductive coating material may further contain a conductive polymer, a crosslinking agent, a catalyst, an antioxidant, an antifoaming agent, a rheology control agent, a neutralizing agent, a thickener, and the like.
Examples of the conductive polymer include polythiophene, polypyrrole, polyaniline, polyacetylene, poly (phenylene vinylene), polynaphthalene, and derivatives thereof. These may be used alone or in combination of two or more. Among them, from the viewpoint of easy formation of a highly conductive molecule, a conductive polymer containing at least 1 thiophene ring in the molecule is preferable. The conductive polymer may be a complex with a dopant such as a polyanion.
The composite of the conductive polymer and the polyanion is preferably a composite of poly (3, 4-ethylenedioxythiophene) and polystyrenesulfonic acid, because of its particularly excellent conductivity.
The crosslinking agent is not particularly limited, and examples thereof include melamine-based, polycarbodiimide-based, polyoxazoline-based, polyepoxy-based, polyisocyanate-based, and polyacrylate-based crosslinking agents. These may be used alone or in combination of two or more.
The catalyst is not particularly limited, and examples thereof include a photopolymerization initiator, a thermal polymerization initiator, an acid, and a base. These may be used alone or in combination of two or more.
The thickness of the conductive layer is preferably 1nm to 500nm, more preferably 10nm to 300nm, and still more preferably 20nm to 200 nm.
The surface resistivity of the conductive layer is preferably 1X 102Ω/sq～1×1011Omega/sq, more preferably 1X 102Ω/sq～5×1010Omega/sq, more preferably 1X 102Ω/sq～1×1010Ω/sq。
The content of the carbon material in the conductive layer is preferably 50mg/m2Less than, more preferably 0.1mg/m2～50mg/m2More preferably 0.5mg/m2～45mg/m2More preferably 1mg/m2～45mg/m2。
As described above, the conductive layer can be formed by applying the conductive coating material to at least one side of the substrate and then performing heat treatment. The coating method is not particularly limited, and examples thereof include roll coating, bar coating, dip coating, spin coating, casting, die coating, blade coating, bar coating, gravure coating, curtain coating, spray coating, blade coating, slit coating, relief (letterpress) printing, stencil (screen) printing, offset (offset) printing, gravure (gravure) printing, spray printing, inkjet printing, and pad printing.
In the case of applying the conductive coating material to a large-area substrate, it is advantageous from the viewpoint of production efficiency to form the conductive layer using an application device composed of, for example, a tank, a pump for feeding liquid, a filter for removing foreign matters, and an application device.
The filter constituting the coating apparatus is not particularly limited, and is preferably a filter having a pore size of 1 μm to 20 μm, more preferably 2 μm to 10 μm, and further preferably 2 μm to 5 μm.
The material of the filter is not particularly limited, and examples thereof include nylon, cellulose, a mixture of cellulose acetate and cellulose nitrate, cellulose derivatives such as cellulose ester, fluorine resins such as polytetrafluoroethylene, polyvinylidene fluoride, teflon and polyvinyl fluoride, polyolefins such as polypropylene and polyethylene, ceramics, metals, polycarbonate, glass, polyester, polyamide, polysulfone, polyimide, polyvinyl chloride, polystyrene and perfluorosulfonic acid (carboxylic acid). Among these, polyolefins are preferred. Depending on the material of the filter, the carbon material may be adsorbed on the filter, and the surface resistivity may become too high when the conductive layer is formed using a conductive paint.
By forming the conductive layer using a coating apparatus provided with such a filter, a step of filtering the carbon material with the filter can be performed before the step of forming the conductive layer, and a conductive layer having excellent conductivity and transparency can be obtained.
The heat treatment for forming the conductive layer is not particularly limited, and may be performed using, for example, a forced air oven, an infrared oven, a vacuum oven, or the like. In the case where the conductive paint contains a solvent, the solvent is preferably removed by heat treatment.
