Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G33/00—Compounds of niobium
• • 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
  • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances

Definitions

• the present invention relates to a niobium compound-based sol, and more specifically, to a niobium compound-based sol, a sol coating film, and a film-supporting substrate that can obtain a film in which the generation of interference fringes is suppressed.
• Niobic acid compounds are attracting attention as functional thin film materials because of their high refractive index and high light transmittance, and their application to optoelectronic materials, surface protective materials, antireflection materials, and refractive index adjusting materials is being studied. There is.
• the method for producing a thin film made of a niobic acid compound can be roughly divided into a dry method and a wet method.
• the dry method include a sputtering method, an ion plating method, an atomic layer deposition (ALD) method, and a chemical vapor deposition (CVD) method.
• examples of the wet method include a sol-gel method and an organometallic coating decomposition (MOD) method.
• the dry method generally requires equipment such as a large vacuum device, whereas the wet method has the advantage that a thin film can be formed at low cost because such equipment is not required. Further, it is generally said that the wet method is superior to the dry method for forming a thin film having a large area.
• niobium alkoxide or niobium sol is generally used, but niobium alkoxide is very easily decomposed and difficult to handle. Therefore, various niobsols have been proposed.
• a peroxyniobate sol using hydrogen peroxide Patent Document 1 etc.
• a niobsol stabilized with oxalic acid or citric acid Patent Document 2 etc.
• a sol prepared by electrolysis of a niobic acid compound Patent Document 1 etc. 3 etc.
• ammonium niobate sol Patent Document 4 etc.
• the thin film from the sol as described above is usually obtained by applying the sol to the surface of a base material such as glass and heating and drying the coating film.
• a base material such as glass
• interference fringes may occur in the obtained thin film, and there is a problem in film quality such as aesthetics.
• an object of the present invention is to provide a niobium compound-based sol that can obtain a film in which the generation of interference fringes is suppressed.
• Another object of the present invention is to provide a coating film of the above niobium compound-based sol and a film-supporting substrate using the same.
• the present inventors have recently obtained the finding that the generation of interference fringes can be suppressed in the obtained film by using a sol in which a specific oxide or fluoride is added to the niobium compound.
• the present invention is based on such findings.
• Niobium compounds and At least one compound selected from the group consisting of metal oxides selected from zirconium, tin, zinc, and cerium, and fluorides of metals selected from magnesium and calcium. Is included.
• a film containing the above sol is also provided.
• a film-supporting substrate having the above-mentioned film on the surface of the substrate is also provided.
• the present invention by using a sol containing a niobium compound and a specific oxide or fluoride, it is possible to suppress the occurrence of interference fringes on the film obtained from the sol.
• the film can be applied to a transparent conductive film, a high dielectric constant film, an insulating film, an antireflection film, a hard coat layer, a photocatalytic member, etc. in a semiconductor device or an optical device.
• the sol of the present invention contains a niobic acid compound and at least one specific oxide or fluoride.
• a known niobate compound sol can be used as the niobate compound sol.
• the term "sol” refers to particles dispersed in a dispersion medium, but when a film is formed using a sol, the film becomes a gel containing a dispersion medium. It is also defined as a concept that includes a xerogel that does not contain a dispersion medium.
• the "niobium compound” includes niobium oxide (Nb 2 O 5 ), niobium hydroxide, and niobium polyacid.
• interference fringes of the film obtained when the film was formed using the sol may occur.
• the interference fringes are considered to be due to the high refractive index of the niobate compound.
• a specific oxide or fluoride to the niobate compound sol while maintaining this high refractive index, the generation of interference fringes on the film obtained from the sol can be suppressed. Is.
• niobium compounds are known to have a negative charge as a surface charge, and the addition of a specific oxide or fluoride changes the potential of the sol, resulting in a film. It is considered that it has some influence on the characteristics.
• the niobic acid compound sol used in the sol of the present invention is obtained by dispersing fine particles containing niobic acid as a main component in a dispersion medium.
