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WO2015001979A1 - Procédé de production de substrat doté d'un film de revêtement - Google Patents

Procédé de production de substrat doté d'un film de revêtement Download PDF

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Publication number
WO2015001979A1
WO2015001979A1 PCT/JP2014/066329 JP2014066329W WO2015001979A1 WO 2015001979 A1 WO2015001979 A1 WO 2015001979A1 JP 2014066329 W JP2014066329 W JP 2014066329W WO 2015001979 A1 WO2015001979 A1 WO 2015001979A1
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Prior art keywords
substrate
coating film
coating
film
inorganic particles
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Ceased
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PCT/JP2014/066329
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English (en)
Japanese (ja)
Inventor
雄一 ▲桑▼原
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AGC Inc
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Asahi Glass Co Ltd
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Publication date
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Publication of WO2015001979A1 publication Critical patent/WO2015001979A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1291—Process of deposition of the inorganic material by heating of the substrate
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
    • C23C18/127—Preformed particles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C03C2217/45—Inorganic continuous phases
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/465—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific shape
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials
    • C03C2217/478—Silica
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1245—Inorganic substrates other than metallic

Definitions

  • the present invention relates to a method for producing a coated substrate.
  • a coating film (inorganic film) made of an inorganic material has an advantage of higher heat resistance and ultraviolet resistance than a coating film (organic film) made of an organic material. Therefore, if a thick (large) inorganic film can be formed on a substrate, it is useful as a binder for fixing particles that impart various optical characteristics, electrical characteristics, and chemical characteristics to the substrate. It is also possible to give the above properties to the inorganic film itself.
  • a method for forming an inorganic film As a method for forming an inorganic film, a method of forming a coating film containing a film forming precursor on a substrate using a liquid containing a film forming precursor and then baking and solidifying the coating film is known. ing. However, thermal shrinkage of the coating film is likely to occur during baking and solidification, thereby generating shrinkage stress. This shrinkage stress increases as the film thickness increases, causing cracks or film peeling. For this reason, a method that can suppress the occurrence of cracks or film peeling even when the film thickness increases is desired.
  • Patent Document 1 an organic substance that gels by heating or cooling, such as methylcellulose or agar, is contained in a dispersion of silica glass particles, the dispersion is applied onto a substrate, and the coating is gelled and dried. Thereafter, a method of firing at a temperature equal to or higher than the glass transition point of the silica glass particles is described, and in the examples, it is described that a silica film having a film thickness of about 60 to 200 ⁇ m is formed. In the examples, it is described that a series of steps of coating, gelation and drying was repeated three times, followed by firing to form a silica film having a film thickness of about 0.3 to 0.6 mm.
  • Patent Document 2 an organic-inorganic composite coating film is formed using a sol solution containing an organic molecular assembly and an inorganic precursor, and then the coating film is dried to remove moisture, followed by organic irradiation by ultraviolet irradiation. It describes a method of forming an inorganic film having nanopores with a film thickness of 1 ⁇ m or more while removing cracking or peeling by removing components. However, since this method includes many steps for film formation, productivity is low.
  • a method of spraying a liquid containing a film formation precursor onto a substrate heated to a firing temperature or higher is known.
  • This method is different from the conventional method in which a coating film is formed on a substrate with a liquid containing a film-forming precursor and then fired and solidified, and the droplets sprayed on the substrate are immediately fired and solidified.
  • the number is small and the productivity is good.
  • the solvent component and the organic component in the sprayed droplets are easily removed before the droplets reach the substrate. For this reason, the shrinkage stress which arises in a film
  • Patent Document 3 discloses that a film forming solution containing an organometallic compound and an organosilicon compound is sprayed onto a substrate heated to a temperature higher than the firing temperature, and a refractive index-reducing transparent coating comprising a silicon oxide thin film containing a metal oxide. A method of forming is described.
  • Patent Document 4 a coating liquid containing an organopolysiloxane, inorganic particles, and a liquid medium is applied to a glass substrate in a temperature range of 400 to 650 ° C. by a spray method or the like to oxidize containing inorganic particles.
  • Patent Document 5 describes a method for obtaining glass with an infrared shielding film by dispersing ITO fine particles in a hydrolyzate of tetramethoxysilane using ethanol or 2-propanol, and baking after applying by spin coating or the like. Has been. Further, in Patent Document 6, ethanol or 2-propanol is used, and metal oxide fine particles such as tin oxide and titania are dispersed in a hydrolyzate of tetramethoxysilane. A method for obtaining a glass of is described.