The temperature conditions of the heat treatment in forming the conductive layer are preferably 200 ℃ or less, more preferably 60 to 180 ℃, and further preferably 80 to 150 ℃.
The treatment time of the heat treatment is preferably 0.1 to 60 minutes, more preferably 0.5 to 30 minutes.
The transparent conductive laminate of the present invention is characterized in that the content of the carbon material having a major axis of 10 μm or more and a minor axis of 2 μm or more is 10 particles/cm2Less (less than 10 per 1 square centimeter), preferably 4/cm2The number of molecules is preferably 3/cm2The following. Here, the carbon material having a major axis of 10 μm or more and a minor axis of 2 μm or more has the above structure except that 1 molecule thereofThe carbon material having the above-mentioned size includes carbon materials having the above-mentioned size, which are agglomerated together or formed into a lump together with other components in the conductive paint. In the case where the carbon material has a plate-like shape, a needle-like shape, a bundle-like shape, or the like, the longer side (the length at which the distance between 2 points is maximized) when the laminate is observed from the stacking direction is defined as the longer diameter, and the other is defined as the shorter diameter.
In the present specification, the major axis, minor axis and number of the carbon material are values measured and evaluated by an optical microscope as described in the examples below.
The Haze (Haze) value of the transparent conductive laminate of the present invention is not particularly limited, but is preferably 3% or less, more preferably 2% or less, and still more preferably 0.6% or less. When the haze value is 3% or less, the transparency of the laminate becomes good. The lower limit of the haze value is not particularly limited, but is preferably 0.01%, for example.
The haze value in the present invention is a value measured according to JIS K7136.
< conductive coating >)
The conductive coating material is also one of the embodiments of the present invention, and the transparent conductive laminate of the present invention can be produced by using the conductive coating material of the present invention.
The conductive paint can be produced, for example, by performing the following steps: the carbon material is subjected to a dispersion treatment in water or an organic solvent in the presence of a dispersant. The dispersion treatment can be carried out using, for example, a vibration mill, a planetary mill, a ball mill, a bead mill, a sand mill, a jet mill, a roll mill, a homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, an ultrasonic device, or the like. In order to obtain a conductive coating material capable of exhibiting high conductivity and transparency, it is preferable to perform a dispersion treatment using at least either an ultrasonic homogenizer or a high-pressure homogenizer.
In general, the carbon material may be subjected to dispersion treatment under conditions that minimize the surface resistivity (surface resistivity minimum) when the conductive layer is formed immediately after the dispersion treatment without adding any optional component other than the dispersant, but the carbon material or the carbon material and other components form a mass by aggregation or the like due to the addition of the optional component or a certain storage period after the production of the conductive coating material, and transparency and conductivity are reduced when the conductive layer is formed. In view of the reasons for the decrease in transparency and conductivity, when the carbon material is subjected to the dispersion treatment, the high strength condition exceeding the minimum point of the surface resistivity is set, and therefore, even when an optional component is added or when a certain storage period is generated after the production of the conductive coating material, the conductive coating material excellent in transparency and conductivity when the conductive layer is produced can be obtained.
Here, the dispersion treatment under the condition exceeding the minimum point of the surface resistivity can be appropriately set based on the technical common knowledge in the field according to the treatment method and the treatment amount of the apparatus to be used.
Before the step of performing the dispersion treatment, the carbon material may be subjected to a high-speed stirring treatment as a pretreatment. The high-speed stirring treatment is a dispersion treatment under a relatively low intensity condition as compared with a dispersion treatment using an ultrasonic homogenizer or the like, and has an effect of alleviating aggregation of the carbon material by high-speed rotation of the stirring body. By performing the high-speed stirring treatment in advance before the dispersion treatment, the dispersion treatment of the carbon material can be performed more efficiently.
In the case where aggregates or the like (including aggregates in which carbon materials are aggregated with each other or with other components to form a lump) remain after the dispersion treatment of the carbon material, these aggregates or the like may be removed by performing a centrifugal separation treatment, or these aggregates or the like may be removed by using a filter. When these aggregates and the like are removed by using a filter, the above-mentioned filter can be used.
