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WO2016121662A1 - Film électroconducteur transparent - Google Patents

Film électroconducteur transparent Download PDF

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Publication number
WO2016121662A1
WO2016121662A1 PCT/JP2016/051951 JP2016051951W WO2016121662A1 WO 2016121662 A1 WO2016121662 A1 WO 2016121662A1 JP 2016051951 W JP2016051951 W JP 2016051951W WO 2016121662 A1 WO2016121662 A1 WO 2016121662A1
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WO
WIPO (PCT)
Prior art keywords
transparent conductive
conductive film
metallic particles
binder resin
conductive layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2016/051951
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English (en)
Japanese (ja)
Inventor
祥一 松田
由紀 長谷川
寛 友久
一正 岡田
武本　博之
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
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Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2015179341A external-priority patent/JP6580432B2/ja
Priority claimed from JP2015179340A external-priority patent/JP6580431B2/ja
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to CN201680007507.7A priority Critical patent/CN107210091B/zh
Priority to US15/546,928 priority patent/US20180017715A1/en
Publication of WO2016121662A1 publication Critical patent/WO2016121662A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields

Definitions

  • the present invention relates to a transparent conductive film.
  • transparent conductive films are used for electrodes of electronic device parts such as touch panels, electromagnetic wave shields that block electromagnetic waves that cause malfunction of electronic devices, and the like.
  • a method of forming a conductive layer composed of a metal oxide layer such as ITO, a metal nanowire, a metal mesh, or the like has been proposed (for example, Patent Documents 1 and 2).
  • a protective layer is formed on such a conductive layer, particularly a conductive layer including metal nanowires.
  • the present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a transparent conductive film excellent in both scratch resistance and conductivity.
  • the transparent conductive film of the present invention includes a transparent substrate and a transparent conductive layer disposed on one side or both sides of the transparent substrate, and the transparent conductive layer includes a binder resin, metal nanowires, and metallic particles. And part of the metallic particles protrudes from the region constituted by the binder resin.
  • the average particle diameter X of the metallic particles and the thickness Y of the region constituted by the binder resin satisfy the relationship of Y ⁇ X ⁇ 20Y.
  • the metallic particles have an average primary particle size of 5 nm to 100 ⁇ m.
  • the content ratio of the metallic particles is 0.1 to 20 parts by weight with respect to 100 parts by weight of the binder resin.
  • the average flatness of the metallic particles is 40% or less.
  • the metallic particles are silver particles.
  • the metallic particles are silver-coated copper particles.
  • an optical laminate is provided. This optical laminate includes the transparent conductive film and a polarizing plate.
  • the present invention by including metallic particles protruding from the transparent conductive layer, it is possible to provide a transparent conductive film excellent in both scratch resistance and conductivity.
  • FIG. 1 is a schematic sectional view of a transparent conductive film according to one embodiment of the present invention.
  • the transparent conductive film 100 includes a transparent substrate 10 and a transparent conductive layer 20 disposed on both sides or one side (one side in the illustrated example) of the transparent substrate 10.
  • the transparent conductive layer 20 includes a binder resin 21, metal nanowires 22, and metallic particles 23.
  • a part of the metallic particles 23 protrudes from the region constituted by the binder resin 21 toward the surface of the transparent conductive film. That is, metallic particles are exposed in the transparent conductive film.
  • electrical_connection can be taken favorably in the surface of a transparent conductive film.
  • the contact resistance can be lowered.
  • the binder resin can protect the metal nanowires.
  • the amount of the binder resin used is increased (that is, the region constituted by the binder resin is thickened). be able to.
  • a transparent conductive film excellent in scratch resistance can be obtained. Thickening the binder resin region as a protective layer to increase scratch resistance, while being able to achieve a transparent conductive film excellent in conductivity, ensuring conduction from the surface, and having low contact resistance, This is one of the achievements of the present invention.
  • the surface resistance value of the transparent conductive film of the present invention is preferably 0.1 ⁇ / ⁇ to 1000 ⁇ / ⁇ , more preferably 0.5 ⁇ / ⁇ to 300 ⁇ / ⁇ , and particularly preferably 1 ⁇ / ⁇ to 200 ⁇ . / ⁇ .
  • the haze value of the transparent conductive film of the present invention is preferably 20% or less, more preferably 10% or less, and further preferably 0.1% to 5%.
  • the total light transmittance of the transparent conductive film of the present invention is preferably 30% or more, more preferably 35% or more, still more preferably 40% or more, and particularly preferably 89% or more. Preferably it is 90% or more. The higher the total light transmittance of the transparent conductive film is, the better. However, the upper limit is, for example, 98%.
  • the transparent conductive layer includes a binder resin, metal nanowires, and metallic particles.
  • the binder resin is present so as to cover at least part of the metal nanowires and the metallic particles, and the region constituted by the binder resin can function as a protective layer. A part of the metallic particles protrudes from a region constituted by a binder resin.
  • the total light transmittance of the transparent conductive layer is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more.
  • the thickness Y of the region constituted by the binder resin is preferably 0.15 ⁇ m to 5 ⁇ m, more preferably 0.15 ⁇ m to 3 ⁇ m, and still more preferably 0.15 ⁇ m to 2 ⁇ m.
  • the thickness Y of the region constituted by the binder resin is a distance from one flat surface to the other flat surface of the transparent conductive layer, as shown in FIG. It means the thickness of the transparent conductive layer when it is assumed that the protruding part of the conductive particles is excluded.