  • Patent Document 3 does not contain inorganic particles in the film forming solution, and the film deposition efficiency expressed by the film thickness of the formed film per unit volume of the spray amount of the coating liquid is inferior, It is difficult to efficiently thicken the coating film.
  • the organopolysiloxane since the organopolysiloxane is nonpolar, the liquid medium of the coating liquid is limited to a nonpolar one, and the inorganic particles can be dispersed in the nonpolar liquid medium or previously hydrophobized. Limited to processed.
  • the methods described in Patent Documents 5 and 6 have a problem that cracks are likely to occur when the film thickness increases.
  • the present invention has been made in view of the above circumstances, and is a method of forming a coating film made of an inorganic material on a substrate, which can efficiently increase the thickness of the coating film, and the thickness of the coating film is large. Even if it becomes, it aims at providing the manufacturing method of the board
  • the gist of the present invention is the following [1] to [11].
  • a coating liquid containing inorganic particles, an alkoxysilane hydrolyzate, a liquid medium containing at least one of a polyhydric hydroxyl group-containing compound and water, and having an average aggregate particle diameter of the inorganic particles of less than 100 nm is prepared. Preparing a substrate; holding the substrate at 200 to 650 ° C .; spraying the coating liquid onto the substrate; obtaining a substrate with a coating film;
  • [3] The method for producing a coated substrate according to [1] or [2], wherein the liquid medium is a polyvalent hydroxyl group-containing compound or a mixture of water and a polyvalent hydroxyl group-containing compound.
  • [4] The method for producing a coated substrate according to any one of [1] to [3], wherein the inorganic particles are silica particles.
  • [5] The method for producing a coated substrate according to any one of [1] to [4], wherein the inorganic particles are chain particles.
  • [6] The method for producing a coated substrate according to any one of [1] to [5], wherein the substrate is a glass substrate.
  • the method for manufacturing a substrate with a coating film of the present invention it is possible to efficiently and thickly form a coating film made of an inorganic material while preventing the occurrence of cracks or film peeling.
  • the average aggregate particle diameter of inorganic particles in the present specification is an average particle diameter obtained by measuring inorganic particles in a dispersion medium by a dynamic light scattering method.
  • the value of the average aggregated particle diameter obtained by this method means the value of the average primary particle diameter.
  • the temperature of the substrate in this specification is the surface temperature on the side where the coating liquid is applied.
  • the thickness (film thickness) of the coating film in this specification is defined by an interval in a direction parallel to the substrate surface (in-plane direction) in an image obtained by observing a cross section of the substrate with a coating film with a scanning electron microscope. The film thickness from the surface of the substrate to the surface of the coating film was measured at three points of 1.5 ⁇ m, and the average value (average film thickness) of the film thicknesses at the three points was determined as the film thickness (film thickness). It was.
  • the substrate with a coating film in the present invention is sprayed with a liquid containing inorganic particles, an alkoxysilane hydrolyzate and a liquid medium (hereinafter also referred to as a coating liquid (X)) on a substrate maintained at 200 to 650 ° C.
  • a coating film hereinafter sometimes referred to as a coating film (Y)
  • the substrate is not particularly limited as long as it can be heated to 200 to 650 ° C.
  • a glass substrate is suitable. Examples of the material for the glass substrate include soda lime silica glass, borosilicate glass, and aluminosilicate glass.
  • the substrate may have a layer other than the coating film (Y) on the surface of the substrate body.
  • you may have layers other than a coating film (Y) on a coating film (Y).
  • a functional layer may be provided on the surface of the substrate body, and a coating film (Y) may be formed on the functional layer.
  • the functional layer include an undercoat layer, a stress relaxation layer, an adhesion improving layer, and a protective layer.
  • the undercoat layer functions as an alkali barrier layer or a wide band low refractive index layer.
  • the undercoat layer is preferably a layer formed by applying an undercoat coating liquid containing alkoxysilane or a hydrolyzate thereof (sol-gel silica) to the surface of the substrate body.
  • the stress relaxation layer is a material for suppressing cracks arising from the difference in thermal expansion coefficient between the glass substrate and the coating film (Y), and is a material having a thermal expansion coefficient intermediate between the glass and the coating film (Y). Preferably it is formed.
  • the inorganic particles those having an average aggregate particle diameter of less than 100 nm are used.
  • the coating liquid (X) contains the inorganic particles, so that the film deposition efficiency is improved and the effect of increasing the film thickness of the coating film (Y) is sufficient. Easy to obtain.
  • the lower limit of the average agglomerated particle diameter is preferably 1 nm from the viewpoint of dispersion stability, and more preferably 3 nm.
