EP1430001A2 - Verre a revetement superficiel poreux antireflechissant, et procede de fabrication d'un tel verre - Google Patents

Verre a revetement superficiel poreux antireflechissant, et procede de fabrication d'un tel verre

Info

Publication number
EP1430001A2
EP1430001A2 EP02799412A EP02799412A EP1430001A2 EP 1430001 A2 EP1430001 A2 EP 1430001A2 EP 02799412 A EP02799412 A EP 02799412A EP 02799412 A EP02799412 A EP 02799412A EP 1430001 A2 EP1430001 A2 EP 1430001A2
Authority
EP
European Patent Office
Prior art keywords
glass
particles
particle size
surface coating
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02799412A
Other languages
German (de)
English (en)
Inventor
Walther Glaubitt
Monika Kursawe
Andreas Gombert
Thomas Hofmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DUCATT NV
Original Assignee
Flabeg Solarglas GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Flabeg Solarglas GmbH and Co KG filed Critical Flabeg Solarglas GmbH and Co KG
Publication of EP1430001A2 publication Critical patent/EP1430001A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid 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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S80/00—Details, accessories or component parts of solar heat collectors not provided for in groups F24S10/00-F24S70/00
    • F24S80/50—Elements for transmitting incoming solar rays and preventing outgoing heat radiation; Transparent coverings
    • F24S80/52—Elements for transmitting incoming solar rays and preventing outgoing heat radiation; Transparent coverings characterised by the material
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C03C2217/732—Anti-reflective coatings with specific characteristics made of a single 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
    • C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers
    • 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

  • the invention relates to a glass provided with a porous antireflective surface coating based on Si0 2 particles. It also relates to a method for producing such a glass and to the use of such a glass.
  • multiple layers can be applied to the surface.
  • layers with a high and a low refractive index are applied alternately. Due to interference of the partial waves reflected at the respective interfaces between the materials with different refractive indices, these cancel each other out in a certain wavelength range, so that a particularly high-level transmission can be achieved for these wavelengths.
  • alternating layer systems are wavelength-selective and therefore not suitable for use in a broadband spectrum. Glasses coated in this way are therefore not suitable for covering, for example, solar collectors, in which the best possible introduction of light in the entire solar spectrum is important.
  • An alternative way to anti-reflective glass is to apply a single layer on the respective glass surface.
  • a particularly high transmission can be achieved for physical reasons if the surface layer has a refractive index equal to the root of the refractive index for glass, that is to say a refractive index of approximately 1.22.
  • the reflection for light with a wavelength of 4 times the layer thickness is almost zero, so that light of this wavelength is completely transmitted.
  • this is also particularly high for wavelengths that deviate from it.
  • a coating with a material is desired which has a refractive index as close as possible to 1, 22.
  • Such a surface coating of a glass can be produced on the one hand by selective etching of the glass. For example, by etching soda-lime glass with e.g. Hydrofluoric acid or hexafluorosilicic acid surface layers with a refractive index of about 1.27 can be produced, which already comes very close to the desired result.
  • the surface layers produced in this way also have comparatively good mechanical properties, in particular high mechanical abrasion resistance. Glasses manufactured in this way are therefore comparatively well suited for daily use.
  • a disadvantage of this manufacturing process is that the use of extremely environmentally harmful and aggressive acids is necessary, which requires a correspondingly high level of disposal and appropriate care when handling these materials.
  • a coating of glass can also be provided by the additive application of coating material.
  • coated glasses produced in this way have to meet high requirements with regard to the optical properties, in particular with regard to a comparatively small refractive index of as close as possible to 1, 22.
  • these glasses also have high demands on the mechanical properties of the coating, in particular on the resistance to abrasion, to make it suitable for daily use even in a comparatively adverse environment.
  • antireflective surface coatings based on Si0 2 particles have proven to be particularly suitable.
  • the antireflective surface coatings based on SiO 2 particles are usually porous, since only an acceptable low refractive index can be achieved due to the dilution of the coating material with air is.
  • Such porous anti-reflective surface coatings based on SiO 2 particles are usually characterized by more or fewer loose, joined SiO 2 particles of an essentially uniform particle size.
  • the coating of a glass with such a porous antireflective surface coating based on Si0 2 particles is usually carried out using so-called brine, in which [SIO ⁇ (OH) ⁇ ] n particles are mixed with solvents and possibly with a stabilizer.
  • brine in which [SIO ⁇ (OH) ⁇ ] n particles are mixed with solvents and possibly with a stabilizer.
  • coating solutions can be provided, into which the glass to be coated can be immersed, the layer-forming sol being deposited on the glass surface.
  • DE 199 18 811 A1 discloses the use of such a sol based on an alcohol-water mixture for producing a porous antireflective surface coating based on SiO 2 particles.
  • the antireflective surface coating produced in this way has comparatively good optical properties and is also sinter-stable, so that an antireflective surface coating applied in this way does not significantly deteriorate its optical properties even during subsequent thermal treatment of the coated glass, for example for the production of thermally toughened safety glass.
  • the abrasion resistance does not meet the requirements for continuous use.
  • the test shows the abrasion resistance according to DIN EN 1096-2 using the Crockmeter test that significant layer damage occurs after 10 cycles and very severe layer damage after 100 cycles.
  • brine based on aqueous systems containing less than 1% organic components can be used to produce a porous anti-reflective surface coating on a glass.
  • the surface layers which can be produced by using such surfactant-containing, essentially purely aqueous brine increase the solar transmission of a low-iron soda-lime glass coated therewith up to 95.3%, the antireflective surface coating having a refractive index of 1.29.
  • an antireflective surface coating produced in this way is mechanically very stable and abrasion-resistant, the abrasion resistance test using a crock meter test according to DIN EN 1096-2 showing only slight changes in the layer even after 100 cycles.
