WO2005049757A1 - Silica films and method of production thereof - Google Patents
Silica films and method of production thereof Download PDFInfo
- Publication number
- WO2005049757A1 WO2005049757A1 PCT/AU2004/001622 AU2004001622W WO2005049757A1 WO 2005049757 A1 WO2005049757 A1 WO 2005049757A1 AU 2004001622 W AU2004001622 W AU 2004001622W WO 2005049757 A1 WO2005049757 A1 WO 2005049757A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silica
- alcohol
- precursor formulation
- coating
- film
- Prior art date
Links
Classifications
-
- 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
- C09D183/02—Polysilicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
- C03C1/008—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route for the production of films or coatings
-
- 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
- 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
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/213—SiO2
-
- 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
- C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249967—Inorganic matrix in void-containing component
- Y10T428/249969—Of silicon-containing material [e.g., glass, etc.]
Definitions
- This invention relates to silica films, a method of production thereof and the use of the silica films as anti-reflective and/or anti-fogging and/or protective coatings.
- the invention relates to silica films having a refractive index lower than or equal to typical silica glass.
- WO 02/41043 is directed to a method of forming a meso-structured inorganic/block copolymer composite or inorganic porous solid doped with a dye or dye sensitive agents, formed by creating a silica sol-gel from tetraethoxysilicate (TEOS), ethanol and water.
- TEOS tetraethoxysilicate
- the sol-gel is then templated with block copolymers, such as poly(ethylene oxide)- poly(alkyene oxide)-poly( ethylene oxide).
- US 6,379,776 is directed to a multi-layer, anti-fogging and stain preventing glass coating comprising an alkaline shut-off film, a silica oxide/zirconium oxide composite, and a photocatalytic film, of titanium oxide. Both the silica oxide/zirconium oxide composite layer and the titanium oxide layers are formed using known sol-gel processes.
- US 2002/0090519 describes a method of hydrolytically polycondensing tetraalkoxysilanes to form a silica oxide sol.
- the hydrolytic polycondensation occurs by placing the tetraalkoxysilane in an aqueous alcohol ammoniacal solution to encourage hydrolysis of the tetraalkoxysilane and produce silica oxide particles.
- the sol is subject to steam distillation in order to remove the alcohol and ammonia prior to the pH being adjusted to between 3 and 8.
- Surfactants are then added to the silica sol to act as pore templates during the coating of a substrate.
- the coating is calcined to cure the silica film and remove the surfactants.
- US 5,948,482 is directed to a method of forming an aerogel thin film at ambient pressure, by forming a silica oxide sol-gel using standard processes before derivatizing the surface of the gel with a hyrdolysable organic substituent, reliquefying the sol with sonication and depositing the gel onto a substrate.
- US 5,698,266 is directed to a modification of the standard sol-gel method of forming an anti-reflective coating by mixing ethanol, tetraethoxysilicate (TEOS) and ammonia and hydrolysing for up to 48 hours to form a colloidal silicon oxide suspension dispersed in an aliphatic alcohol.
- TEOS tetraethoxysilicate
- the silica sol is then filtered to obtain silica particles for deposition onto a substrate, prior to drying.
- the coated substrate is placed in an ammoniacal environment for up to twelve hours to form an anti-reflective coating. This finals step is claimed to improve the binding between the silica particles, and so renders the film more robust.
- C. Shelle et al, J. Non-Cryst. Solids, 218, pg 163, 1997 describes a method of producing anti-glare glass films using sol-gel coatings formed from methyltriethoxysilane, tetraethoxysilicate and tin oxide. The sol-gel is aged at 0°C prior to deposition onto a substrate and calcining at 500°C.
- the TEOS is initially aged in an ammonia-ethanol solution, pH adjusted, refluxed and a second pH adjustment made.
- G. Wu et al deposit the sol-gel onto a substrate and expose to an ammoniacal environment.
- Hass D. D. et al, NASA Contractor Report, 201733 teaches the coating of fibrous insulation with a reflective film such as silica, titanium dioxide, zirconium oxide and/or combinations thereof.
- the oxides are formed using known sol-gel processes into which the fibrous insulation is submersed to coat the fibres prior to vacuum or heat drying.
- sol-gel processes which rely on sol-gel techniques for producing thin films are complex, multi-step processes which are costly, involve high temperature steps in fabrication, and/or require a surfactant for templating.
- the films produced by these sol-gel processes are typically easy to damage and/or liable to delamination.
- One of the few prior art processes for producing silica coatings without directly following the conventional sol-gel process is described in United States patent number 6231989 assigned to Dow Corning Corporation.
- the patent describes a process of forming a coating from a solution comprising a resin containing at least two Si-H groups in a solvent, such as methylisobutylketone.
- the solution is coated to a substrate with about 5% of the solvent remaining in the coating.
- An aqueous basic catalyst causes condensation of the Si-H groups.
- the solvent is evaporated to leave a porous coating.
- the method uses an ammonia vapour step to improve adhesion and mechanical strength of the resultant film, but relies in the main part upon conventional sokjel methods to produce the coating at room temperature and pressure.
- the preparation of suitable starting materials containing two Si- H groups is difficult, which limits the usefulness of the technique.
- the invention resides in a method of forming a silica film coated on a substrate including the steps of: forming a solvent solution; producing a silica precursor formulation by adding silicic acid tetramethyl ester homopolymer to the aqueous-alcohol solution; coating a substrate with the silica precursor formulation; and curing the silica precursor formulation onto the substrate in an ammoniacal environment.
- the solvent solution is suitably alcohol or an aqueous-alcohol solution.
- the silica precursor formulation will typically contain an amount of silicic acid tetramethyl ester monomer (tetramethoxysilane).
