WO2012023553A1 - Matériau conducteur d'électricité, panneau tactile et cellule solaire - Google Patents

Matériau conducteur d'électricité, panneau tactile et cellule solaire Download PDF

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Publication number
WO2012023553A1
WO2012023553A1 PCT/JP2011/068549 JP2011068549W WO2012023553A1 WO 2012023553 A1 WO2012023553 A1 WO 2012023553A1 JP 2011068549 W JP2011068549 W JP 2011068549W WO 2012023553 A1 WO2012023553 A1 WO 2012023553A1
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conductive
conductive material
group
layer
conductive layer
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PCT/JP2011/068549
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English (en)
Japanese (ja)
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直井　憲次
規 宮城島
谷　武晴
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富士フイルム株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0445—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using two or more layers of sensing electrodes, e.g. using two layers of electrodes separated by a dielectric layer
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/045—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means using resistive elements, e.g. a single continuous surface or two parallel surfaces put in contact
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells

Definitions

  • the present invention relates to a conductive material, a touch panel using the conductive material, and a solar cell.
  • Patent Document 1 includes (1) a method of lowering the ratio of binder to Ag (binder / Ag) in the conductive layer of the conductive material, (2) a method of immersing the conductive layer of the conductive material, (3) At present, no mention is made of a change in the shape of the spectral absorption spectrum due to a method of heat-treating a conductive layer of a conductive material.
  • the present invention provides a conductive material that has high permeability, low resistance, improved durability and flexibility, and that can be easily patterned, and a touch panel using the conductive material that has high visibility.
  • An object is to provide a solar cell with high conversion efficiency.
  • a conductive material having one absorption peak at 325 nm to 390 nm in a spectral absorption spectrum of a conductive layer containing a conductive fiber is obtained as a conductive fiber. It was found that the contacts between each other were strengthened, and conductivity, transmittance, haze, flexibility, and durability were improved.
  • the present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is, ⁇ 1> A conductive material having a conductive layer containing conductive fibers, In the spectral absorption spectrum of the conductive layer, the conductive material has one absorption peak at 325 nm to 390 nm. ⁇ 2> The conductive material according to ⁇ 1>, wherein a half width at an absorption peak of 325 nm to 390 nm is 100 nm or less. ⁇ 3> The conductive material according to ⁇ 2>, wherein a half width at an absorption peak of 325 nm to 390 nm is 20 nm to 70 nm.
  • the ratio (A / B) between the peak top absorbance A of 325 nm to 390 nm and the absorbance B of 800 nm is 1.5 or more
  • ⁇ 6> The conductive material according to any one of ⁇ 1> to ⁇ 5>, wherein the conductive fiber is a metal nanowire.
  • ⁇ 7> The conductive material according to ⁇ 6>, wherein the metal nanowire is made of any of silver and an alloy of silver and a metal other than silver.
  • the ratio (X / A) of the silver content Xg / m 2 in the conductive layer to the peak top absorbance A of 325 nm to 390 nm in the spectral absorption spectrum of the conductive layer is 0.4 or more.
  • ⁇ 10> The conductive material according to any one of ⁇ 1> to ⁇ 9>, wherein the total visible light transmittance in the conductive layer is 85% or more.
  • ⁇ 11> The conductive material according to any one of ⁇ 1> to ⁇ 10>, wherein the conductive layer has a surface resistance of 0.1 ⁇ / ⁇ to 5,000 ⁇ / ⁇ .
  • ⁇ 12> The conductive material according to any one of ⁇ 1> to ⁇ 11>, wherein the conductive layer is patterned.
  • ⁇ 13> A touch panel using the conductive material according to any one of ⁇ 1> to ⁇ 12>.
  • ⁇ 14> A solar cell using the conductive material according to any one of ⁇ 1> to ⁇ 12>.
  • the present invention it is possible to solve the conventional problems, high permeability, low resistance, improved durability and flexibility, and a conductive material that can be easily patterned, and the conductive material.
  • the used touch panel with good visibility and a solar cell with high conversion efficiency can be provided.
  • FIG. 1 shows the sample No. 1 of Example 1.
  • 101-Sample No. 10 is a spectral absorption spectrum of a conductive layer in 106 conductive materials.
  • FIG. 2 is a drawing for explaining the definition of the half width of the absorption peak at wavelengths of 325 nm to 390 nm.
  • FIG. 3 is a schematic cross-sectional view showing an example of a touch panel.
  • FIG. 4 is a schematic explanatory diagram illustrating another example of the touch panel.
  • FIG. 5 is a schematic plan view showing an arrangement example of the conductive film in the touch panel shown in FIG.
  • FIG. 6 is a schematic cross-sectional view showing still another example of the touch panel.
  • the conductive material of the present invention has at least a conductive layer containing conductive fibers.
  • the conductive material of the present invention may further have other layers such as a substrate, a photosensitive layer, an antifouling layer, a UV cut layer, and an antireflection layer.
  • the present invention is characterized in that the spectral absorption spectrum of the conductive layer has one absorption peak at a wavelength of 325 nm to 390 nm.
  • the contact point between the conductive fibers is strengthened, and the conductivity, transmittance, haze, flexibility, and durability against wet heat are enhanced.
  • the conductive fiber is oxidized or deformed into particles and the like, resulting in deterioration of conductivity, and haze, flexibility, and wet heat durability are reduced.
  • FIG. 1 shows a sample No. in Example 1 described later. 101-No. It is the figure which showed the spectral absorption spectrum of the conductive layer in the conductive material of 106.
  • the maximum absorbance of the absorption peak in the wavelength range of 325 nm to 700 nm is normalized as 1.0.
  • As shown in part A of FIG. 101-No. 105 has one absorption peak in the wavelength range of 325 nm to 390 nm. More precisely, the wavelength range where the absorption peak is present is 335 nm to 375 nm.
  • sample No. which is a conventional conductive material. No.
  • 106 does not have an absorption peak in the wavelength range of 325 nm to 390 nm, has a gentle waveform, has high absorption or scattering in the visible light range, and it is recognized that transmittance and haze are deteriorated. .
  • the half width of the absorption peak at a wavelength of 325 nm to 390 nm is preferably 100 nm or less, more preferably 20 nm to 90 nm, and still more preferably 20 nm to 70 nm.
  • the half width exceeds 100 nm, spherical nanoparticles may be mixed, and the conductive material may be yellowish.
  • the half width is less than 20 nm, the thickness (average minor axis length) of the metal nanowire becomes too thin, and the wet heat durability may deteriorate.
  • the half width of the absorption peak at the wavelength of 325 nm to 390 nm is, as shown in FIG.
  • the sample No. 101 in the spectral absorption spectrum of the conductive layer (in FIG. 2, the sample No. 101 is representatively represented).
  • An absorption spectrum in the wavelength range of 600 nm to 800 nm is approximated by a straight line and used as a baseline. The base line is extended, and the intersection point with the perpendicular drawn from the top of the absorption peak is taken as the reference position. Then, the value indicated by the lateral width (nm) when the absorption peak is cut horizontally at a position that is half the height between the height of the absorption peak and the reference position is defined as the half width.
  • the spectral absorption spectrum of the conductive layer can be measured by, for example, a spectrophotometer (Jasco V-670, manufactured by JASCO Corporation).
  • the ratio (A / B) between the peak top absorbance A at a wavelength of 325 nm to 390 nm and the absorbance B at 800 nm is preferably 1.5 or more, and preferably 2.0 to 5.0. Is more preferable, 2.0 to 3.0 is more preferable, and 2.1 to 2.4 is particularly preferable.
  • the ratio (A / B) is less than 1.5, the absorption in the visible light region becomes relatively large, and thus the transparency may be deteriorated.
  • the ratio (X / A) between the silver content Xg / m 2 in the conductive layer and the peak top absorbance A at a wavelength of 325 nm to 390 nm in the spectral absorption spectrum of the conductive layer is preferably 0.4 or more. .6 or more is more preferable, 0.6 to 1.0 is more preferable, and 0.6 to 0.8 is particularly preferable.