  • the region constituted by the binder resin can be made relatively thick. As a result, a transparent conductive film excellent in scratch resistance can be obtained.
  • any appropriate resin can be used as the binder resin.
  • the resin include acrylic resins; polyester resins such as polyethylene terephthalate; aromatic resins such as polystyrene, polyvinyltoluene, polyvinylxylene, polyimide, polyamide, and polyamideimide; polyurethane resins; epoxy resins; Resin; Acrylonitrile-butadiene-styrene copolymer (ABS); Cellulose; Silicon resin; Polyvinyl chloride; Polyacetate; Polynorbornene; Synthetic rubber;
  • a curable resin is used as the binder resin.
  • the curable resin can be obtained from a monomer composition containing a polyfunctional monomer.
  • the polyfunctional monomer include tricyclodecane dimethanol diacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol tetra (meth) acrylate, and dimethylolpropanthate.
  • Tetraacrylate dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol diacrylate, 1,10-decanediol (meth) acrylate, polyethylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, dipropylene glycol diacrylate, isocyanuric acid tri (meth) acrylate, ethoxylated glycerin Examples include triacrylate and ethoxylated pentaerythritol tetraacrylate.
  • a polyfunctional monomer may be used independently and may be used in combination of multiple.
  • the monomer composition may further contain a monofunctional monomer.
  • the content ratio of the monofunctional monomer is preferably 40 parts by weight or less, more preferably 20 parts by weight or less with respect to 100 parts by weight of the monomer in the monomer composition. is there.
  • Examples of the monofunctional monomer include ethoxylated o-phenylphenol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-ethylhexyl acrylate, lauryl acrylate, isooctyl acrylate, and isostearyl.
  • Examples include acrylate, cyclohexyl acrylate, isophoronyl acrylate, benzyl acrylate, 2-hydroxy-3-phenoxy acrylate, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and hydroxyethyl acrylamide. .
  • a monomer having a hydroxyl group is used as the monofunctional monomer.
  • the metal nanowire is a conductive material having a metal material, a needle shape or a thread shape, and a diameter of nanometer.
  • the metal nanowire may be linear or curved. If a transparent conductive layer composed of metal nanowires is used, the metal nanowires can be formed into a mesh shape, so that even with a small amount of metal nanowires, a good electrical conduction path can be formed, and transparent with low electrical resistance. A conductive film can be obtained. Furthermore, when the metal nanowire has a mesh shape, an opening is formed in the mesh space, and a transparent conductive film having high light transmittance can be obtained.
  • the ratio between the thickness d and the length L of the metal nanowire is preferably 10 to 100,000, more preferably 50 to 100,000, and particularly preferably 100 to 100,000. 10,000. If metal nanowires having a large aspect ratio are used in this way, the metal nanowires can cross well and high conductivity can be expressed by a small amount of metal nanowires. As a result, a transparent conductive film having a high light transmittance can be obtained.
  • the “thickness of the metal nanowire” means the diameter when the cross section of the metal nanowire is circular, and the short diameter when the cross section of the metal nanowire is elliptical. In some cases it means the longest diagonal. The thickness and length of the metal nanowire can be confirmed by a scanning electron microscope or a transmission electron microscope.
  • the thickness of the metal nanowire is preferably less than 500 nm, more preferably less than 200 nm, particularly preferably 10 nm to 100 nm, and most preferably 10 nm to 50 nm. If it is such a range, a transparent conductive layer with high light transmittance can be formed.
  • the length of the metal nanowire is preferably 1 ⁇ m to 1000 ⁇ m, more preferably 10 ⁇ m to 500 ⁇ m, and particularly preferably 10 ⁇ m to 100 ⁇ m. If it is such a range, a highly conductive transparent conductive film can be obtained.
  • any appropriate metal can be used as long as it is a conductive metal.
  • a metal which comprises the said metal nanowire silver, gold
  • silver, copper, or gold is preferable from the viewpoint of conductivity, and silver is more preferable.
  • any appropriate method can be adopted as a method for producing the metal nanowire.
  • a method of reducing silver nitrate in a solution a method in which an applied voltage or current is applied to the precursor surface from the tip of the probe, a metal nanowire is drawn out at the probe tip, and the metal nanowire is continuously formed, etc. .
  • silver nanowires can be synthesized by liquid phase reduction of a silver salt such as silver nitrate in the presence of a polyol such as ethylene glycol and polyvinylpyrrolidone.
  • Uniform sized silver nanowires are, for example, Xia, Y. et al. etal. , Chem. Mater. (2002), 14, 4736-4745, Xia, Y. et al. etal. , Nano letters (2003) 3 (7), 955-960, mass production is possible.
  • the content ratio of the metal nanowires in the transparent conductive layer is preferably 0.1 to 50 parts by weight, more preferably 0.1 parts by weight to 100 parts by weight of the binder resin constituting the transparent conductive layer. 30 parts by weight. If it is such a range, the transparent conductive film excellent in electroconductivity and light transmittance can be obtained.
  • the metallic particles in the transparent conductive layer may exist as single particles or may exist as aggregates. Single particles and aggregates may be mixed.