  • Inorganic particles include metal oxide particles or metal particles. Inorganic particles may be used alone or in combination of two or more. From the viewpoint of availability, silica particles (silicon oxide particles) are preferably used as the inorganic particles. Moreover, when what has various functions as an inorganic particle is used, the coating film (Y) which acts as a functional layer will be obtained. As an example of the material of the inorganic particle which has a function, the following are mentioned according to a function. UV shielding: zinc oxide, cerium oxide, etc. Infrared shielding: Indium tin oxide (ITO), antimony tin oxide (ATO), tungsten oxide, erbium, etc. Antistatic: ITO, ATO, silver, etc.
  • ITO Indium tin oxide
  • ATO antimony tin oxide
  • Antistatic ITO, ATO, silver, etc.
  • Photocatalyst titanium oxide and the like. Wavelength conversion: zinc oxide, europium doped zinc oxide, zinc sulfide, europium doped zinc sulfide, indium phosphide, bismuth doped calcium sulfide, europium doped calcium fluoride, europium doped yttrium vanadate, and the like.
  • the function imparted to the coating film (Y) is a function that provides a higher effect as the film thickness is larger in that the effect of applying the present invention is greater. Examples of the functional layer having a higher effect as the film thickness is larger include a light scattering layer, an alkali barrier layer, an ultraviolet absorption layer, and an infrared absorption layer.
  • the shape of the inorganic particles examples include a spherical shape, an elliptical shape, a needle shape, a rod shape, a plate shape, a rod shape, a conical shape, a columnar shape, a cubic shape, a rectangular shape, a diamond shape, a star shape, and an indefinite shape.
  • the inorganic particles may exist in a state where each particle is independent, each particle may be linked in a chain, or each particle may be aggregated.
  • chain particles in which each inorganic particle is connected in a chain the coating efficiency when forming a coating film by spraying the coating liquid (X) onto a heated substrate is greatly increased. To improve.
  • the alkoxysilane hydrolyzate produced when the coating liquid (X) is supplied onto the heated substrate by forming chain-structured inorganic particles and a network structure with the alkoxysilane hydrolyzate. It is conceivable that the vaporization or scattering of the water is suppressed.
  • the number of linked inorganic particles is preferably 2 to 1000, more preferably 3 to 500.
  • the inorganic particles may be linearly linked or branched.
  • the inorganic particles only have to have an average aggregate particle diameter of less than 100 nm, and may be core-shell type particles in which one component is coated with another component.
  • the aggregate particle diameter of the core-shell type particles means the outer diameter of the shell.
  • the inorganic particles may be surface-treated with a surfactant, a polymer dispersant, a silane coupling agent or the like.
  • the aggregate particle diameter of the inorganic particles after the surface treatment is preferably 1 to 100 nm.
  • Inorganic particles are inert to heat of 400 to 650 ° C., that is, when a dispersion liquid containing only inorganic particles and not containing an alkoxysilane hydrolyzate is supplied on a heated substrate, no film is formed. Or a film having a significantly low film deposition efficiency.
  • the alkoxysilane hydrolyzate is obtained by hydrolyzing alkoxysilane with a catalyst in the presence of one or more hydroxy compounds selected from the group consisting of water and a polyhydric hydroxyl group-containing compound.
  • the polyvalent hydroxyl group-containing compound used here is the same as that described later.
  • water is preferred.
  • the alkoxysilane hydrolyzate may contain unreacted alkoxysilane.
  • the hydrolyzate of alkoxysilane is a precursor of silicon oxide, and silicon oxide is obtained by firing this.
  • alkoxysilane examples include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc.), monoalkyltrialkoxysilane (methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane).
  • tetraalkoxysilane is preferable, and tetraethoxysilane or tetramethoxysilane is more preferable from the viewpoint of high hydrolysis rate and high productivity.
  • Alkoxysilane may be used alone or in combination of two or more.
  • Hydrolysis of the alkoxysilane is performed using a hydroxy compound (preferably water) and a catalyst. It is preferable to use an acid or an alkali as the catalyst.
  • the acid include inorganic acids (such as nitric acid, sulfuric acid, and hydrochloric acid) and organic acids (such as formic acid, oxalic acid, tartaric acid, citric acid, monochloroacetic acid, dichloroacetic acid, and trichloroacetic acid).
  • the alkali include ammonia, sodium hydroxide, potassium hydroxide and the like.
  • the catalyst is preferably an acid from the viewpoint of long-term storage. Moreover, as a catalyst, what does not prevent dispersion
  • a hydroxy medium is used as a liquid medium, and an alkoxysilane and a catalyst are present in the liquid medium, whereby a liquid medium containing an alkoxysilane hydrolyzate is obtained.