  • the ratio (X / A) is less than 0.4, the light absorbency becomes relatively high with respect to the amount of the conductive fiber, so that the transparency may be deteriorated.
  • the peak top absorbance A and the absorbance B at 800 nm are measured values.
  • the silver content in the conductive layer can be measured, for example, with a fluorescent X-ray analyzer (SEA1100, manufactured by SII).
  • the thickness of the conductive layer is preferably 0.01 ⁇ m to 1 ⁇ m, more preferably 0.05 ⁇ m to 0.5 ⁇ m, still more preferably 0.05 ⁇ m to 0.3 ⁇ m.
  • a conductive layer using conductive fibers exhibits high conductivity while making the thickness of the conductive layer very thin.
  • the thickness of the conductive layer is less than 0.01 ⁇ m, sufficient film strength cannot be obtained, and there is a possibility that film peeling and fluctuation of surface resistance may occur in the manufacturing process of the conductive layer and subsequent processing steps.
  • the thickness of the conductive layer exceeds 1 ⁇ m, there is a concern that the conductivity is lowered by the binder contained in the conductive layer and the surface resistance is increased.
  • One method for obtaining one absorption peak at a wavelength of 325 nm to 390 nm in the spectral absorption spectrum of the conductive layer is to subject the conductive layer of the conductive material to a contact strengthening treatment.
  • a contact strengthening treatment By subjecting the conductive layer of the conductive material to a contact strengthening treatment, binders, particles, dispersants and the like between the conductive fibers are removed, and the number of metal nanowires as conductive fibers increases. As a result, it is considered that the plasmon absorption component of the metal nanowire as the conductive fiber decreases or the refractive index around the conductive fiber decreases.
  • Examples of the contact-strengthening treatment of the conductive layer include (1) a method of reducing the mass ratio (A / B) of the binder content (A) and the conductive fiber content (B) in the conductive layer, (2 ) A method of immersing the conductive layer with an immersion liquid, and (3) a method of heat-treating the conductive layer.
  • the methods (1) to (3) can be appropriately combined.
  • the addition amount of the coating binder to be added is reduced, Examples include increasing the amount of the additive fiber and reducing the amount of the dispersant used.
  • the mass ratio (A / B) between the binder content (A) and the conductive fiber content (B) in the conductive layer is the conductive fiber content (A) and the water-soluble polymer content.
  • the mass ratio (A / B) to (B) is preferably from 0.1 to 3, more preferably from 0.5 to 2.
  • Examples of the method for immersing the conductive layer of the conductive material of (2) include (i) a method of putting an immersion liquid in a container and immersing the conductive material in the immersion liquid, and (ii) an immersion liquid of the conductive material. And (iii) a method of showering, spraying and rinsing the conductive layer of the conductive material with an immersion liquid.
  • Examples of the immersion liquid include water, methanol, ethanol, normal propanol, isopropanol, ethylene glycol, and acetone. These may be used individually by 1 type and may use 2 or more types together.
  • water, ethanol, normal propanol, isopropanol, or a mixed solvent thereof is preferable
  • water, ethanol, a mixed solvent of water and normal propanol is preferable
  • a mixed solvent of water and normal propanol is particularly preferable.
  • the mixing volume ratio (water: normal propanol) in the mixed solvent of water and normal propanol is preferably 3: 7 to 7: 3, particularly preferably 5: 5.
  • the immersion liquid for example, when the immersion liquid is ethanol, it is preferably in the range of 5 ° C. to 40 ° C. for 1 second to 30 minutes, more preferably in the range of 10 ° C. to 30 ° C. for 3 seconds to 3 minutes. .
  • the immersion liquid is a mixed solvent of water and normal propanol (volume ratio 1: 1)
  • a temperature of 5 ° C. to 40 ° C. is preferably 1 second to 30 minutes, and a temperature of 10 ° C. to 30 ° C. for 5 seconds to 10 minutes is more preferable.
  • the temperature is preferably 5 ° C. to 40 ° C. for 1 second to 30 minutes, more preferably 10 ° C. to 30 ° C. for 5 seconds to 15 minutes.
  • the rinsing liquid may be the immersion liquid itself or a combination of the immersion liquid and another solvent. Examples of the other solvent include water. After the immersion treatment (2) is performed, it is preferable to perform rinsing with pure water a plurality of times.
  • the conductive layer of the conductive material is heated at a temperature of 50 ° C. to 250 ° C. for 1 minute to 60 minutes, preferably at a temperature of 80 ° C. to 200 ° C.
  • the method include baking for 30 minutes to 30 minutes in air or nitrogen by an oven, or heating a conductive material through a substrate using a hot plate or the like.
  • the contact strengthening treatment (1) a method of reducing the mass ratio (A / B) of the binder content (A) and the conductive fiber content (B) in the conductive layer, and (2) immersion of the conductive layer (1) a method for reducing the ratio (A / B) of the binder content (A) and the conductive fiber content (B) in the conductive layer; and (3) It is preferable to combine the methods for heat-treating the conductive layer.
  • the shape, structure, size and the like of the conductive material are not particularly limited as long as the conductive material has the above characteristic points, and can be appropriately selected according to the purpose.
  • the shape may be a film, a sheet
  • the structure includes a single-layer structure, a laminated structure, and the like, and the size can be appropriately selected depending on the application.
  • the conductive material has flexibility and is preferably transparent, and the transparent includes colorless and transparent, colored transparent, translucent, colored translucent and the like.
  • the conductive layer in the conductive material is preferably patterned.
  • Examples of the patterning include patterning performed with an existing ITO transparent conductive film, and examples thereof include a rectangular pattern and a diamond pattern.
  • the conductive layer contains at least conductive fibers, a binder, and further contains other components as necessary.
  • [Conductive fiber] There is no restriction
  • the solid structure fiber may be referred to as a wire
  • the hollow structure fiber may be referred to as a tube.
  • a conductive fiber having an average minor axis length of 5 nm to 1,000 nm and an average major axis length of 1 ⁇ m to 100 ⁇ m may be referred to as “nanowire”.
  • a conductive fiber having an average minor axis length of 1 nm to 1,000 nm and an average major axis length of 0.1 ⁇ m to 1,000 ⁇ m and having a hollow structure may be referred to as a “nanotube”.
  • the material of the conductive fiber is not particularly limited as long as it has conductivity, and can be appropriately selected according to the purpose. However, at least one of metal and carbon is preferable, and among these, The conductive fiber is preferably at least one of metal nanowires, metal nanotubes, and carbon nanotubes.
  • Metal nanowires >> -material-
  • At least one metal selected from Group 12, Group 13, and Group 14 is more preferable, and it is particularly preferable that it is included as a main component.
  • metal examples include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, antimony, and lead. Or alloys thereof. Among these, silver and an alloy with silver are preferable in terms of excellent conductivity. Examples of the metal used in the alloy with silver include platinum, osmium, palladium, and iridium. These may be used alone or in combination of two or more.
  • a shape of the said metal nanowire there is no restriction
  • the cross-sectional shape of the metal nanowire can be examined by applying a metal nanowire aqueous dispersion on a substrate and observing the cross-section with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the average minor axis length of the metal nanowire (sometimes referred to as “average minor axis diameter” or “average diameter”) is preferably 50 nm or less, more preferably 1 nm to 50 nm, still more preferably 10 nm to 40 nm, 15 nm to 35 nm is particularly preferable.
  • the average minor axis length is less than 1 nm, the oxidation resistance may be deteriorated and the durability may be deteriorated.
  • the average minor axis length is more than 50 nm, scattering due to metal nanowires occurs and sufficient transparency is obtained. There are times when you can't.
  • the average minor axis length of the metal nanowires was determined by observing 300 metal nanowires using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). The average minor axis length was determined. In addition, the shortest axis length when the short axis of the metal nanowire is not circular is the shortest axis.
