WO2015137195A1 - Stratifié conducteur, procédé de fabrication de stratifié conducteur, panneau tactile et commutateur tactile - Google Patents

Stratifié conducteur, procédé de fabrication de stratifié conducteur, panneau tactile et commutateur tactile Download PDF

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Publication number
WO2015137195A1
WO2015137195A1 PCT/JP2015/056208 JP2015056208W WO2015137195A1 WO 2015137195 A1 WO2015137195 A1 WO 2015137195A1 JP 2015056208 W JP2015056208 W JP 2015056208W WO 2015137195 A1 WO2015137195 A1 WO 2015137195A1
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conductive laminate
conductive
undercoat layer
layer
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PCT/JP2015/056208
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English (en)
Japanese (ja)
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今津直樹
増田昇三
渡邊修
太田一善
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東レ株式会社
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Priority to CN201580006821.9A priority Critical patent/CN105960684B/zh
Priority to JP2015512925A priority patent/JPWO2015137195A1/ja
Publication of WO2015137195A1 publication Critical patent/WO2015137195A1/fr

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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
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon

Definitions

  • the present invention relates to a conductive laminate, a method for manufacturing a conductive laminate, a touch panel, and a touch switch. In more detail, it is related with the manufacturing method of the electrically conductive laminated body which is excellent in transparent conductivity, and an electrically conductive laminated body.
  • Conductive laminates are widely used in electronic display devices such as flat panel displays and touch panels.
  • the conductive material used for the conductive laminate is represented by tin-doped indium oxide (hereinafter abbreviated as ITO), and the demand and usage of ITO continue to increase.
  • ITO tin-doped indium oxide
  • indium is a rare metal
  • a new conductive material that replaces indium is required.
  • ITO Alternatively, there is a need for a novel conductive material that compensates for the disadvantages peculiar to conductive laminates using ITO, such as weakness to bending, and difficulty in reducing costs due to vacuum film formation.
  • the CNT has a substantially cylindrical shape by winding one surface of graphite, and a single-layer CNT is wound in one layer, a multi-layer CNT is wound in multiple layers, especially two layers. This was called double-walled CNT.
  • CNTs themselves have excellent intrinsic conductivity and are expected to be used as conductive materials.
  • ionic dispersants are generally insulating materials. There is a problem that the conductivity of the conductive laminate using CNTs is lowered. Therefore, it is thought that it is necessary to remove the ionic dispersant from the conductive layer in order to produce a conductive laminate excellent in transparent conductivity.
  • Patent Document 1 describes a method for producing a conductive film in which a carbon nanotube dispersion liquid is applied on various films to obtain a conductive film.
  • Patent Document 2 describes a production method for obtaining a highly conductive conductive film by removing a surplus ionic dispersant by rinsing with water after coating a carbon nanotube dispersion on the film. Yes.
  • Patent Document 3 in order to stabilize the resistance value of the carbon nanotube transparent conductive laminate, a hydrophilic undercoat layer made of silica fine particles and polysilicate is provided under the carbon nanotube layer, and transparent conductive Examples of improving resistance value stability are also described.
  • Patent Document 4 a porous layer containing fine particles and a resin binder is provided on a support, and a conductive pattern is formed thereon, whereby the adhesion of the conductive pattern is high and excellent.
  • save property was obtained is described.
  • Patent Document 1 does not have a layer configuration that removes the ionic dispersant contained in the conductive layer. Therefore, a highly conductive conductive film cannot be obtained.
  • the present invention has been made in view of the above-mentioned problems and situations, and the object thereof is to provide a conductive laminate that is excellent in transparent conductivity and humidity resistance dependency and is less likely to cause bone appearance when patterned. is there.
  • the present invention provides the following conductive laminate.
  • the undercoat layer (X) contains the organic binder (A) and the particles (B).
  • the content of the particles (B) contained in the undercoat layer (X) is 100% by mass of the entire undercoat layer.
  • the conductive layer (Y) contains carbon nanotubes (C) and a carbon nanotube dispersant (D).
  • the present invention it is possible to provide a conductive laminate that is excellent in transparent conductivity and humidity resistance dependency and is less likely to cause bone appearance when patterned.
  • the conductive laminate of the present invention has an undercoat layer (X) and a conductive layer (Y) on a base material in this order from the base material side, and satisfies the following (i) to (iii): Is the body.
  • the undercoat layer (X) contains the organic binder (A) and the particles (B).
  • the content of the particles (B) contained in the undercoat layer (X) is 100% by mass of the entire undercoat layer.
  • the conductive layer (Y) contains 15% by mass or more and 95% by mass or less of the carbon nanotube (C) and the carbon nanotube dispersant (D).
  • the conductive laminate of the present invention can improve the conductivity of the device when used in an electronic device using the conductive laminate by having such a configuration.
  • the transparent conductivity can be stabilized even when the humidity of the environment where the device is placed changes.
  • the method for producing a conductive laminate of the present invention comprises an undercoat layer (X) forming step of providing an undercoat layer (X) having a wetting tension of 76 to 105 mN / m on a substrate, a carbon nanotube (C) and A conductive layer (Y) forming step of forming a conductive layer (Y) by providing a dispersion containing the carbon nanotube dispersant (D) on the undercoat layer (X).
  • the touch panel of the present invention is a touch panel using the conductive laminate of the present invention or the conductive laminate obtained by the method for producing the conductive laminate of the present invention.
  • the touch switch of the present invention is a touch switch using the conductive laminate of the present invention or the conductive laminate obtained by the manufacturing method of the conductive laminate of the present invention.
  • the conductive laminate of the present invention has a substrate.
  • Resin, glass, etc. can be mentioned as a raw material of the base material used for this invention.
  • the resin include polyethylene terephthalate (hereinafter abbreviated as PET), polyester such as polyethylene naphthalate (PEN), polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • PMMA polymethyl methacrylate
  • polyimide polyphenylene sulfide
  • aramid polypropylene
  • polyethylene polylactic acid.
  • Polyvinyl chloride, polymethyl methacrylate, alicyclic acrylic resin, cycloolefin resin, triacetyl cellulose, and the like can be used.
  • soda glass soda glass, white plate glass, non-alkali glass, or the like can be used.
  • these several base materials can also be used in combination.
  • a composite base material such as a base material in which a resin and glass are combined and a base material in which two or more kinds of resins are laminated may be used.
  • the resin film may be provided with a hard coat.
  • the kind of base material is not limited to the base material, and an optimal one can be selected from durability, cost, etc. according to the application.
  • the thickness of the base material is not particularly limited, but when used for a display-related electrode such as a touch panel, a touch switch, a liquid crystal display, organic electroluminescence, and electronic paper, it is preferably in the range of 10 ⁇ m to 1,000 ⁇ m. .
  • the conductive laminate of the present invention has an undercoat layer (X) on the substrate.
  • the undercoat layer (X) includes an organic binder (A) and particles (B).
  • the undercoat layer (X) preferably has a wetting tension of 76 mN / m or more and 105 mN / m or less as defined in ISO 8296 (2003). By setting the wetting tension to 76 mN / m or more, when the CNT dispersion liquid is applied on the undercoat layer (X), it is difficult to cause application repellency and the CNT dispersion liquid can be uniformly applied. preferable.
  • the wetting tension of the undercoat layer (X) is 105 mN / m or less, coating unevenness due to spreading of the coating liquid during coating and coating unevenness affected by wind during drying are less likely to occur, and CNT dispersion This is preferable because the liquid can be uniformly applied.
  • the wetting tension is preferably 76 mN / m or more and 105 mN / m or less, and more preferably 76 mN / m or more and 90 mN / m or less.