  • a disadvantage of the antireflection surface coatings produced in this way is, however, that layer-related inhomogeneities can occur due to the production process. In particular, there is a streaking in the optical appearance, which is due to periodic differences in layer thickness in the range of a few nanometers. Such controversies can be disruptive. In addition, the antireflection surface layers that can be produced by using such an aqueous sol give only insufficient optical results when coating prismatic glasses, the achievable transmittance being only about 93.6%.
  • the invention is therefore based on the object of specifying a glass provided with a porous antireflective surface coating based on Si0 2 particles which, on the one hand, has particularly good optical properties with regard to a high degree of transmission of light in the entire solar spectrum and, on the other hand, a particularly good one has high mechanical strength, in particular a particularly high mechanical abrasion resistance. Furthermore, a method for producing such a glass and a particularly favorable use of the glass are to be specified. With regard to glass, this object is achieved according to the invention in that the anti-reflective surface coating based on SiO 2 particles comprises at least two particle fractions which differ from one another in their characteristic particle size.
  • the structural structure of the antireflection surface coating should be particularly flexible.
  • Structural components or sub-components of the surface coating should be provided, each of which can be optimized specifically to meet one of the requirements mentioned.
  • a suitable parameter for differentiating between these different components, each of which can be optimized for a different requirement is the particle size of the SiO 2 particles.
  • comparatively small Si0 2 particles have a particularly high surface reactivity.
  • the SiO 2 particles with a comparatively small particle size therefore tend to aggregate or agglomerate, which in particular enables uniform layer thickness formation, particularly with regard to possible streak formation.
  • the comparatively small particles can be offered comparatively large particles for reaction.
  • the surface of the comparatively large Si0 2 particles is modified in such a way that they also tend to form layers with a particularly homogeneous layer thickness.
  • Such comparatively larger-sized Si0 2 particles which can be present in particular in the form of similar, round spheres or “monosphers”, make a particular contribution to the overall stability of the system, in particular to the stability of the framework and to the adherence of the surface layer to the underlying glass the combination of these comparatively large Si0 2 particles with the comparatively small Si0 2 particles is a deterioration in the opti- see properties practically avoided by using the comparatively large Si0 2 particles.
  • the at least two particle fractions with different characteristic particle sizes manifest themselves, for example, in a particle size distribution in the SiO 2 particles forming the antireflective surface coating, which has particularly significant contributions in at least two size ranges.
  • there are therefore two particle fractions with different characteristic particle sizes for example, if the particle size distribution in each of two particle size intervals is recognizably large, the area integral under the particle size distribution is comparatively large, and / or relative maxima occur in the particle size distribution.
  • the characteristic particle size of the respective particle fraction can then be defined, for example, by the maximum point in the respective particle size interval, by the mean value of the particle size distribution in the respective particle size interval or also by the mean value of the particle sizes in the respective particle size interval, the particles of each particle fraction having a certain distribution or bandwidth in their particle size around the characteristic particle size.
  • the surface coating therefore advantageously has a first particle fraction with particle sizes in the range from 4 nm to 15 nm.
  • the surface coating has a second particle fraction with an average particle size of 20 to 60 nm, the standard deviation of the particle size distribution of this particle fraction preferably being at most 20%.
  • a comparatively large number of small-sized Si0 2 particles are expediently combined with a comparatively small number of larger-sized Si0 2 particles.
  • the surface coating has a ratio of the number of particles of the first fraction to the number of particles of the second fraction of 3000: 1 to 100: 1, preferably 1000: 1 to 250: 1.
  • the coated glass is designed as a so-called toughened safety glass.
  • safety glass is characterized by the fact that in the event of a glass break it does not break up into comparatively large, sharp-edged fragments, but rather into a large number of comparatively small, blunt-edged fragments.
  • the design of the glass as such safety glass can be achieved by a so-called thermal prestress, the glass first being heated to temperatures of at least 600 ° C. and then thermally quenched, for example by blowing with air.
  • the actual tempering process can be carried out using conventional tempering methods.
  • the so-called vertical pretensioning technology the so-called horizontal pretensioning technology in the continuous process or the so-called horizontal pretensioning technology in the oscillation process can be used in particular.
  • the glass can be exposed to radiant heating and / or convection heating in a furnace area, temperatures of about 700 ° C. usually being set in the furnace area.
  • tempering the glass usually remains in the furnace area until the softening point is reached.
  • glass with a glass thickness of approximately 4 mm is usually heated to at least 600 ° C. for approximately 160 seconds.
  • the glass in an adjacent segment of a tempering system is evenly blown with air from both sides via regularly arranged air nozzles. The glass is cooled to temperatures of up to about 40 ° C.
  • the heated glass can also be subjected to a shaping process before thermal quenching.
  • the heated glass can be bent prior to quenching, so that curved glasses, such as for applications as automotive windshields, are available.
  • a glass with the properties mentioned can be obtained in a particularly favorable manner by depositing a hybrid sol specifically designed for the properties to be set, expediently on a conventional soda-lime glass, but for example also on a borosilicate glass.
  • the hybrid sol aimed at providing the porous anti-reflective surface coating expediently comprises [SiO x (OH) y ] n particles, where 0 ⁇ y ⁇ 4 and 0 ⁇ x ⁇ 2, and where the particles are a first particle fraction with a comprise first particle size range and a second particle fraction with a second particle size range, and furthermore contains water and 2 to 97% by weight of solvent, in a preferred embodiment it can contain 15 to 30% by weight of solvent, 40 to 70% by weight Stabilizer and 10 to 35 wt .-% water included.
  • the hybrid sol used to produce the antireflective surface coating thus comprises a mixture of large and small SiO 2 particles, from which the two coating portions tailored to the task result when deposited on the actual glass.