  • the average major axis length (sometimes referred to as “average length”) of the metal nanowire is preferably 2 ⁇ m or more, more preferably 2 ⁇ m to 40 ⁇ m, still more preferably 3 ⁇ m to 35 ⁇ m, and particularly preferably 5 ⁇ m to 30 ⁇ m. . If the average major axis length is less than 2 ⁇ m, it may be difficult to form a dense network, and sufficient conductivity may not be obtained. If the average major axis length exceeds 40 ⁇ m, the metal nanowire is too long and manufactured. Sometimes entangled and agglomerates may occur during the manufacturing process.
  • the average major axis length of the metal nanowire is, for example, observed with 300 metal nanowires using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). The average major axis length of the wire was determined. In addition, when the said metal nanowire was bent, the circle
  • TEM transmission electron microscope
  • the solvent is preferably a hydrophilic solvent, and examples thereof include water, alcohols, ethers, and ketones. These may be used alone or in combination of two or more.
  • the alcohols include methanol, ethanol, propanol, isopropanol, butanol, and ethylene glycol.
  • the ethers include dioxane and tetrahydrofuran.
  • the ketones include acetone.
  • the heating temperature during the heating is preferably 250 ° C. or less, more preferably 20 ° C. to 200 ° C., further preferably 30 ° C. to 180 ° C., and particularly preferably 40 ° C. to 170 ° C. If the heating temperature is less than 20 ° C., the lower the heating temperature, the lower the nucleation probability, and the metal nanowires become too long, so the metal nanowires are likely to be entangled, and the dispersion stability may deteriorate. When it exceeds 250 ° C., the corner of the cross section of the metal nanowire becomes steep, and the transmittance in the evaluation of the coating film may be lowered.
  • the temperature may be changed during the formation process of the metal nanowires, and by changing the temperature during the process, the nucleation of the metal nanowires can be controlled, the renucleation can be suppressed, and the monodispersity by promoting selective growth The improvement effect can be improved.
  • the heating is preferably performed by adding a reducing agent.
  • the reducing agent is not particularly limited and can be appropriately selected from those usually used.
  • borohydride metal salt, aluminum hydride salt, alkanolamine, aliphatic amine, heterocyclic amine, Aromatic amines, aralkylamines, alcohols, organic acids, reducing sugars, sugar alcohols, sodium sulfite, hydrazine compounds, dextrin, hydroquinone, hydroxylamine, ethylene glycol, glutathione and the like can be mentioned.
  • reducing sugars, sugar alcohols as derivatives thereof, and ethylene glycol are particularly preferable.
  • the borohydride metal salt include sodium borohydride and potassium borohydride.
  • Examples of the aluminum hydride salt include lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, aluminum beryllium hydride, magnesium aluminum hydride, and calcium aluminum hydride.
  • Examples of the alkanolamine include diethylaminoethanol, ethanolamine, propanolamine, triethanolamine, dimethylaminopropanol, and the like.
  • Examples of the aliphatic amine include propylamine, butylamine, dipropyleneamine, ethylenediamine, and triethylenepentamine.
  • Examples of the heterocyclic amine include piperidine, pyrrolidine, N-methylpyrrolidine, morpholine and the like.
  • Examples of the aromatic amine include aniline, N-methylaniline, toluidine, anisidine, phenetidine and the like.
  • Examples of the aralkylamine include benzylamine, xylenediamine, N-methylbenzylamine and the like.
  • Examples of the alcohol include methanol, ethanol, 2-propanol and the like.
  • Examples of the organic acids include citric acid, malic acid, tartaric acid, succinic acid, ascorbic acid, and salts thereof.
  • Examples of the reducing saccharide include glucose, galactose, mannose, fructose, sucrose, maltose, raffinose, stachyose and the like.
  • Examples of the sugar alcohols include sorbitol.
  • the reducing agent may function as a dispersion additive or solvent as a function, and can be preferably used in the same manner.
  • a dispersion additive and a halogen compound or metal halide fine particles In the production of the metal nanowire, it is preferable to add a dispersion additive and a halogen compound or metal halide fine particles.
  • the timing of the addition of the dispersion additive and the halogen compound may be before or after the addition of the reducing agent, and may be before or after the addition of metal ions or metal halide fine particles, but is better in monodispersity.
  • the dispersion additive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an amino group-containing compound, a thiol group-containing compound, a sulfide group-containing compound, an amino acid or a derivative thereof, a peptide compound, and a polysaccharide. Synthetic polymers, gels derived from these, and the like. Among these, gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, polyalkyleneamine, partial alkyl ester of polyacrylic acid, polyvinyl pyrrolidone, and polyvinyl pyrrolidone copolymer are particularly preferable.
  • the description of “Encyclopedia of Pigments” (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd., 2000) can be referred to.
  • the shape of the metal nanowire obtained can also be changed with the kind of dispersion additive to be used.
  • the halogen compound is not particularly limited as long as it is a compound containing bromine, chlorine, or iodine, and can be appropriately selected according to the purpose.
  • sodium bromide, sodium chloride, sodium iodide, potassium iodide Further, preferred are alkali halides such as potassium bromide and potassium chloride, and compounds that can be used in combination with the following dispersion additives.
  • Some halogen compounds may function as a dispersion additive, but can be preferably used in the same manner.
  • silver halide fine particles may be used, or both a halogen compound and silver halide fine particles may be used.
  • the dispersant and the halogen compound may be used in the same substance.
  • the compound in which the dispersant and the halogen compound are used in combination include HTAB (hexadecyl-trimethylammonium bromide) containing an amino group and a bromide ion, HTAC (hexadecyl-trimethylammonium chloride) containing an amino group and a chloride ion, and an amino group.
  • the desalting treatment can be performed by a method such as ultrafiltration, dialysis, gel filtration, decantation, and centrifugation after forming metal nanowires.
  • Metal Nanotubes >> -material-
  • What kind of metal may be sufficient,
  • the material of the above-mentioned metal nanowire etc. can be used.
  • the shape of the metal nanotube may be a single layer or a multilayer, but a single layer is preferable in terms of excellent conductivity and thermal conductivity.
  • the thickness of the metal nanotube (difference between the outer diameter and the inner diameter) is preferably 3 nm to 80 nm, and more preferably 3 nm to 30 nm. When the thickness is less than 3 nm, the oxidation resistance is deteriorated and the durability may be deteriorated. When the thickness is more than 80 nm, scattering due to the metal nanotube may occur.
  • the average major axis length of the metal nanotube is preferably 1 ⁇ m to 40 ⁇ m, more preferably 3 ⁇ m to 35 ⁇ m, and even more preferably 5 ⁇ m to 30 ⁇ m.
  • the carbon nanotube is a substance in which a graphite-like carbon atomic surface (graphene sheet) is a single-layer or multilayer coaxial tube.
  • the single-walled carbon nanotubes are called single-walled nanotubes (SWNT)
  • the multi-walled carbon nanotubes are called multi-walled nanotubes (MWNT)
  • the double-walled carbon nanotubes are also called double-walled nanotubes (DWNT).
  • the carbon nanotube may be a single wall or a multilayer, but a single wall is preferable from the viewpoint of excellent conductivity and thermal conductivity.
  • the carbon nanotube production method is not particularly limited and can be appropriately selected depending on the purpose.
  • catalytic hydrogen reduction of carbon dioxide arc discharge method, laser evaporation method, thermal CVD method, plasma CVD method
  • Known means such as a vapor phase growth method and a HiPco method in which carbon monoxide is reacted with an iron catalyst at a high temperature and high pressure to grow in a vapor phase can be used.
  • the carbon nanotubes obtained by these methods have been highly purified to remove residues such as by-products and catalytic metals by methods such as washing, centrifugation, filtration, oxidation, and chromatography. It is preferable at the point which can obtain a carbon nanotube.
  • the aspect ratio of the conductive fiber is preferably 10 or more.
  • the aspect ratio generally means the ratio between the long side and the short side of a fibrous material (ratio of average major axis length / average minor axis length).
  • ratio of average major axis length / average minor axis length There is no restriction
  • the aspect ratio of the conductive fiber with an electron microscope, it is only necessary to confirm whether the aspect ratio of the conductive fiber is 10 or more with one field of view of the electron microscope.