  • the wetting tension of the undercoat layer (X) increases the copolymerization amount of the hydrophilic functional group contained in the organic binder (A) in the coating composition forming the undercoat layer (X)
  • the thickness can be increased by increasing the thickness of X). Therefore, the wetting tension of the undercoat layer (X) is appropriately determined depending on the copolymerization amount of the hydrophilic functional group contained in the organic binder (A), the type of the hydrophilic functional group, and the thickness of the undercoat layer (X) described later. Can be adjusted.
  • the thickness of the undercoat layer (X) is not particularly limited as long as it is in a range in which a phenomenon such as curling is unlikely to occur when the conductive laminate is formed.
  • the wettability of the surface of the undercoat layer is preferably within the range of the preferred wetting tension, and the thickness varies depending on the type of organic binder, the type of functional group, the content of functional group, and the amount of particles to be added. . Therefore, it is preferably in the range of 8 nm to 3 ⁇ m.
  • a thickness that can effectively obtain an antireflection effect due to optical interference is preferable because the light transmittance is improved. For this reason, it is more preferable that the thickness combined with the thickness of the overcoat layer described later is in the range of 20 nm to 600 nm.
  • the effect of incorporating the ionic dispersant into the undercoat layer is increased, and therefore it is preferably in the range of 300 nm to 600 nm.
  • the center surface average roughness SRa of the undercoat layer (X) is preferably 2 to 15 nm.
  • SRa is 2 nm or more, the unevenness of the surface of the undercoat layer becomes large, and when the CNT dispersion containing the ionic dispersant is applied, it becomes easy to incorporate the ionic dispersant into the undercoat layer (X). Since the removal of the ionic dispersant from is effectively performed, it is preferable. Further, it is preferable to set SRa to 15 nm or less because the optical characteristics of the conductive laminate can be improved. When it is larger than 15 nm, light scattering at the interface with the CNT layer and the overcoat layer increases, and haze may increase.
  • the SRa of the undercoat layer (X) is preferably 2 nm or more and 15 nm or less, and more preferably 5 nm or more and 15 nm or less.
  • SRa of the undercoat layer (X) in the present invention can be measured using a three-dimensional surface roughness measuring machine.
  • the center plane average roughness SRa of the undercoat layer (X) can be controlled by the following particles (B).
  • the undercoat layer (X) contains a binder because the ionic dispersant can be more adsorbed to the undercoat layer (X).
  • the binder include an organic binder and an inorganic binder, and it is preferable to use the organic binder (A) from the viewpoint that the ionic dispersant can be more adsorbed and the undercoat layer is difficult to crack during patterning.
  • the organic binder (A) contained in the undercoat layer (X) preferably contains an organic compound.
  • An organic compound is a compound in which carbon atoms are assembled as a skeleton, and is a compound in which a molecule having a covalent bond and having two or more kinds of atoms is a minimum unit.
  • the organic compound for example, phenol, silicon, nylon, polyethylene, polyester, olefin, vinyl, acrylic, cellulose and the like are preferable.
  • the organic binder (A) preferably contains an organic binder having a hydrophilic functional group from the viewpoint of applicability to a substrate. Moreover, it is more preferable that an organic binder (A) contains the polyester resin which has a hydrophilic functional group, and / or the acrylic resin which has a hydrophilic functional group from a viewpoint of the applicability
  • the polyester resin having a hydrophilic functional group refers to a polyester resin having a hydrophilic functional group at the terminal or side chain of the polyester resin in order to increase the hydrophilicity of the polyester resin and dissolve or disperse it in an aqueous solvent.
  • hydrophilic functional groups include sulfonate groups and carboxylate groups.
  • the polyester resin In order to make the polyester resin contain a hydrophilic functional group, a dicarboxylic acid having a sulfonate group and an ester-forming derivative thereof, a diol having a sulfonate group and an ester-forming derivative thereof (a compound containing a sulfonate group), A polyvalent carboxylic acid having three or more carboxylate groups and an ester-forming derivative thereof (a compound containing a trivalent or more polyvalent carboxylate group) can be used as a raw material for polyester.
  • Examples of the compound containing a sulfonate group include alkali metal salts, alkaline earth metal salts, and ammonium salts such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 5-sodium sulfoisophthalic acid, and 4-sulfoisophthalic acid. However, it is not limited to these.
  • Examples of the compound containing a trivalent or higher polyvalent carboxylate group include trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexene-1,2,3-tricarboxylic acid, trimesin
  • Examples thereof include alkali metal salts such as acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, alkaline earth metal salts and ammonium salts. It is not limited to.
  • Examples of the carboxylic acid component constituting the polyester include aromatic, aliphatic, and alicyclic dicarboxylic acids and trivalent or higher polyvalent carboxylic acids.
  • Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 5-sodium sulfoisophthalic acid, 1,4-naphthalenedicarboxylic acid, and ester-forming derivatives thereof Can be mentioned.
  • glycol component of the polyester ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, etc. should be used. Can do.
  • a compound containing a sulfonate group that is a hydrophilic functional group or a trivalent or higher polyvalent carboxylic acid group is 1 when the total amount of the raw material components of the polyester constituting the polyester resin containing the hydrophilic functional group is 100 mol%. It is preferably ⁇ 25 mol%.
  • a polyester resin containing a hydrophilic functional group can be stably produced by copolymerization by setting a compound containing a sulfonate group that is an aqueous functional group or a trivalent or higher polyvalent carboxylate group to 25 mol% or less. Is preferable.
  • the polyester resin having a hydrophilic functional group can be produced, for example, as follows.
  • a process for producing a polycarboxylic acid component after a first step of esterification or transesterification of a compound containing a dicarboxylic acid component and a glycol component, a sulfonate group or a trivalent or higher polyvalent carboxylate group After the first step of esterifying or transesterifying the dicarboxylic acid component and the glycol component, a compound containing a sulfonate group or a trivalent or higher polyvalent carboxylate group is added to produce a first step reaction. It can manufacture by the method of manufacturing by the process of the 2nd step made to polycondensate with a product.
  • the reaction catalyst for example, alkali metal, alkaline earth metal, manganese, cobalt, zinc, antimony, germanium, titanium compound, or the like can be used.
  • the polyester resin having a hydrophilic functional group obtained by the above production method is preferably dispersed or dissolved in a solvent to form a coating composition.
  • means for dispersing or dissolving in an aqueous solvent include a method in which a polyester resin is dissolved or dispersed in an aqueous solution of an alkaline compound such as ammonia water, sodium hydroxide, potassium hydroxide, and various amines while stirring.
  • an alkaline compound such as ammonia water, sodium hydroxide, potassium hydroxide, and various amines while stirring.
  • a water-soluble organic solvent such as methanol, ethanol, isopropanol, butyl cellosolve, or ethyl cellosolve may be used in combination.
  • the organic binder (A) preferably contains an acrylic resin having a hydrophilic functional group from the viewpoint of applicability to the substrate.
  • Any acrylic resin having a hydrophilic functional group may be used as long as it contains a repeating structural unit derived from an acrylic monomer having a hydrophilic functional group.
  • the acrylic resin having a hydrophilic functional group a repeating structural unit derived from an acrylic monomer having the hydrophilic functional group, and a repeating structural unit derived from an acrylic monomer having no hydrophilic group, Those consisting of are preferred. It is preferable to use an acrylic resin having such a hydrophilic functional group because it is excellent in transparency and can hardly be repelled when a CNT dispersion is applied.
  • an acrylic monomer having a hydrophilic functional group a known acrylic monomer having a hydrophilic group that is a polar atomic group having a strong interaction with water, that is, a cationic group that dissociates as a cation in water. And known acrylic monomers having an anionic group that dissociates as an anion in water, or known acrylic monomers having a nonionic group that does not dissociate in water.
  • acrylic monomer having a cationic group examples include dimethylaminoethyl (meth) acrylate and salts thereof, ethyl trimethylammonium chloride (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl. Examples include trimethylammonium chloride.