- the monomer may be provided as part of any one of a number of commercially available formulations such as methyl-silicate-51 (MS51 - ColCoat Co. Ltd., Japan).
- the silica precursor formulation is formed by adding MS-51 , comprising >94% silicic acid tetramethyl ester homopolymer, ⁇ 3% tetramethoxysilane and ⁇ 3% methanol; to the solvent solution.
- the silica precursor formulation may comprise about 0.01-1 parts water and 0.01-100 parts alcohol for each part of MS-51.
- the solvent solution is formed by adding about 0 to 15 parts alcohol and 0 to 1 part water for each part of MS-51.
- An example ratio of reagents in the silica precursor formulation is 1.0 part MS-51 : 0.1 part water: 10 parts alcohol.
- the coating step is suitably performed by spin coating or dip coating.
- the method may further include the step of allowing the coating to settle before curing.
- the curing step of the above method may be carried out by placing the coated substrate in a closed ammoniacal environment.
- the environment preferably contains water, ammonia and alcohol.
- the alcohol is suitably the same alcohol as used in the formation of the precursor. It will be appreciated that the precursor is liquid during the coating step (before complete hydrolysis), and so the method does not follow the conventional sol-gel process described in the prior art.
- the alcoholic ammoniacal curing environment is responsible for controlling the rates of hydrolysis and polycondensation in the post-deposited film, to create a nanoporous, stable, highly cross- linked silica network.
- the method may further include the steps of controlling the alcohol content of the precursor and/or controlling the alcohol content in the ammoniacal environment, to control characteristics of the film.
- the pore size may be related to the size of the alcohol molecule.
- the alcohol content in the precursor relates to the pore density which may also be related to the alcohol content in the ammoniacal environment.
- the method is suitably carried out at or near room temperature and atmospheric pressure.
- Another form of the invention provides a method of forming a silica precursor formulation, including the steps of: forming a solvent solution; and mixing silicic acid tetramethyl ester homopolymer with the solvent solution.
- the invention resides in a silica precursor formulation comprising; about 1 part including >94% silicic acid tetramethyl ester homopolymer and ⁇ 3% tetramethoxysilane; about 0.01-100 parts alcohol; and about 0.01-1 part water.
- the invention resides in a silica film having a refractive index between 1.1 and 1.56 and a film thickness less than 100 microns formed by a method including the steps of; forming a solvent solution; producing a silica precursor formulation by adding silicic acid tetramethyl ester homopolymer to the solvent solution; coating a substrate with the silica precursor formulation; and curing the silica precursor formulation onto the substrate in an ammoniacal environment.
- the invention provides for the use of the silica film coated on a transparent substrate to provide an anti-reflective and/or anti-fogging and/or protective coating.
- the term "low refractive index" is intended to refer to a silica film of the invention having a refractive index
- silica glass in the wavelength range 200nm to 20 ⁇ m.
- FIG. 1 is a spin profile for coating a substrate
- FIG. 2 is a schematic of a curing chamber
- FIG. 3 is a graph of the UV-visible optical transmission spectrum of the film of Example 1
- FIG. 4 is a graph of the UV-visible optical transmission spectrum of a spin coated film of silica on glass produced by the method of the invention
- FIG. 5 is a UV-visible optical transmission spectra for an uncoated glass slide and a glass slide coated with an anti-reflective silica film formed by the method of the invention
- FIG. 6 is an x-ray diffraction image of a film on a glass substrate
- FIG. 7 is an optical transmission spectra of a film designated S2;
- FIG. 8 is an optical transmission spectra of a film designated S3;
- FIG. 9 is an optical transmission spectra of a film designated S11 ;
- FIG. 10 is an optical transmission spectra of a film designated S12;
- FIG. 11 is an optical transmission spectra of a film designated S21 ;
- FIG. 12 shows refractive index and extinction coefficient data for the film of FIG. 9;
- FIG. 13 shows refractive index and extinction coefficient data for the film of FIG. 10.
- Example 1 10ml of methyl-silicate-51 (comprising silicic acid tetramethyl ester homopolymer >94%, tetramethoxysilane ⁇ 3%, methanol ⁇ 3%) ⁇ supplied by COLCOAT CO. LTD. 3-28-6 Omorinishi, Ota-ku, Tokoyo 143-0015, Japan ⁇ is added to solution of 60ml ethanol or methanol, and 1 ml water to form a silica precursor formulation.
- the silica precursor formulation may comprise any alcohol that creates dispersed droplets throughout the silica precursor formulation and facilitate the formation of pores in the final film.
- Alcohols include but are not limited to: ethanol, methanol, iso-propyl alcohol, butanol, pentanol and certain other polyols such as ethylene glycol.
- a graph of the spin profile is shown in FIG 1. It will be appreciated that spin deposition conditions may be varied depending on the film thickness and refractive index desired. Other deposition techniques such as dip coating and spraying may also be used to apply the silica precursor formulation to a substrate.
- the coated substrate may sit in an alcohol atmosphere for a time to allow equilibrium to be established between the alcohol in the atmosphere and the alcohol content of the silica precursor formulation on the substrate.
- the alcohol content in the silica precursor formulation influences the porosity of the film
- the coated substrate is then place in a closed container containing a curing agent (2.5ml ammonia, 7.5ml water and 20ml alcohol), which creates an appropriate ammoniacal atmosphere for the silica film to cure.
- the container is arranged in such a manner that the film is never in contact with the curing liquid. This curing step continues until the film solidifies and becomes mechanically robust.
- a schematic of a curing chamber 1 is shown in FIG 2.
- the chamber 1 is a closed system having some form of mount 2 in the base for receiving the substrate 3.
- a reservoir 4 is filled with a mixture of ammonia, alcohol and water which evaporates to produce an atmosphere 5 having a composition determined by the partial pressures of the ammonia, water and alcohol at the applicable temperature and pressure.