  • the aspect ratio of the entire conductive fiber can be estimated by measuring the major axis length and the minor axis length of the conductive fiber separately.
  • the said conductive fiber is a tube shape, the outer diameter of this tube is used as a diameter for calculating the said aspect ratio.
  • the aspect ratio of the conductive fiber is not particularly limited as long as it is 10 or more, and can be appropriately selected according to the purpose, but is preferably 50 to 1,000,000, preferably 100 to 1,000,000. More preferred. When the aspect ratio is less than 10, network formation by the conductive fibers may not be performed and sufficient conductivity may not be obtained. When the aspect ratio exceeds 1,000,000, the subsequent handling is performed when the conductive fibers are formed. In this case, since the conductive fibers are entangled and aggregate before film formation, a stable liquid may not be obtained.
  • the ratio of the conductive fibers having an aspect ratio of 10 or more is preferably 50% or more, more preferably 60% or more, and particularly preferably 75% or more in volume ratio in the total conductive composition.
  • the ratio of these conductive fibers may be referred to as “the ratio of conductive fibers”. If the ratio of the conductive fibers is less than 50%, the conductive material contributing to the conductivity may decrease and the conductivity may decrease. At the same time, a voltage concentration may occur because a dense network cannot be formed. , Durability may be reduced.
  • particles having a shape other than the conductive fiber are not preferable because they do not greatly contribute to conductivity and have absorption. In particular, in the case of metal, transparency may be deteriorated when plasmon absorption such as a spherical shape is strong.
  • the ratio of the conductive fibers is, for example, when the conductive fibers are silver nanowires, the silver nanowire aqueous dispersion is filtered to separate the silver nanowires from the other particles.
  • the ratio of the conductive fibers can be determined by measuring the amount of silver remaining on the filter paper and the amount of silver that has passed through the filter paper using an ICP emission analyzer. By observing the conductive fibers remaining on the filter paper with a TEM, observing the short axis lengths of 300 conductive fibers and examining their distribution, the short axis length is 200 nm or less and the long axis length is It confirms that it is an electroconductive fiber whose length is 1 micrometer or more.
  • the filter paper is a TEM image obtained by a transmission electron microscope (TEM), and the longest axis of particles other than conductive fibers having a short axis length of 200 nm or less and a long axis length of 1 ⁇ m or more is measured. It is preferable to use one having a length that is twice or more of the longest axis and not longer than the shortest length of the long axis of the conductive fiber.
  • TEM transmission electron microscope
  • the average minor axis length and the average major axis length of the conductive fiber can be determined by observing a TEM image and an optical microscope image using, for example, a transmission electron microscope (TEM) and an optical microscope.
  • TEM transmission electron microscope
  • the average minor axis length and the average major axis length of the conductive fibers are obtained by observing 300 conductive fibers with a transmission electron microscope (TEM) and obtaining the average value. is there.
  • both a water-soluble polymer and a water-insoluble polymer can be suitably used.
  • a water-insoluble polymer is particularly preferable from the viewpoint of humidity durability.
  • the water-soluble polymer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include gelatin, gelatin derivatives, casein, agar, starch, polyvinyl alcohol, polyacrylic acid copolymer, carboxymethyl cellulose, hydroxy Examples include ethyl cellulose, polyvinyl pyrrolidone, and dextran. These may be used individually by 1 type and may use 2 or more types together.
  • the mass ratio (A / B) between the conductive fiber content (A) and the water-soluble polymer content (B) is preferably 0.2 to 3, more preferably 0.5 to 2.5. .
  • the mass ratio (A / B) is less than 0.2, the amount of the polymer is excessive with respect to the conductive fiber, and there is a concern that the resistance may increase due to slight fluctuations in the coating amount. In some cases, the film strength may not be practically sufficient due to a small amount of polymer.
  • the water-insoluble polymer has a function as a binder, and is a polymer that does not substantially dissolve in water near neutrality.
  • the “water-insoluble” means that the binder is “water-insoluble” when the binder is dissolved in 1,000 g of pure water at 25 ° C. and the amount dissolved is 3 g or less.
  • the SP value of the water-insoluble polymer (calculated by the Okitsu method) is preferably 18 MPa 1/2 ⁇ 30 MPa 1/2, more preferably 19MPa 1/2 ⁇ 28MPa 1/2, 19.5MPa 1/2 ⁇ 27MPa 1 / 2 is more preferable.
  • the SP value is less than 18 MPa 1/2, there are cases where to wash the adhered organic stains difficult, exceeds 30 MPa 1/2, the higher the affinity for water, the coating film
  • the conversion efficiency may decrease when a solar cell is manufactured, for example, because the absorption in the infrared region is increased due to the increase in water content.
  • the SP value is calculated by the Okitsu method (Toshinao Okitsu, “Journal of the Adhesion Society of Japan” 29 (3) (1993)). Specifically, the SP value is calculated by the following formula.
  • ⁇ F is a value described in the literature.
  • SP value ( ⁇ ) ⁇ F (Molar Attraction Constants) / V (molar volume)
  • the SP value ( ⁇ ) and the hydrogen bond term ( ⁇ h) of the SP value are calculated by the following equations.
  • ⁇ n is the hydrogen bond term of the SP value or SP value of the water-insoluble polymer and water
  • Mn is the molar fraction of the water-insoluble polymer and water in the mixed solution
  • Vn is the molar volume of the solvent.
  • N each represents an integer of 2 or more representing the type of solvent.
  • the water-insoluble polymer has at least one ethylenically unsaturated group selected from an acryloyl group and a methacryloyl group (hereinafter, these groups are collectively referred to as “(meth) acryloyl group”).
  • a solution of an organic solvent containing these hereinafter referred to as a solution
  • coating liquid which is also referred to as “coating liquid”.
  • the water-insoluble polymer preferably contains at least one ethylenically unsaturated bond in a side chain linked to the main chain.
  • a plurality of the ethylenically unsaturated bonds may be contained in the side chain.
  • the ethylenically unsaturated bond may be included in the side chain of the water-insoluble polymer together with the branched and / or alicyclic structure and / or the acidic group.
  • the ethylenically unsaturated bond is preferably bonded to the main chain of the water-insoluble polymer through a linking group containing at least one ester group (—COO—).
  • a linking group containing an ester group formed together with a carbonyl group contained in the acryloyl group or methacryloyl group is included between the linking group and the ethylenically unsaturated bond (that is, acryloyl group or methacryloyl group). It may be.
  • Examples of the water-insoluble polymer include those represented by the following general formula (I).
  • the general formula (I) X 1, Y 1 and Z 1 represents a hydrogen atom or a methyl group each independently, X 2 represents an organic group having a branched structure or alicyclic structure, Z 2 represents a single bond or a divalent organic group, Z 3 represents an acryloyl group or a methacryloyl group, and x, y, and z are molar ratios of each repeating unit when the sum thereof is 100 mol. Each representing a numerical value greater than 0 and less than 100.
  • Examples of the organic group having a branched structure according to X 2 include carbon numbers such as i-propyl group, s-butyl group, t-butyl group, i-amyl group, t-amyl group, and 2-octyl group. Examples include 3 to 8 branched alkyl groups. Among these, i-propyl group, s-butyl group, and t-butyl group are preferable.
  • Examples of the organic group having an alicyclic structure according to X 2 include alicyclic hydrocarbon groups having 5 to 20 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a norbornyl group. , Isobornyl group, adamantyl group, tricyclodecyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclopentenyl group, tricyclopentanyl group, etc., and these groups are represented by —CH 2 CH 2 O— It may be bonded to COO— in the general formula (I) via a group.
  • a cyclohexyl group, norbornyl group, isobornyl group, adamantyl group, tricyclodecyl group, tricyclopentenyl group, and tricyclopentanyl group are preferable, and a cyclohexyl group, norbornyl group, isobornyl group, and tricyclopentenyl group are particularly preferable.
  • the divalent organic group related to Z 2 include a C 3-7 alkylene group having a hydroxy group such as a 2-hydroxy-1,3-propylene group, such as 2-hydroxy-1, Examples thereof include C6-C9 divalent alicyclic hydrocarbon groups having a hydroxy group such as 4-cyclohexylene group.