  • the average particle diameter X of the metallic particles and the thickness Y of the region constituted by the binder resin preferably satisfy the relationship of Y ⁇ X ⁇ 20Y, and more preferably satisfy the relationship of Y ⁇ X ⁇ 15Y. More preferably, the relationship of Y ⁇ X ⁇ 10Y is satisfied. This is because by setting Y ⁇ X, a part of the metallic particles can protrude from the region constituted by the binder resin, contribute to conduction, and ensure higher conductivity. On the other hand, when X ⁇ 20Y, the metallic particles are favorably retained in the transparent conductive layer. Further, by setting X ⁇ 10Y, the retention of the metallic particles becomes better, and a transparent conductive film having a remarkably low resistance can be obtained.
  • the “average particle diameter” means the average particle diameter (primary particle diameter) of metallic particles existing as single particles and the metallic particles existing as aggregates. This is a concept including both the average particle size (secondary particle size) of the aggregate.
  • the average particle size and the average primary particle size (described later) of the metallic particles constituting the aggregate are randomly determined from the surface of the transparent conductive layer or a cross-sectional image using a microscope (for example, an optical microscope, a scanning electron microscope, or a transmission electron microscope).
  • the median diameter (50% diameter; number basis) of the particle diameter (major axis diameter) measured by observing 100 extracted particles.
  • the average primary particle size of the metallic particles present in the transparent conductive layer is preferably 5 nm to 100 ⁇ m, more preferably 10 nm to 50 ⁇ m, and further preferably 20 nm to 10 ⁇ m. If it is such a range, the transparent conductive layer excellent in conduction
  • the aspect ratio (thickness (minor axis diameter) d to length (major axis diameter) L: L / d) of the metallic particles is preferably 2.0 or less. More preferably, it is 1.5 or less. If it is such a range, the protrusion part (part protruded from the area
  • the average flatness of the metallic particles is preferably 40% or less, more preferably 30% or less, still more preferably 20% or less, and particularly preferably 10% or less. is there.
  • the lower limit of the average flatness of the metallic particles is, for example, 1%.
  • the “average flatness” is calculated from the flatness of metallic particles existing as single particles and the flatness of the aggregates of metallic particles existing as aggregates. More specifically, 30 particles (metallic particles present as single particles, as well as aggregates) randomly extracted from a cross-sectional image of the transparent conductive layer by a microscope (for example, an optical microscope, a scanning electron microscope, or a transmission electron microscope).
  • the average flatness (%) (1 ⁇ D2 / D1) ⁇ from the major median diameter (50% diameter; number basis) D1 of the aggregate) and the short median diameter (50% diameter; number basis) D2. It is calculated by the equation of 100. It should be noted that the definition of “average flatness ratio” also means that not all individual metallic particles (or aggregates of metallic particles) need be in the above range.
  • the number of the metallic particles having an aspect ratio of 40% or less is preferably 80 or more, more preferably 90 or more, with respect to 100 metallic particles.
  • the present invention by using metallic particles having the above average flatness, it is possible to suppress a decrease in light transmittance due to metallic particles.
  • the high flatness particles are oriented so that they fall down (that is, the surface including the major axis is substantially parallel to the front and back surfaces of the transparent conductive film). It is thought that backscattering becomes stronger. In the said embodiment, such backscattering is suppressed and it is thought that the fall of the light transmittance is suppressed as mentioned above.
  • the metallic particles having the above-described flatness can be obtained by any appropriate method as long as the effects of the present invention can be obtained.
  • the metallic particles can be obtained by a wet reduction method.
  • a wet reduction method for example, an alkali or complexing agent is added to a silver salt-containing aqueous solution to produce a silver oxide-containing slurry or a silver complex salt-containing aqueous solution, and the reducing agent is added to reduce silver particles The method of making it precipitate is mentioned. Details of the wet reduction method are described in JP-A-7-76710, JP-A-2013-189704, JP-A-8-176620, and the like. Incorporated.
  • the aggregate having the average flatness is formed by using single particles having a low flatness (for example, an average flatness of 40% or less) by any appropriate method (for example, wet reduction method). Can be done.
  • the content of the metallic particles is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the binder resin. If it is such a range, the transparent conductive film which is excellent in both conduction
  • the content ratio of the metallic particles is preferably 1 to 100 parts by weight, more preferably 10 to 70 parts by weight with respect to 100 parts by weight of the metal nanowires. If it is such a range, the transparent conductive film excellent in electroconductivity and transparency can be obtained.
  • the metallic particles include a conductive metal.
  • single-layered metallic particles are used.
  • metallic particles obtained by coating the surface of any appropriate core particles with the conductive metal are used.
  • the material constituting the core particles include the above conductive metals; insulator particles made of an organic or inorganic substance; and semiconductor particles. Any appropriate metal can be used as the conductive metal.
  • Specific examples of the conductive metal include silver, gold, copper, nickel, palladium and the like.
  • metallic particles using silver, copper or gold are used as the conductive metal, more preferably metallic particles using silver.
  • a silver coat copper particle is mentioned as an example of the metallic particle obtained by a coating process.
  • grains comprised from a metal oxide are used, there exists a possibility that sufficient electroconductivity may not be obtained.
  • the said transparent conductive layer can be formed by applying the composition for transparent conductive layer formation on the said transparent base material, for example.
  • the composition for forming a transparent conductive layer includes a binder resin, metal nanowires, and metallic particles.
  • a transparent conductive layer forming composition (R) containing a binder resin after coating (applying and drying) a transparent conductive layer forming composition (NP) containing metal nanowires and metallic particles.
  • the composition for forming a transparent conductive layer (NP) containing metal nanowires and metallic particles may contain a binder resin or any suitable resin that can improve dispersion stability.