  • acrylic monomer having an anionic group examples include (meth) acrylic acid and its salt, (meth) acrylic acid-2-sulfoethyl and its salt, hydroxyethyl (meth) acryloyl phosphate and its salt, and the like. Can be mentioned.
  • acrylic monomer having a nonionic group examples include hydroxyalkyl (meth) acrylate, polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and the like.
  • (meth) acryl means “acryl” or “methacryl”.
  • acrylic monomer having no hydrophilic functional group examples include, for example, alkyl (meth) acrylate (linear and branched having 1 to 8 carbon atoms) ester, cyclohexyl (meth) acrylate, ( Examples include glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl acrylate, (meth) acrylonitrile, and the like.
  • the organic binder preferably contains both a polyester resin having a hydrophilic functional group and an acrylic resin having a hydrophilic functional group from the viewpoint of removing the ionic dispersant.
  • Mass ratio of content (hereinafter referred to as C) of polyester resin having hydrophilic functional group to content (hereinafter referred to as D) of acrylic resin having hydrophilic functional group contained in undercoat layer (X) ( C / D) is preferably from 1/9 to 8/2. If the (C / D) is less than 1/9, the entire undercoat layer becomes hard and may be easily broken. On the other hand, when (C / D) exceeds 8/2, the polyester resin itself having a hydrophilic functional group hardly cures, so that the film may become too soft. Therefore, (C / D) is preferably 1/9 or more and 8/2 or less. More preferably, it is 2/8 or more and 5/5 or less.
  • the content of the polyester resin having a hydrophilic functional group when the entire undercoat layer is 100% by mass is preferably 20% by mass or more and 50% by mass or less.
  • the content of the acrylic resin having a hydrophilic functional group when the entire undercoat layer is 100% by mass is preferably 50% by mass or more and 80% by mass or less.
  • the organic binder (A) having a hydrophilic functional group may be uniformly dispersed by, for example, an emulsifier and in an emulsion state.
  • the organic binder (A) preferably contains a cross-linking agent.
  • An epoxy compound and / or an oxazoline compound is preferably used as a crosslinking agent in order to strengthen the coating film of the undercoat layer (X) and improve the heat and humidity resistance, the adhesion to the substrate, and the like. Only one of the epoxy compound or the oxazoline compound may be used, or both may be used together.
  • Examples of the epoxy compound include a compound containing an epoxy group in the molecule, a prepolymer and a cured product thereof.
  • Examples thereof include condensates of epichlorohydrin with hydroxyl groups and amino groups such as ethylene glycol, polyethylene glycol, glycerin, polyglycerin, and bisphenol A.
  • polyepoxy compound examples include sorbitol, polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylol.
  • examples include propane polyglycidyl ether.
  • Examples of the diepoxy compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and polypropylene glycol diester. Examples thereof include glycidyl ether and polytetramethylene glycol diglycidyl ether. Examples of the monoepoxy compound include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether.
  • Examples of the glycidylamine compound include N, N, N ′, N ′,-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino) cyclohexane and the like.
  • An oxazoline compound is a compound having an oxazoline group in the molecule.
  • a polymer containing an oxazoline group is preferable, and it can be prepared by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer.
  • Addition-polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples include 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like. One or a mixture of two or more of these can be used. Of these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
  • alkyl (meth) acrylate alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl
  • acrylic acid esters alkyl (meth) acrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl) And (meth) acrylic acid esters.
  • Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.) It is done. And unsaturated nitriles such as acrylonitrile and methacrylonitrile.
  • Examples thereof include vinyl esters such as vinyl acetate and vinyl propionate.
  • vinyl ethers such as methyl vinyl ether and ethyl vinyl ether.
  • Examples include ⁇ -olefins such as ethylene and propylene.
  • halogen-containing ⁇ , ⁇ -unsaturated monomers such as vinyl chloride, vinylidene chloride, and vinyl fluoride.
  • ⁇ , ⁇ -unsaturated aromatic monomers such as styrene and ⁇ -methylstyrene. These 1 type, or 2 or more types of monomers can be used.
  • the amount of the crosslinking agent charged relative to the binder is preferably 5 to 80 parts by mass, more preferably 10 to 30 parts by mass, and still more preferably 10 to 20 parts by mass when the binder is 100 parts by mass.
  • the undercoat layer may be brittle and may not sufficiently withstand moisture and heat.
  • the amount exceeds 80 parts by mass the resin component containing a hydrophilic functional group is relatively reduced. In some cases, it may be difficult to apply the CNT dispersion, or the adhesion to the substrate may not be stable.
  • the undercoat layer (X) preferably contains particles (B).
  • the surface roughness of the undercoat layer is increased, the incorporation of the ionic dispersant into the undercoat layer (X) becomes effective, and the humidity resistance dependency is improved, which is preferable.
  • antiblocking property can also be provided to undercoat layer (X), it is preferable. That is, when the conductive laminate is manufactured by roll to roll, it may be necessary to wind up the substrate on which the undercoat layer is formed after the undercoat layer is formed. At that time, it is preferable to include particles (B) in the undercoat layer because the undercoat layer is difficult to block.
  • the conductive laminate of the present invention has (ii) the content of the particles (B) contained in the undercoat layer (X). It is preferable that it is 15 mass% or more and 95 mass% or less with respect to the whole undercoat layer.
  • the content of the particles (B) is less than 15% by mass, unevenness on the surface of the undercoat layer is insufficient, and the humidity resistance dependency may not be exhibited.
  • the content of the particles (B) exceeds 95% by mass, the particles (B) may be excessive with respect to the organic binder (A), and the particles (B) may fall off.
  • the content of the particles (B) exceeds 50% by mass, when the overcoat layer described later is applied, depending on the solvent of the overcoat layer, the surface of the undercoat is partially eroded and the particles that have come off fall off and aggregate.
  • the content of the particles (B) is 20% by mass or more, humidity resistance dependency is easily exhibited stably by attaching surface irregularities, which is more preferable.
  • the range is 20 to 50% by mass.
  • a range of 25 to 35% by mass is a more preferable range from the viewpoint of stably exhibiting the humidity resistance dependency and stably suppressing an increase in haze.
  • the preferred range of the particle size of the particles (B) is 5 nm to 500 nm.
  • the thickness is less than 5 nm, it is difficult to uniformly disperse the particles, and conversely, the particles may aggregate to increase the apparent particle size in the undercoat layer.
  • a haze will raise and it may become cloudy white when a conductive laminated body is used for a display body.
  • a particle diameter here means the average particle diameter measured by the dynamic light scattering method.
  • the particles (B) may be organic particles, inorganic particles, or both. That is, the particles (B) are preferably inorganic particles and / or organic particles.
  • the organic particles include particles containing acrylic acid, styrene resin, thermosetting resin, silicone, imide compound, and the like as constituent components. Particles (so-called internal particles) that are precipitated by a catalyst added during the polyester polymerization reaction are also preferably used.
  • styrene / acrylic particles are preferable from the viewpoint of dispersibility in a polyester resin having a hydrophilic functional group and versatility.
  • “Movinyl” registered trademark
  • 972 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
  • inorganic particles for example, particles made of silica, colloidal silica, alumina, ceria, kaolin, talc, mica, calcium carbonate, barium sulfate, carbon black, zeolite, titanium oxide, and various metal oxides are preferable.
  • inorganic colloidal particles are preferable from the viewpoint of dispersibility in an organic binder, particle hardness, heat resistance, and alkali resistance, and colloidal silica is most preferable.
  • colloidal silica that is dispersed and stable in a solvent due to electrostatic repulsion between colloidal silica is preferable.
  • Colloidal silica which is dispersed and stable in a solvent due to electrostatic repulsion between colloidal silica, has —SiOH groups and —OH 2 ⁇ ions on the surface of colloidal silica, and an electric double layer is formed in a negatively charged state.