As described above, the conductive coating material may contain other optional components in addition to the carbon material, and the optional components may be added during the step of dispersing the carbon material or after the step of dispersing.
< use >
The transparent conductive laminate of the present invention can be used for applications requiring high conductivity and transparency, and is particularly suitable for applications in display devices and light control devices.
Examples
The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" or "%" means "part by weight" or "% by weight", respectively.
1. Using materials
1-1. base material
Alkali-free glass plate (EAGLE XG, haze 0.1% manufactured by Corning Corp.)
The alkali-free glass plate was subjected to etching treatment and alkali treatment. In the etching treatment, the glass substrate was washed with water and then immersed in an etching solution composed of 1% hydrofluoric acid, 5% hydrochloric acid, 2% sulfuric acid and water, and the glass surface was chemically polished. Thereafter, the mixture was washed with water and dried by a dryer. For the alkali treatment, the surface of the glass substrate was cleaned with an aqueous potassium hydroxide solution. Thereafter, the glass substrate was washed with water and dried by a dryer.
PET film (Lumiror T60, 2.1% haze, manufactured by Toray corporation)
Acrylic resin (PMMA) film (Technilloy S001G, manufactured by Sumitomo chemical Co., Ltd., haze 0.9%)
Cellulose triacetate film (Fujitac TJ25UL, Fujitac)
1-2. conductive material
Single-walled Carbon nanotube (SWCNT) aqueous dispersion 1 (manufactured by Meijo Nano Carbon Co., Ltd., SWNT dispersion liquid, Carbon nanotube concentration 0.1%, solid content 0.5%)
Single-walled carbon nanotube (SWCNT) aqueous dispersion 2 (prepared in production example 1, carbon nanotube concentration 0.1%, solid content 0.5%)
Single-walled carbon nanotube (SWCNT) aqueous dispersion 3 (prepared in production example 2, carbon nanotube concentration 0.1%, solid content 0.5%)
Aqueous double-walled carbon nanotube (DWCNT) dispersion (prepared in production example 3, carbon nanotube concentration 0.1%, solid content 1.1%)
Multilayered carbon nanotube (MWCNT) (manufactured by Fuji Pigment co., ltd., MWNT dispersion, carbon nanotube concentration 5%, solid content 8%)
Graphene (H-5 aqueous dispersion manufactured by XG Science, Inc., solid content: 15%)
1-3 leveling agent
Polyether type (product of Clariant corporation, Emulsogen LCN070, HLB 13)
Fluorine system (CAPSTONE FS-3100, 100% non-volatile matter, manufactured by DuPont corporation)
Siloxane series (8029 Additive manufactured by Dow Corning Toray co., ltd.)
1-4 binder resin
Tetraethoxysilicate (manufactured by Tokyo chemical industry Co., Ltd.)
Polycondensate of tetraethoxy silicate (Ethyl silicate 40, manufactured by COLCOAT Co., Ltd.)
Melamine (BECKAMINE M-3, 77% solid content, manufactured by DIC corporation)
Acrylic resin (manufactured by Toyo Synthesis Co., Ltd., Jurymer FC-80, solid content 30%, glass transition temperature 50 ℃ C.)
Urethane acrylate (urethane acrylate 8965, manufactured by U-PICA company
1-5 catalyst
Nitric acid (Fuji film and Guangdong Kabushiki Kaisha)
Sulfuric acid (Fuji film and Wako pure chemical industries, Ltd.)
Formic acid (Fuji film and Guangdong Kabushiki Kaisha)
Dodecyl benzene sulfonic acid (DBS) (Fuji photo film and Guangdong chemical Co., Ltd.)
Cumene sulfonic acid (CS) (product name: TAYCATOX 500, manufactured by TAYCA Co.)