  • the hybrid sol is advantageously obtainable by hydrolytic polycondensation of a tetraalkoxysilane in an aqueous solvent-containing medium, a hydrolysis mixture with silicon oxide hydroxide particles having a particle size of 4-15 nm being obtained, and addition of a monodisperse silicon oxide hydroxide sol with egg - An average particle size of 20-60 nm and a standard deviation of at most 20%, at a time of at least 5 minutes after the addition of the tetraalkoxysilane in the aqueous solvent-containing medium.
  • the hybrid sol can therefore essentially be provided by a suitable combination of two different brines, but a simple mixture of these sol components is not sufficient to achieve the combination effect.
  • the intended effect of the mutual influencing of the particle fractions is particularly dependent on the fact that a suitable time for bringing together the comparatively large Si0 2 particles with the comparatively small, reactive SiO 2 particles is selected.
  • the particle size of the first fraction of particles of the hybrid sol is advantageously in order to adjust particularly suitable and favorable properties Range from 4 nm to 15 nm selected.
  • the second particle size is advantageously on average 20 to 60 nm with a standard deviation of 20%.
  • the weight ratio of the small particle fraction to the large particle fraction in the hybrid sol is advantageously 25: 1 to 1: 5, preferably 10: 1 to 2: 1, particularly preferably 3: 1 to 2: 1.
  • the concentration of the SiO 2 particles in the hybrid sol is advantageously between 0.3 and 4% by weight, preferably between 1 and 2% by weight.
  • Lower aliphatic alcohols such as, for example, ethanol or i-propanol, but also ketones, preferably 0 lower dialkyl ketones, such as acetone or methyl isobutyl ketone, ether, preferably lower dialkyl ethers, such as diethyl ether or dibutyl ether, tetrahydrofuran, amides, esters, can be used as solvents when providing the hybrid sol , in particular ethyl acetate, dimethylformamide, amines, in particular triethylene and their mixtures, are used.
  • ketones preferably 0 lower dialkyl ketones, such as acetone or methyl isobutyl ketone
  • ether preferably lower dialkyl ethers, such as diethyl ether or dibutyl ether, tetrahydrofuran, amides, esters
  • solvents when providing the hybrid sol , in particular ethyl acetate, dimethylformamide, amines,
  • alcohols are used as solvents, in particular ethanol, methanol, i-propanol, n-propanol.
  • the amount of solvent used depends on the amount of silicon compounds used as the starting material.
  • the concentration of the solvent in the hybrid sol is between 2 and 97% by weight, preferably 15 to 30% by weight.
  • Glycol ethers or ethers of other alcohols with two or more hydroxyl groups in a concentration of 10 to 95, preferably 40 to 70% by weight can be used as stabilizers in the hybrid sol. 1,2-propylene glycol monomethyl ether is preferably used.
  • the objective of the method for producing the glass is achieved by coating a conventional soda-lime glass with a coating solution comprising the hybrid sol and then subjecting it to a drying step.
  • the drying preferably takes place under relatively constant climatic conditions and is preferably carried out in an air atmosphere at a temperature of about 20 ° C to 25 ° C, advantageously at about 22 ° C, and at a relative humidity of 55% 0 to 65%, advantageously of 60%.
  • the use of the hybrid sol mentioned as the base material for the coating of the glass This and, if the parameters mentioned are observed, an antireflective surface coating can be produced in the glass during the drying step, which on the one hand has the desired at least two particle fractions.
  • the coating produced in this way also has a special structural stability and a particularly high bond to the glass substrate even without further aftertreatment, as is the case, for example, for thermal prestressing following the actual coating of the glass may be required.
  • the use of the hybrid sol mentioned as a starting material for the production of the antireflective surface coating ensures that the surface coating has the particle size distribution, which is designed specifically for the task and needs, with preferably at least two areas.
  • the subsequent drying step in compliance with the parameters mentioned, leads to the fact that the surface coating has a particularly high mechanical stability and a particularly resilient connection to the glass substrate, even without the need for thermal aftertreatment measures . Contrary to the previous view that when applying an anti-reflective coating based on SiO 2 particles on a glass substrate to cross-link the silica network and to better connect to the substrate, thermal treatment or exposure to temperature is absolutely necessary for the purpose of thermal solidification , this can now also be achieved without a further thermal treatment step.
  • the glass is particularly suitable for use as a cover for a solar collector or a photovoltaic cell.
  • a covering window of a greenhouse is provided with a window base plate, which is designed in a particularly advantageous development for particularly high transparency or translucency.
  • the window base plate designed as a glass plate advantageously has an anti-reflective surface coating of the type mentioned.
  • the glass plate expediently has an antireflective surface coating with a refractive index of approximately 1.25 to 1.40, advantageously 1.25 to 1.38.
  • the anti-reflective surface coating is applied in a particularly advantageous embodiment on the side of the glass plate provided as the inside of the greenhouse.
  • the Si0 2 coating thus preferably points into the interior of the greenhouse, so that moisture which precipitates there can be removed particularly reliably and in a controlled manner.
  • the glass plate of the cover window can of course also be provided on both sides with such an SiO 2 coating, so that the overall achievable transmittance is particularly high.
  • the roofing window is preferably used in a greenhouse, the greenhouse being equipped with a number of window elements forming roof or side walls, at least one of which is designed as such roofing window.
  • the advantages achieved by the invention consist in particular in that the at least two prevailing particle sizes in the antireflective surface coating in the manner of a binary system or a bimodal particle size distribution make it possible to achieve particular flexibility in the targeted optimization to the divergent specifications.
  • the anti-reflective surface coating can in particular be set in such a way that both particularly high-quality optical and particularly favorable mechanical properties are present, in particular with regard to high abrasion resistance.
  • the coated glass is advantageously used for covering solar energy systems, in particular solar collectors, for motor vehicle windows, for window or building glazing, or in particular also for covering greenhouses.
  • an abrasion resistance according to DIN EN 1096-2 can be achieved, with which with a test weight of 400g even after 100 strokes no damage Coating can be determined.