  • the composition for forming a transparent conductive layer (N) containing metal nanowires is coated (applied and dried), and then the composition for forming a transparent conductive layer containing a binder resin and metallic particles ( RP) can be applied to form a transparent conductive layer.
  • the transparent conductive layer forming composition (N) containing metal nanowires may also contain a binder resin or any appropriate resin that can improve dispersion stability.
  • the composition for forming a transparent conductive layer (P) containing metallic particles is coated (applied and dried), and then the composition for forming a transparent conductive layer containing a binder resin and metal nanowires ( RN) can be applied to form a transparent conductive layer.
  • the transparent conductive layer forming composition (P) containing metallic particles may also contain a binder resin or any appropriate resin that can improve dispersion stability.
  • the composition for forming a transparent conductive layer (NP, N, RP, P, RN) containing the metal particles and / or metal nanowires is dispersed in any appropriate solvent. It is the dispersion liquid obtained by making it.
  • the solvent include water, alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents, aromatic solvents and the like.
  • the dispersion concentration of the metal nanowires in the composition for forming a transparent conductive layer (NP, N, RN) containing the metal nanowires is preferably 0.01% by weight to 5% by weight. If it is such a range, the transparent conductive layer excellent in electroconductivity and light transmittance can be formed.
  • the dispersion concentration of the metallic particles in the transparent conductive layer forming composition (NP, RP, P) containing the metallic particles is preferably 0.001 to 5% by weight. If it is such a range, the transparent conductive layer excellent in electroconductivity and light transmittance can be formed.
  • the transparent conductive layer forming composition (NP, N, RP, P, RN) containing the metallic particles and / or metal nanowires may further contain any appropriate additive depending on the purpose.
  • the additive include a corrosion inhibitor that prevents corrosion of metal nanowires and / or metallic particles, and a surfactant that prevents aggregation of metal nanowires.
  • the composition for forming a transparent conductive layer comprises a plasticizer, a heat stabilizer, a light stabilizer, a lubricant, an antioxidant, an ultraviolet absorber, a flame retardant, a colorant, an antistatic agent, a compatibilizer, a crosslinking agent, Additives such as sticky agents, inorganic particles, surfactants, and dispersants may be included.
  • the composition (R) for transparent conductive layer formation containing binder resin may contain arbitrary appropriate solvents. The type, number and amount of additives used can be appropriately set according to the purpose.
  • any appropriate method can be adopted as a method for applying the transparent conductive layer forming composition.
  • the coating method include spray coating, bar coating, roll coating, die coating, inkjet coating, screen coating, dip coating, letterpress printing method, intaglio printing method, and gravure printing method.
  • Any appropriate drying method (for example, natural drying, air drying, heat drying) can be adopted as a method for drying the coating layer.
  • the drying temperature is typically 80 ° C. to 150 ° C.
  • the drying time is typically 1 to 20 minutes.
  • a hardening process for example, heat processing, an ultraviolet irradiation process
  • Transparent substrate Any appropriate material can be used as the material constituting the transparent substrate .
  • a polymer substrate such as a film or a plastics substrate is preferably used. It is because it is excellent in the smoothness of a transparent base material, and the wettability with respect to the composition for transparent conductive layer formation, and productivity can be improved significantly by the continuous production by a roll.
  • the material constituting the transparent base material is typically a polymer film mainly composed of a thermoplastic resin.
  • the thermoplastic resin include polyester resins; cycloolefin resins such as polynorbornene; acrylic resins; polycarbonate resins; and cellulose resins. Of these, polyester resins, cycloolefin resins, and acrylic resins are preferable. These resins are excellent in transparency, mechanical strength, thermal stability, moisture shielding properties and the like. You may use the said thermoplastic resin individually or in combination of 2 or more types.
  • an optical film used for a polarizing plate for example, a low retardation substrate, a high retardation substrate, a retardation plate, a brightness enhancement film, or the like can be used as the substrate.
  • the thickness of the transparent substrate is preferably 20 ⁇ m to 200 ⁇ m, more preferably 30 ⁇ m to 150 ⁇ m.
  • the total light transmittance of the transparent substrate is preferably 30% or more, more preferably 35% or more, and further preferably 40% or more.
  • the transparent conductive film can be used for a touch sensor.
  • the transparent conductive film can function as an electrode, an electromagnetic wave shield, or the like.
  • an optical laminate obtained by laminating the transparent conductive film and the polarizing plate is provided.
  • the transparent conductive film and the polarizing plate can be bonded together via any appropriate adhesive or pressure-sensitive adhesive. Any appropriate polarizing plate can be used as the polarizing plate.
  • the optical layered body can be suitably used as a polarizing element having touch sensor characteristics or electromagnetic wave shielding characteristics, and is used, for example, as a viewing side polarizing plate or a back side polarizing plate of a liquid crystal cell of a liquid crystal display device.
  • Examples A1 to 11, Comparative Examples A1 and 2 Evaluation methods in Examples A1 to 11 and Comparative Examples A1 and A2 are as follows.
  • the thickness was measured by using a scanning electron microscope “S-4800” manufactured by Hitachi High-Technologies Corporation by forming a cross section by cutting with an ultramicrotome after embedding with an epoxy resin.
  • Haze value A sample was attached to a glass with an adhesive, and measured at 23 ° C. using a trade name “HR-100” manufactured by Murakami Color Research Laboratory.