- a port 6 may be provided so that the mixture in the reservoir can be adjusted without opening the chamber. It will be appreciated that any quantities of water, alcohol and ammonia/ammonium hydroxide may be used to create the ammoniacal atmosphere to cure the silica film.
- the porosity of the produced film is determined, at least in part, by the alcohol in the silica precursor prior to curing.
- the alcohol in the silica precursor formulation is understood to produce pores in the film which remain after curing.
- the density of the pores is determined, at least in part, by the amount of alcohol present in the silica precursor formulation during curing, whereas the size of the pores is determined by the type of alcohol.
- a large polyol produces a larger pore size than, say, methanol or ethanol.
- Equilibrium is established between the alcohol in the silica precursor formulation and the alcohol in the ammoniacal atmosphere. This means that the final porosity of the film can be controlled by placing the coated substrate in an alcohol environment prior to introducing ammonia to the chamber to catalyse the silica cross-linking reaction.
- Optical transparency The optical transparency of the film of Example 1 , and similar films was determined using a Perkin Elmer Lamba 40 UV-Visible Spectrophotometer, having the following scan settings: Slit width 2nm, Scan speed 240nm/min, Data interval 1 nm. An empty sample arm was used to determine the background spectra for correction purposes.
- the UV-Visible optical transmission spectrum was measured for the thin film (film thickness of less than 2 microns) of Example 1. The spectrum is shown in FIG. 3.
- the key feature of these spectra is the high optical transmission of the coated glass substrate over the entire visible spectrum. This observation may also be confirmed by simply looking a the coated glass substrate which appears transparent to the eye.
- FIG 4 is a UV-Visible optical transmission spectrum for a silica film, having a film thickness of approximately 4 microns, formed in a similar manner to Example 1.
- the film used for this test was thicker than that used in FIG.3 evidenced by the interference fringes, peaks and troughs, as a function of wavelength.
- the fringe contrast is appreciable ( ⁇ 5%), indicating that the refractive index of the film is ⁇ 1.3.
- FIG 5 shows a transmission spectrum of a film similar to that of FIG 3 with the transmission spectrum of an uncoated glass slide.
- the silica films formed by the method of Example 1 have been found to provide effective anti-fogging properties.
- the porosity or surface area of the silica films is approximately 150m 2 /g, using standard nitrogen adsorption-absorption techniques. It is believed that coatings having a minimum surface area of 10m 2 /g will exhibit anti-fogging properties. It is believed that the anti-fogging properties of the silica films of the invention are due to the hydrophilicity and high surface area of the films.
- Example 2 Another silica film was formed in a manner similar to Example 1. To compare the features of the silica film of this example with that of its substrate, a glass slide, UV-visible optical transmission spectra was recorded for both a coated substrate and uncoated substrate, shown in FIG 5. Ordinarily, -4% of incident light is reflected from each glass-air interface, leading to a normal transmission of -92% for an uncoated glass substrate.
- FIG. 3 shows the increase (-94.6%) in transmission that can be achieved by coating one side of a glass substrate with a low refractive index film produced by the new process.
- Example 3 A substrate, for example a mirror, is sprayed with the silica precursor formulation. An aqueous ammonia solution is sprayed over the silica precursor formulation. The silica precursor is allowed to cure at room temperature forming a silica film.
- Example 4 A number of films were produced to demonstrate anti-reflection
- Films less than 1 ⁇ m are generally required for anti-reflection
- Each film was produced according to the following procedure. Table 1 sets out the variation that was made to the procedure for each film.
- the general procedure was to add 20ml of methyl-silicate-51 (comprising silicic acid tetramethyl ester homopolymer >94%, tetramethoxysilane ⁇ 3%, methanol ⁇ 3%) ⁇ supplied by COLCOAT CO. LTD. 3-28-6 Omorinishi, Ota-ku, Tokoyo 143-0015, Japan ⁇ to a solution of 120ml ethanol or methanol to form a silica precursor formulation. It should be noted that no additional water above that provided by the environment is added to the formulation.
- the silica precursor solution is applied to both sides of a cleaned glass substrate by dip coating.
- the coated substrate is placed in a closed container containing alcohol vapour and the coating allowed to settle for 5 mins.
- the coated substrate is placed in a closed container containing a curing agent (10ml of alcohol and 10ml of 25% aqueous ammonia solution). This creates an appropriate ammoniacal atmosphere for the film to cure.
- the container is arranged in such a manner that the film is never in contact with the curing liquid as in Example 1. This curing step continues until the film solidifies and becomes mechanically robust.
- Example 4 Four films were produced according to the method of Example 4 but with the ratio of alcohol to MS-51 varied. A fifth film was produced with a slower withdrawal rate of 70mm/min.
- the following table summarises the samples including a designated code, the MS-51 to alcohol ratio, the dipping withdrawal speed, the refractive index at 550nm and the thickness in nanometres.
- FIGs 7-11 shows the optical transmission spectra for the films designated S2, S3, S11 , S12 and S21 in Table 1.
- FIGs 12-13 show the refractive index and extinction coefficient for the films designated S11 and S12. These spectra demonstrate the usefulness of the produced films for anti-reflection applications.
- the silica thin films produced by this method have been found to have a number of favourable characteristics, including: a low refractive index in the visible spectrum, typically 1.1 to 1.56; high optical transparency; high optical and thickness uniformity; mechanical robustness similar to glass; chemical and photochemical properties similar to glass; high porosity, leading to efficient anti-fogging behaviour; excellent adhesion to conventional substrates, such as glasses, plastics, metals, ceramics, semiconductors, and the like; and durability / long term stability.