  • the anti-reflective surface coating also has a particularly homogeneous appearance without a recognizable stripe structure.
  • the anti-reflective surface coating can also be used for prismatic or otherwise structured glass while maintaining its particularly good optical properties.
  • FIG. 2 shows a top view of the coated surface of the glass according to FIG. 1,
  • FIG. 3 shows a diagram of the particle size distribution of the surface coating of the glass according to FIG. 1, and FIG. 4 schematically shows a greenhouse with a number of window elements.
  • the glass 1 is intended for use as a cover glass for a solar collector, a photovoltaic module or as a covering window for a greenhouse.
  • the glass 1 is designed for broadband particularly high light transmission, with a comparatively high transmission being aimed for essentially all wavelengths of the solar spectrum.
  • the glass 1 has a porous antireflective surface coating 2 based on SiO 2 particles, which are applied to a glass substrate 4, expediently on both sides.
  • the antireflective surface coating 2 namely comprises, in the manner of two subsystems, a combination of a first fraction of SiO 2 particles with a second fraction of SiO 2 particles, the two fractions differing from one another in terms of their particle size.
  • the first fraction comprises Si0 2 particles with a particle size in the range from about 4 to 15 nm
  • the second fraction has SiO 2 particles with an average particle size of about 35 nm with a standard deviation of at most 20%.
  • a supramolecular network 6 composed of small SiO 2 particles with an average particle size of 4 nm to 15 nm.
  • spherical SiO 2 particles 8 Embedded in this supramolecular network 6 are spherical SiO 2 particles 8 with an average particle size of 20 nm to 60 nm in the manner of a second fraction.
  • a combination of these two fractions results in high abrasion resistance with a particularly aesthetic appearance of the layer.
  • the antireflection surface coating 2 in the present exemplary embodiment has a particle size distribution, as is shown schematically in the diagram in FIG. 3.
  • the particle size distribution has a first particle size range 10 between approximately 4 nm and approximately 15 nm, which is occupied by a comparatively high number of particles.
  • a second particle size range 12 which is also occupied by a significant number of particles, and in which the particle size distribution can be described in the exemplary embodiment approximated by a Gaussian 'sche distribution with a standard deviation of about 15%.
  • the particle size range 12 can be the second characteristic
  • Particle size for example, the maximum of the Gaussian distribution, that is to say a value of approximately 35 nm.
  • the targeted combination of the two fractions of SiO 2 particles is particularly useful due to the particle size ranges 10, 12.
  • the number of particles attributable to the first particle fraction dominates far more than the number of particles attributable to the second particle fraction.
  • the ratio of the number of particles of the first particle fraction to the number of particles of the second particle fraction is approximately 500.
  • the glass substrate 4 is first coated with a hybrid sol specifically designed to provide the at least two-component surface coating 2.
  • the hybrid sol in turn is produced according to the following procedure.
  • a tetraalkoxysilane is placed in an aqueous solvent-containing medium, the hydrolytic polycondensation starting.
  • the process is carried out essentially in accordance with DE 196 42 419 and with thorough mixing.
  • a basic catalyst for the hydrolytic polycondensation, which shortens the reaction times, can optionally also be added to this mixture.
  • Ammonia is preferably used.
  • the solvents contained in the hydrolysis mixture can be selected from the solvents already mentioned above. Ethanol, methanol, i-propanol, n-propanol and very particularly preferably ethanol are preferably used.
  • the hydrolysis takes place at temperatures of 5 to 90 ° C., preferably 10 to 30 ° C.
  • the small silicon oxide hydroxide particles with a particle size of 4 - 15 nm are formed from the tetraalkoxysilane used.
  • the hydrolysis mixture is mixed intensively over a period of at least 5 minutes, for example by stirring.
  • a sol of monodisperse silicon oxide hydroxide particles having an average particle size of 20 to 60 nm and a standard deviation of at most 20% is then added to the hydrolysis mixture described above.
  • the time until the silicon oxide hydroxide sol from monodisperse particles is added to the hydrolysis mixture depends on the use of condensation catalysts for the hydrolytic condensation of the silicon compounds.
  • the monodisperse silicon oxide hydroxide sol is added to this mixture at the earliest 5 minutes after the addition of the tetraalkoxysilane into the aqueous hydrolysis mixture containing solvents.
  • the time of this addition can be delayed up to 48 hours after the addition of the tetraalkoxysilane in the hydrolysis mixture. This time is preferably 5 minutes to 24 hours after the start of the formation of silicon oxide hydroxide particles having a particle size of 4 -15 nm.
  • a time frame of 20 to 180 minutes after the start of the reaction is particularly preferred.
  • the time at which the silicon oxide hydroxide sol from monodisperse particles is added to the hydrolysis mixture crucially determines the properties of the hybrid sol according to the invention. In this way, a statistical distribution of the monodisperse particles in the small silicon oxide hydroxide particles is achieved and an accumulation of the monodisperse particles in the sense of "island formation" is avoided, which would lead to poor abrasion stability.
  • the monodisperse silicon oxide hydroxide sol is preferably added to the hydrolysis mixture in one portion.
  • the silicon oxide hydroxide sol is produced from monodisperse particles by the process described in US Pat. No. 4,775,520.
  • the tetraalkoxysilane is brought into an aqueous-alcoholic-ammoniacal hydrolysis mixture and mixed thoroughly, primary silicon oxide hydroxide particles being produced.
  • Suitable tetraalkoxysilanes which can be used are all readily hydrolyzable ortho esters of aliphatic alcohols.
  • the esters of aliphatic alcohols with 1-5 C atoms, such as methanol, ethanol, n- or i-propanol and the isomeric butanols and pentanols, are primarily considered here. These can be used individually or in a mixture.
  • silicic acid orthoesters of the CrC 3 alcohols in particular tetraethoxysilane.
