Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/24—Electrically-conducting paints
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
  • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
• • 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

Definitions

• the present invention relates to a dispersion containing conductive chain particles, and a coating liquid for forming a conductive film and a substrate with a conductive film prepared using this dispersion.
• a conductive film is formed on a substrate using a coating liquid containing conductive particles.
• Transparent conductive films are used in display devices, touch panels, solar cells, and the like.
• a coating liquid containing chain-like conductive particles is used.
• Patent Document 1 discloses a coating liquid containing, as a binder component, an alkoxysilane oligomer that easily bonds with chain-like conductive particles in order to improve the strength of the film.
• Patent Document 2 JP-A-2006-339113 discloses the use of chain-like particles to obtain a film excellent in antistatic and electromagnetic wave shielding properties.
• Patent Document 2 a step of subjecting a dispersion of conductive primary particles to an ion exchange treatment and then adjusting the pH to arrange the primary particles in a chain form, and adding alcohol to hydrolyze an organosilicon compound to form a primary Chain-like particles are produced by a step of linking particles.
• the insulating binder component gradually covers the surfaces of the chain-like conductive particles, and when the film is formed, the insulating component exists between the chain-like conductive particles. It becomes difficult to form a conductive path. That is, there is a problem that the conductivity decreases with the lapse of time, and the same conductivity as the film formed by the initial coating liquid cannot be obtained.
• an object of the present invention is to provide conductive particles that enable a conductive film to have a low resistance.
• the present invention relates to dispersions of conductive particles containing antimony-doped tin oxide (ATO).
• the conductive particles contain clusters of chain particles formed by connecting primary particles.
• the dispersion contains 1 to 20% by weight of the conductive particles, and 0.05% to 0.5% by weight of the cluster forming agent relative to the content of the conductive particles.
• the volume average particle size is 10 to 50 nm, and the volume basis is 16% cumulatively from the small particle size side.
• the difference (D 84 ⁇ D 16 ) between the particle diameter D 16 at the time and the particle diameter D 84 at 84% is 3 to 50 nm.
• a clustering agent is added to cluster the chain-like particles. Acids or polymeric flocculants are used as clustering agents.
• the method for producing a dispersion of conductive particles according to the present invention includes the steps of preparing a dispersion of chain particles in which primary particles containing ATO are linked, and the mass of the primary particles present in the dispersion. and adding 0.05% to 0.5% by mass of a dispersant relative to the sum of the masses present in chain particles.
• the present invention is a dispersion of conductive particles containing ATO, wherein the conductive particles contain clusters of chain particles formed by connecting primary particles.
• This dispersion contains 1 to 20% by mass of the conductive particles, and 0.05 to 0.5% by mass of the cluster forming agent based on the content of the conductive particles.
• the volume average particle size is 10 to 50 nm, and the cumulative volume is 16% from the small particle size side.
• the difference (D 84 -D 16 ) between the particle diameter D 16 at the time of 84% and the particle diameter D 84 at the time of 84% is 3 to 50 nm.
• this particle size difference (D 84 -D 16 ) will be referred to as the width of the particle size distribution.
• the average particle diameter of the primary particles is preferably 3 to 10 nm.
• the mass of the cluster forming agent must be 0.05% or more of the content of the conductive particles, and if it exceeds 0.5%, the conductivity may be significantly reduced. .
• the existence of clusters formed of chain-like particles can be known from the particle size distribution measured by the dynamic light scattering method. That is, when many clusters are present, the volume average particle size is increased and the particle size distribution is broadened. If the volume average particle size and the width of the particle size distribution are within the ranges described above, the effect of the presence of clusters can be obtained. For example, a low resistance can be achieved because the conductive path is well formed. In a coating liquid using such a dispersion liquid, since the area where the conductive particles contact (react with) other components (such as a binder) is small, change over time is suppressed. Since the size of the clusters in the film obtained by this coating liquid is controlled, light scattering (haze) is suppressed and the optical properties are not impaired.
• Alkoxysilanes are generally represented by “R 1 n —Si(OR 2 ) 4-n [Formula 1]”.
• R 1 and R 2 are a hydrogen atom, a halogen atom, or an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different.
• n is an integer of 0-3. Specific examples of alkoxysilanes are shown in Table 1.
• Chain particles are particles in which three or more primary particles containing ATO as a component are linked in a chain. There may be a portion where the particles are branched and connected. That is, it has a structure in which three or more primary particles are linked at the main chain portion, and branched portions may be present.
• Primary particles are inorganic particles in a monodisperse state.
• the average particle size of primary particles is preferably 3 to 10 nm. From an image taken with a transmission electron microscope (TEM), the particle diameter is measured for arbitrary 100 primary particles, and the average value is taken as the average particle diameter of the primary particles. Furthermore, 50 arbitrary particles are selected from this image, and the number of connections of each particle is measured.
• TEM transmission electron microscope
• the average value of the number of linkages of 50 particles was taken as the average number of linkages.