- a number of features of the silica films of the current invention may be tailored or tunable to suit the final application of the film, for example; Tunable refractive index -
- the refractive index may be tuned according to need by adjusting the composition, in particular the alcohol and water content.
- Table 1 shows the effect of precursor composition on refractive index.
- Tunable film thickness The film thickness can be tuned by adjusting the initial alcohol and water contents in the precursor formulation and, can also be adjusted by varying the parameters relating to the deposition method, such as spin speed, viscosity, dip coating withdrawal rate, and the like using standard methods for the chosen coating technique.
- the viscosity of the silica precursor formulation may be altered to facilitate its use in a range of applications, for example, a highly viscous formulation may be formed so that when sprayed onto a substrate to create a thin coverage of the precursor it does not flow significantly whilst curing.
- the method of the current invention provides a low cost simple method for producing robust films with effective control over the thickness and refractive index of the coating, along with being able to coat a range of substrate materials and shapes.
- the above properties make the films ideal candidates for cheap, robust, efficient optical coatings for applications including antireflection coatings, chemical and mechanical barrier coatings, anti-fogging coatings, anti-glare coatings (light diffusing effect), high reflectivity coatings, low refractive index supports and cladding and dielectric barrier layers.
- the silica thin films of the invention may be employed as low refractive index optical coatings for anti-reflection coatings or as low and high refractive index materials in high-low refractive index multilayer coatings.
- the silica thin films may be applied to all forms of glass including spectacles, windows, windscreens, decorative, etc.; coatings for CRT and other display devices such as computer monitors, televisions, etc.; coatings for solar cells; optical instrument coatings such as lenses, mirrors, and the like; active and passive optical waveguides in telecommunications, and advanced photonics; and optoelectronic devices.
- the silica thin films may also be used as physical and chemical barrier coatings including, invisible metal and plastics protection, invisible protection for delicate optical surfaces.
- the silica thin films may also be used as anti-fogging coatings for applications including automotive and marine glass, architectural glass, spectacles, windows of all sorts, bathroom mirrors and shower screens.
- the films may also be produced with an additional component imbedded in the porous network to make the film an active coating.
- the nanoporous structure of the film also makes it potentially useful as a nanoseive.
- the above films may be formed on or applied to glass surfaces that are already in place, such as existing windows and mirrors.
- the silica precursor formulation may be mixed with the curing agent immediately prior to application, mixed during application such as through a common spray nozzle or after the silica precursor has been applied to a substrate.
- the silica precursor may be applied by coating, wiping or spraying the respective component onto the substrate being treated.
- the curing agent may be any gaseous or aqueous strong alkali, including ammonia, alkali metal hydroxides, quaternary alkyl ammonium hydroxides and the like.
- the aim has been to describe the preferred embodiments of the invention without limiting the invention to any one embodiment or specific collection of features.
- the word "comprises”, and variations such as “comprise” or “comprising”, will be understood to imply the inclusion of a stated integer or group of integers or steps but not to the exclusion of any other integer or group of integers.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Surface Treatment Of Glass (AREA)
- Laminated Bodies (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Paints Or Removers (AREA)
- Silicon Compounds (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006540084A JP5183066B2 (en) | 2003-11-21 | 2004-11-22 | Silica membrane and method for producing the same |
US10/579,654 US7919145B2 (en) | 2003-11-21 | 2004-11-22 | Silica films and method of production thereof |
EP04797070.2A EP1689824B1 (en) | 2003-11-21 | 2004-11-22 | Silica films and method of production thereof |
AU2004291564A AU2004291564B2 (en) | 2003-11-21 | 2004-11-22 | Silica films and method of production thereof |
US11/444,283 US7642199B2 (en) | 2004-11-22 | 2006-05-31 | Silica and silica-like films and method of production |
US13/065,218 US8734906B2 (en) | 2003-11-21 | 2011-03-16 | Films and method of production thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003906427A AU2003906427A0 (en) | 2003-11-21 | Silica films and method of production thereof | |
AU2003906427 | 2003-11-21 |
Related Child Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/579,654 A-371-Of-International US7919145B2 (en) | 2003-11-21 | 2004-11-22 | Silica films and method of production thereof |
US11/444,283 Continuation-In-Part US7642199B2 (en) | 2004-11-22 | 2006-05-31 | Silica and silica-like films and method of production |