  • X is preferably 10 to 75, more preferably 20 to 60, and particularly preferably 25 to 55.
  • Y is preferably 7 to 50, and more preferably 10 to 40.
  • Z is preferably 10 to 70, more preferably 10 to 50, and particularly preferably 20 to 45.
  • the method for introducing a (meth) acryloyl group into the side chain of the water-insoluble polymer is not particularly limited and may be appropriately selected from known methods.
  • a repeating unit having an acidic group A method of adding a compound having an epoxy group and a (meth) acryloyl group to the acidic group of the polymer containing, (2) an isocyanate group and (meth) on the hydroxyl group of the polymer containing a repeating unit having a hydroxyl group
  • Examples include a method of adding a compound having an acryloyl group, and (3) a method of adding a compound having a hydroxy group and a (meth) acryloyl group to the isocyanate group of a polymer containing a repeating unit having an isocyanate group.
  • the method of adding a compound having an epoxy group and a (meth) acryloyl group to the acidic group of the polymer containing a repeating unit having an acidic group is the easiest to manufacture and low cost. Particularly preferred in terms.
  • the compound having an epoxy group and a (meth) acryloyl group is not particularly limited as long as it is a compound having both of these groups, and can be appropriately selected according to the purpose.
  • the following structural formula (1 ) And a compound represented by the following structural formula (2) are preferred.
  • R 1 represents a hydrogen atom or a methyl group.
  • L 1 represents a divalent organic group.
  • the organic group is preferably a hydrocarbon group, and more preferably a hydrocarbon group having 1 to 4 carbon atoms.
  • an alkylene group is preferable, and a methylene group is more preferable.
  • R 2 represents a hydrogen atom or a methyl group.
  • L 2 represents a divalent organic group.
  • the organic group is preferably a hydrocarbon group, and more preferably a hydrocarbon group having 1 to 4 carbon atoms.
  • the hydrocarbon group an alkylene group is preferable, and a methylene group is more preferable.
  • W represents a 4- to 7-membered aliphatic hydrocarbon group.
  • the 4- to 7-membered aliphatic hydrocarbon group is preferably a 4- to 6-membered ring, more preferably a 5- to 6-membered ring, and particularly preferably a cyclohexane ring.
  • the compounds represented by the structural formulas (1) and (2) when used as a negative photosensitive resin composition in combination with a photocurable composition, the developability is good and the film strength is excellent. Therefore, the compound represented by the structural formula (1) is preferable.
  • the compounds represented by the structural formulas (1) and (2) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the following compounds (1) to (10). It is done.
  • water-insoluble polymer examples include compounds represented by the following structures (Exemplary Compounds P-1 to P-35). These exemplary compounds P-1 to P-35 all have a weight average molecular weight in the range of 5,000 to 300,000. Moreover, x, y, and z in exemplary compounds represent the composition ratio (molar ratio) of each repeating unit.
  • the water-insoluble polymer can be synthesized from a two-stage process including a (co) polymerization reaction process of a monomer and a process of introducing an ethylenically unsaturated group.
  • the (co) polymerization reaction is made by a (co) polymerization reaction of various monomers, and is not particularly limited and can be appropriately selected from known ones.
  • radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like can be appropriately selected for the active species of polymerization.
  • radical polymerization is preferable from the viewpoint of easy synthesis and low cost.
  • the polymerization method there is no restriction
  • the water-insoluble polymer having a weight average molecular weight of 10,000 to 100,000 is easy to manufacture and provides a conductive layer excellent in conductivity, durability, and long wavelength transmittance. preferable.
  • the weight average molecular weight is more preferably 12,000 to 60,000, and particularly preferably 15,000 to 45,000.
  • the water-insoluble polymer preferably has an acid value of 20 mgKOH / g or more.
  • a negative photosensitive resin composition containing the conductive composition used in the present invention is prepared, and this is formed on a substrate, and then a desired pattern is exposed and developed to form a conductive pattern. In this case, good developability is ensured, and the obtained conductive pattern is excellent in conductivity, durability, and long wavelength transmittance.
  • the acid value is more preferably 50 mgKOH / g or more, particularly preferably 70 mgKOH / g to 130 mgKOH / g.
  • the mass ratio (A / C) of the conductive fiber content (A) and the water-insoluble polymer content (C) is preferably 0.2 to 3, more preferably 0.5 to 2.5. preferable.
  • the content of the conductive fibers (coating amount) is preferably 0.005g / m 2 ⁇ 0.5g / m 2, more preferably 0.01g / m 2 ⁇ 0.45g / m 2, 0.015g / m 2 to 0.4 g / m 2 is more preferable.
  • the dispersant is used for preventing and dispersing the conductive fibers.
  • the dispersant is not particularly limited as long as the conductive fibers can be dispersed, and can be appropriately selected according to the purpose.
  • commercially available low molecular pigment dispersants and polymer pigment dispersants can be used.
  • a polymer dispersant having a property of adsorbing to conductive fibers is preferably used.
  • Polyvinyl pyrrolidone, BYK series manufactured by Big Chemie
  • Solsperse series manufactured by Nihon Lubrizol, etc.
  • the content of the dispersant is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight, and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the polymer. Further preferred.
  • the content is less than 0.1 parts by mass, the conductive fibers may aggregate in the dispersion, and when it exceeds 50 parts by mass, a stable coating film cannot be formed in the coating process. Application unevenness may occur.
  • ⁇ Other ingredients examples include various additives such as surfactants, antioxidants, sulfurization inhibitors, metal corrosion inhibitors, viscosity modifiers, preservatives, and the like as necessary.
  • the mass ratio (A / B) between the total content A of components other than the conductive fibers in the conductive layer (a single content in the case of only one type) and the content B of the conductive fibers is 0. 1 to 5 is preferable, and 0.5 to 3 is more preferable.
  • the mass ratio (A / B) is less than 0.1, the conductivity due to the aggregation of conductive fibers, the deterioration of optical properties such as transmittance and haze, the mechanical strength of the conductive layer, and the adhesion to the substrate Deterioration, in particular, the quality of the pattern obtained by patterning using photolithography (faithful reproducibility of the exposure pattern) may occur.
  • the mass ratio (A / B) exceeds 5, there may be a decrease in conductivity due to a decrease in the number of contact points between the conductive fibers, deterioration of optical characteristics such as haze and light transmittance.
  • the coating method is not particularly limited and can be appropriately selected depending on the purpose.
  • the printing method include letterpress (letterpress) printing, stencil (screen) printing, lithographic (offset) printing, and intaglio (gravure) printing.
  • ⁇ Base material> There is no restriction
  • the structure include a single layer structure and a laminated structure. The size can be appropriately selected according to the application.
  • a transparent substrate for example, a transparent substrate, a synthetic resin sheet (film), a metal substrate, a ceramic board, a semiconductor substrate which has a photoelectric conversion element, etc.
  • the substrate can be subjected to pretreatment such as chemical treatment such as a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition and the like.
  • the transparent glass substrate include white plate glass, blue plate glass, and silica-coated blue plate glass.
  • Examples of the synthetic resin sheet include a polyethylene terephthalate (PET) sheet, a polycarbonate sheet, a polyethersulfone sheet, a polyester sheet, an acrylic resin sheet, a vinyl chloride resin sheet, an aromatic polyamide resin sheet, a polyamideimide sheet, and a polyimide sheet.
  • Examples of the metal substrate include an aluminum plate, a copper plate, a nickel plate, and a stainless plate.
  • the total visible light transmittance of the substrate is preferably 70% or more, more preferably 85% or more, and still more preferably 90% or more. If the total visible light transmittance is less than 70%, the transmittance may be low and may cause a problem in practical use.
  • a substrate that is colored to the extent that the object of the present invention is not hindered can also be used.