  • Aliphatic Ci-Cs alcohols preferably C 1 -C 3 alcohols such as methanol, ethanol and n- or i-propanol are suitable as the alcohol component. These can be present individually or in a mixture with one another.
  • the tetraalkoxysilane is preferably added to the mixture in one portion, it being possible for the reactant to be present in pure form or in solution in one of the alcohols mentioned.
  • a concentration of tetraalkoxysilane in the reaction mixture between about 0.01 and about 1 mol / l can be selected. After the reactants have been brought together, the reaction starts immediately or after a few minutes, which is shown by an immediate opalescence of the reaction mixture by the resulting particles.
  • the hydrolysis mixture which contains primary silicon oxide hydroxide particles, is then continuously mixed with further tetraalkoxysilane in such a way that essentially no new silicon oxide hydroxide particles are formed. Rather, the primary silicon oxide hydroxide particles already present grow into larger, monodisperse particles.
  • particles with an average particle size between 20 nm and 60 nm and with a standard deviation of at most 20% can be obtained. It has proven to be advantageous to carry out the reaction to generate these particles at a higher temperature. Temperatures between 35 ° C. and 80 ° C., preferably between 40 ° C. and 70 ° C., are favorable. It was found that the particle size scatter decreases at elevated temperature, but also the mean particle size. At lower temperatures, ie around room temperature, larger particles with larger size scatter are obtained under otherwise identical conditions.
  • a further increase in the stability of the monodisperse silicon oxide hydroxide sol may make it necessary to remove alcohol and / or ammonia from the sol. This is done according to the known methods according to the prior art, for example by increasing the temperature to remove the volatile ammonia.
  • particles are referred to as monodisperse which have a standard deviation of at most 20%, in particular of at most 15% and particularly preferably of at most 12% and which are essentially in the form of discrete particles.
  • the silicon oxide hydroxide sol made of monodisperse particles is added to the hydrolysis mixture.
  • this mixing is continued for a period of 1 minute to 48 hours, preferably 10 minutes to 5 hours.
  • a stabilizer can be added to the hybrid sol.
  • Glycol ethers or ethers of other alcohols, for example, are used as stabilizers.
  • 1,2-propylene glycol 1-monomethyl ether is preferably used.
  • the stabilized sol mixture is then intensively mixed over a period of 1 minute to 24 hours, preferably 5 minutes to 1 hour.
  • the resulting hybrid sol can then be filtered.
  • the desired sol is obtained, which can be used for further use.
  • the hybrid sol can be prepared according to the following examples:
  • the hybrid sol obtained in this way is applied to the glass substrate 4 in order to produce the glass 1.
  • the hybrid sol can be kept in a coating solution into which the glass substrate 4 is immersed.
  • a dip coating also referred to as dip coating
  • a spray method or a rotary coating method also referred to as spin coating, can also be used.
  • the glass substrate 4 can be a glass pane with dimensions of approximately 1 that has previously been cleaned with demineralized water and then dried Meter by 1 meter and a thickness of 4 mm are immersed in the coating solution. This is pulled out of the coating solution at a constant drawing speed of 5.5 mm / s.
  • the glass substrate 4 coated in this way is then subjected to a drying step in an air atmosphere.
  • the coated glass substrate 4 is dried at a temperature of approximately 22 ° C. and at a relative atmospheric humidity of approximately 60%. This drying can be done either by simply standing and venting or by blowing with air.
  • an abrasion-resistant surface coating 2 with very good optical properties and special mechanical stability is produced in this drying step, which, when viewed from above, roughly corresponds to the pattern shown in FIG. 2, that is to say in particular a combination of two particle fractions with a clearly distinguishable average particle size , having.
  • no further thermal treatment of the coated glass 1 obtained in this way is necessary, for example in order to obtain sufficient mechanical strength or abrasion resistance.
  • the glass 1 is designed as a toughened safety glass. Because of the particularly favorable properties of the surface coating 2, which in fact does not require a subsequent further thermal treatment after the actual coating, the thermal prestressing is already carried out on the uncoated glass substrate 4. However, the prestressing could also take place after the coating.
  • a conventional prestressing method is used for the prestressing, vertical prestressing technology, horizontal prestressing technology in the continuous process or horizontal prestressing technology in the oscillation process being able to be used.
  • the glass substrate 4 is heated in a furnace area to a temperature of 700 ° C., whereby radiant heating and / or convection heating can be used.
  • the glass substrate 4 remains sufficiently long in the furnace area until the reaching point is reached.
  • the glass substrate 4 is heated, for example, to at least 600 ° C. for about 160 seconds.
  • the heated glass substrate 4 is quenched, the glass substrate 4 being blown off uniformly with air, for example, from both sides via regularly arranged air nozzles.
  • the glass substrate 4 is cooled to temperatures up to 40 ° C. During this thermal pretreatment in order to achieve a pretension, the glass substrate 4 can also be subjected to a shaping process, for example bent. If glass 1 has not already been coated, the glass substrate 4 is then exposed to the surface layer 2 in the manner described, after the tempering process has been completed.
  • the thermally toughened and coated glass 1 produced in this way is particularly suitable on the one hand for use as a cover for a solar collector, a photovoltaic module or other optically sensitive elements, and on the other hand also for use in a roof window of a greenhouse 20, as is shown schematically in FIG. 4 is shown.
  • the greenhouse 20 according to FIG. 4 comprises a number of window elements 22 which form roof or side walls, which in their entirety form the outer wall of the greenhouse 20 and which, depending on the intended use, can be designed to be fixed or foldable.
  • the window elements 22 are held by a scaffold frame 24 for mechanical stabilization; alternatively, the window elements 22 can also be designed in the manner of a self-supporting version without an independent tubular frame.