• the main component in the niobic acid fine particles is niobium, and preferred examples include amorphous niobium oxide, niobium hydroxide, and niobium polyacid.
• Ammonia is strongly bonded or adsorbed on the surface of niobic acid fine particles.
• Ammonia may be contained as an arbitrary component in the sol of the present invention.
• Ammonia-containing means may be in the form of an ammonium salt containing niobium and an ammonium moiety (NH 4+ ) in addition to the form in which ammonia (NH 3 ) is contained in the sol.
• Preferred examples of the ammonium salt include (NH 4 ) 3 Nb (O 2 ) 4 , (NH 4 ) 3 Nb (O 2 ) 3 F 2, and the like, and one of these compounds alone. It may be a combination of two or more kinds.
• the above-mentioned niobic acid compound sol can be produced by a conventionally known method.
• an aqueous solution prepared by dissolving a niobic compound in hydrofluoric acid or a mixed acid of hydrofluoric acid and sulfuric acid and an aqueous ammonia solution have a pH of 8 or more.
• After mixing and reacting while maintaining to obtain a dispersion containing fine hydrofluoric acid fine particles solid-liquid separation and washing as necessary were performed to isolate a solid precipitate, and the obtained hydrofluoric acid compound was dispersed.
• a hydrofluoric acid compound sol can be obtained by dispersing in a medium.
• the oxide added to the above-mentioned niobium compound sol is an oxide of at least one metal selected from zirconium, tin, zinc, and cerium.
• zirconium oxide, tin oxide, zinc oxide, and cerium oxide By adding at least one of zirconium oxide, tin oxide, zinc oxide, and cerium oxide to the niobium compound sol, interference fringes of the film obtained from the sol can be suppressed.
• the fluoride added to the niobium compound sol include magnesium fluoride and calcium fluoride. These oxides and fluorides may be used in combination of two or more.
• one or more compounds selected from the above-mentioned specific oxides or fluorides and silicon oxide are contained.
• the addition of silicon oxide to the niobic acid compound sol does not improve the interference fringes of the film obtained from the sol, but it is more due to the inclusion of silicon oxide in combination with the specific oxides or fluorides mentioned above. It was unexpected that a film without interference fringes could be obtained.
• the amount of oxide or fluoride added to the niobic acid compound sol is 0.1 part by mass or more, 40 parts by mass with respect to 100 parts by mass of the total amount (solid content equivalent) of the niobic acid compound and oxide or fluoride. It is preferably 1 part by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, and further preferably 3 parts by mass or more and 15 parts by mass or less. If the amount of oxide or fluoride is too small, the suppression of interference fringes of the film obtained from the sol may be insufficient.
• esters examples include formic acid esters such as methyl formate, ethyl formate, propyl formate and isopropyl formate, acetate esters such as methyl acetate, ethyl acetate, propyl acetate and isopropyl acetate, and cyclic esters such as ⁇ -butyrolactone.
• the niobium compound sol of the present invention may contain a known additive used as a film-forming material, and if necessary, a leveling agent, a defoaming agent, a thickener, a rheology adjuster, etc. Can be added.
• the content of the dispersed particles can be within the above range by appropriately adjusting the blending amount of each component including the dispersion medium.
• the concentration of the sol may be adjusted according to the blending amount of the dispersion medium. For example, a sol having a concentration higher than the desired concentration can be prepared, and the concentration can be adjusted to the desired concentration by adding and mixing a dispersion medium to the sol. Further, when the concentration of the sol is adjusted by the dispersion medium, the additional dispersion medium may be the same as or different from the dispersion medium in the sol.
• the above-mentioned sol of the present invention can be formed into a film by applying it to the surface of a base material.
• the obtained membrane may be changed from a sol state to a gel state containing a dispersion medium or a xerogel state not containing a dispersion medium.
• the film forming method include methods known in the film forming process by the wet method. Specific examples include a spin coating method, a dip coating method, a spray coating method, a flow coating method, a roll coating method, a curtain coating method, a bar coating method, a screen printing method, etc., from the viewpoint of forming a high-quality film. , Spin coating method, dip coating method, spray coating method, bar coating method are preferable.