  • the thickness of the substrate is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 ⁇ m to 500 ⁇ m, more preferably 3 ⁇ m to 400 ⁇ m, and even more preferably 5 ⁇ m to 300 ⁇ m. If the thickness is less than 1 ⁇ m, the yield may decrease due to difficulty in handling in the coating process, and if it exceeds 500 ⁇ m, the thickness and mass may be a problem in portable applications. is there.
  • -Other layers examples include a photosensitive layer, an antifouling layer, a UV cut layer, and an antireflection layer.
  • the surface resistance of the conductive layer in the conductive material of the present invention is preferably from 0.1 ⁇ / ⁇ to 5,000 ⁇ / ⁇ , and more preferably from 0.1 ⁇ / ⁇ to 1,000 ⁇ / ⁇ .
  • the low surface resistance itself is not harmful, but if it is less than 0.1 ⁇ / ⁇ , it may be difficult to obtain a conductor with high light transmittance, and if it exceeds 5,000 ⁇ / ⁇ , There may be a problem that disconnection due to Joule heat generated during energization is likely to occur, a voltage drop occurs upstream and downstream of the wiring, and the area used for the touch panel is limited.
  • the surface resistance can be measured using, for example, a surface resistance meter (Loresta-GP MCP-T600, manufactured by Mitsubishi Chemical Corporation).
  • the total visible light transmittance of the conductive layer in the conductive material of the present invention is preferably 85% or more, and more preferably 90% or more.
  • the total visible light transmittance is less than 85%, the conductive pattern becomes conspicuous when used for an image display medium such as a touch panel, and the image quality is deteriorated or the power consumption is increased to compensate for the decrease in luminance. There may be negative effects such as necessity.
  • the total visible light transmittance can be measured by, for example, a self-recording spectrophotometer (UV2400-PC, manufactured by Shimadzu Corporation).
  • the contact point between the conductive fibers is reinforced and the conductivity, transmittance, haze, flexibility, and durability are improved.
  • the touch panel, the electrode for display, the electromagnetic wave shield, and the organic EL It is widely applied to electrodes for displays, electrodes for inorganic EL displays, electronic paper, electrodes for flexible displays, solar cells, display elements, and other various devices. Among these, a touch panel and a solar cell are particularly preferable.
  • a liquid crystal display element as a display element used in the present invention is obtained by aligning an element substrate provided with the conductor patterned on the substrate as described above and a color filter substrate as a counter substrate. After pressure bonding, it is manufactured by heat treatment and combination, injecting liquid crystal, and sealing the injection port. At this time, the conductor formed on the color filter is also preferably the conductor. Further, after the liquid crystal is spread on the element substrate, the liquid crystal display element may be manufactured by superimposing the substrates and sealing the liquid crystal so as not to leak.
  • the touch panel of this invention has the said electrically-conductive material (electric conductor) of this invention, and also has another member as needed.
  • the touch panel of the present invention is provided with an antireflection layer, a hard coat layer, an antifouling layer, etc. in order to prevent difficulty in panel operation due to reflection of external light, and to prevent scratches and dirt on the panel surface. Can do. These layers can be provided in the order of the hard coat layer, the antireflection layer, and the antifouling layer from the touch panel surface side.
  • the antifouling layer may have the function of the antireflection layer.
  • the hard coat layer may be provided directly on the outermost surface of the touch panel, or a hard coat layer is formed on a transparent film such as polyethylene terephthalate (PET), and the film surface on which the hard coat layer is not formed is formed on the outermost surface of the touch panel. You may affix on the surface.
  • PET polyethylene terephthalate
  • a colorless film such as a polyester film and a cellulose ester film having a high light transmittance and a small haze can be used.
  • the aspect in which the antireflection layer and the hard coat layer are formed on the transparent film can be prepared based on the description in paragraphs [0107] to [0141] of JP-A-2007-140497.
  • the hard coat layer is provided to give strength to the antireflection layer.
  • the touch panel of the present invention does not have a transparent film outside the first electrode on the operator side, in order to give strength to function as a protective film for the first electrode, and to install an antireflection layer In order to provide a smooth flat surface.
  • the hard coat layer preferably has a thickness of 5 ⁇ m to 15 ⁇ m and a pencil hardness of 2H to 6H. In order to impart the pencil hardness, it is preferable to appropriately select a crosslinkable binder and increase the film strength by using fine particles such as silica having a diameter of 10 nm to 200 nm.
  • the binder the compounds described in paragraphs [0120] to [0125] of JP-A-2007-140497 can be used.
  • the fine particles fine particles described in paragraph [0130] of JP-A-2007-140497 can be used.
  • the antireflection layer may be a single layer, but if a lower reflectance is required, a plurality of antireflection layers are laminated.
  • a plurality of antireflection layers are laminated, there are an aspect in which optical interference layers having different refractive indexes are alternately laminated, and an aspect in which two or more optical interference layers having different refractive indexes are laminated.
  • an embodiment in which only a low refractive index layer is provided on the hard coat layer an embodiment in which a high refractive index layer and a low refractive index layer are provided in this order on the hard coat layer, an intermediate refractive index layer, a high refractive index layer on the hard coat layer
  • An aspect such as an aspect in which a refractive index layer and a low refractive index layer are provided in this order is preferably used.
  • the antireflection layer uses optical interference, it is preferable that the antireflection layer has a refractive index and a thickness described in paragraphs [0094], [0106], and [0107] of JP-A-2009-204727.
  • a preferred composition for forming the low refractive index layer is preferably a composition containing at least one of the following.
  • a composition containing a fluorine-containing polymer having a crosslinkable or polymerizable functional group (2) A composition comprising as a main component a hydrolysis-condensation product of a fluorine-containing organosilane material (3) Two or more ethylenes Composition containing monomer having unsaturated unsaturated group and inorganic fine particles having hollow structure
  • the above specific compounds and methods using them are described in paragraphs [0054] to [0064] of JP 2010-54737 A. Can be used.
  • the polysiloxane compound described in paragraph [0063] of JP-A-2010-54737 may be formed by forming an antifouling layer on the low refractive index layer and including the antifouling layer.
  • the high refractive index layer and medium refractive index layer are preferably formed from a curable composition containing high refractive inorganic fine particles and a binder.
  • a curable composition containing high refractive inorganic fine particles and a binder As the high refractive index inorganic fine particles and binder that can be used here, the fine particles and binder described in the hard coat layer can be used in accordance with a desired refractive index.
  • Examples of the touch panel of the present invention include a surface capacitive touch panel, a projected capacitive touch panel, and a resistive touch panel.
  • the touch panel includes a so-called touch sensor and a touch pad.
  • the layer structure of the touch panel sensor electrode part in the touch panel is a bonding method in which two transparent electrodes are bonded, a method in which transparent electrodes are provided on both surfaces of a single substrate, a single-sided jumper, a through-hole method, and a single-area layer Either method is preferred.
  • the touch panel 10 includes a transparent conductor 12 so as to uniformly cover the surface of the transparent substrate 11, and an external detection circuit (not shown) is formed on the transparent conductor 12 at the end of the transparent substrate 11.
  • the electrode terminal 18 for electrical connection is formed.
  • 13 indicates a transparent conductor serving as a shield electrode
  • 14 and 17 indicate protective films
  • 15 indicates an intermediate protective film
  • 16 indicates an antiglare film.
  • the touch panel 20 includes a transparent conductor 22 and a transparent conductor 23 disposed so as to cover the surface of the transparent substrate 21, and an insulating layer 24 that insulates the transparent conductor 22 and the transparent conductor 23.
  • the insulating cover layer 25 that generates capacitance between the contact object such as a finger and the transparent conductor 22 or the transparent conductor 23 detects the position of the contact object such as the finger.
  • the transparent conductors 22 and 23 may be configured integrally, and the insulating layer 24 or the insulating cover layer 25 may be configured as an air layer.
  • the touch panel 20 as a projected capacitive touch panel will be schematically described through an arrangement in which the transparent conductor 22 and the transparent conductor 23 are viewed from the plane.
  • the touch panel 20 is provided with a plurality of transparent conductors 22 capable of detecting positions in the X-axis direction and a plurality of transparent conductors 23 in the Y-axis direction so as to be connectable to external terminals.