  • the window elements 22 forming the envelope or outer surface of the greenhouse 20 As with a corresponding use in other buildings or in technical devices such as solar collectors, different requirements can be placed on the transparency of the respective components. For example, these requirements may vary depending on the time of day and season. Moreover, covering materials for greenhouses and solar collectors are usually expected to be as transparent as possible. Therefore, the window elements 22 are designed for an overall particularly high transparency, which enables a particularly high daylight yield in the interior of the greenhouse 20 and thus a particularly low product-specific energy requirement in plant cultivation.
  • the or each window element 22 is provided with a glass plate as the window base plate, which is designed as an anti-reflective coated glass 1.
  • the window base plate is designed as a thermally hardened safety glass.
  • the Si0 2 -Be- Stratifications have a refractive index of about 1.25 for setting a particularly high transparency.

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Abstract

L'invention concerne un verre (1)-muni d'un revêtement superficiel poreux antiréfléchissant (2), à base de particules de SiO2 et a pour but d'obtenir un verre de ce type présentant, d'une part, d'excellentes propriétés optiques eu égard à un degré élevé de transmission de la lumière dans l'ensemble du spectre solaire et, d'autre part, une résistance mécanique particulièrement élevée, en particulier, une haute résistance mécanique à l'usure par frottement. A cet effet, l'invention est caractérisée en ce que ledit revêtement superficiel antiréfléchissant (2) à base de particules de- SiO2 présente au moins deux fractions de particules ayant des granulométries caractéristiques différentes. Pour la production d'un tel verre revêtu (1), on enduit un substrat en verre (4) d'un sol hybride dont les particules de [SiOx(OH)y]n comprennent une première fraction de particules d'une première granulométrie et une seconde fraction de particules d'une seconde granulométrie.
EP02799412A 2001-09-21 2002-09-19 Verre a revetement superficiel poreux antireflechissant, et procede de fabrication d'un tel verre Withdrawn EP1430001A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10146687A DE10146687C1 (de) 2001-09-21 2001-09-21 Glas mit einer porösen Antireflex-Oberflächenbeschichtung sowie Verfahren zur Herstellung des Glases und Verwendung eines derartigen Glases
DE10146687 2001-09-21
PCT/EP2002/010495 WO2003027034A2 (fr) 2001-09-21 2002-09-19 Verre a revetement superficiel poreux antireflechissant, et procede de fabrication d'un tel verre

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EP1430001A2 true EP1430001A2 (fr) 2004-06-23

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EP02799412A Withdrawn EP1430001A2 (fr) 2001-09-21 2002-09-19 Verre a revetement superficiel poreux antireflechissant, et procede de fabrication d'un tel verre

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US (1) US7575809B2 (fr)
EP (1) EP1430001A2 (fr)
JP (1) JP4435566B2 (fr)
AU (1) AU2002362546A1 (fr)
DE (1) DE10146687C1 (fr)
WO (1) WO2003027034A2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011157820A1 (fr) 2010-06-18 2011-12-22 Dsm Ip Assets B.V. Revêtement d'oxyde inorganique
WO2012107392A1 (fr) 2011-02-11 2012-08-16 Dsm Ip Assets B.V. Procédé de dépôt de couche antireflet sur un substrat
WO2013174754A2 (fr) 2012-05-22 2013-11-28 Dsm Ip Assets B.V. Composition et procédé pour la formation d'un revêtement d'oxyde inorganique poreux
WO2014023716A1 (fr) 2012-08-09 2014-02-13 Dsm Ip Assets B.V. Processus et appareil de revêtement au rouleau

Families Citing this family (94)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2002333388A1 (en) 2001-08-11 2003-02-24 Flabeg Solarglas Gmbh And Co Kg Heat insulating element
IL149236A0 (en) * 2002-04-21 2002-11-10 Solel Solar Systems Ltd Casing for solar collecting system
DE102004019575A1 (de) * 2004-04-20 2005-11-24 Innovent E.V. Technologieentwicklung Verfahren zur Herstellung von transmissionsverbessernden und/oder reflexionsmindernden optischen Schichten
DE102005020168A1 (de) * 2005-04-28 2006-11-02 Schott Ag Entspiegelungsschicht und Verfahren zu deren Aufbringung
US20070074757A1 (en) * 2005-10-04 2007-04-05 Gurdian Industries Corp Method of making solar cell/module with porous silica antireflective coating
US20070116934A1 (en) * 2005-11-22 2007-05-24 Miller Scott M Antireflective surfaces, methods of manufacture thereof and articles comprising the same
US20070115554A1 (en) * 2005-11-22 2007-05-24 Breitung Eric M Antireflective surfaces, methods of manufacture thereof and articles comprising the same
US8153282B2 (en) * 2005-11-22 2012-04-10 Guardian Industries Corp. Solar cell with antireflective coating with graded layer including mixture of titanium oxide and silicon oxide
US20070113881A1 (en) * 2005-11-22 2007-05-24 Guardian Industries Corp. Method of making solar cell with antireflective coating using combustion chemical vapor deposition (CCVD) and corresponding product
DE102006041469B3 (de) 2006-09-02 2008-01-31 Schott Ag Verfahren und Beschichtungslösung zur Herstellung einer wischfesten Antireflexionsschicht auf einem Borosilikatglaskörper
US20080072956A1 (en) * 2006-09-07 2008-03-27 Guardian Industries Corp. Solar cell with antireflective coating comprising metal fluoride and/or silica and method of making same
FR2908406B1 (fr) 2006-11-14 2012-08-24 Saint Gobain Couche poreuse, son procede de fabrication et ses applications.