  • Colloidal silica that is dispersed and stable in a solvent due to electrostatic repulsion between colloidal silica includes “Snowtex” (registered trademark) series manufactured by Nissan Chemical Industries, Ltd. and “JGC Catalysts Chemical Co., Ltd.” The “Cataloid” series is preferably used.
  • the shape of the particles (B) is not particularly limited.
  • grains of the shape of a primary particle are spherical (a spheroidal shape and a geometric shape (a cube, rod shape, plate shape, fiber shape, tetrapod shape, triangular prism shape) are mentioned).
  • the secondary particle shape is a chain shape (a beaded particle in which isomorphic particles are randomly connected two-dimensionally) or a pearl necklace shape (a beaded particle in which isomorphic particles are randomly connected in three dimensions) ) And the like. From the viewpoint of imparting surface irregularities, a spherical shape, a chain shape, and a pearl necklace shape are preferable. Moreover, these particles can be mixed and used together as necessary.
  • the spherical shape of the particle means that the particle is a three-dimensional spherical particle.
  • Spherical inorganic particles include “Snowtex” “Nanouse”, “CELNAX” (registered trademark) series manufactured by Nissan Chemical Industries, Ltd., “Cataloid” series manufactured by JGC Catalysts & Chemicals Co., Ltd. and Nippon Shokubai Co., Ltd. “Sea Hoster” (registered trademark) series manufactured by Co., Ltd. is preferably used.
  • Spherical organic particles include the “Ganz Pearl” series manufactured by Aika Kogyo Co., Ltd., “Toughtic” (registered trademark) series manufactured by Toyobo Co., Ltd., and “Eposter” manufactured by Nippon Shokubai Co., Ltd. (registered) Trademark) series and the like are preferably used.
  • the chain shape of the particles is a bead-like particle (secondary particle) in which isomorphous particles (primary particles) are randomly connected two-dimensionally, and has a long and narrow shape in which the primary particles are crushed. It means that.
  • As the chain-like inorganic particles “Snowtex” (registered trademark) series manufactured by Nissan Chemical Industries, Ltd., “Cataloid” series manufactured by JGC Catalysts & Chemicals Co., Ltd., etc. are preferably used.
  • As the chain-like organic particles “Toughtic” (registered trademark) series manufactured by Toyobo Co., Ltd. is preferably used.
  • the pearl necklace shape of the particle is a bead-like particle (secondary particle) in which isomorphous particles (primary particles) are randomly connected in three dimensions, and has a structure branched in each direction of three dimensions. Focusing on one pearl necklace-shaped particle, this particle is composed of spherical particles (primary particles) corresponding to beaded spheres and particles (primary particles) corresponding to yarns.
  • this particle is composed of spherical particles (primary particles) corresponding to beaded spheres and particles (primary particles) corresponding to yarns.
  • “Snowtex” (registered trademark) series manufactured by Nissan Chemical Industries, Ltd. and the like are preferably used.
  • As the pearl necklace-shaped organic particles “Toughtic” (registered trademark) series manufactured by Toyobo Co., Ltd. is preferably used. *
  • undercoat layer The organic binder (A), the particles (B), and, if necessary, a coating composition containing an additive and a solvent are applied onto a substrate, and if necessary, By drying the solvent, the undercoat layer (X) can be formed on the substrate.
  • an aqueous solvent as a solvent for the coating composition.
  • an aqueous solvent rapid evaporation of the solvent in the drying step can be suppressed, and not only a uniform undercoat layer (X) can be formed, but also the environmental load is excellent.
  • the aqueous solvent is soluble in water such as water or water and alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, and glycols such as ethylene glycol, diethylene glycol and propylene glycol.
  • alcohols such as methanol, ethanol, isopropyl alcohol and butanol
  • ketones such as acetone and methyl ethyl ketone
  • glycols such as ethylene glycol, diethylene glycol and propylene glycol.
  • a certain organic solvent is mixed in an arbitrary ratio.
  • the coating method of the coating composition on the substrate either an in-line coating method or an off-coating method can be used.
  • the in-line coating method is a method of applying in the manufacturing process of the substrate. Specifically, it refers to a method of coating at any stage from melt extrusion of the thermoplastic resin constituting the substrate to heat treatment after biaxial stretching, and usually, after melt extrusion, it is rapidly cooled.
  • the off-coating method is a known wet coating method such as spray coating, dip coating, spin coating, knife coating, kiss coating, gravure coating, slot die coating, roll coating, bar coating, screen printing, inkjet printing, pad printing, Other types of printing can be used.
  • a dry coating method may be used.
  • physical vapor deposition such as sputtering or vapor deposition, chemical vapor deposition, or the like can be used.
  • coating may be performed in multiple times and it may combine two different types of application
  • Preferred coating methods are gravure coating, bar coating, and slot die coating, which are wet coatings.
  • the conductive laminate of the present invention has the undercoat layer (X) and the conductive layer (Y) in this order from the substrate side on the substrate.
  • the conductive layer (Y) includes a carbon nanotube (C) and a carbon nanotube dispersant (D).
  • the conductive layer (Y) is a layer that functions as a display-related electrode such as a touch panel, a touch switch, a liquid crystal display, organic electroluminescence, and electronic paper.
  • Carbon nanotube (C) used in the present invention is not particularly limited as long as it has a shape obtained by substantially winding one sheet of graphite into a cylindrical shape. Both single-walled CNTs wound in one layer and multi-walled CNTs wound in multiple layers can be applied. Among them, CNTs in which 50 or more of 100 double-layered CNTs in which one surface of graphite is wound in two layers are included. If it exists, it is preferable from electroconductivity and the dispersibility of CNT in the coating dispersion liquid becoming very high. More preferably, 75 or more of 100 are double-walled CNTs, and most preferably 80 or more of 100 are double-walled CNTs.
  • the fact that 50 double-walled CNTs are contained in 100 may indicate that the ratio of double-walled CNTs is 50%.
  • the surface of the two-walled CNT is functionalized by acid treatment or the like, it is preferable from the viewpoint that the original functions such as conductivity are hardly impaired.
  • CNT is manufactured as follows, for example.
  • a powdered catalyst in which iron is supported on magnesia is present in the entire horizontal cross-sectional direction of the reactor in a vertical reactor, and methane is supplied in the vertical direction into the reactor.
  • CNTs are produced by contacting them at 200 ° C., and then oxidizing the CNTs to obtain CNTs containing single to five layers of CNTs.
  • CNTs can be manufactured and then subjected to an oxidation treatment to increase the ratio of single layers to five layers, particularly the ratio of two layers to five layers.
  • the oxidation treatment is performed, for example, by a nitric acid treatment method.
  • Nitric acid is preferable because it also acts as a dopant for CNT. Dopants are those that give surplus electrons to CNTs or take away electrons to form holes, and improve the conductivity of CNTs by generating carriers that can move freely. is there.
  • the conditions for the nitric acid treatment are not particularly limited as long as the CNTs of the present invention can be obtained, but are usually performed in an oil bath at 140 ° C.
  • the time for nitric acid treatment is not particularly limited, but is preferably in the range of 5 to 50 hours.
  • Carbon nanotube dispersant (D) As the carbon nanotube dispersant (hereinafter referred to as CNT dispersant) (D), a surfactant, various dispersants (water-soluble dispersant, etc.) and the like can be used, but an ionic dispersant having high dispersibility. It is preferable to contain.
  • the ionic dispersant include an anionic dispersant, a cationic dispersant, and an amphoteric dispersant. Any type can be used as long as it has a high CNT dispersibility and can maintain dispersibility, but an anionic dispersant is preferred because of its excellent dispersibility and dispersion retention.
  • carboxymethylcellulose and its salts (sodium salt, ammonium salt, etc.) and polystyrenesulfonic acid salt are preferable because CNT can be efficiently dispersed in the CNT dispersion.
  • the ionic dispersant is preferably carboxymethylcellulose.
  • the whole CNT dispersing agent is 100 mass%, it is preferable to occupy 60 mass% or more.