Tert-butyl peroxy-2-ethylhexanoate (TBPO) (manufactured by Mitsubishi chemical corporation: Luperox 26)
1-6 filter
Polyolefin (PO) filter (Betapure AU0911120, product of 3M Co., Ltd., pore diameter: 1 μ M)
Polyolefin (PO) filter (2.5 μm pore diameter manufactured by Nihon Entegris Co., Ltd.)
Polyolefin (PO) filter (5 μm pore size, made by Taiwan Grace corporation)
Polyolefin (PO) filter (Micro-Klean DPPPC-2-A, pore size 10 μ M, 3M Co., Ltd.)
Teflon (registered trademark) (PTFE) filter (FPF-500, 5 μm pore diameter, manufactured by Wintec Co., Ltd.)
Teflon (registered trade name) (PTFE) filter (FPF-045, manufactured by Wintec Co., Ltd., pore size: 0.45 μm)
Production example 1 preparation of aqueous Single-walled carbon nanotube Dispersion 2
The single-walled carbon nanotube (SWCNT) aqueous dispersion 1 was adjusted to 20 ℃, and then dispersed at 80Mpa using a high-pressure homogenizer (Starburst Mini manufactured by sutinomachine), and immediately cooled to 20 ℃. This dispersing step and cooling step were repeated 20 times to obtain a single-walled carbon nanotube aqueous dispersion 2 having a solid content of 0.5%. After each cooling step, a small amount of drawing was performed, the dispersion was applied to glass using a wire bar No.16, dried on a hot plate at 120 ℃ for 2 minutes, and the surface resistivity of the obtained coating film was measured, and as a result, it was confirmed that the surface resistivity was the lowest (a condition that the surface resistivity was extremely small) after the 3 rd cooling step and then gradually increased.
Production example 2 preparation of aqueous Single-walled carbon nanotube Dispersion 3
The single-walled carbon nanotube (SWCNT) aqueous dispersion 1 was charged into a glass beaker, and dispersion treatment was performed at 50W and a frequency of 30kHz for 200 minutes by an ultrasonic homogenizer (HP 50H manufactured by hielscher) while keeping the liquid temperature at 25 ℃.
In the dispersion step, a small amount of suction was performed every 10 minutes, the dispersion was applied to glass using a wire bar No.16, dried on a hot plate at 120 ℃ for 2 minutes, and the surface resistivity of the obtained coating film was measured, and it was confirmed that the surface resistivity of the coating film in the dispersion step was the lowest (condition that the surface resistivity was extremely low) in 30 minutes and the surface resistivity of the coating film in which the time of the dispersion step was further prolonged was gradually increased.
Production example 3 production of double-walled carbon nanotube aqueous Dispersion 1
1 part by weight of a carbon nanotube bilayer dispersion having an average length of 10 μm and a diameter of about 4nm (product No. 755168, manufactured by Aldrich Co., Ltd.), 10 parts by weight of sodium dodecylbenzenesulfonate (manufactured by Fuji film and Wako pure chemical industries, Ltd.) as a dispersant, and 989 parts by weight of pure water were charged in a glass beaker and subjected to a dispersion treatment with an ultrasonic homogenizer (HP 50H, manufactured by Hielscher Co., Ltd.) at 50W and a frequency of 30kHz for 30 minutes, whereby a carbon nanotube bilayer dispersion 1 having a solid content of 1.1% was obtained.
In the dispersion step, a small amount of suction was performed every 5 minutes, the dispersion was applied to glass using a wire bar No.16, dried on a hot plate at 120 ℃ for 2 minutes, and the surface resistivity of the obtained coating film was measured, and it was confirmed that the surface resistivity of the coating film subjected to the dispersion step for 25 minutes was the lowest (condition that the surface resistivity was extremely small), and the coating film subjected to the dispersion step for 30 minutes was a slightly higher value.