  • the liquid medium contains at least one of a polyhydric hydroxyl group-containing compound and water. That is, at least a polyvalent hydroxyl group-containing compound, water, or a mixture thereof is used as the liquid medium.
  • the liquid medium contains neither a polyvalent hydroxyl group-containing compound nor water, even if the coating liquid is sprayed onto the substrate, no coating film is formed on the substrate, or even if a coating film is formed, the film is deposited. Efficiency is significantly reduced.
  • the alkoxysilane is hydrolyzed in a liquid medium, it is preferable to use both a polyhydric hydroxyl group-containing compound and water as the liquid medium.
  • the polyhydric hydroxyl group-containing compound is a compound having two or more hydroxyl groups in one molecule, and for example, one or more selected from the group consisting of polyhydric alcohols, alkanolamines, and phenol derivatives can be used.
  • the polyhydric alcohol is preferably one or more selected from the group consisting of (poly) alkylene glycol, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, sorbitol, dipentaerythritol, and sucrose.
  • the alkanolamine is preferably at least one selected from the group consisting of monoethanolamine, propanolamine, and diethanolamine.
  • the phenol derivative is preferably at least one selected from the group consisting of bisphenol A, catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, and hexahydroxybenzene.
  • the (poly) alkylene glycol in this specification is an alkylene glycol represented by HO—C n H 2n —OH (n is an integer of 1 or more), or HO— (C n H 2n —O—) m H ( n is an integer of 1 or more, and m is an integer of 2 or more).
  • (poly) alkylene glycol is preferable in that good film formation efficiency of the coating film can be easily obtained.
  • the (poly) alkylene glycol a (poly) alkylene glycol having a molecular weight of 300 or less is preferable.
  • trialkylene glycol or tetraalkylene glycol is preferable, and tetraalkylene glycol is preferable from the viewpoint that good film formation efficiency of the coating film can be easily obtained.
  • the carbon number (n) of the alkylene group (—C n H 2n —) in the (poly) alkylene glycol is preferably 2 to 6 in terms of being able to disperse the inorganic fine particles satisfactorily and in terms of viscosity (handleability). 4 is more preferable.
  • (Poly) alkylene glycol is preferably (poly) ethylene glycol, (poly) propylene glycol, or (poly) tetramethylene glycol. Diethylene glycol, triethylene glycol, or tetraethylene glycol is particularly preferred.
  • the liquid medium may contain other components other than water or (poly) alkylene glycol as long as the effects of the present invention are not impaired.
  • examples of other components include monohydric alcohols such as ethanol and 2-propanol, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, and sulfur-containing compounds.
  • the content thereof is preferably more than 0% by mass and 30% by mass or less, and more preferably 10% by mass or less with respect to the total amount of the liquid medium.
  • a coating liquid containing inorganic particles, an alkoxysilane hydrolyzate, and a liquid medium is prepared.
  • the inorganic particles are preferably used in the form of a dispersion previously dispersed in a liquid medium.
  • a commercially available silica sol colloidal silica in which silica particles are dispersed in water can be used for preparing the coating liquid.
  • alkoxysilane is hydrolyzed in a liquid medium containing at least a hydroxy compound in the presence of a catalyst to obtain a liquid medium containing an alkoxysilane hydrolyzate, and a dispersion liquid of inorganic particles is added to this to obtain a uniform medium.
  • a method of obtaining a coating liquid by mixing with the above can be used.
  • the solid content concentration of coating liquid (total concentration of inorganic particles and alkoxysilane hydrolyzate (in terms of SiO 2 ) in the coating liquid) is based on the film deposition efficiency of the coating film and the viscosity (handleability) of the coating liquid. 0.3 to 70% by mass is preferable, and 3 to 25% by mass is more preferable.
  • the proportion of inorganic particles is preferably 1 to 60 mass%, more preferably 3 to 30 mass%.
  • the coating liquid (X) contains the inorganic particles, so that the deposition efficiency is improved and the film thickness of the coating film (Y) is sufficiently increased. Easy to obtain.
  • the proportion of the inorganic particles is 60% by mass or less, the aggregation of the inorganic particles is satisfactorily suppressed and a film in which the inorganic particles are uniformly dispersed is easily obtained.
  • the proportion of the alkoxysilane hydrolyzate is 40 to 99 mass% of 100 mass% of the solid content of the coating liquid (total of inorganic particles and alkoxysilane hydrolyzate in the coating liquid). 70 to 97% by mass is more preferable.