  • (2) Surface Resistance Value The surface resistance value of the transparent conductive film was measured by an eddy current method using a non-contact surface resistance meter trade name “EC-80” manufactured by Napson Corporation. The measurement temperature was 23 ° C.
  • a silver paste line (length 20 mm x width 1 mm) is applied at a predetermined interval (5 mm, 15 mm and 35 mm), and the resistance value between the two points is calculated by Sanwa Electric Meter. It measured using the brand name "Digital Multimeter CD800a" made by a company. A linear form was obtained from the correlation between the distance between the two points and the resistance value, and the value obtained by dividing the intercept by 2 was defined as the contact resistance value of the transparent conductive film.
  • the average particle diameter was defined as the median diameter (50% diameter; several standards) of the particle diameter measured by observing 100 particles randomly extracted on the surface or cross section of the transparent conductive layer with the microscope.
  • the ten-point average roughness Rz having a measurement area of 200 ⁇ m ⁇ was defined as the protrusion height.
  • the reaction was carried out until the AgNO 3 was completely reduced by heating to 160 ° C. over 1 hour to produce silver nanowires. Then, acetone is added to the reaction mixture containing silver nanowires obtained as described above until the volume of the reaction mixture becomes 5 times, and then the reaction mixture is centrifuged (2000 rpm, 20 minutes), Silver nanowires were obtained.
  • the obtained silver nanowire had a minor axis of 30 nm to 40 nm, a major axis of 30 nm to 50 nm, and a length of 5 ⁇ m to 50 ⁇ m.
  • the silver nanowire (concentration: 0.2% by weight) and pentaethylene glycol dodecyl ether (concentration: 0.1% by weight) were dispersed in pure water to prepare a silver nanowire dispersion liquid a.
  • Example A1 (Preparation of first transparent conductive layer forming composition (PN)) 25 parts by weight of the silver nanowire dispersion a, 1% by weight of silver particles (average primary particle size: 1.3 ⁇ m) 2 parts by weight of the aqueous dispersion was diluted with 73 parts by weight of pure water to obtain a solid content concentration of 0.07% by weight. 1 transparent conductive layer forming composition (PN) was prepared.
  • Second transparent conductive layer forming composition (R) Pentaerythritol triacrylate (trade name “Biscoat # 300” manufactured by Osaka Organic Chemical Industries, Ltd.) 3.6 parts by weight, organosilica sol (product name “MEK-AC-2140Z” manufactured by Nissan Chemical Industries, Ltd., concentration 40%) 2 7 parts by weight, 0.2 parts by weight of photopolymerization initiator (BASF, trade name “Irgacure 907”) was diluted with 93 parts by weight of cyclopentanone to give a second transparent conductive material having a solid content concentration of 5% by weight. A layer forming composition (R) was obtained.
  • the first transparent conductive layer forming composition (PN) was applied using 26 (Mitsui Electric Seiki Co., Ltd.) and dried. Furthermore, the second transparent conductive layer forming composition (R) was applied by spin coating (1000 rpm, 5 seconds), dried at 90 ° C. for 1 minute, and then irradiated with 300 mJ / cm 2 of ultraviolet rays, A transparent conductive film (content ratio of metallic particles to 100 parts by weight of binder resin: 2.5 parts by weight) was obtained.
  • the thickness Y of the region constituted by the binder resin (for convenience, expressed as the film thickness of the transparent conductive layer in Table 1) is 0.3 ⁇ m, and the height of the protruding portion of the metallic particles Z was 0.9 ⁇ m. Further, this transparent conductive film had a surface resistance value of 50.3 ⁇ / ⁇ , a contact resistance value of 1.2 ⁇ , a haze value of 2.9%, and a scratch resistance of ⁇ .
  • Example A2 The thickness Y of the region composed of the binder resin is 1 ⁇ m in the same manner as in Example A1, except that the spin coating conditions at the time of applying the second transparent conductive layer forming composition (R) are 400 rpm and 5 seconds.
  • a transparent conductive film (content ratio of metallic particles to 0.7 parts by weight with respect to 100 parts by weight of binder resin) was obtained in which the height Z of the protruding part of the metallic particles was 0.4 ⁇ m.
  • the transparent conductive film had a surface resistance value of 51.2 ⁇ / ⁇ , a contact resistance value of 3.7 ⁇ , a haze value of 3.0%, and an abrasion resistance of ⁇ .
  • Example A3 Similar to Example A1, except that 1 wt% silver particles (average primary particle size: 20 nm) aqueous dispersion was used instead of the 1 wt% silver particles (average primary particle size: 1.3 ⁇ m) aqueous dispersion. Thus, a transparent conductive film (content ratio of metallic particles with respect to 100 parts by weight of binder resin: 2.4 parts by weight) was obtained. In this transparent conductive film, the thickness Y of the region constituted by the binder resin was 0.3 ⁇ m, and the height Z of the protruding portion of the metallic particles was 1.3 ⁇ m.
  • the transparent conductive film had a surface resistance value of 49.8 ⁇ / ⁇ , a contact resistance value of 0.4 ⁇ , a haze value of 2.5%, and an abrasion resistance of ⁇ .
  • a transmission electron microscope silver aggregates having an average particle diameter (major axis diameter) of 1.5 ⁇ m were observed.
  • Example A4 Example A1 except that 1 wt% silver particles (average primary particle size: 1.7 ⁇ m) aqueous dispersion was used instead of the 1 wt% silver particles (average primary particle size: 1.3 ⁇ m) aqueous dispersion.