2. Examples of the embodiments
Examples 1 to 16 and comparative examples 1 to 5
The carbon material dispersion, the binder resin, and the leveling agent were mixed in the weight ratio (solid content ratio) shown in table 1. The conductive coating material was prepared by diluting the conductive coating material with a diluting solvent composed of water and/or various alcohols described in table 1 so as to reach the solid content described in table 1. The conductive paint was filtered by passing through a filter shown in table 1, and then applied using a wire bar. The obtained coating film was dried at 120 ℃ for 5 minutes by using a forced air dryer, thereby forming a conductive layer, and a transparent conductive layer laminate was obtained. The film thickness of the conductive layer was adjusted to the film thickness shown in table 1 by appropriately selecting the number of the winding bars. The performance of the conductive layer was evaluated by the method described below, and the results are shown in table 1.
3. Evaluation method
(size and number of carbon Material)
10 pieces of the transparent conductive laminates obtained in examples 1 to 16 and comparative examples 1 to 5 were prepared into square test pieces of 5cm × 5cm each. For the test piece, 1cm at the center by an optical microscope2The size and number of the carbon material were observed to obtain an average of 10 test pieces.
(surface resistivity (SR))
The surface resistivity of the conductive layer was measured on 10 test pieces selected from the following methods based on the surface resistivity and the measurable range of the apparatus, and then the average value of the 10 test pieces was determined.
Surface resistivity of 1X 106Ω/sq～1×108In the case of Ω/sq: the measurement was performed at an applied voltage of 10V using a UA probe of Hiresta UP (MCP-HT450 type) manufactured by Mitsubishi chemical corporation.
Surface resistivity exceeding 1 x 108In the case of Ω/sq: the voltage was measured at 250V using a UA probe of Hirestauup (MCP-HT450 type) manufactured by Mitsubishi chemical corporation.
(haze value)
The TEST pieces were measured on 10 sheets according to JIS K7150 using a haze calculator HGM-2B manufactured by SUGA TEST INSTRUMENTS, and then the average value of the 10 TEST pieces was determined.
(film thickness)
The measurement was performed on 10 pieces of the above-mentioned test pieces by using an atomic force microscope (SPM-9600, manufactured by Shimadzu corporation), and then the average value of the 10 pieces was determined.
(theoretical content of carbon Material)
The content of the carbon material in the conductive layer is calculated by the following equation.
Theoretical content of carbon material (mg/m)2) Thickness of film (. mu.m). times.weight percentage of carbon material in conductive paint (solid content ratio)
[ Table 1]
As a result of the examples, the more carbon materials having a major axis of 10 μm or more and a minor axis of 2 μm or more are present in the conductive layer, the higher the haze value of the laminate and the lower the transparency. The same tendency is observed with respect to the surface resistivity.
Claims (15)
1. A transparent conductive laminate having a substrate and a surface resistivity of 1 x 10, the substrate comprising a carbon material2Ω/sq～1×1011A transparent conductive laminate of an omega/sq conductive layer,
the carbon material having a major axis of 10 μm or more and a minor axis of 2 μm or more is contained in an amount of 10 particles/cm2The following.
2. The transparent conductive laminate according to claim 1, wherein the haze value of the transparent conductive laminate is 3% or less.
3. The transparent conductive laminate according to claim 1 or 2, wherein the carbon material is at least one selected from the group consisting of graphene, fullerene and carbon nanotube.
4. The transparent conductive laminate as claimed in any one of claims 1 to 3, wherein the content of the carbon material in the conductive layer is 50mg/m2The following.
5. A conductive coating material for forming a conductive layer in the transparent conductive laminate according to any one of claims 1 to 4.
6. A display device comprising the transparent conductive laminate according to any one of claims 1 to 4.
7. A light control device comprising the transparent conductive laminate according to any one of claims 1 to 4.
8. The method for producing a transparent conductive laminate according to any one of claims 1 to 4, which comprises a step of forming a conductive layer on a substrate by using a conductive coating material comprising a carbon material.