  • examples of the cationic substance constituting the salt include alkali metal cations such as lithium, sodium and potassium, and alkaline earth such as calcium, magnesium and barium.
  • alkali metal cations such as lithium, sodium and potassium
  • alkaline earth such as calcium, magnesium and barium.
  • Metal cation, ammonium ion, or onium ion of organic amines such as monoethanolamine, diethanolamine, triethanolamine, morpholine, ethylamine, butylamine, coconut oil amine, beef tallow amine, ethylenediamine, hexamethylenediamine, diethylenetriamine, polyethyleneimine, Alternatively, these polyethylene oxide adducts can be used, but are not limited thereto.
  • a method for preparing a CNT dispersion it is performed by surface modification of CNT used as a raw material and / or selection of a CNT dispersant.
  • the method of the CNT surface modification treatment for adjusting the CNT dispersion is not particularly limited, but carboxyl groups, hydroxyl groups can be obtained by physical treatment such as corona treatment, plasma treatment and flame treatment, and chemical treatment such as acid treatment and alkali treatment. It is preferable to introduce an anionic group such as a group into the CNT side wall.
  • the CNT dispersant for adjusting the CNT dispersion liquid any type can be used as long as it has high CNT dispersion ability and can maintain dispersibility.
  • the anionic dispersant described above is most preferable.
  • an anionic dispersant if the pH of the CNT dispersion is 5.5 to 11, an acidic functional group such as a carboxylic acid modifying the CNT surface or a dispersant located around the CNT is used.
  • the ionization degree of acidic functional groups such as carboxylic acid contained is improved, and as a result, the CNT or the dispersant around the CNT has a negative potential.
  • the anionic CNT present in the CNT dispersion is more cationic than the CNT dispersion. It is considered that a highly dispersed state was realized by electrostatic attraction and attracted to the surface of the film. Therefore, similarly, the cationic CNT present in the CNT dispersion is attracted to the surface of the undercoat layer having an anionic property compared to the CNT dispersion, and a high dispersion state is realized by electrostatic adsorption. Is also possible.
  • the weight average molecular weight of the CNT dispersant is preferably 100 or more. This is because when the weight average molecular weight is 100 or more, the interaction with CNT occurs more effectively and the dispersion of CNT becomes better. Although it depends on the length of the CNT, it is preferable that the weight average molecular weight is large because the CNT dispersant interacts with the CNT and improves dispersibility. For example, in the case of a polymer, when the polymer chain becomes long, the polymer is entangled with the CNT, and very stable dispersion is possible. However, if the weight average molecular weight is too large, the dispersibility may be reduced. Therefore, the weight average molecular weight is preferably 10 million or less, and more preferably 1 million or less. The most preferred range of weight average molecular weight is 10,000 to 500,000.
  • the pH of the CNT dispersion liquid can be adjusted by adding an acidic substance or a basic substance defined by Arrhenius to the CNT dispersion liquid.
  • Acidic substances include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, borohydrofluoric acid, hydrofluoric acid, perchloric acid, organic carboxylic acids, phenols, organic sulfonic acids, etc. Is mentioned.
  • examples of the organic carboxylic acid include formic acid, acetic acid, succinic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, and trichloroacetic acid. Trifluoroacetic acid, nitroacetic acid, triphenylacetic acid and the like.
  • organic sulfonic acid examples include alkylbenzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl naphthalene disulfonic acid, naphthalene sulfonic acid formalin polycondensate, melamine sulfonic acid formalin polycondensate, naphthalene disulfonic acid, naphthalene trisulfonic acid, dinaphthylmethane.
  • examples include disulfonic acid, anthraquinone sulfonic acid, anthraquinone disulfonic acid, anthracene sulfonic acid, and pyrene sulfonic acid.
  • volatile acids that volatilize during coating and drying, such as hydrochloric acid and nitric acid.
  • Examples of basic substances include sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia.
  • a volatile base that volatilizes during coating and drying, such as ammonia.
  • the pH of the CNT dispersion is adjusted by adding the acidic substance and / or basic substance until the desired pH is reached while measuring the pH.
  • the pH measurement method include a method using a pH test paper such as litmus test paper, a hydrogen electrode method, a quinhydrone electrode method, an antimony electrode method, a glass electrode method, etc.
  • the glass electrode method is simple and requires the required accuracy. Is preferable.
  • a substance having the opposite characteristics may be added to adjust the pH.
  • Nitric acid is preferable as an acidic substance applied for such adjustment
  • ammonia is preferable as a basic substance.
  • the dispersion medium used in the preparation of the CNT dispersion used in the present invention is preferably water from the viewpoint of easy treatment of the waste liquid.
  • the method for preparing the CNT dispersion used in the present invention is not particularly limited, and can be performed, for example, by the following procedure. Since the treatment time at the time of dispersion can be shortened, once a dispersion liquid containing CNT in a concentration range of 0.003 to 0.15 mass% in the dispersion medium is prepared and diluted, a predetermined concentration is obtained. It is preferable.
  • the mass ratio of the dispersion medium to CNT (that is, the mass of the dispersion medium when the mass of CNT is 1) is preferably 10 or less. Within such a preferable range, it is easy to uniformly disperse, but there is little influence of the decrease in conductivity.
  • the mass ratio of the dispersion medium to CNT is more preferably 0.5 to 9, further preferably 1 to 6, and particularly preferably 2 to 3.
  • a CNT and a dispersant are mixed and dispersed in a dispersion medium, which is commonly used for coating liquid production (for example, a ball mill, a bead mill, a sand mill, a roll mill, a homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, A sonic device, an attritor, a resolver, a paint shaker, etc.).
  • the method of preliminarily dispersing with a vibration ball mill and then dispersing using an ultrasonic device is preferable because the dispersibility of CNT in the obtained coating dispersion liquid is good.
  • Transparent conductivity means having both transparency and conductivity.
  • As an index of transparency there is a carbon nanotube layer light absorptivity (hereinafter sometimes simply referred to as “light absorptance”).
  • the carbon nanotube layer optical absorptance is an index represented by the following formula at a wavelength of 550 nm.
  • a surface resistance value is used as an index of conductivity, and the lower the surface resistance value, the higher the conductivity.
  • Carbon nanotube layer light absorbance (550 nm) 100 ⁇ total light transmittance (550 nm) ⁇ relative reflectance (550 nm).
  • the conductive laminate of the present invention preferably satisfies any one of the following (a) to (h) in terms of light absorption rate and surface resistance value.
  • a typical index of transparency is a light absorptance
  • the light absorptivity of a transparent conductive laminate including one conductive layer has a practical meaning.
  • a representative example of the conductivity index is the surface resistance value of the conductive laminate, and the surface resistance value of the conductive laminate including one conductive layer has a practical meaning.
  • Such conductivity (surface resistance value) and transparency (carbon nanotube layer light absorption rate) can be adjusted by the coating amount of carbon nanotubes.
  • the coating amount of the carbon nanotube is small, the conductivity is low, while the transparency is high.
  • the coating amount is large, the conductivity is high, but the transparency is low. That is, both are in a trade-off relationship, and it is difficult to satisfy both. Because of this relationship, in order to compare the transparent conductivity, it is necessary to fix one index and then compare the other index.
  • the light absorption rate and the surface resistance value satisfy any of the following (a1) to (h1).
  • (A1) Light absorption is 1% or more and less than 2%, surface resistance is 500 ⁇ / ⁇ or more and 1,500 ⁇ / ⁇ or less
  • (b1) Light absorption is 2% or more and less than 3%, and surface resistance is 200 ⁇ .
  • the light absorption rate and the surface resistance value satisfy any of the following (a2) to (h2).
  • the conductive laminate of the present invention preferably has a surface resistance value change rate of 20% or less at 25 ° C. and a relative humidity of 30% to 90%.