  • a transparent conductive film content ratio of metallic particles to 2.5 parts by weight with respect to 100 parts by weight of the binder resin
  • the thickness Y of the region constituted by the binder resin was 0.3 ⁇ m
  • the height Z of the protruding portion of the metallic particles was 1.5 ⁇ m.
  • the transparent conductive film had a surface resistance value of 49.1 ⁇ / ⁇ , a contact resistance value of 2.8 ⁇ , a haze value of 2.0%, and a scratch resistance of ⁇ .
  • Example A5 Example A1 except that 1 wt% silver particles (average primary particle size: 5.1 ⁇ m) aqueous dispersion was used instead of the 1 wt% silver particles (average primary particle size: 1.3 ⁇ m) aqueous dispersion.
  • a transparent conductive film content ratio of metallic particles to 2.5 parts by weight with respect to 100 parts by weight of the binder resin
  • the thickness Y of the region constituted by the binder resin was 0.3 ⁇ m
  • the height Z of the protruding portion of the metallic particles was 4.8 ⁇ m.
  • this transparent conductive film had a surface resistance value of 53.0 ⁇ / ⁇ , a contact resistance value of 11.3 ⁇ , a haze value of 1.8%, and a scratch resistance of ⁇ .
  • Example A6 Instead of an aqueous dispersion of 1% by weight silver particles (average primary particle size: 1.3 ⁇ m), an aqueous dispersion of 1% by weight silver-coated copper particles (average primary particle size: 1.1 ⁇ m, 10% of silver coating) is used.
  • a transparent conductive film (content ratio of metallic particles to 2.5 parts by weight with respect to 100 parts by weight of the binder resin) was obtained in the same manner as Example A1 except for the above.
  • the thickness Y of the region constituted by the binder resin was 0.3 ⁇ m, and the height Z of the protruding portion of the metallic particles was 0.7 ⁇ m.
  • the transparent conductive film had a surface resistance value of 52.1 ⁇ / ⁇ , a contact resistance value of 3.0 ⁇ , a haze value of 2.5%, and an abrasion resistance of ⁇ .
  • Example A7 (Preparation of first transparent conductive layer forming composition (N)) 25 parts by weight of the silver nanowire dispersion a was diluted with 75 parts by weight of pure water to prepare a first transparent conductive layer forming composition (N) having a solid content concentration of 0.05%.
  • Second transparent conductive layer forming composition (RP) Pentaerythritol triacrylate (trade name “Biscoat # 300” manufactured by Osaka Organic Chemical Industries, Ltd.) 3.6 parts by weight, organosilica sol (product name “MEK-AC-2140Z” manufactured by Nissan Chemical Industries, Ltd., concentration 40%) 2 0.7 parts by weight, photopolymerization initiator (manufactured by BASF, trade name “Irgacure 907”) and 1 part by weight of silver particles (average primary particle size: 1.3 ⁇ m) 15 parts by weight of cyclopentanone dispersion Was diluted with 78.5 parts by weight of cyclopentanone to obtain a second transparent conductive layer forming composition (N) having a solid concentration of 5% by weight.
  • organosilica sol product name “MEK-AC-2140Z” manufactured by Nissan Chemical Industries, Ltd., concentration 40%
  • photopolymerization initiator manufactured by BASF, trade name “Irgacure 907”
  • the transparent conductive film (Preparation of transparent conductive film) Implementation was performed except that the first transparent conductive layer forming composition (N) and the second transparent conductive layer forming composition (RP) were used as the first and second transparent conductive layer forming compositions.
  • a transparent conductive film (content ratio of metallic particles to 3.1 parts by weight of binder resin: 3.1 parts by weight) was obtained in the same manner as Example A1.
  • the thickness Y of the region constituted by the binder resin was 0.3 ⁇ m
  • the height Z of the protruding portion of the metallic particles was 1.1 ⁇ m.
  • the transparent conductive film had a surface resistance value of 53.2 ⁇ / ⁇ , a contact resistance value of 1.5 ⁇ , a haze value of 2.8%, and a scratch resistance of ⁇ .
  • Example A8 Implementation was performed except that 1 wt% silver particles (average primary particle size: 1.3 ⁇ m) cyclopentanone dispersion was used instead of 1 wt% silver particles (average primary particle size: 20 nm) cyclopentanone dispersion.
  • a transparent conductive film (content ratio of metallic particles to 3.1 parts by weight with respect to 100 parts by weight of binder resin) was obtained in the same manner as Example A7. In this transparent conductive film, the thickness Y of the region constituted by the binder resin was 0.3 ⁇ m, and the height Z of the protruding portion of the metallic particles was 0.7 ⁇ m.
  • the transparent conductive film had a surface resistance value of 50.9 ⁇ / ⁇ , a contact resistance value of 0.8 ⁇ , a haze value of 2.6%, and a scratch resistance of ⁇ .
  • a transmission electron microscope silver aggregates having an average particle diameter (major axis diameter) of 1.5 ⁇ m were observed.
  • Example A9 1 wt% silver particles (average primary particle size: 1.3 ⁇ m) A cyclopentanone dispersion was used instead of 1 wt% silver particles (average primary particle size: 1.7 ⁇ m).
  • a transparent conductive film content ratio of metallic particles to 3.1 parts by weight with respect to 100 parts by weight of the binder resin
  • the thickness Y of the region constituted by the binder resin was 0.3 ⁇ m
  • the height Z of the protruding portion of the metallic particles was 1.6 ⁇ m.