  • the proportion of the alkoxysilane hydrolyzate is 40% by mass or more, the deposition efficiency is likely to be sufficiently high, and a thick coating film is easily obtained.
  • the ratio of the alkoxysilane hydrolyzate is 99% by mass or less, the coating liquid (X) contains inorganic particles, so that the effect of increasing the film thickness of the coating film (Y) is easily obtained.
  • the prepared coating solution is applied to the substrate by spraying.
  • the spraying method of the coating liquid is preferably a spraying method in which the coating liquid is sprayed using a nozzle (such as a spray gun).
  • Specific application methods by the spray method include the following methods (i), (ii), (iii) and the like.
  • the method (ii) is preferable because the number of steps is small and a substrate with a coating film can be produced more efficiently.
  • (I) A method of spraying the coating liquid from the nozzle onto the substrate while moving the nozzle above the fixed substrate.
  • (Ii) A method of spraying a coating liquid from a nozzle onto a belt-like substrate (for example, a glass ribbon) moving in one direction.
  • (Iii) A method in which the coating liquid is sprayed from the nozzle onto the substrate while moving the nozzle over a belt-like substrate (for example, a glass ribbon) moving in one direction.
  • the temperature of the substrate when applying the coating liquid is 200 to 650 ° C., preferably 300 to 600 ° C.
  • the alkoxysilane hydrolyzate is baked to become silicon oxide, and a coating film (Y) is formed on the substrate. Since the alkoxysilane hydrolyzate on a board
  • the temperature of the substrate is preferably 300 ° C. or higher.
  • the upper limit of the temperature of the substrate is not particularly limited, but if it is too high, the equipment for heating becomes large and the material of the substrate is also limited.
  • the temperature of the substrate is maintained at a predetermined temperature within the range of 200 to 650 ° C., and the coating liquid is sprayed thereon.
  • the temperature of the substrate may be controlled to a predetermined temperature within a range of 200 to 650 ° C. at least immediately before the coating liquid is sprayed.
  • the molten glass is formed into a glass ribbon, the glass ribbon is slowly cooled, and then cut to produce a glass substrate.
  • a method of forming a coating film (Y) on the glass ribbon by applying a coating liquid to the glass ribbon can be used.
  • the glass ribbon is then cut.
  • the glass substrate in this case is preferably a green glass substrate that is not strengthened. That is, a method of forming a coating film (Y) on a glass ribbon by applying a coating liquid (X) to a glass ribbon to be a glass substrate and baking a hydrolyzate of alkoxysilane can be used.
  • the glass ribbon obtained by molding the molten glass in a float bath has a glass ribbon of 200 to 650 between the float bath and the slow cooling step or during the slow cooling step. It is preferable to spray the coating liquid at a position in the temperature range of ° C.
  • the temperature of the glass ribbon at the position immediately after the float bath is usually about 650 ° C., although it depends on the glass composition of the glass substrate, and the glass ribbon exiting the float bath is a slow cooling step. And is cooled to 400 ° C. or lower during the slow cooling process.
  • the temperature of the substrate when spraying the coating liquid is 650 ° C. or less. It is preferable that In this method (ii) or (iii), the glass ribbon obtained by forming molten glass by drawing down is coated at a position where the glass ribbon is in the temperature range of 200 to 650 ° C. during the slow cooling process. It is also preferable to spray the liquid.
  • the draw down molding method include a fusion draw method, a tube draw method, and a slot draw method.
  • the coating film (Y) thus formed on the substrate comprises a silicon oxide phase obtained by baking the alkoxysilane hydrolyzate at a predetermined temperature of 200 to 650 ° C. and inorganic particles.
  • the phase of silicon oxide plays a role of a binder for fixing inorganic particles to the substrate. Therefore, superior heat resistance and weather resistance can be obtained as compared with the case where the binder is an organic material.
  • the coating film (Y) may be a film composed of silicon oxide and inorganic particles, and may be a film formed by continuously spraying one type of coating liquid on the substrate.
  • the thickness (film thickness) of the coating film (Y) is preferably 100 nm or more, and more preferably 1000 nm or more (1 ⁇ m or more). When the thickness of the coating film (Y) is 100 nm or more, the function of the coating film (Y) is sufficiently exhibited. In addition, when a coating film (Y) is a multilayer film, let the thickness of a coating film (Y) be the film thickness of the layer formed by one spraying. However, one spray means a continuous series of sprays.
  • the upper limit of the integrated thickness when the coating film (Y) is a multilayer film is not particularly limited, but is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and particularly preferably 10 ⁇ m or less from the viewpoint of productivity.