• the average number of connections is preferably 3 or more, particularly preferably 5 or more. If the average number of linkages of the primary particles is small, the effect of improving conductivity may not be sufficiently obtained. If the average particle size is too small, the crystallinity is low, and the primary particles themselves may not have sufficient electrical conductivity. Conversely, if the average particle size is too large, it will be difficult to develop a chain-like structure, and even if a chain-like structure is formed, it will be difficult to effectively form a conductive path, and there is a risk that sufficient conductivity of the film cannot be obtained. be. Elements other than antimony and tin oxide may be contained in the primary particles as long as they do not significantly impair conductivity.
• a method for producing a dispersion of conductive particles will be described.
• a dispersion of chain particles formed by connecting primary particles containing ATO is prepared.
• a dispersion of chain particles can be prepared using a known method such as the method disclosed in JP-A-2006-339113.
• a cluster forming agent is added in an amount of 0.05% to 0.5% by mass of the conductive particle component (the total amount of the conductive particles present as primary particles and the conductive particles present as chain particles in the dispersion). Added.
• clusters of chain-like particles are formed.
• the structure of clusters can be controlled by the concentration, pH, temperature, and stirring time of the chain-like particles in the dispersion.
• the chain-like particles are two-dimensionally and three-dimensionally connected by the cluster-forming agent to form a three-dimensional cluster.
• Acids and polymer flocculants can be used as cluster forming agents.
• polymer flocculants include nonionic, anionic, cationic, amphoteric, polyamine, and dicyandiamide flocculants. Appropriate addition amount varies depending on the type of cluster forming agent.
• acids include organic acids such as formic acid, acetic acid, citric acid and benzoic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydroiodic acid and tetrafluoroboric acid. Hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, which are readily soluble in water and readily available industrially, are preferred.
• a coating liquid is prepared by adding a binder component and a solvent to such a dispersion liquid of conductive particles. That is, the coating liquid of the present invention contains conductive particles containing ATO, an alkoxysilane oligomer (binder component), and a solvent. The conductive particles contain clusters of chain particles formed by connecting primary particles. The coating liquid contains 0.05 to 0.5% by mass of the cluster forming agent based on the content of the conductive particles and 25 to 300% by mass of the alkoxysilane oligomer on the basis of the content of the conductive particles.
• the volume average particle size is 70 to 600 nm, and the cumulative volume from the small particle size side is 16%.
• the difference (D 84 ⁇ D 16 ) between the particle diameter D 16 at the time and the particle diameter D 84 at 84% is 60 to 800 nm.
• Hydrophilic organic solvents such as alcohols, glycols, glycol ethers, ketones, etc., which do not inhibit the structural control of clusters, are suitable. Specific examples include 1-methoxy-2-propanol, diacetone alcohol, ethylene glycol, diethylene glycol, methanol, ethanol, isopropyl alcohol, and acetone.
• the weight average molecular weight of the alkoxysilane oligomer is preferably 1,000 to 20,000.
• the alkoxysilane oligomer is a hydrolyzed polymer of the alkoxysilane represented by Formula 1 above, where n is an integer of 0-2. When n is 3, only two-molecular bonds are possible, so oligomers cannot be formed. A smaller n is more preferable, and an alkoxysilane in which n is 0 is most preferable. By using such an alkoxysilane, the amount of organic components that do not easily conduct electricity between clusters is reduced, and high conductivity is obtained.
• the alkoxysilane oligomer is present in the coating liquid in an amount of 25 to 300% of the content of the conductive particles. That is, the mass ratio of the conductive particles and the alkoxysilane oligomer is in the range of 80:20 to 25:75. If the amount of the alkoxysilane oligomer is too small, the amount of the binder component is too small, and there is a possibility that sufficient film hardness cannot be obtained. On the other hand, if it is too large, the reaction with the surface of the particles forming the clusters in the coating liquid may proceed excessively, resulting in deterioration of the storage stability of the coating liquid.
• an aqueous dispersion containing ATO particles (primary particles) is prepared (average particle size of ATO particles: 5 nm, solid concentration: 20.0% by mass, pH: 6.9).
• An amphoteric ion-exchange resin in a mass corresponding to 40% of the solid content of the ATO particles is added to this dispersion, and the mixture is stirred at 25° C. for 2 hours.
• the amphoteric ion exchange resin is then separated using a wire mesh.
• the ATO particles are linked in a chain form, and an aqueous dispersion of chain particles is obtained.
• the aqueous dispersion of chain particles is diluted with pure water so that the solid content concentration is 5% by mass.
• 0.5 g of hydrochloric acid concentration: 1.0 mass % is added as a cluster forming agent, and the mixture is stirred at 25° C. for 5 minutes.
• the chain-like particles form clusters, and the dispersion liquid of the conductive particles of the present invention is obtained.
• a coating liquid is prepared by adding a binder component and a solvent to the dispersion liquid of the conductive particles.
• a binder component an ethanol dispersion product of an alkoxysilane oligomer having a molecular weight of 4980 (solid concentration: 9.9 mass) obtained by hydrolyzing tetramethoxysilane was used.
• Tables 2 and 3 show the preparation conditions of the conductive particle dispersion liquid and the coating liquid.