• the base material for providing the film is not particularly limited, and polyimide resin, polyethylene terephthalate resin, polyethylene resin, polypropylene resin, polycarbonate resin, acrylic resin, polyester resin, ABS resin, AAS resin, polyvinyl chloride resin, polyethylene naphthalate, etc.
• Resin substrates and composite resin substrates, ceramics such as glass, quartz, and pottery, silicon, various metals, various metal oxide films, and inorganic substrates such as these composite materials can also be used.
• the sol can be made more stable by applying the above-mentioned sol to the surface of the base material and further heating it.
• the heat treatment method may be heating at 100 ° C. or lower, hydrothermal treatment at 100 ° C. or higher, and the treatment can be performed under arbitrary conditions for about 1 minute to 10 hours. The longer the heat treatment time, the more the crystallization of the niobate compound progresses, so that the refractive index of a generally obtained film is improved.
• the film provided on the surface of the base material can be not only a single-layer film but also a multi-layer film having two or more layers.
• a sequential laminating method in which the method of applying and heat-treating one layer at a time is repeated, or a laminating method in which the coating is repeated to form a multilayer and then heat-treated at once is also possible.
• a film formed on the surface of a substrate can be applied to various uses as a film-supporting substrate. For example, it can be applied to transparent conductive films, high dielectric constant films, insulating films, antireflection films, hard coat layers, photocatalytic members and the like in semiconductor devices and optical devices.
• the following materials were used as raw materials for sol preparation.
• the volume cumulative particle size (D 90 ) of the raw material was measured by measuring the particle size distribution using a particle size distribution measuring device (DelsaNano HC, manufactured by Beckman Coulter Co., Ltd.), but the particle size of the niobic acid compound was measured. Therefore, the particle size distribution was measured using the Microtrack MT3300EXII (manufactured by Microtrack Bell Co., Ltd.), which is a laser diffraction method particle size distribution measuring device.
• a sol was prepared by mixing the above-mentioned raw materials in a predetermined ratio according to the composition shown in Table 1 below. Specifically, a total of 99.9 g of each component excluding silicone oil was charged into a 200 mL polybin having a 100 mL calibration curve, and zirconia beads having a diameter of 0.05 mm were charged up to the 100 mL calibration curve of the polybin. Next, the lid of the polybin was closed, and the mixture was set in a paint shaker (manufactured by Asada Iron Works Co., Ltd.) and crushed for 5 hours.
• the zirconia beads were separated and removed by passing through a test sieve having an opening of 20 ⁇ m, and 0.1 g of silicone oil was added and mixed to prepare a sol.
• the volume cumulative particle diameter (D 90 ) of the dispersed particles in the sol was measured using a particle size distribution measuring device (DelsaNano HC, manufactured by Beckman Coulter, Inc.).
• the device When measuring the volume cumulative particle size using a particle size distribution measuring device, the device first injects the obtained sol as it is into the marked line of the measuring cell, and then the device can measure the sample concentration. After confirming that it was displayed, the particle distribution was measured.
• the measurement results are as shown in Table 1 below.
• a glass substrate (76 x 26 mm) is used as a base material, the surface of the glass substrate is washed with a detergent, and then ultrasonically washed in alcohol for 10 minutes. Then, ultraviolet rays are applied to the surface of the glass substrate immediately before the sol coating. UV cleaning was performed by irradiating (wavelength 325 nm) for 30 seconds. Subsequently, the glass substrate was placed on a spin coater, and each sol obtained as described above was collected with a micropipette and 0.7 mL was dropped onto the glass substrate to form a film (condition: 1000 rpm ⁇ ). 20 seconds). Next, the film-formed glass substrate was dried at 100 ° C. for 10 minutes to prepare a film-supporting substrate.

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• 2020
  • 2020-08-07 WO PCT/JP2020/030329 patent/WO2021025144A1/ja not_active Ceased
  • 2020-08-07 JP JP2021537401A patent/JP7597715B2/ja active Active

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