US13/065,218 Continuation-In-Part US8734906B2 (en) | 2003-11-21 | 2011-03-16 | Films and method of production thereof |
US13/065,218 Continuation US8734906B2 (en) | 2003-11-21 | 2011-03-16 | Films and method of production thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005049757A1 true WO2005049757A1 (en) | 2005-06-02 |
Family
ID=34596430
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AU2004/001622 WO2005049757A1 (en) | 2003-11-21 | 2004-11-22 | Silica films and method of production thereof |
Country Status (4)
Country | Link |
---|---|
US (1) | US7919145B2 (en) |
EP (1) | EP1689824B1 (en) |
JP (1) | JP5183066B2 (en) |
WO (1) | WO2005049757A1 (en) |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006128232A1 (en) * | 2005-05-31 | 2006-12-07 | Xerocoat Pty Ltd | Control of morphology of silica films |
US7585919B2 (en) | 2006-09-26 | 2009-09-08 | 3M Innovative Properties Company | Polymer derived from monomers with long-chain aliphatic, poly(oxyalkylene) and substrate-reactive groups |
AU2006254719B2 (en) * | 2005-05-31 | 2011-08-11 | Brismat Inc. | Control of morphology of silica films |
EP2423172A1 (en) | 2006-11-14 | 2012-02-29 | Saint-Gobain Glass France | Porous layer, method for manufacturing same and uses thereof |
US8420069B2 (en) | 2008-09-26 | 2013-04-16 | 3M Innovative Properties Company | Antimicrobial and antifouling polymeric materials |
US8864898B2 (en) | 2011-05-31 | 2014-10-21 | Honeywell International Inc. | Coating formulations for optical elements |
US8975311B2 (en) | 2010-12-06 | 2015-03-10 | Valspar Sourcing, Inc. | Radiation curable composite coating composition useful to form protective coatings |
EP3483638A1 (en) | 2006-09-06 | 2019-05-15 | DSM IP Assets B.V. | Core-shell nanoparticles |
US10544329B2 (en) | 2015-04-13 | 2020-01-28 | Honeywell International Inc. | Polysiloxane formulations and coatings for optoelectronic applications |
WO2021053138A1 (en) | 2019-09-20 | 2021-03-25 | Saint-Gobain Glass France | Laminated vehicle glazing and device having an associated near-infrared vision system |
WO2021136908A1 (en) | 2020-01-03 | 2021-07-08 | Saint-Gobain Glass France | Laminated vehicle glazing and device having an associated near-infrared vision system and production thereof |
WO2021136907A1 (en) | 2020-01-03 | 2021-07-08 | Saint-Gobain Glass France | Laminated vehicle glazing, associated device having a near-infrared vision system, and production thereof |
WO2021156567A1 (en) | 2020-02-06 | 2021-08-12 | Saint-Gobain Glass France | Coated glazing and production of same |
FR3116758A1 (en) | 2020-12-01 | 2022-06-03 | Saint-Gobain Glass France | LAMINATED VEHICLE GLAZING AND DEVICE WITH ASSOCIATED NEAR INFRARED VISION SYSTEM |
WO2022175634A1 (en) | 2021-02-19 | 2022-08-25 | Saint-Gobain Glass France | Laminated vehicle glazing, manufacture thereof and device with associated near-infrared vision system |
WO2022175635A1 (en) | 2021-02-19 | 2022-08-25 | Saint-Gobain Glass France | Laminated vehicle glazing and device comprising an associated near-infrared vision system |
FR3120012A1 (en) | 2021-02-19 | 2022-08-26 | Saint-Gobain Glass France | LAMINATED VEHICLE GLAZING, ITS MANUFACTURE AND DEVICE WITH ASSOCIATED NEAR INFRARED VISION SYSTEM |
FR3120013A1 (en) | 2021-02-19 | 2022-08-26 | Saint-Gobain Glass France | LAMINATED VEHICLE GLAZING AND DEVICE WITH ASSOCIATED NEAR INFRARED VISION SYSTEM |
WO2022200735A1 (en) | 2021-03-24 | 2022-09-29 | Saint-Gobain Glass France | Vehicle glazing and associated device with near-infrared vision system |
WO2022219273A1 (en) | 2021-04-14 | 2022-10-20 | Saint-Gobain Glass France | Laminated vehicle glazing and device comprising an associated near-infrared detection system |
FR3130684A1 (en) | 2021-12-22 | 2023-06-23 | Saint-Gobain Glass France | LAMINATED VEHICLE GLAZING AND DEVICE WITH ASSOCIATED NEAR INFRARED VISION SYSTEM |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5159680B2 (en) * | 2009-03-24 | 2013-03-06 | 株式会社東芝 | Forming method of coating type film |
US8864897B2 (en) | 2009-04-30 | 2014-10-21 | Enki Technology, Inc. | Anti-reflective and anti-soiling coatings with self-cleaning properties |
US9353268B2 (en) | 2009-04-30 | 2016-05-31 | Enki Technology, Inc. | Anti-reflective and anti-soiling coatings for self-cleaning properties |
US9376593B2 (en) | 2009-04-30 | 2016-06-28 | Enki Technology, Inc. | Multi-layer coatings |
WO2011075370A1 (en) * | 2009-12-18 | 2011-06-23 | 3M Innovative Properties Company | Systems and methods for making monolithic gel bodies |
FR2967992B1 (en) * | 2010-11-26 | 2015-05-29 | Commissariat Energie Atomique | SOIL PREPARATION OF STABLE METAL OXIDES USEFUL IN THE MANUFACTURE OF THIN FILMS WITH OPTICAL AND ABRASION RESISTANT PROPERTIES |
US20140037841A1 (en) * | 2012-08-03 | 2014-02-06 | Intermolecular, Inc. | Antireflective coatings with controllable porosity and durability properties using controlled exposure to alkaline vapor |
US8668960B1 (en) | 2013-02-08 | 2014-03-11 | Enki Technology, Inc. | Flow coating apparatus and method of coating |
JP5867649B2 (en) | 2013-02-19 | 2016-02-24 | 旭硝子株式会社 | Optical device |
JP5957620B2 (en) * | 2014-03-27 | 2016-07-27 | リンテック株式会社 | Antifouling sheet and method for producing the same |