• the table also shows the results of measuring the following physical properties. In addition, it carried out similarly about the below-mentioned Example and the comparative example.
• the dispersion is measured using an inductively coupled plasma atomic emission spectrometer to determine the abundance of each element contained in the dispersion. can be used to specify the amount of conductive particles.
• Pencil Hardness The pencil hardness of the film-coated substrate was measured using a pencil specified in JIS S-6006 and a surface property measuring machine (Tribogear manufactured by Shinto Kagaku Co., Ltd.). A pencil of each hardness was swept over the surface with a load of 500 g according to the operating manual of the measuring machine. The sweep traces were checked, and the highest hardness value at which no scratches were observed was taken as the pencil hardness value.
• Example 2 polyaluminum chloride (highly basic aluminum chloride PAC#1000 manufactured by Taki Kagaku Co., Ltd.) was used as the cluster forming agent.
• the solution was diluted with pure water to a concentration of 0.2% by mass, and 5.0 g of this was added.
• Example 3 In this example, polyethyleneimine (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., average molecular weight 600) was used as the cluster forming agent. It was diluted with pure water so that the concentration was 2.0%, and 0.8 g of this was added.
• Example 4 the aqueous dispersion of chain-like particles was diluted with pure water so that the solid content concentration was 10.0% by mass. Further, 1.0 g of hydrochloric acid (concentration: 1.0% by mass) is added, and the mixture is stirred at 25° C. for 5 minutes. Furthermore, tetramethoxysilane was added to fix the cluster structure. Here, 4.9 g of the alkoxysilane oligomer used as the binder component in Example 1 was added and stirred at 25° C. for 1 hour. A dispersion of conductive particles was prepared in the same manner as in Example 1 except for this.
• Example 5 In this example, the amount of alkoxysilane oligomer added to fix the cluster structure was 24.5 g. A dispersion of conductive particles was prepared in the same manner as in Example 4 except for this.
• Example 6 the aqueous dispersion of chain particles was diluted with pure water so that the solid content concentration was 20.0% by mass. To 100.0 g of this dispersion, 1.0 g of hydrochloric acid (concentration: 1.0% by mass) was added as a cluster forming agent.
• Example 7 the aqueous dispersion of chain-like particles was diluted with pure water so that the solid content concentration was 15.0% by mass. To 100.0 g of this dispersion, 1.5 g of hydrochloric acid (concentration: 1.0% by mass) was added as a cluster forming agent.
• Example 8 the aqueous dispersion of chain-like particles was diluted with pure water so that the solid content concentration was 10.0% by mass. To 100.0 g of this dispersion, 1.0 g of hydrochloric acid (concentration: 1.0% by mass) was added as a cluster forming agent.
• Example 9 the aqueous dispersion of chain-like particles was diluted with pure water so that the solid content concentration was 10.0% by mass. To 100.0 g of this dispersion, 1.0 g of phosphoric acid (concentration: 1.0 mass %) was added as a cluster forming agent.
• Example 10 the aqueous dispersion of chain-like particles was diluted with pure water so that the solid content concentration was 10.0% by mass. To 100.0 g of this dispersion, 1.0 g of nitric acid (concentration: 1.0 mass %) was added as a cluster forming agent.
• Example 1 the clustering agent was added directly to the ATO particles (primary particles) without preparing chain particles. That is, 5.0 g of hydrochloric acid (concentration: 1.0% by mass) was added as a cluster forming agent to 100.0 g of the same aqueous dispersion of ATO particles (solid concentration: 20.0% by mass) as in Example 1, and the resulting dispersion thickened and became gel-like. Therefore, it was not possible to obtain a dispersion liquid of conductive particles or a coating liquid.
• hydrochloric acid concentration: 1.0% by mass
• Example 2 In this comparative example, an aqueous dispersion of chain-like particles was prepared in the same manner as in Example 1, but no cluster forming agent was used. A coating liquid was prepared by adding 15.0 g of the aqueous dispersion of the chain-like particles and adding 48.0 g of pure water.
• Example 3 In this comparative example, 3.0 g of hydrochloric acid (concentration: 1.0% by mass) was added as a cluster forming agent. A coating liquid was prepared in the same manner as in Example 1, except that 61.5 g of the conductive particle dispersion liquid and 1.5 g of pure water were added.
• Comparative Example 4 In this comparative example, 1.0 g of the same polyaluminum chloride as in Example 2 diluted with pure water to a concentration of 5.0% was added as a cluster forming agent.
• a coating liquid was prepared in the same manner as in Example 1 except that the conductive particle dispersion liquid was 60.6 g and the amount of pure water added was 2.4 g, but aggregation occurred and it could not be used as a paint.
• Comparative Example 5 In this comparative example, 1.0 g of the same polyethyleneimine as in Example 3 diluted with pure water to a concentration of 5.0% was added as a cluster forming agent.
• a coating liquid was prepared in the same manner as in Example 1 except that the conductive particle dispersion liquid was 60.6 g and the amount of pure water added was 2.4 g, but aggregation occurred and it could not be used as a paint.

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• 2021
  • 2021-03-30 JP JP2021057036A patent/JP7216135B2/ja active Active
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