9. The method for producing a transparent conductive laminate according to claim 8, wherein the step of forming the conductive layer comprises a step of filtering the conductive paint containing a carbon material with a filter having a pore size of 1 to 20 μm.
10. The method for producing a transparent conductive laminate according to claim 9, wherein the filter is made of polyolefin.
11. A method for producing an electrically conductive coating material comprising a carbon material,
according to the content of the carbon material of 50mg/m2When the conductive coating material is applied to a substrate to form a conductive layer, the conductive layer satisfies the following conditions (a) to (c):
(a) surface resistivity of 102Ω/sq～1011Ω/sq；
(b) A haze value of 3% or less; and
(c) the carbon material having a major axis of 10 μm or more and a minor axis of 2 μm or more is contained in an amount of 10 particles/cm2The following.
12. The method for producing a conductive paint according to claim 11, wherein the carbon material is at least one selected from the group consisting of graphene, fullerene, and carbon nanotube.
13. The method for producing the conductive paint according to claim 11 or 12, wherein the method comprises a step of filtering the conductive paint by using a filter having a pore size of 1 μm to 20 μm.
14. The method for producing an electrically conductive paint according to claim 13, wherein the filter is made of polyolefin.
15. The method for producing a conductive paint as claimed in any one of claims 11 to 14, which comprises a step of dispersing the carbon material under a condition exceeding the minimum point of surface resistivity.
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| JP2018-146815 | 2018-08-03 | ||
| JP2018146815A JP2020021700A (en) | 2018-08-03 | 2018-08-03 | Transparent conductive laminate |
| JP2018146816 | 2018-08-03 | ||
| JP2018-146816 | 2018-08-03 |
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|---|---|---|---|---|
| CN114437595A (en) * | 2022-03-24 | 2022-05-06 | 广东邦固化学科技有限公司 | Flexible transparent electric heating composite coating and preparation method thereof |
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| JP2006171336A (en) * | 2004-12-15 | 2006-06-29 | Takiron Co Ltd | Transparent electrode member for image display, and the image display device |
| US20070065651A1 (en) * | 2003-01-30 | 2007-03-22 | Glatkowski Paul J | Articles with protruding conductive coatings |
| JP2012066580A (en) * | 2010-08-18 | 2012-04-05 | Toray Ind Inc | Transparent conductive laminate |
| CN104067354A (en) * | 2012-01-31 | 2014-09-24 | 东丽株式会社 | Transparent electroconductive laminate, method for manufacturing same, electronic paper using same, and touch panel using same |
| WO2016114389A1 (en) * | 2015-01-16 | 2016-07-21 | 東レフィルム加工株式会社 | Electroconductive laminate and method for manufacturing electroconductive laminate |
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2019
- 2019-07-30 CN CN201910692566.8A patent/CN110797139A/en active Pending
- 2019-07-31 TW TW108127144A patent/TW202018737A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070065651A1 (en) * | 2003-01-30 | 2007-03-22 | Glatkowski Paul J | Articles with protruding conductive coatings |
| JP2006171336A (en) * | 2004-12-15 | 2006-06-29 | Takiron Co Ltd | Transparent electrode member for image display, and the image display device |
| JP2012066580A (en) * | 2010-08-18 | 2012-04-05 | Toray Ind Inc | Transparent conductive laminate |
| CN104067354A (en) * | 2012-01-31 | 2014-09-24 | 东丽株式会社 | Transparent electroconductive laminate, method for manufacturing same, electronic paper using same, and touch panel using same |
| WO2016114389A1 (en) * | 2015-01-16 | 2016-07-21 | 東レフィルム加工株式会社 | Electroconductive laminate and method for manufacturing electroconductive laminate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437595A (en) * | 2022-03-24 | 2022-05-06 | 广东邦固化学科技有限公司 | Flexible transparent electric heating composite coating and preparation method thereof |
| CN114437595B (en) * | 2022-03-24 | 2023-02-14 | 广东邦固化学科技有限公司 | Flexible transparent electric heating composite coating and preparation method thereof |
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