  • the transparent conductive film had a surface resistance value of 52.3 ⁇ / ⁇ , a contact resistance value of 2.4 ⁇ , a haze value of 3.0%, and a scratch resistance of ⁇ .
  • Example A10 Except for using 1 wt% silver particles (average primary particle size: 5.1 ⁇ m) cyclopentanone dispersion instead of 1 wt% silver particles (average primary particle size: 1.3 ⁇ m) cyclopentanone dispersion.
  • a transparent conductive film (content ratio of metallic particles to 3.1 parts by weight with respect to 100 parts by weight of the binder resin) was obtained.
  • the thickness Y of the region constituted by the binder resin was 0.3 ⁇ m
  • the height Z of the protruding portion of the metallic particles was 4.9 ⁇ m.
  • the transparent conductive film had a surface resistance value of 54.2 ⁇ / ⁇ , a contact resistance value of 8.4 ⁇ , a haze value of 2.0%, and a scratch resistance of ⁇ .
  • Example A11 1% by weight silver particles (average primary particle size: 1.3 ⁇ m) instead of cyclopentanone dispersion 1% by weight silver-coated copper particles (average primary particle size: 1.1 ⁇ m, silver-coated content 10%) cyclopentanone
  • a transparent conductive film (content ratio of metallic particles with respect to 100 parts by weight of binder resin: 3.1 parts by weight) was obtained in the same manner as Example A7, except that the dispersion was used.
  • the thickness Y of the region constituted by the binder resin was 0.3 ⁇ m, and the height Z of the protruding portion of the metallic particles was 0.9 ⁇ m.
  • the transparent conductive film had a surface resistance value of 57.4 ⁇ / ⁇ , a contact resistance value of 3.4 ⁇ , a haze value of 2.1%, and an abrasion resistance of ⁇ .
  • the thickness Y of the region constituted by the binder resin was 0.3 ⁇ m.
  • the surface resistance value of this transparent conductive film was 52.1 ⁇ / ⁇ , the contact resistance value exceeded 300 ⁇ and was not measurable.
  • the haze value was 1.6%, and the scratch resistance was ⁇ .
  • Examples B1 to B3, Reference examples B1 to B2> The evaluation methods in Examples B1 to B3 and Reference Examples B1 and B2 are as follows.
  • the thickness was measured by using a scanning electron microscope “S-4800” manufactured by Hitachi High-Technologies Corporation by forming a cross section by cutting with an ultramicrotome after embedding with an epoxy resin.
  • Total light transmittance A transparent conductive film was attached to a glass with an adhesive, and measured at 23 ° C. using a trade name “HR-100” manufactured by Murakami Color Research Laboratory.
  • (3) Contact resistance value Measured in the same manner as in Examples A1 to A11.
  • the average particle size is the median of the particle size (major axis) measured by observing 100 particles (metallic particles and aggregates present as single particles) randomly extracted from the surface of the transparent conductive layer by the microscope. The diameter (50% diameter; number basis) was used.
  • Example B1 (Preparation of first transparent conductive layer forming composition (NP-1)) 25 parts by weight of the above-mentioned silver nanowire dispersion a and 1% by weight silver particle aqueous dispersion A (containing the trade name “Silbest AgS-050” manufactured by Tokuke Chemical Laboratory as silver particles; average primary particle diameter of silver particles:
  • the first transparent conductive layer-forming composition (NP-) having a solid content of 0.07% by weight was diluted with 75 parts by weight of pure water by 2 parts by weight of 5 ⁇ m and the average flatness of silver particles: 10.3%. 1) was prepared.
  • a transparent conductive film was obtained in the same manner as in Production Example B2, except that the first transparent conductive layer forming composition (NP-1) was used as the first transparent conductive layer forming composition.
  • the thickness of the region constituted by the binder resin was 0.3 ⁇ m.
  • region comprised with binder resin, and the height of the protrusion part was 0.1 micrometer.
  • the obtained transparent conductive film had a surface resistance value of 52.0 ⁇ / ⁇ , a contact resistance value of 0.6 ⁇ , a total light transmittance of 89.3%, and a total light transmittance of the reference film.
  • the difference ⁇ T from the rate was 0.5%.
  • Example B2 (Preparation of first transparent conductive layer forming composition (NP-2)) Instead of the 1% by weight silver particle aqueous dispersion A, 1% by weight silver particle aqueous dispersion B (containing trade name “SPN05S” manufactured by Mitsui Kinzoku Kogyo Co., Ltd. as silver particles; average primary particle diameter of silver particles: 1.
  • a first transparent conductive layer forming composition (NP-2) was prepared in the same manner as in Example B1, except that 3 ⁇ m and the average flatness of silver particles: 4.0% were used.
  • a transparent conductive film was obtained in the same manner as in Example B1, except that the first transparent conductive layer forming composition (NP-2) was used as the first transparent conductive layer forming composition.
  • the thickness of the region constituted by the binder resin was 0.3 ⁇ m.
  • region comprised with binder resin, and the height of the protrusion part was 0.9 micrometer.
  • the obtained transparent conductive film has a surface resistance value of 53.0 ⁇ / ⁇ , a contact resistance value of 2.7 ⁇ , a total light transmittance of 89.1%, and a total light transmittance of the reference film.
  • the difference ⁇ T from the rate was 0.7%.