  • the relative humidity is 30%, 20 minutes at 50%, 20 minutes at 50%, 30 minutes at 90%, 30 %
  • the surface resistance obtained by the following equation (1) It is the value change rate.
  • Surface resistance value change rate (M ⁇ m) / m ⁇ 100 (1).
  • the surface resistance value change rate is set to 20% or less, which is preferable in that an erroneous operation can be prevented when the touch panel is used. More preferably, the rate of change in the surface resistance value is 15% or less, more preferably 10% or less.
  • an undercoat layer (X) forming step of providing an undercoat layer (X) having a wetting tension of 76 to 105 mN / m on a substrate, a carbon nanotube (C And a conductive layer (Y) forming step of forming a conductive layer (Y) by providing a dispersion containing the carbon nanotube dispersant (D) on the undercoat layer (X) is preferable.
  • Each step will be described below.
  • the conductive layer (Y) is formed through a coating process in which the CNT dispersion is applied on the undercoat layer, and a drying process in which the dispersion medium is subsequently removed.
  • the coating step when the CNT dispersion obtained by the above method is applied on the undercoat layer provided on the substrate, the CNT dispersant having a hydrophilic portion and surrounding the CNT is a hydrophilic undercoat. It is thought to be attracted to the surface of the layer.
  • the dispersion medium is then dried to fix the CNTs on the undercoat layer to form a conductive layer (Y).
  • the dispersion medium remains on the undercoat layer, and the CNT dispersant (D) While being able to move from the conductive layer (Y) to the surface of the undercoat layer, it is considered that the CNT dispersant is attracted and adsorbed to the surface of the undercoat layer having a hydrophilic group as in the case of application.
  • the amount of the CNT dispersant in the conductive layer (Y) is reduced by attracting the dispersant to the undercoat layer (X).
  • the phenomenon of attracting the CNT dispersant to the undercoat layer (X) proceeds more preferably by using a hydrophilic undercoat layer having a wetting tension of 76 to 105 mN / m.
  • the CNT dispersion is applied in a coating thickness range of 1 ⁇ m to 50 ⁇ m and the dispersion medium is removed from the conductive layer (Y) by drying in the range of 0.1 seconds to 100 seconds, this mechanism is used. Since adsorption of a dispersing agent can be produced more effectively, it is preferable.
  • a conductive laminate produced by applying a CNT dispersion onto a substrate and drying it the concentration of the dispersion during drying after application and electrostatic repulsion generated between the CNT dispersion and the substrate are increased. Due to the force, CNTs may be bundled. However, CNTs are negatively charged in the dispersion, and the CNT dispersion is applied onto the undercoat layer and dried, so that the CNT dispersed in the CNT dispersion is electrostatically adsorbed to the undercoat layer. It is preferable because the bundling of CNT that has occurred during drying on the substrate can be suppressed. Thereby, the conductive laminated body excellent in transparent conductivity can be obtained.
  • the method for applying the dispersion onto the substrate is not particularly limited.
  • Known application methods such as spray coating, dip coating, spin coating, knife coating, kiss coating, gravure coating, slot die coating, bar coating, roll coating, screen printing, inkjet printing, pad printing, other types of printing, etc. Available.
  • coating may be performed in multiple times and it may combine two different types of application
  • the coating thickness at the time of applying the CNT dispersion on the substrate depends on the concentration of the CNT dispersion, and therefore may be appropriately adjusted so as to obtain a desired surface resistance value.
  • the amount of CNT applied in the present invention can be easily adjusted in order to achieve various applications that require electrical conductivity. For example, a coating amount of 0.1 mg / m 2 to 30 mg / m 2 is preferable because the light absorption after the formation of the overcoat layer described below can be 20% or less.
  • the conductive laminate of the present invention preferably has an overcoat layer on the conductive layer (Y).
  • an overcoat layer consists of a transparent film in order to improve transparency. It is preferable to have an overcoat layer because the transparent conductivity, heat resistance stability, and heat and humidity resistance can be further improved.
  • both an organic material and an inorganic material can be used, but an inorganic material is preferable from the viewpoint of resistance value stability.
  • the inorganic material include metal oxides such as silica, tin oxide, alumina, zirconia, and titania. Silica is preferable from the viewpoint of resistance value stability.
  • the method for providing the overcoat layer on the conductive layer (Y) is not particularly limited.
  • Known wet coating methods such as spray coating, dip coating, spin coating, knife coating, kiss coating, roll coating, gravure coating, slot die coating, bar coating, screen printing, inkjet printing, pad printing, other types of printing, Or other types of printing can be used.
  • a dry coating method may be used.
  • physical vapor deposition such as sputtering or vapor deposition, chemical vapor deposition, or the like can be used.
  • the operation of providing the overcoat layer on the conductive layer may be performed in a plurality of times, or two different methods may be combined.
  • Preferred methods are gravure coating, bar coating, slot die coating, which are wet coatings.
  • an organic silane compound is preferably used, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxy.
  • a silica sol prepared by hydrolyzing an organosilane compound such as tetraalkoxysilane such as silane dissolved in a solvent the wet coating is performed, and when the solvent is dried, dehydration condensation occurs between silanol groups, The method of forming a silica thin film is mentioned.
  • the thickness of the overcoat layer is controlled by adjusting the silica sol concentration in the coating solution and the coating thickness at the time of coating.
  • the thickness of the overcoat layer is more preferably 10 nm or more and 200 nm or less. When the thickness of the overcoat layer is less than 10 nm, the scattering of dopants such as nitric acid improving the conductivity of the CNTs cannot be suppressed, and the heat resistance may be lowered. If the thickness of the overcoat layer is greater than 200 nm, the difference in the amount of reflected light between where the CNT is present and where it is absent may be visible.
  • the conductive laminate of the present invention can be preferably used as a display-related electrode such as a touch panel, a touch switch, a liquid crystal display, organic electroluminescence, and electronic paper.
  • the conductive laminate of the present invention or the conductive laminate obtained by the production method of the present invention is excellent in transparent conductivity, a touch panel, a touch switch, and the like are preferable.
  • the conductive laminate of the present invention and the method for producing the conductive laminate of the present invention will be specifically described based on examples.
  • the present invention is not limited to the following examples.
  • Wetting tension measurement Wetting tension of the undercoat layer was measured according to the method specified in ISO8296 (2003) Plastics- Film and sheeting-Determination of wetting tension.
  • a variety of wet tension test mixtures with different surface tensions were prepared. After forming an undercoat layer to be described later, a wet tension test mixture was quickly spread on the surface of the undercoat layer using a cotton swab or a brush in an atmosphere of room temperature 23 ° C. and relative humidity 50%. The presence or absence of the wet tension was determined by observing the liquid film of the mixed liquid for the wet tension test and in the state of the liquid film after 2 seconds. A liquid film that has been applied without tearing after 2 seconds is wet, that is, has a wetting tension of its surface tension. If the liquid film after 2 seconds breaks and the applied state is not maintained, it will not be wet.
  • the process further proceeds to a liquid mixture for wet tension test having the next highest surface tension, and conversely if it is not wet, the process proceeds to the next liquid mixture having a lower surface tension. This operation was repeated to determine the highest wetting tension value.
  • the test ink made from Arcotest was used as the liquid mixture for the wet tension test.
  • a touch panel was created using the conductive laminate having the pattern.
  • a transparent adhesive film (TI14A manufactured by Yodogawa Paper Co., Ltd., thickness 25 ⁇ m)
  • a surface having a conductive layer of one conductive laminate and a hard coat film (“Tough” manufactured by Toray Film Processing Co., Ltd.) Laminates were face-to-face facing each other without a hard coat of “top” (registered trademark) THS, thickness 50 ⁇ m).
  • a touch panel was prepared, and a three-wavelength fluorescent tube was installed at a distance of 50 cm directly above the touch panel.