US7767253B2 (en) 2007-03-09 2010-08-03 Guardian Industries Corp. Method of making a photovoltaic device with antireflective coating
DE102007017241A1 (de) * 2007-04-12 2008-10-16 Robert Bosch Gmbh Fahrzeugscheibe
US8237047B2 (en) * 2007-05-01 2012-08-07 Guardian Industries Corp. Method of making a photovoltaic device or front substrate for use in same with scratch-resistant coating and resulting product
US20080295884A1 (en) * 2007-05-29 2008-12-04 Sharma Pramod K Method of making a photovoltaic device or front substrate with barrier layer for use in same and resulting product
DE102007025590A1 (de) 2007-05-31 2008-12-04 Ferro Gmbh Einbrennbare siebdruckfähige Antireflexbeschichtung für Glas
US8450594B2 (en) * 2007-07-26 2013-05-28 Guardian Industries Corp. Method of making an antireflective silica coating, resulting product and photovoltaic device comprising same
US8445774B2 (en) * 2007-07-26 2013-05-21 Guardian Industries Corp. Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same
DE102007039164A1 (de) 2007-08-20 2009-02-26 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Mit einer staub- und aerosolabweisenden Beschichtung versehene Substrate, Verfahren zur Herstellung derselben und Materialien dafür
US20090075092A1 (en) * 2007-09-18 2009-03-19 Guardian Industries Corp. Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same
US20090101209A1 (en) * 2007-10-19 2009-04-23 Guardian Industries Corp. Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same
US20110019277A1 (en) * 2007-11-08 2011-01-27 Sager Brian M anti-reflective coating
US8319095B2 (en) * 2007-11-27 2012-11-27 Guardian Industries Corp. Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same
US8114472B2 (en) * 2008-01-08 2012-02-14 Guardian Industries Corp. Method of making a temperable antiglare coating, and resulting products containing the same
US20090181256A1 (en) * 2008-01-14 2009-07-16 Guardian Industries Corp. Methods of making silica-titania coatings, and products containing the same
DE102008005283B4 (de) * 2008-01-19 2009-10-29 Schott Solar Gmbh Verfahren zur Herstellung einer mit einem transparenten, Metalloxid beschichtetn Glasscheibe für ein photovoltaisches Modul und eine solche beschichtete Glasscheibe
DE102008006785B3 (de) * 2008-01-30 2009-06-10 Schott Ag Verfahren zur Herstellung einer wischfesten Antireflexionsschicht auf einem Borosilicatglaskörper und Verwendung des beschichteten Glaskörpers zur Herstellung von Lampenkolben von Entladungslampen
EP2124247A1 (fr) * 2008-05-20 2009-11-25 CENTROSOLAR Glas GmbH & Co. KG Unité d'éclairage pour un affichage et procédé de fabrication d'une chambre d'éclairage pour une unité d'éclairage
US8668961B2 (en) * 2008-07-31 2014-03-11 Guardian Industries Corp. Titania coating and method of making same
EP2151466A1 (fr) * 2008-08-01 2010-02-10 SiNatur GmbH Acide silicique actif biologiquement
DE102009008141A1 (de) 2009-02-09 2010-08-19 Saint-Gobain Sekurit Deutschland Gmbh & Co. Kg Transparenter Glaskörper, Verfahren zu dessen Herstellung und dessen Verwendung
JP5819198B2 (ja) 2009-02-12 2015-11-18 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフトＢａｙｅｒ ＭａｔｅｒｉａｌＳｃｉｅｎｃｅ ＡＧ 反射防止／防曇コーティング
US9376593B2 (en) 2009-04-30 2016-06-28 Enki Technology, Inc. Multi-layer coatings
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
DE102009023512B4 (de) * 2009-05-30 2020-08-06 Devine Gmbh & Co. Kg Solarkollektor zur Gewinnung von Wärme und elektrischer Energie
US8557877B2 (en) 2009-06-10 2013-10-15 Honeywell International Inc. Anti-reflective coatings for optically transparent substrates
DE102009035797A1 (de) * 2009-07-31 2011-02-03 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Verfahren zur Herstellung von Beschichtungen mit Antireflexionseigenschaften
DE102009042159B4 (de) * 2009-09-11 2017-09-28 Schott Ag Verfahren zur Verbesserung der tribologischen Eigenschaften einer Glasoberfläche
US8617641B2 (en) * 2009-11-12 2013-12-31 Guardian Industries Corp. Coated article comprising colloidal silica inclusive anti-reflective coating, and method of making the same
GB0922407D0 (en) 2009-12-22 2010-02-03 Pilkington Group Ltd Coated substrate
GB0922395D0 (en) 2009-12-22 2010-02-03 Pilkington Group Ltd Deposition process
US9272949B2 (en) 2010-07-09 2016-03-01 Guardian Industries Corp. Coated glass substrate with heat treatable ultraviolet blocking characteristics
CN103403073B (zh) * 2011-02-03 2015-10-14 3M创新有限公司 硬涂膜
US8864898B2 (en) 2011-05-31 2014-10-21 Honeywell International Inc. Coating formulations for optical elements
US20120312295A1 (en) * 2011-06-08 2012-12-13 Conley Gary D Solar thermal collection apparatus and methods
US9938185B2 (en) 2012-07-02 2018-04-10 Owens-Brockway Glass Container Inc. Antireflective coating for glass containers
CN102718412B (zh) * 2012-07-11 2014-11-19 哈尔滨工业大学 二维有序六方紧密堆积结构SiO2膜的制备方法