  • Hardness of the coating film (Y) is preferably from 200 ⁇ 3000N / mm 2 in Martens hardness, and more preferably 400 ⁇ 1200N / mm 2. By increasing the temperature at the time of spraying, the hardness of the film can be increased.
  • FIG. 7 is a schematic view showing an example of a glass production apparatus suitable for producing a glass substrate with a coating film in which a coating film is formed on the glass substrate using the method of the present invention.
  • the glass manufacturing apparatus 20 melts the glass raw material to form the molten glass 30 and floats the molten glass 30 supplied from the melting furnace 22 on the surface of the molten tin 24, thereby causing the molten glass 30 to become the glass ribbon 32.
  • a spray gun 34 of the type is the type.
  • a coating liquid is sprayed from a spray gun 34 onto a glass ribbon 32 moving at a predetermined conveying speed at a position where the surface temperature of the glass ribbon 32 is 200 to 650 ° C. between the float bath 26 and the slow cooling furnace 28.
  • An inorganic film is formed on the glass ribbon 32.
  • the glass ribbon 32 exiting the slow cooling furnace 28 is cut by a cutting device (not shown) to form a glass substrate with a coating film.
  • a coating liquid containing inorganic particles of less than 100 nm, an alkoxysilane hydrolyzate, and a specific liquid medium is sprayed on a substrate maintained at 200 to 650 ° C.
  • the inorganic film can be formed thick while preventing the occurrence of cracks or film peeling.
  • inorganic particles having an average aggregate particle diameter of less than 100 nm by using inorganic particles having an average aggregate particle diameter of less than 100 nm, a structure in which inorganic particles are stacked on a substrate via a continuous phase made of silicon oxide is easily obtained, and a film It is easy to obtain a coating film having a large thickness.
  • the larger the average aggregated particle diameter of the inorganic particles contained in the coating liquid the higher the film deposition efficiency, and the smaller the average aggregated particle diameter.
  • the surface smoothness is improved and a denser coating film is obtained.
  • the use of chain particles can dramatically increase the deposition efficiency.
  • a polar liquid medium can be used.
  • Select inorganic particles because inorganic particles that can be dispersed in a polar liquid medium have more types than inorganic particles that can be dispersed in a non-polar liquid medium, and there is no need for surface treatment such as hydrophobization. The width of becomes wide.
  • Example 1 To triethylene glycol, tetraethoxysilane (manufactured by Kanto Chemical Co., Inc., SiO 2 conversion solid content: 99.9% by mass) is added so as to be 30% by mass in the coating liquid, and nitric acid (70% by mass aqueous solution) is further added. It added so that it might become 0.35 mass% in a coating liquid, and it stirred for 1 hour.
  • tetraethoxysilane manufactured by Kanto Chemical Co., Inc., SiO 2 conversion solid content: 99.9% by mass
  • nitric acid 70% by mass aqueous solution
  • a chain silica sol manufactured by Nissan Chemical Industries, (product name: Snowtex OUP), average aggregated particle size: 65 nm, solid content: 15% by mass, medium: water
  • the mixture was stirred for 5 to 10 minutes, the solid content concentration in terms of SiO 2 : 9.65% by mass, the ratio of silica particles in the solid content: 10.4% by mass, the hydrolyzate of alkoxysilane in the solid content ( Ratio of solid content in terms of SiO 2 : A coating liquid of 89.6% by mass was obtained.
  • KM-100 manufactured by SPD Laboratory
  • glass substrate 10 cm ⁇ 10 cm ⁇ 4 mm high transmission glass (soda lime silica glass, manufactured by Asahi Glass Co., Ltd.) was used.
  • a glass substrate was placed on the stage, and a heater was installed on the back side of the stage without contact with the stage.
  • the glass substrate was heated to 400 ° C. through the stage by the radiant heat of the heater.
  • the temperature of the glass substrate was measured by bringing a thermocouple into contact with one side of the glass substrate. Since the glass substrate was heated for a sufficient time before spraying the coating liquid with the spray gun, the temperature measured here may be regarded as almost the same as the surface temperature of the glass substrate.
  • the coating liquid was sprayed onto the glass substrate from a spray gun disposed above the glass substrate.
  • the liquid feed pressure to the spray gun was adjusted so that the liquid feed speed was 0.3 to 0.6 mL / second, and the spray pressure was 1 MPa.
  • the coating time was 45 seconds.
  • the stage, glass substrate, and spray gun were sprayed in a state surrounded by an explosion-proof device, and the ambient temperature was not adjusted.