  • the transparent conductor 22 and the transparent conductor 23 are in contact with a plurality of contact objects such as fingertips, and contact information can be input at multiple points.
  • contact information can be input at multiple points.
  • the coordinates in the X-axis direction and the Y-axis direction are specified with high positional accuracy.
  • other structures such as a transparent substrate and a protective layer
  • the structure of the said surface type capacitive touch panel can be selected suitably, and can be applied.
  • the example of the pattern of the transparent conductor by the some transparent conductor 22 and the some transparent conductor 23 was shown in the touch panel 20, the shape, arrangement
  • the touch panel 30 can contact the transparent conductor 32 via the substrate 31 on which the transparent conductor 32 is disposed, the spacers 36 disposed on the transparent conductor 32, and the air layer 34.
  • a transparent conductor 33 and a transparent film 35 disposed on the transparent conductor 33 are supported.
  • the touch panel 30 is touched from the transparent film 35 side, the transparent film 35 is pressed, the pressed transparent conductor 32 and the transparent conductor 33 come into contact with each other, and a potential change at this position is not illustrated.
  • the coordinates of the touched point are specified.
  • the solar cell of the present invention uses the conductive material (conductor) of the present invention.
  • conductive material conductor
  • mold solar cell hereinafter a solar cell device
  • What is generally used as a solar cell device can be used.
  • Group III-V compound semiconductor solar cell devices II-VI compound semiconductor solar cell devices such as cadmium telluride (CdTe), copper / indium / selenium system (so-called CIS system), copper / indium / gallium / selenium system ( So-called CIGS-based), copper / indium / gallium / selenium / sulfur-based (so-called CIGS-based) I-III-VI group compound semiconductor solar cell devices, dye-sensitized solar cell devices, organic solar cell devices, etc. Can be mentioned.
  • CdTe cadmium telluride
  • CIS system copper / indium / selenium system
  • So-called CIGS-based copper / indium / gallium / selenium system
  • I-III-VI group compound semiconductor solar cell devices dye-sensitized solar cell devices, organic solar cell devices, etc.
  • the solar cell device is an amorphous silicon solar cell device constituted by a tandem structure type or the like, a copper / indium / selenium system (so-called CIS system), copper / indium / gallium / Selenium-based (so-called CIGS-based), copper / indium / gallium / selenium / sulfur-based (so-called CIGS-based) I-III-VI group compound semiconductor solar cell devices are preferred.
  • CIS system copper / indium / selenium system
  • CIGS-based copper / indium / gallium / Selenium-based
  • I-III-VI group compound semiconductor solar cell devices are preferred.
  • an amorphous silicon solar cell device composed of a tandem structure type, etc.
  • an amorphous silicon, a microcrystalline silicon thin film layer, a thin film containing germanium, and a tandem structure of these two or more layers is a photoelectric conversion layer.
  • plasma CVD or the like is used.
  • (Preparation Example 1) Preparation of silver nanowire aqueous dispersion (1)- A silver nitrate solution in which 0.51 g of silver nitrate powder was dissolved in 50 mL of pure water was prepared. Thereafter, 1N ammonia water was added to the silver nitrate solution until it became transparent, and pure water was added so that the total amount became 100 mL, whereby an additive solution A was prepared. An additive solution G was prepared by dissolving 0.5 g of glucose powder in 140 mL of pure water. An additive solution H was prepared by dissolving 0.5 g of HTAB (hexadecyl-trimethylammonium bromide) powder in 27.5 mL of pure water.
  • HTAB hexadecyl-trimethylammonium bromide
  • additive liquid A 20.6 mL was placed in a three-necked flask and stirred at room temperature. To this solution, 41 mL of pure water, 20.6 mL of additive solution H, and 16.5 mL of solution B were added by a funnel in this order, and heated with stirring at 200 rpm at 90 ° C. for 5 hours to disperse silver nanowires in water. A liquid (1) was obtained.
  • the obtained silver nanowire aqueous dispersion (1) After cooling the obtained silver nanowire aqueous dispersion (1), polyvinyl pyrrolidone (K-30, manufactured by Wako Pure Chemical Industries, Ltd.) was added with stirring so as to be 0.05 with respect to the mass of silver 1 Thereafter, the mixture was centrifuged and purified until the conductivity was 50 ⁇ S / cm or less to prepare an aqueous silver nanowire dispersion (1).
  • the average minor axis length, the average major axis length, the coefficient of variation of the minor axis length, and the conductive fibers having an aspect ratio of 10 or more are as follows. The ratio of silver nanowires was measured. The results are shown in Table 1.
  • TEM transmission electron microscope
  • ⁇ Ratio of conductive fibers having an aspect ratio of 10 or more> Each silver nanowire aqueous dispersion is filtered to separate silver nanowires and other particles, and the amount of silver remaining on the filter paper using an ICP emission spectrometer (ICPS-8000, manufactured by Shimadzu Corporation) The amount of silver that has passed through the filter paper is measured, and the ratio of the conductive fibers having an aspect ratio of 10 or more to metal nanowires having a minor axis length of 50 nm or less and a major axis length of 5 ⁇ m or more (% ). The metal nanowires were separated when determining the ratio of conductive fibers using a membrane filter (Millipore, FALP 02500, pore size: 1.0 ⁇ m).
  • silver nanowire aqueous dispersion (2) Water was added and the mixture was centrifuged and purified until the conductivity was 50 ⁇ S / cm or less to prepare a silver nanowire aqueous dispersion (2).
  • the obtained silver nanowire particles were in the form of a wire having an average minor axis length of 105 nm and an average major axis length of 34 ⁇ m.
  • the ratio of (wire) was measured similarly to the silver nanowire aqueous dispersion (1). The results are shown in Table 1.
  • the “ratio of conductive fibers” represents the ratio of conductive fibers (silver nanowires) having an aspect ratio of 10 or more.
  • Example 1 As shown below, the sample numbers shown in Table 2 below were used. 101-Sample No. 110 conductive materials (1) to (10) were produced.
  • PET polyethylene terephthalate
  • sample No. 101 except that the silver nanowire aqueous dispersion (1) was replaced with the silver nanowire solvent dispersion (1) and hydroxyethyl cellulose was replaced with the water-insoluble polymer (1) of Synthesis Example 1.
  • Sample No. 102 conductive materials (2) were produced. Sample No. It was 0.07 g / m ⁇ 2 > when the silver nanowire content of the electroconductive layer in the electroconductive material (2) of 102 was measured with the fluorescent X ray analyzer (the product made by SII, SEA1100).
  • Sample No. 102 silver nanowire solvent dispersion (1) and the following negative photoresist are mixed so that the mass ratio (solid content of silver nanowire / negative photoresist) is 2/1 (contact strengthening treatment). Thus, a conductive composition (3) was prepared.
  • the molecular weight was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight (Mw) in terms of polystyrene was 30,000, and the molecular weight distribution (Mw / Mn) was 2.21.
  • the conductive composition (3) was applied to the surface of a commercially available biaxially stretched heat-fixed polyethylene terephthalate (PET) support having a thickness of 100 ⁇ m using a doctor coater and dried to obtain a thickness of 0.
  • a conductive layer having a thickness of 09 ⁇ m was formed.
  • the obtained conductive material was exposed to a high pressure mercury lamp i-line (365 nm) at 100 mJ / cm 2 (illuminance 20 mW / cm 2 ).
  • the substrate after the exposure was subjected to shower development for 30 seconds with a developer in which 5 g of sodium bicarbonate and 2.5 g of sodium carbonate were dissolved in 5,000 g of pure water.
  • the shower pressure was 0.04 MPa.
  • Sample No. In 101, the mass ratio of silver nanowire aqueous dispersion (1) and hydroxyethylcellulose (silver nanowire / hydroxyethylcellulose) is mixed to 3.6 / 1 (contact strengthening treatment) to obtain a conductive composition. (4) was prepared. Next, the conductive composition (4) was applied to the surface of a commercially available biaxially stretched heat-fixed polyethylene terephthalate (PET) support having a thickness of 100 ⁇ m by using a doctor coater, and 170 ° C. in an air oven. For 5 minutes (contact strengthening treatment) to form a conductive layer having a thickness of 0.08 ⁇ m. 104 conductive materials (4) were produced. Sample No. It was 0.07 g / m ⁇ 2 > when the silver nanowire content of the conductive layer in 104 conductive material (4) was measured with the fluorescent-X-ray-analysis apparatus (the product made by SII, SEA1100).