WO2015148312A1 (en) | 2014-03-27 | 2015-10-01 | Innosense, Llc | Hydrophilic anti-fog coatings |
US9598586B2 (en) | 2014-07-14 | 2017-03-21 | Enki Technology, Inc. | Coating materials and methods for enhanced reliability |
US9376589B2 (en) | 2014-07-14 | 2016-06-28 | Enki Technology, Inc. | High gain durable anti-reflective coating with oblate voids |
US9382449B2 (en) | 2014-09-19 | 2016-07-05 | Enki Technology, Inc. | Optical enhancing durable anti-reflective coating |
KR101673720B1 (en) * | 2014-12-30 | 2016-11-23 | 현대자동차주식회사 | Method for manufacturing antifogging porous silica thin film |
KR101789371B1 (en) | 2015-02-13 | 2017-10-23 | 주식회사 엘지화학 | Preparation method of silica aerogel-containing blanket and silica aerogel-containing blanket prepared by using the same |
KR101931569B1 (en) | 2015-11-03 | 2018-12-21 | 주식회사 엘지화학 | Preparation method of hydrophobic metal oxide-silica complex aerogel and hydrophobic metal oxide-silica complex aerogel produced by the same |
KR101953371B1 (en) | 2016-01-19 | 2019-02-28 | 주식회사 엘지화학 | Preparation method and apparatus of aerogel sheet |
KR101953346B1 (en) | 2016-01-19 | 2019-02-28 | 주식회사 엘지화학 | Preparation method and apparatus of aerogel sheet |
KR101966358B1 (en) | 2016-02-16 | 2019-04-08 | 주식회사 엘지화학 | Preparation method and apparatus of aerogel sheet |
KR101953347B1 (en) | 2016-02-16 | 2019-05-22 | 주식회사 엘지화학 | Preparation apparatus for aerogel sheet |
KR101968648B1 (en) * | 2016-02-19 | 2019-04-12 | 주식회사 엘지화학 | Preparation method and apparatus of aerogel sheet |
KR102024140B1 (en) | 2016-03-16 | 2019-09-23 | 주식회사 엘지화학 | Aerogel precursor and aerogel preparaed by using the same |
KR20170110993A (en) | 2016-03-24 | 2017-10-12 | 주식회사 엘지화학 | Silica aerogel manufacturing system |
WO2018048289A1 (en) | 2016-09-12 | 2018-03-15 | 주식회사 엘지화학 | Method for manufacturing silica aerogel and silica aerogel manufactured thereby |
WO2019039909A1 (en) | 2017-08-24 | 2019-02-28 | 주식회사 엘지화학 | Silica membrane production method |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04180977A (en) * | 1990-11-15 | 1992-06-29 | Hitachi Chem Co Ltd | Production of coating fluid for forming silica film, coating fluid for forming silica film, production of silica film, silica film, and semiconductor device coated with silica film |
JPH08120225A (en) * | 1994-10-19 | 1996-05-14 | Mitsubishi Chem Corp | Composition for forming coating silica film |
EP0834488A1 (en) * | 1996-10-04 | 1998-04-08 | Showa Denko Kabushiki Kaisha | Process for forming silica film and composition therefor |
JPH10226767A (en) * | 1997-02-14 | 1998-08-25 | Mitsubishi Chem Corp | Coating liquid for forming silica film |
JPH10316934A (en) * | 1997-05-19 | 1998-12-02 | Mitsubishi Chem Corp | Coating solution for forming silica film |
EP1074859A2 (en) * | 1999-08-04 | 2001-02-07 | Tomoegawa Paper Co. Ltd. | Anti-reflective material |
US6291697B1 (en) * | 1996-03-25 | 2001-09-18 | Mitsubishi Chemical Corporation | Siloxane compounds, process for preparing the same, and liquid composition containing the same |
US6403183B1 (en) * | 1999-06-09 | 2002-06-11 | Kazari-Ichi Co., Ltd. | Coated materials, and films, sheets and the like for packing foods using them |
US6599976B2 (en) * | 2001-11-26 | 2003-07-29 | Mitsubishi Chemical Corporation | Coating process and silicon-containing liquid composition |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2225973C2 (en) | 1972-05-27 | 1974-07-04 | Merck Patent Gmbh, 6100 Darmstadt | Process for coating non-porous material with a porous silicon dioxide layer |
US5262201A (en) * | 1990-06-04 | 1993-11-16 | Dow Corning Corporation | Low temperature process for converting silica precursor coatings to ceramic silica coatings by exposure to ammonium hydroxide or an environment to which water vapor and ammonia vapor have been added |
JPH04160020A (en) * | 1990-10-25 | 1992-06-03 | Sumitomo Electric Ind Ltd | Production of thin film |
WO1992009665A1 (en) * | 1990-11-21 | 1992-06-11 | Catalysts & Chemicals Industries Co., Ltd. | Coating solution for forming transparent electrically conductive film, method of preparation thereof, electrically conductive substrate, method of preparation thereof, and display device having transparent electrically conductive substrate |
FR2693558B1 (en) | 1992-07-09 | 1994-08-19 | Commissariat Energie Atomique | Method for manufacturing thin layers having optical properties. |
FR2703791B1 (en) * | 1993-04-05 | 1995-05-19 | Commissariat Energie Atomique | Method for manufacturing thin layers having optical properties and abrasion resistance properties. |
US5698266A (en) * | 1993-04-05 | 1997-12-16 | Commissariat A L'energie Atomique | Process for the production of thin coatings having optical and abrasion resistance properties |
US6335296B1 (en) | 1998-08-06 | 2002-01-01 | Alliedsignal Inc. | Deposition of nanoporous silica films using a closed cup coater |
EP1013730A1 (en) * | 1998-12-25 | 2000-06-28 | Kaneka Corporation | Curable composition for coatings, coated articles and resin composition for coatings |
JP2001028368A (en) * | 1999-05-12 | 2001-01-30 | Kobe Steel Ltd | Method and apparatus for forming film |
JP3270422B2 (en) * | 1999-05-31 | 2002-04-02 | ヤマハリビングテック株式会社 | Glass goods |
JP2001137776A (en) * | 1999-11-11 | 2001-05-22 | Jsr Corp | Method for forming silica-based film |