  • a substrate with a coating film was obtained, in which a coating film composed of silica particles and a calcined product of hydrolyzed alkoxysilane (silicon oxide) was formed on the glass substrate.
  • FIG. 1 is a photograph of an image obtained by observing the obtained substrate with a coating film with a scanning electron microscope, where (A) is a cross-sectional image and (B) is a surface image (hereinafter the same). It was 1.7 micrometers when the average value of the film thickness (distance illustrated with an arrow in a figure) from the surface of a glass substrate to the surface of a coating film was measured from the cross-sectional image of (A).
  • the shape of the silica particles used in this example, the average aggregate particle diameter, the coating time, and the film thickness (average film thickness) of the obtained coating film are shown in Table 1 (hereinafter the same).
  • Table 1 hereinafter the same.
  • the surface smoothness of the coating film was evaluated by the following method. The results are shown in Table 1.
  • the obtained coating film had a Martens hardness of 830 N / mm 2 .
  • the Martens hardness was measured with a microhardness measuring device (PICODERTOR HM500 manufactured by Fischer Instruments). An indentation depth of 0.1 ⁇ m and an indentation time of 20 seconds were measured at five points at different locations to obtain an average value.
  • Example 2 instead of the chain silica sol in Example 1, spherical silica sol (manufactured by Nissan Chemical Industries, (product name: Snowtex OS), average aggregated particle size: 11 nm, solid content: 20% by mass, medium: water) This was added so that it might become 5.0 mass% in a coating liquid.
  • Example 3 instead of the chain silica sol in Example 1, spherical silica sol (manufactured by Nissan Chemical Co., Ltd., (product name: Snowtex O-40), average aggregate particle size: 30 nm, solid content: 40% by mass, medium: This was added to 2.5% by mass in the coating solution.
  • Example 4 instead of the chain silica sol in Example 1, spherical silica sol (manufactured by Nissan Chemical Industries, (product name: Snowtex OL), average aggregated particle size: 50 nm, solid content: 20% by mass, medium: water) This was added so that it might become 5.0 mass% in a coating liquid.
  • spherical silica sol instead of the chain silica sol in Example 1, spherical silica sol (manufactured by Nissan Chemical Co., Ltd. (product name: Snowtex MP-2040), average aggregate particle size: 200 nm, solid content: 40% by mass, medium: This was added to 2.5% by mass in the coating solution. Except for the above, a substrate with a coating film was obtained in the same manner as in Example 1, observed with a scanning electron microscope, measured for film thickness, and evaluated surface smoothness. The results are shown in Table 1.
  • Reference Example 2 In Reference Example 2, instead of the chain silica sol in Example 1, spherical silica sol (manufactured by Nissan Chemical Co., Ltd., (Product name: Snowtex MP-4540M), average aggregate particle size: 450 nm, solid content: 40% by mass, medium: This was added to 2.5% by mass in the coating solution. The application time was changed to 21 seconds. Except for the above, a substrate with a coating film was obtained in the same manner as in Example 1, observed with a scanning electron microscope, measured for film thickness, and evaluated surface smoothness. The results are shown in Table 1.
  • Comparative Example 1 is an example in which the coating liquid does not contain inorganic particles. That is, tetraethoxysilane (manufactured by Kanto Chemical Co., Inc., SiO 2 conversion solid content: 99.9% by mass) was added to triethylene glycol so as to be 33.5% by mass in the coating solution, and nitric acid (70% by mass) was further added. the aqueous solution), added in an amount of 0.35 wt% in the coating solution, and stirred for 1 hour, SiO 2 in terms of solid concentration: was obtained 9.65 mass% of the coating solution. Using the obtained coating solution, a substrate with a coating film was obtained in the same manner as in Example 1, and observed with a scanning electron microscope, the film thickness was measured, and the surface smoothness was evaluated. The results are shown in Table 1.
  • Example 1 As shown in the results of Table 1, in Examples 1 to 4, an inorganic film having a thickness of 400 nm or more could be formed on the substrate in a coating time of 45 seconds, and good film deposition efficiency was obtained. Further, no cracks or film peeling occurred in the coating film. Comparing Examples 2 to 4, it can be seen that the larger the average aggregate particle size of the silica particles, the larger the film thickness of the coating film, that is, the higher the film deposition efficiency in the same coating time. On the other hand, the smaller the average agglomerated particle diameter of the silica particles, the higher the smoothness of the surface, and a denser coating film can be obtained as can be seen from the photograph. It can be seen that Example 1 using chain silica had a larger film thickness than Examples 2 to 4, and the deposition efficiency was dramatically improved. The coating film of Example 1 also had good surface smoothness.