  • the observer stands at a distance of 30 cm with respect to the touch panel, and the angle formed by the line connecting the touch panel and the three-wavelength fluorescent tube and the line connecting the touch panel and the observer is 45 degrees. . If all 5 out of 5 observers cannot see the bones, S, 4 cannot see the bones, and 1 person can see the bones. A, 1 to 3 people can see the bones. B was shown when two or more people could see the bone, and C when all the five people could see the bone.
  • Humidity resistance evaluation The rate of change in surface resistance value at 25 ° C. and a relative humidity of 30% to 90%, that is, the evaluation of humidity resistance dependency was carried out as follows.
  • the resistance value was 5 cm ⁇ 10 cm, and the conductive laminate “ECM” (registered trademark) -100AF manufactured by Taiyo Ink Co., Ltd. was applied to a width of 5 mm at the end of the conductive laminate to a thickness of 80 ⁇ m, and the temperature was 90 ° C. for 60 minutes.
  • the mixture was heated to dryness, and the dried conductive paste part was measured using a custom digital tester CDM-17D.
  • the surface resistance value change rate was determined according to the following formula (1), where m is the minimum value and M is the maximum value of each resistance value measured after holding at each relative humidity and temperature for a predetermined time.
  • Surface resistance value change rate (M ⁇ m) / m ⁇ 100 (1).
  • Substrate A Polyethylene terephthalate film ("Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) -Thickness 50 ⁇ m.
  • Base material B Polycarbonate film (“Iupilon” (registered trademark) FE-2000 manufactured by Mitsubishi Gas Chemical Company, Inc.) -Thickness 100 ⁇ m.
  • Base material C PET pellets (extreme viscosity 0.63 dl / g) substantially free of particles are sufficiently vacuum dried, then supplied to an extruder, melted at 285 ° C., extruded into a sheet form from a T-shaped die, and electrostatically applied Using a casting method, it was wound around a mirror casting drum having a surface temperature of 25 ° C. to be cooled and solidified. This unstretched PET film was heated to 90 ° C. and stretched 3.4 times in the longitudinal direction to obtain a uniaxially stretched PET film.
  • Organic binder (B) Organic binder containing an acrylic resin having a hydrophilic functional group (“Nostra” (registered trademark) DBH, solid content concentration 40% by mass, methanol 1-methoxy-2-propanol (hereinafter referred to as PGME) solvent manufactured by Mitsui Chemicals, Inc.) was diluted with methanol and PGME so that the ratio of methanol to PGME was 5: 5 by mass and the solid content concentration of the resin was 20% by mass.
  • Nostra registered trademark
  • PGME methanol 1-methoxy-2-propanol
  • Organic binder (C) An organic binder containing a polyester resin having a hydrophilic functional group and an acrylic resin having a hydrophilic functional group (A645-GEX manufactured by Takamatsu Yushi Co., Ltd., solid content concentration: 20% by mass, water solvent) is diluted with water and IPA, The ratio of IPA to IPA was 7: 3 by mass, and the solid content concentration of the resin was 5% by mass.
  • Organic binder (D) An organic binder containing a polyester resin having a hydrophilic functional group and an acrylic resin having a hydrophilic functional group (A647-GEX, solid content concentration 20% by mass, water solvent, manufactured by Takamatsu Yushi Co., Ltd.) is diluted with water and IPA to obtain water. The ratio of IPA to IPA was 7: 3 by mass, and the solid content concentration of the resin was 5% by mass.
  • Inorganic binder (E) An inorganic binder containing hydrophilic silica fine particles with a diameter of about 30 nm and polysilicate (Mega Aqua hydrophilic DM coat DM30-26G-N1, solid content concentration 5 mass%, IPA solvent, manufactured by Shukaken Co., Ltd.) is diluted with IPA to obtain a solid resin The partial concentration was adjusted to 0.4% by mass.
  • polysilicate Mega Aqua hydrophilic DM coat DM30-26G-N1, solid content concentration 5 mass%, IPA solvent, manufactured by Shukaken Co., Ltd.
  • Inorganic binder An inorganic binder containing ethyl silicate ("Colcoat” (registered trademark) N103X solid content concentration 2 mass%, IPA solvent) manufactured by Colcoat Co., Ltd., IPA solvent) was diluted with IPA so that the solid content concentration of the resin was 1 mass%. .
  • Organic binder (G) An organic binder containing a polyester resin having no hydrophilic functional group (Pesresin S-180, solid content concentration 20% by mass, water solvent, manufactured by Takamatsu Yushi Co., Ltd.) is diluted with water and IPA, and the ratio of water to IPA Was 7: 3 by mass ratio, and the solid content concentration of the resin was 5 mass%.
  • Organic binder (H) 50 parts by mass of terephthalic acid, 50 parts by mass of isophthalic acid, 50 parts by mass of ethylene glycol, 30 parts by mass of neopentyl glycol, 0.3 parts by mass of antimony trioxide as a polymerization catalyst and 0 zinc acetate
  • the reactor was purged with nitrogen together with 3 parts by mass, and the polymerization reaction was carried out at 190 to 220 ° C. for 12 hours under atmospheric pressure while removing water to obtain polyester glycol.
  • Crosslinking agent A Oxazoline group-containing polymer (“Epocross” (registered trademark) WS-700 manufactured by Nippon Shokubai Co., Ltd.).
  • Particle E Colloidal silica having a particle size of 4 nm to 6 nm (“Snowtex” (registered trademark) ST-OXS, spherical, manufactured by Nissan Chemical Industries, Ltd.).
  • Particle G Colloidal silica particle size 70 nm to 110 nm “Snowtex” (registered trademark) ST-PS-SO, pearl necklace shape, manufactured by Nissan Chemical Industries, Ltd.).
  • Particles H Colloidal silica “Snowtex” (registered trademark) OL (average primary particle size 45 nm, manufactured by Nissan Chemical Industries, Ltd.) on the surface by hydroxyl groups by the following methods (i) to (iv)
  • the introduced acrylic resin was modified on the surface of the silica particles.
  • (I) A method in which a mixture in which an inorganic oxide and an acrylic resin are mixed in advance is added to a solvent and dispersed.
  • IIi A method in which an inorganic oxide and an acrylic resin are sequentially added and dispersed in a solvent.
  • Iii A method in which an inorganic oxide and an acrylic resin are dispersed in advance in separate solvents and the obtained dispersions are mixed.
  • Iv A method of adding an acrylic resin to the obtained dispersion after dispersing the inorganic oxide in the solvent.
  • Catalyst preparation example catalyst metal salt support on magnesia 2.46 g of ammonium iron citrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 500 mL of methanol (manufactured by Kanto Chemical Co., Ltd.). To this solution, 100.0 g of magnesium oxide (MJ-30 manufactured by Iwatani Chemical Industry Co., Ltd.) was added, vigorously stirred for 60 minutes with a stirrer, and the suspension was concentrated to dryness at 40 ° C. under reduced pressure. The obtained powder was heated and dried at 120 ° C. to remove methanol, and a catalyst body in which a metal salt was supported on magnesium oxide powder was obtained.
  • methanol manufactured by Kanto Chemical Co., Ltd.
  • the obtained solid content was collected on a sieve with a particle size in the range of 20 to 32 mesh (0.5 to 0.85 mm) while being finely divided in a mortar.
  • the iron content contained in the obtained catalyst body was 0.38% by mass.
  • the bulk density was 0.61 g / mL. The above operation was repeated and subjected to the following experiment.
  • the reactor 503 is a cylindrical quartz tube having an inner diameter of 75 mm and a length of 1,100 mm.
  • a quartz sintered plate 502 is provided at the center, a mixed gas introduction pipe 508 serving as an inert gas and source gas supply line is provided at the lower part of the quartz pipe, and a waste gas pipe 506 is provided at the upper part.
  • three electric furnaces 501 are provided as heaters surrounding the circumference of the reactor so that the reactor can be maintained at an arbitrary temperature.