JP2002241121A (en) | 2000-07-25 | 2002-08-28 | Canon Inc | Method for manufacturing porous structure |
JP2003327911A (en) * | 2002-05-15 | 2003-11-19 | Dainippon Ink & Chem Inc | Method for forming coating film, coating film produced thereby, antireflection film and photocatalytic film |
US7122880B2 (en) | 2002-05-30 | 2006-10-17 | Air Products And Chemicals, Inc. | Compositions for preparing low dielectric materials |
JP3631236B2 (en) | 2002-07-12 | 2005-03-23 | 東京応化工業株式会社 | Method for producing silica-based organic coating |
-
2004
- 2004-11-22 JP JP2006540084A patent/JP5183066B2/en not_active Expired - Fee Related
- 2004-11-22 EP EP04797070.2A patent/EP1689824B1/en not_active Not-in-force
- 2004-11-22 US US10/579,654 patent/US7919145B2/en not_active Expired - Fee Related
- 2004-11-22 WO PCT/AU2004/001622 patent/WO2005049757A1/en active Application Filing
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04180977A (en) * | 1990-11-15 | 1992-06-29 | Hitachi Chem Co Ltd | Production of coating fluid for forming silica film, coating fluid for forming silica film, production of silica film, silica film, and semiconductor device coated with silica film |
JPH08120225A (en) * | 1994-10-19 | 1996-05-14 | Mitsubishi Chem Corp | Composition for forming coating silica film |
US6291697B1 (en) * | 1996-03-25 | 2001-09-18 | Mitsubishi Chemical Corporation | Siloxane compounds, process for preparing the same, and liquid composition containing the same |
EP0834488A1 (en) * | 1996-10-04 | 1998-04-08 | Showa Denko Kabushiki Kaisha | Process for forming silica film and composition therefor |
JPH10226767A (en) * | 1997-02-14 | 1998-08-25 | Mitsubishi Chem Corp | Coating liquid for forming silica film |
JPH10316934A (en) * | 1997-05-19 | 1998-12-02 | Mitsubishi Chem Corp | Coating solution for forming silica film |
US6403183B1 (en) * | 1999-06-09 | 2002-06-11 | Kazari-Ichi Co., Ltd. | Coated materials, and films, sheets and the like for packing foods using them |
EP1074859A2 (en) * | 1999-08-04 | 2001-02-07 | Tomoegawa Paper Co. Ltd. | Anti-reflective material |
US6599976B2 (en) * | 2001-11-26 | 2003-07-29 | Mitsubishi Chemical Corporation | Coating process and silicon-containing liquid composition |
Non-Patent Citations (2)
Title |
---|
ISHINO ET AL.: "Mass production of hydrophobic silica and readout optics of Cherenkov light", NUCEAL INSTRUMENTS AND METHODS IN PHYSICS RESERACH, vol. 457, no. 3, 2001, pages 581 - 587, XP004314569 * |
PATENT ABSTRACTS OF JAPAN * |
Cited By (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006128232A1 (en) * | 2005-05-31 | 2006-12-07 | Xerocoat Pty Ltd | Control of morphology of silica films |
EP1734016A1 (en) * | 2005-05-31 | 2006-12-20 | The University Of Queensland | Silica and silica-like films and method of production |
JP2008542009A (en) * | 2005-05-31 | 2008-11-27 | ゼロコート・ピーティーワイ・リミテッド | Silica film morphology control |
AU2006254719B2 (en) * | 2005-05-31 | 2011-08-11 | Brismat Inc. | Control of morphology of silica films |
US8007868B2 (en) | 2005-05-31 | 2011-08-30 | Xerocoat Inc. | Control of morphology of silica films |
JP2013039570A (en) * | 2005-05-31 | 2013-02-28 | Brismat Inc | Control of morphology of silica film |
EP3483638A1 (en) | 2006-09-06 | 2019-05-15 | DSM IP Assets B.V. | Core-shell nanoparticles |
US7585919B2 (en) | 2006-09-26 | 2009-09-08 | 3M Innovative Properties Company | Polymer derived from monomers with long-chain aliphatic, poly(oxyalkylene) and substrate-reactive groups |
EP2423171A1 (en) | 2006-11-14 | 2012-02-29 | Saint-Gobain Glass France | Porous layer, method for manufacturing same and uses thereof |
EP2423173A1 (en) | 2006-11-14 | 2012-02-29 | Saint-Gobain Glass France | Porous layer, method for manufacturing same and uses thereof |
EP2423172A1 (en) | 2006-11-14 | 2012-02-29 | Saint-Gobain Glass France | Porous layer, method for manufacturing same and uses thereof |
US8420069B2 (en) | 2008-09-26 | 2013-04-16 | 3M Innovative Properties Company | Antimicrobial and antifouling polymeric materials |
US8975311B2 (en) | 2010-12-06 | 2015-03-10 | Valspar Sourcing, Inc. | Radiation curable composite coating composition useful to form protective coatings |
US8864898B2 (en) | 2011-05-31 | 2014-10-21 | Honeywell International Inc. | Coating formulations for optical elements |
US10544329B2 (en) | 2015-04-13 | 2020-01-28 | Honeywell International Inc. | Polysiloxane formulations and coatings for optoelectronic applications |
WO2021053138A1 (en) | 2019-09-20 | 2021-03-25 | Saint-Gobain Glass France | Laminated vehicle glazing and device having an associated near-infrared vision system |
FR3101014A1 (en) | 2019-09-20 | 2021-03-26 | Saint-Gobain Glass France | VEHICLE LEAF WINDOW AND DEVICE WITH ASSOCIATED INFRARED NEAR VISION SYSTEM |
WO2021136907A1 (en) | 2020-01-03 | 2021-07-08 | Saint-Gobain Glass France | Laminated vehicle glazing, associated device having a near-infrared vision system, and production thereof |
WO2021136908A1 (en) | 2020-01-03 | 2021-07-08 | Saint-Gobain Glass France | Laminated vehicle glazing and device having an associated near-infrared vision system and production thereof |
FR3105943A1 (en) | 2020-01-03 | 2021-07-09 | Saint-Gobain Glass France | VEHICLE LEAF WINDOW AND DEVICE WITH ASSOCIATED INFRARED NEAR VISION SYSTEM AND ITS MANUFACTURING |