  • the coated substrate produced in the present invention has high visible light transmittance and good UV durability, and covers solar cells, display protective plates, automotive glass, railway vehicle glass, and ships. Widely used as glass for construction and glass for building materials. It should be noted that the entire content of the specification, claims, drawings and abstract of Japanese Patent Application No. 2013-142052 filed on July 5, 2013 is cited herein as the disclosure of the specification of the present invention. Incorporated.

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Abstract

L'invention concerne un procédé de formation d'un film de revêtement comprenant un matériau inorganique sur un substrat permettant d'épaissir efficacement le film de revêtement et de rendre difficiles la craquelure ou le décollement du film même si l'épaisseur du film de revêtement augmente. Le procédé de production d'un substrat doté d'un film de revêtement selon l'invention comprend une étape de pulvérisation d'une solution de revêtement contenant des particules inorganiques, un hydrolysat d'alkoxysilane et un milieu liquide sur un substrat maintenu à 200-650°C, le diamètre total moyen des particules inorganiques étant inférieur à 100 nm et le milieu liquide contenant un composé contenant un groupe hydroxyle polyvalent et/ou de l'eau.
PCT/JP2014/066329 2013-07-05 2014-06-19 Procédé de production de substrat doté d'un film de revêtement Ceased WO2015001979A1 (fr)

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CN106053934A (zh) * 2015-04-02 2016-10-26 Ls产电株式会社 电力测量系统和利用该系统的负荷电力监测系统及其操作方法
WO2022196218A1 (fr) * 2021-03-19 2022-09-22 日本電気硝子株式会社 Fluide de revêtement pour revêtement par pulvérisation, son procédé de production et procédé de production d'un substrat revêtu d'une couche antireflet
JP2022145461A (ja) * 2021-03-19 2022-10-04 日本電気硝子株式会社 スプレーコート用コーティング液及びその製造方法、並びにアンチグレア層付き基材の製造方法
CN116897194A (zh) * 2021-03-19 2023-10-17 日本电气硝子株式会社 喷涂用涂敷液和其制造方法以及带防眩光层的基材的制造方法

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JP7252011B2 (ja) * 2019-02-28 2023-04-04 株式会社カーメイト コーティング組成物。

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WO1999052986A1 (fr) * 1998-04-10 1999-10-21 Matsushita Electric Works, Ltd. Procede permettant de former un film de revetement inorganique hydrophile et composition de revetement inorganique
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WO2006090795A1 (fr) * 2005-02-25 2006-08-31 Ishihara Sangyo Kaisha, Ltd. Procede de revetement pour former un film de revetement contenant un photocatalyseur
WO2007058016A1 (fr) * 2005-11-15 2007-05-24 Central Glass Company, Limited Processus de production d'un materiau de base pour la formation d'un film de protection thermique

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JPH0797237A (ja) * 1993-09-30 1995-04-11 Nippon Sheet Glass Co Ltd 屈折率低減透明被膜の形成方法
WO1999052986A1 (fr) * 1998-04-10 1999-10-21 Matsushita Electric Works, Ltd. Procede permettant de former un film de revetement inorganique hydrophile et composition de revetement inorganique
JP2002019007A (ja) * 2000-07-11 2002-01-22 Sumitomo Osaka Cement Co Ltd 防汚性及び易洗浄性の高い無機、金属及び樹脂成形製品及びその製造方法
WO2006090795A1 (fr) * 2005-02-25 2006-08-31 Ishihara Sangyo Kaisha, Ltd. Procede de revetement pour former un film de revetement contenant un photocatalyseur
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CN106053934A (zh) * 2015-04-02 2016-10-26 Ls产电株式会社 电力测量系统和利用该系统的负荷电力监测系统及其操作方法
JP2016197988A (ja) * 2015-04-02 2016-11-24 エルエス産電株式会社Lsis Co., Ltd. 電力測定システム及びそれを利用した負荷電力モニタリングシステム及びその動作方法
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WO2022196218A1 (fr) * 2021-03-19 2022-09-22 日本電気硝子株式会社 Fluide de revêtement pour revêtement par pulvérisation, son procédé de production et procédé de production d'un substrat revêtu d'une couche antireflet
JP2022145461A (ja) * 2021-03-19 2022-10-04 日本電気硝子株式会社 スプレーコート用コーティング液及びその製造方法、並びにアンチグレア層付き基材の製造方法
CN116897194A (zh) * 2021-03-19 2023-10-17 日本电气硝子株式会社 喷涂用涂敷液和其制造方法以及带防眩光层的基材的制造方法

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