  • Example B3 (Preparation of first transparent conductive layer forming composition (NP-3)) Instead of the 1% by weight silver particle aqueous dispersion A, 1% by weight silver particle aqueous dispersion C (containing trade name “SPN08S” manufactured by Mitsui Kinzoku Kogyo Co., Ltd. as silver particles; average primary particle diameter of silver particles: 1.
  • a first transparent conductive layer-forming composition (NP-3) was prepared in the same manner as in Example B1, except that 7 ⁇ m and the average flatness of silver particles: 2.7% were used.
  • a transparent conductive film was obtained in the same manner as in Example B1, except that the first transparent conductive layer forming composition (NP-3) was used as the first transparent conductive layer forming composition.
  • the thickness of the region constituted by the binder resin was 0.3 ⁇ m.
  • region comprised with binder resin, and the height of the protrusion part was 1.3 micrometers.
  • the obtained transparent conductive film had a surface resistance value of 49.1 ⁇ / ⁇ , a contact resistance value of 2.8 ⁇ , a total light transmittance of 89.2%, and a total light transmission of the reference film.
  • the difference ⁇ T from the rate was 0.6%.
  • a transparent conductive film was obtained in the same manner as in Example B1, except that the first transparent conductive layer forming composition (NP-4) was used as the first transparent conductive layer forming composition.
  • the thickness of the region constituted by the binder resin was 0.3 ⁇ m.
  • region comprised with binder resin, and the height of the protrusion part was 0.7 micrometer.
  • the obtained transparent conductive film had a surface resistance value of 51.1 ⁇ / ⁇ , a contact resistance value of 1.2 ⁇ , a total light transmittance of 88.1%, and a total light transmittance of the reference film.
  • the difference ⁇ T from the rate was 1.7%.
  • the thickness of the region constituted by the binder resin was 0.3 ⁇ m. Moreover, a part of metallic particle protruded from the area
  • the obtained transparent conductive film had a surface resistance value of 51.9 ⁇ / ⁇ , a contact resistance value of 1.5 ⁇ , a total light transmittance of 87.9%, and a total light transmittance of the reference film. The difference ⁇ T from the rate was 1.9%.
  • the transparent conductive film of the present invention can be used in electronic devices such as display elements.

Landscapes

  • Non-Insulated Conductors (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un film électroconducteur transparent possédant une excellente résistance aux rayures et une excellente conductivité électrique. Ce film électroconducteur transparent comprend un substrat transparent et une couche électroconductrice transparente disposée sur un seul côté ou les deux côtés du substrat transparent. La couche électroconductrice transparente comprend une résine liante, des nanofils métalliques et des particules métalliques. Une partie des particules métallique fait saillie d'une région composée de la résine liante. Dans un mode de réalisation, la taille de grain moyenne X des particules métalliques et l'épaisseur Y de la région composée de la résine liante satisfont la relation Y ≤ X ≤ 20Y.
PCT/JP2016/051951 2015-01-27 2016-01-25 Film électroconducteur transparent Ceased WO2016121662A1 (fr)

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US15/546,928 US20180017715A1 (en) 2015-01-27 2016-01-25 Transparent conductive film

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JP2015-013652 2015-01-27
JP2015013652 2015-01-27
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JP2015-052126 2015-03-16
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JP2015179341A JP6580432B2 (ja) 2015-03-16 2015-09-11 透明導電性フィルム
JP2015179340A JP6580431B2 (ja) 2015-01-27 2015-09-11 透明導電性フィルム
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002514342A (ja) * 1996-10-28 2002-05-14 トーマス アンド ベッツ インターナショナル インコーポレイテッド 導電性エラストマーと、これを作る方法
JP2011029098A (ja) * 2009-07-28 2011-02-10 Panasonic Electric Works Co Ltd 透明導電膜付き基材
JP2011029099A (ja) * 2009-07-28 2011-02-10 Panasonic Electric Works Co Ltd 透明導電膜付き基材
JP2011198642A (ja) * 2010-03-19 2011-10-06 Panasonic Electric Works Co Ltd 透明導電膜付き基材及びその製造方法
JP2012204023A (ja) * 2011-03-23 2012-10-22 Panasonic Corp 透明導電膜、透明導電膜付き基材、及びそれを用いた有機エレクトロルミネッセンス素子、並びにその製造方法
JP2013246976A (ja) * 2012-05-25 2013-12-09 Panasonic Corp 導電性光学部材用支持材、この導電性光学部材用支持材を備える導電性光学部材、及びこの導電性光学部材を備える電子デバイス

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002514342A (ja) * 1996-10-28 2002-05-14 トーマス アンド ベッツ インターナショナル インコーポレイテッド 導電性エラストマーと、これを作る方法
JP2011029098A (ja) * 2009-07-28 2011-02-10 Panasonic Electric Works Co Ltd 透明導電膜付き基材
JP2011029099A (ja) * 2009-07-28 2011-02-10 Panasonic Electric Works Co Ltd 透明導電膜付き基材
JP2011198642A (ja) * 2010-03-19 2011-10-06 Panasonic Electric Works Co Ltd 透明導電膜付き基材及びその製造方法
JP2012204023A (ja) * 2011-03-23 2012-10-22 Panasonic Corp 透明導電膜、透明導電膜付き基材、及びそれを用いた有機エレクトロルミネッセンス素子、並びにその製造方法
JP2013246976A (ja) * 2012-05-25 2013-12-09 Panasonic Corp 導電性光学部材用支持材、この導電性光学部材用支持材を備える導電性光学部材、及びこの導電性光学部材を備える電子デバイス

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