  • the fluorescent-X-ray-analysis apparatus the product made by SII,
  • Sample No. 101 except that the silver nanowire aqueous dispersion (1) was replaced with the silver nanowire aqueous dispersion (2).
  • Sample No. 106 conductive materials (6) were produced.
  • Sample No. 103 except that the silver nanowire solvent dispersion (1) was replaced with the silver nanowire solvent dispersion (2). 103, sample No. 108 conductive materials (8) were produced.
  • Sample No. 104 except that the silver nanowire aqueous dispersion (1) was replaced with the silver nanowire aqueous dispersion (2).
  • sample no. 109 conductive materials (9) were produced.
  • Sample No. 105 except that the silver nanowire aqueous dispersion (1) was replaced with the silver nanowire aqueous dispersion (2). Similar to sample No. 105, sample no. 110 conductive materials (10) were produced.
  • ratio (A / B) and ratio (X / A)> From the spectral absorption spectrum of the conductive layer of each conductive material, the ratio (A / B) between the peak top absorbance A at a wavelength of 325 nm to 390 nm and the absorbance B at 800 nm was determined. Here, this calculation was not performed when there was no absorption peak in the wavelength range of 325 nm to 390 nm.
  • the ratio (X / A) is obtained from the silver content Xg / m 2 in the conductive layer of each conductive material and the peak top absorbance A at a wavelength of 325 nm to 390 nm in the spectral absorption spectrum of the conductive layer of each conductive material. It was. Here, this calculation was not performed when there was no absorption peak in the wavelength range of 325 nm to 390 nm.
  • the peak top absorbance A and the absorbance B at 800 nm are measured values.
  • an absorption spectrum in the wavelength range of 600 nm to 800 nm was linearly approximated and used as a baseline. The base line was extended, and the intersection with the perpendicular drawn from the top of the absorption peak was taken as the reference position. Then, the value indicated by the lateral width (nm) when the absorption peak was cut horizontally at a position having a half value between the height of the absorption peak and the reference position was defined as the half width.
  • the resistance change rate is less than 300%, 200% or more, which is a practically problematic level.
  • “3” The resistance change rate is less than 200% and 150% or more, which is a practically problematic level.
  • 4 The resistance change rate is less than 150% and 110% or more, and is a practically problematic level.
  • “5” Resistance The rate of change is less than 110%, which is a level that is practically acceptable.
  • “2” The rate of change in resistance is less than 300%, 150% or more, which is a practically problematic level.
  • “3” Resistance The rate of change is less than 150% and 130% or more, which is a level that is not a problem in practice.
  • “4” The rate of change in resistance is less than 130% and is a level that is not a problem in practice. %, A level that is practically acceptable
  • the water-insoluble polymer (1) (the water-insoluble polymer P-26) was converted into the water-insoluble polymer P-1, P-29, P-5, P-10, P-12 of Synthesis Examples 2-8. , P-18, and P-20, except that sample No.
  • a conductive material was manufactured.
  • Each of the obtained conductive materials was evaluated in the same manner as in Example 1. As a result, there was one absorption peak at 325 nm to 390 nm in the spectral absorption spectrum of the conductive layer. It was found that the film had good surface resistance, transmittance, haze value, durability, and flexibility equivalent to 102.
  • Example 2 Fabrication of touch panel- Sample No.
  • the touch panel includes a so-called touch sensor and a touch pad.
  • Example 3 ⁇ Production of integrated solar cell> -Fabrication of amorphous solar cells (super straight type)- On the glass substrate, the sample No. 101 conductive material was formed. A p-type film having a thickness of about 15 nm is formed thereon by plasma CVD, an i-type film having a thickness of about 350 nm is formed on the p-type, and an n-type amorphous silicon film having a thickness of about 30 nm is formed on the i-type.
  • a gallium-doped zinc oxide layer having a thickness of 20 nm was formed on the upper surface of the gallium-doped silicon oxide layer, and a silver layer having a thickness of 200 nm was formed on the gallium-doped zinc oxide layer, thereby producing an integrated solar cell.
  • Example 4 ⁇ Production of integrated solar cell> -Fabrication of CIGS solar cells (substrate type)-
  • a molybdenum electrode having a thickness of about 500 nm is formed on a glass substrate by a direct current magnetron sputtering method, and Cu (In 0.6 Ga 0.4 ) which is a chalcopyrite semiconductor material having a thickness of about 2.5 ⁇ m is formed on the electrode by a vacuum deposition method.
  • a conductive material 101 was formed to produce an integrated solar cell.
  • the conductive material of the present invention is, for example, a touch panel, antistatic for display, electromagnetic wave shield, electrode for organic EL display, electrode for inorganic EL display, electronic paper, electrode for flexible display, antistatic film for flexible display, solar cell, etc. It can be widely used for various devices.

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  • Engineering & Computer Science (AREA)
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  • Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Human Computer Interaction (AREA)
  • Electromagnetism (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Computer Hardware Design (AREA)
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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Non-Insulated Conductors (AREA)
  • Photovoltaic Devices (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Position Input By Displaying (AREA)

Abstract

L'invention vise à fournir un matériau conducteur d'électricité qui a une perméabilité élevée et une faible résistance, améliore une durabilité et une flexibilité, et sur lequel des motifs peuvent être formés facilement, et un panneau tactile ayant une lisibilité élevée et une cellule solaire ayant un rendement de conversion élevé qui utilisent ce matériau conducteur d'électricité. A cet effet, l'invention porte sur un matériau conducteur d'électricité ayant une couche conductrice d'électricité contenant une fibre conductrice d'électricité, de sorte que le spectre d'absorption de lumière de la couche conductrice d'électricité ait un pic d'absorption à 325 nm - 390 nm. Une demi-largeur dans le pic d'absorption à 325 nm - 390 nm de 100 nm ou moins et 1,5 fois supérieure pour le rapport (A/B) de l'absorbance la plus haute (A) au niveau du pic 325 nm - 390 nm et une absorbance (B) à 800 nm et similaires sont préférables.
PCT/JP2011/068549 2010-08-16 2011-08-16 Matériau conducteur d'électricité, panneau tactile et cellule solaire WO2012023553A1 (fr)

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CN110431520A (zh) * 2017-03-24 2019-11-08 大日本印刷株式会社 导电性膜、触控面板和图像显示装置

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SG11201605513TA (en) * 2014-01-31 2016-08-30 Champ Great Int L Corp Tandem organic photovoltaic devices that include a metallic nanostructure recombination layer
JP2016095562A (ja) * 2014-11-12 2016-05-26 凸版印刷株式会社 タッチパネル、リアプロジェクションスクリーン、リアプロジェクションボードおよび電子黒板

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JP2010507199A (ja) * 2006-10-12 2010-03-04 カンブリオス テクノロジーズ コーポレイション ナノワイヤベースの透明導電体およびその適用
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JP2010507199A (ja) * 2006-10-12 2010-03-04 カンブリオス テクノロジーズ コーポレイション ナノワイヤベースの透明導電体およびその適用
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105027046A (zh) * 2013-03-08 2015-11-04 富士胶片株式会社 导电膜
CN105027046B (zh) * 2013-03-08 2017-05-10 富士胶片株式会社 导电膜
CN110431520A (zh) * 2017-03-24 2019-11-08 大日本印刷株式会社 导电性膜、触控面板和图像显示装置
CN110431520B (zh) * 2017-03-24 2023-05-26 大日本印刷株式会社 导电性膜、触控面板和图像显示装置
US11669211B2 (en) 2017-03-24 2023-06-06 Dai Nippon Printing Co., Ltd. Electroconductive film, touch panel, and image display device

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