FR3105942A1 (en) | 2020-01-03 | 2021-07-09 | Saint-Gobain Glass France | VEHICLE LEAF WINDOW AND DEVICE WITH ASSOCIATED INFRARED NEAR VISION SYSTEM AND ITS MANUFACTURING |
US12005679B2 (en) | 2020-01-03 | 2024-06-11 | Saint-Gobain Glass France | Laminated vehicle glazing, associated device having a near-infrared vision system, and production thereof |
WO2021156567A1 (en) | 2020-02-06 | 2021-08-12 | Saint-Gobain Glass France | Coated glazing and production of same |
FR3107056A1 (en) | 2020-02-06 | 2021-08-13 | Saint-Gobain Glass France | LAYERED GLAZING AND ITS MANUFACTURING |
FR3116758A1 (en) | 2020-12-01 | 2022-06-03 | Saint-Gobain Glass France | LAMINATED VEHICLE GLAZING AND DEVICE WITH ASSOCIATED NEAR INFRARED VISION SYSTEM |
WO2022117943A1 (en) | 2020-12-01 | 2022-06-09 | Saint-Gobain Glass France | Laminated vehicle glazing and device comprising an associated near-infrared vision system |
WO2022175635A1 (en) | 2021-02-19 | 2022-08-25 | Saint-Gobain Glass France | Laminated vehicle glazing and device comprising an associated near-infrared vision system |
FR3120012A1 (en) | 2021-02-19 | 2022-08-26 | Saint-Gobain Glass France | LAMINATED VEHICLE GLAZING, ITS MANUFACTURE AND DEVICE WITH ASSOCIATED NEAR INFRARED VISION SYSTEM |
FR3120013A1 (en) | 2021-02-19 | 2022-08-26 | Saint-Gobain Glass France | LAMINATED VEHICLE GLAZING AND DEVICE WITH ASSOCIATED NEAR INFRARED VISION SYSTEM |
WO2022175634A1 (en) | 2021-02-19 | 2022-08-25 | Saint-Gobain Glass France | Laminated vehicle glazing, manufacture thereof and device with associated near-infrared vision system |
WO2022200735A1 (en) | 2021-03-24 | 2022-09-29 | Saint-Gobain Glass France | Vehicle glazing and associated device with near-infrared vision system |
FR3121235A1 (en) | 2021-03-24 | 2022-09-30 | Saint-Gobain Glass France | VEHICLE GLAZING AND DEVICE WITH ASSOCIATED NEAR INFRARED VISION SYSTEM |
WO2022219273A1 (en) | 2021-04-14 | 2022-10-20 | Saint-Gobain Glass France | Laminated vehicle glazing and device comprising an associated near-infrared detection system |
FR3121873A1 (en) | 2021-04-14 | 2022-10-21 | Saint-Gobain Glass France | LAMINATED VEHICLE GLAZING, DEVICE WITH ASSOCIATED NEAR INFRARED DETECTION SYSTEM |
FR3130684A1 (en) | 2021-12-22 | 2023-06-23 | Saint-Gobain Glass France | LAMINATED VEHICLE GLAZING AND DEVICE WITH ASSOCIATED NEAR INFRARED VISION SYSTEM |
WO2023118710A1 (en) | 2021-12-22 | 2023-06-29 | Saint-Gobain Glass France | Laminated vehicle glazing and device comprising an associated near-infrared vision system |
Also Published As
Publication number | Publication date |
---|---|
EP1689824B1 (en) | 2016-10-12 |
EP1689824A4 (en) | 2007-06-27 |
JP2007511356A (en) | 2007-05-10 |
US7919145B2 (en) | 2011-04-05 |
JP5183066B2 (en) | 2013-04-17 |
US20070148435A1 (en) | 2007-06-28 |
EP1689824A1 (en) | 2006-08-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7919145B2 (en) | Silica films and method of production thereof | |
EP1734016B1 (en) | Silica and silica-like films and method of production | |
US5394269A (en) | Reflectance reducing film and method of forming same on glass substrate | |
AU2011267007B2 (en) | Inorganic oxide coating | |
US5413865A (en) | Water-repellent metal oxide film and method of forming same on glass substrate | |
EP1574881A1 (en) | Film and antireflection film having fine irregularities on surface, production method for the same, and optical member using the same | |
US6372354B1 (en) | Composition and method for a coating providing anti-reflective and anti-static properties | |
US8734906B2 (en) | Films and method of production thereof | |
EP1984765A1 (en) | Coating system | |
WO2014159181A1 (en) | Anti-reflection glass made from sol made by blending tri-alkoxysilane and tetra-alkoxysilane inclusive sols | |
US20100009195A1 (en) | Transparent porous SiO2 coating for a transparent substrate material | |
AU2004291564B2 (en) | Silica films and method of production thereof | |
AU2006202314B2 (en) | Silica and silica-like films and method of production | |
AU2006254719B2 (en) | Control of morphology of silica films | |
WO2009075371A1 (en) | Oxide film, coating solution for forming oxide film, optical member using the oxide film, and method of producing the optical member |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DPEN | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2004291564 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007148435 Country of ref document: US Ref document number: 10579654 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2006540084 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11444283 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2004291564 Country of ref document: AU Date of ref document: 20041122 Kind code of ref document: A |
|
WWP | Wipo information: published in national office |
Ref document number: 2004291564 Country of ref document: AU |
|
REEP | Request for entry into the european phase |
Ref document number: 2004797070 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2004797070 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 2004797070 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 11444283 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 10579654 Country of ref document: US |