  • a thermocouple 505 is provided to detect the temperature in the reaction tube.
  • the catalyst layer 504 was formed by taking 132 g of the solid catalyst body prepared in the catalyst preparation example and introducing the solid catalyst body onto the quartz sintered plate at the center of the reactor installed in the vertical direction. While heating the catalyst layer until the temperature in the reaction tube reaches about 860 ° C., nitrogen gas is supplied from the bottom of the reactor toward the top of the reactor using the mass flow controller 507 at 16.5 L / min. It was circulated through the layers. Thereafter, while supplying nitrogen gas, methane gas was further introduced at 0.78 L / min for 60 minutes using the mass flow controller 507, and the gas was passed through the catalyst body layer to cause reaction.
  • the contact time (W / F) obtained by dividing the mass of the solid catalyst body by the flow rate of methane at this time was 169 minutes ⁇ g / L, and the linear velocity of the gas containing methane was 6.55 cm / second.
  • the quartz reaction tube was cooled to room temperature while the introduction of methane gas was stopped and nitrogen gas was passed through at 16.5 L / min.
  • the heating was stopped and the mixture was allowed to stand at room temperature, and after reaching room temperature, the CNT-containing composition containing the catalyst body and CNTs was taken out from the reactor.
  • the CNT-containing composition was stored in a wet state containing water after washing with ion-exchanged water until the suspension of the filtered material became neutral. At this time, the mass of the entire wet CNT-containing composition containing water was 102.7 g (CNT-containing composition concentration: 3.12% by mass).
  • this CNT paste was diluted with ion-exchanged water so that the concentration of CNT was 0.15% by mass, and adjusted to pH 10 with 28% by mass ammonia aqueous solution again with respect to 10 g of the diluted solution.
  • the aqueous solution was subjected to dispersion treatment under ice-cooling for 1.5 minutes (0.6 kW ⁇ min / g) at an output of an ultrasonic homogenizer (manufactured by Ieda Trading Co., Ltd., VCX-130) at 20 W.
  • the liquid temperature during dispersion was adjusted to 10 ° C. or lower.
  • the obtained liquid was centrifuged at 10,000 G for 15 minutes with a high-speed centrifuge (Tomy Seiko Co., Ltd., MX-300) to obtain 9 g of a CNT dispersion. Thereafter, water was added to prepare a CNT dispersion liquid so that the final concentration of the CNT aggregate was 0.03% by mass.
  • Examples 1 to 40 Comparative Examples 1 to 3
  • the organic binders A to D and G, the inorganic binders E and F, and the particles A to G were mixed at a blending ratio shown in the table to prepare a coating material.
  • the prepared paint is applied to one side of the substrate at a transfer speed of 10 m / min using a slit die coat (coating width 550 mm) with a shim (shim thickness 50 ⁇ m) made of stainless steel (sus), dried and undercoated Layers were laminated. Only when the organic binder B was used, it was cured by irradiating with ultraviolet rays at a dose of 95.1 mJ / cm 2 in a nitrogen atmosphere.
  • the substrate surface was subjected to corona treatment under the condition of an E value of 100 W ⁇ s.
  • the CNT dispersion was applied onto the undercoat layer using a slit die coat (coating width 550 mm) with a stainless steel (sus) shim (shim thickness 50 ⁇ m), and dried at 100 ° C. for 1 minute. Conductive components were laminated. Further, a coating speed of 10 m / min using a slit die coat (coating width 550 mm) in which the inorganic binder F is made of a shim (shim thickness 50 ⁇ m) made of the inorganic binder F on the side where the conductive layer is laminated. The coating was carried out under the conditions shown in Table 1 and dried at 125 ° C. for 1 minute to form a laminate.
  • Example 41 to 52 The organic binder H and particles B and H were mixed at a blending ratio shown in the table to prepare a paint.
  • the prepared paint was applied to the corona discharge treated surface of a substrate C (uniaxially stretched film) that had been subjected to a corona discharge treatment in air using a bar coat.
  • the both ends in the width direction of the applied uniaxially stretched film are held by clips and guided to a preheating zone, and after setting the ambient temperature to 75 ° C, the ambient temperature is set to 110 ° C using a radiation heater, and then the ambient temperature is set to 90 ° C.
  • the coating composition was dried to form a composition layer.
  • the thickness of the PET film was 50 ⁇ m.
  • the thickness of the undercoat layer produced by this method was about 40 nm.
  • the CNT dispersion was applied onto the substrates A and B using a slit die coat (coating width 550 mm) with a stainless steel (sus) shim (shim thickness 50 ⁇ m), and dried at 100 ° C. for 1 minute to conduct electricity.
  • the components were laminated. Since the CNT dispersion could not be coated due to insufficient wettability of the substrate, the surface of the substrate was subjected to corona treatment.
  • a coating speed of 10 m / min using a slit die coat (coating width 550 mm) in which the inorganic binder F is made of a shim (shim thickness 50 ⁇ m) made of the inorganic binder F on the side where the conductive layer is laminated was performed under the conditions shown in the table, and the laminate was formed by drying at 125 ° C. for 1 minute.
  • the binder content [% by mass] is the binder content [% by mass] when the entire undercoat layer is 100% by mass.
  • the particle content [% by mass] is the particle content [% by mass] when the entire undercoat layer is taken as 100% by mass.
  • the charged amount [parts by mass] is the charged amount [parts by mass] of the crosslinking agent when the component of the binder is 100 parts by mass.
  • the conductive laminate of the present invention having excellent transparent conductivity can be preferably used as, for example, a display-related electrode such as a touch panel, a touch switch, a liquid crystal display, organic electroluminescence, and electronic paper.
  • a display-related electrode such as a touch panel, a touch switch, a liquid crystal display, organic electroluminescence, and electronic paper.

Landscapes

  • Laminated Bodies (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

L'invention porte sur un stratifié conducteur qui comprend, sur une base, une sous-couche (X) et une couche conductrice (Y) dans cet ordre à partir du côté de base, et qui satisfait les conditions (i)- (iii) décrites ci-dessous. (i) La sous-couche (X) contient un liant organique (A) et des particules (B). (ii) Le contenu des particules (B) contenues dans la sous-couche (X) est de 15 % en masse à 95 % en masse (inclus) par rapport à 100 % en masse de la totalité de la sous-couche. (iii) La couche conductrice (Y) contient des nanotubes de carbone (C) et un agent dispersant de nanotube de carbone (D). La présente invention porte sur un stratifié conducteur qui présente d'excellentes propriétés de gravure laser et une faible dépendance à l'humidité en plus d'une excellente transparence et d'une excellente conductivité.
PCT/JP2015/056208 2014-03-12 2015-03-03 Stratifié conducteur, procédé de fabrication de stratifié conducteur, panneau tactile et commutateur tactile WO2015137195A1 (fr)

Priority Applications (2)

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CN201580006821.9A CN105960684B (zh) 2014-03-12 2015-03-03 导电层合体、导电层合体的制造方法、触摸面板及触摸开关
JP2015512925A JPWO2015137195A1 (ja) 2014-03-12 2015-03-03 導電積層体、導電積層体の製造方法、タッチパネルおよびタッチスイッチ

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JP2022060234A (ja) * 2015-12-15 2022-04-14 エージーシー ケミカルズ アメリカズ，インコーポレイテッド 層状チューブ、及び層状チューブ用の層

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CN110941358A (zh) * 2018-09-21 2020-03-31 宸鸿光电科技股份有限公司 触控面板、其制作方法与触控传感器卷带
CN111384270B (zh) 2018-12-29 2021-07-30 Tcl科技集团股份有限公司 量子点发光二极管的制备方法
JP6656450B1 (ja) * 2019-04-25 2020-03-04 株式会社マルアイ 電子部品搬送トレイ・キャリアテープ用のシートとそれを用いた電子部品搬送トレイ・キャリアテープ

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