WO2014022609A1 (fr) * 2012-08-01 2014-02-06 Ferro Corporation Nanocouche influençant la lumière
US9499434B1 (en) 2012-08-31 2016-11-22 Owens-Brockway Glass Container Inc. Strengthening glass containers
DE102013010105A1 (de) 2013-06-18 2014-12-18 Ferro Gmbh Verfahren zur Herstellung einer wässrigen Zusammensetzung umfassend ein Kondensat auf Basis von Silicium-Verbindungen zur Herstellung von Antireflexionsbeschichtungen
US9840639B2 (en) 2014-03-27 2017-12-12 Innosense Llc Hydrophilic anti-fog coatings
US9598586B2 (en) 2014-07-14 2017-03-21 Enki Technology, Inc. Coating materials and methods for enhanced reliability
US9382449B2 (en) 2014-09-19 2016-07-05 Enki Technology, Inc. Optical enhancing durable anti-reflective coating
US9376589B2 (en) 2014-07-14 2016-06-28 Enki Technology, Inc. High gain durable anti-reflective coating with oblate voids
EP3194502A4 (fr) 2015-04-13 2018-05-16 Honeywell International Inc. Formulations de polysiloxane et revêtements pour applications optoélectroniques
JP2019511447A (ja) 2016-03-09 2019-04-25 コーニング インコーポレイテッド 複雑に湾曲したガラス物品の冷間成形
CN115570743A (zh) 2016-06-28 2023-01-06 康宁公司 将薄强化玻璃层压到用于装饰和显示器盖应用的曲面成型塑料表面
KR102434980B1 (ko) 2016-07-05 2022-08-22 코닝 인코포레이티드 냉간-형성 유리 물품 및 그의 조립 방법
KR102429148B1 (ko) 2016-10-25 2022-08-04 코닝 인코포레이티드 디스플레이에 냉간-성형 유리 적층
US10712850B2 (en) 2017-01-03 2020-07-14 Corning Incorporated Vehicle interior systems having a curved cover glass and a display or touch panel and methods for forming the same
EP3978236A1 (fr) * 2017-01-03 2022-04-06 Corning Incorporated Système d'intérieur de véhicule
US11016590B2 (en) 2017-01-03 2021-05-25 Corning Incorporated Vehicle interior systems having a curved cover glass and display or touch panel and methods for forming the same
US11685684B2 (en) 2017-05-15 2023-06-27 Corning Incorporated Contoured glass articles and methods of making the same
CN111094050B (zh) 2017-07-18 2023-11-07 康宁公司 复杂弯曲玻璃制品的冷成型
CN111356662B (zh) 2017-09-12 2022-10-04 康宁公司 用于装饰玻璃上的包括触摸面板的显示器的死前端及相关方法
US11065960B2 (en) 2017-09-13 2021-07-20 Corning Incorporated Curved vehicle displays
TWI806897B (zh) 2017-09-13 2023-07-01 美商康寧公司 用於顯示器的基於光導器的無電面板、相關的方法及載具內部系統
TWI844520B (zh) 2017-10-10 2024-06-11 美商康寧公司 具有改善可靠性的彎曲的覆蓋玻璃的車輛內部系統及其形成方法
WO2019103469A1 (fr) 2017-11-21 2019-05-31 Corning Precision Materials Co., Ltd. Miroir asphérique pour système d'affichage tête haute et ses procédés de formation
KR102605341B1 (ko) 2017-11-30 2023-11-24 코닝 인코포레이티드 곡선형 미러를 성형하기 위한 진공 몰드 장치, 시스템, 및 방법
US11767250B2 (en) 2017-11-30 2023-09-26 Corning Incorporated Systems and methods for vacuum-forming aspheric mirrors
CN111989302B (zh) 2018-03-13 2023-03-28 康宁公司 具有抗破裂的弯曲覆盖玻璃的载具内部系统及用于形成这些载具内部系统的方法
CN112566782A (zh) 2018-07-16 2021-03-26 康宁公司 具冷弯玻璃基板的车辆内部系统及其形成方法
EP3771695A1 (fr) 2019-07-31 2021-02-03 Corning Incorporated Procédé et système pour verre formé à froid
GB201910980D0 (en) 2019-08-01 2019-09-18 Pilkington Group Ltd coated Substrate
GB201910988D0 (en) 2019-08-01 2019-09-18 Pilkington Group Ltd Touchenable coated substrate
GB201910976D0 (en) 2019-08-01 2019-09-18 Pilkington Group Ltd Toughenable coated substrate
CN110451815A (zh) * 2019-08-07 2019-11-15 杭州杭科光电集团股份有限公司 一种古典曲线形led灯丝灯用增透膜的制备方法
FR3101014B1 (fr) 2019-09-20 2021-12-31 Saint Gobain Vitrage feuillete de vehicule et dispositif avec systeme de vision proche infrarouge associe
FR3105943B1 (fr) 2020-01-03 2023-05-19 Saint Gobain Vitrage feuillete de vehicule et dispositif avec systeme de vision proche infrarouge associe et sa fabrication
FR3105942B1 (fr) 2020-01-03 2021-12-31 Saint Gobain Vitrage feuillete de vehicule et dispositif avec systeme de vision proche infrarouge associe et sa fabrication
FR3107056B1 (fr) 2020-02-06 2023-01-20 Saint Gobain Vitrage à couches et sa fabrication
US11772361B2 (en) 2020-04-02 2023-10-03 Corning Incorporated Curved glass constructions and methods for forming same
FR3116758B1 (fr) 2020-12-01 2022-11-18 Saint Gobain Vitrage feuillete de vehicule et dispositif avec systeme de vision proche infrarouge associe
FR3121873A1 (fr) 2021-04-14 2022-10-21 Saint-Gobain Glass France Vitrage feuillete de vehicule, dispositif avec systeme de detection proche infrarouge associe
FR3120012B1 (fr) 2021-02-19 2023-12-29 Saint Gobain Vitrage feuillete de vehicule, sa fabrication et dispositif avec systeme de vision proche infrarouge associe
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FR3130684B1 (fr) 2021-12-22 2024-02-16 Saint Gobain Vitrage feuillete de vehicule et dispositif avec systeme de vision proche infrarouge associe
CN115226396A (zh) 2021-02-19 2022-10-21 法国圣戈班玻璃厂 层压窗玻璃、具有近红外视觉系统的相关设备
WO2022175634A1 (fr) 2021-02-19 2022-08-25 Saint-Gobain Glass France Vitrage feuillete de vehicule, sa fabrication et dispositif avec systeme de vision proche infrarouge associe
FR3121235B1 (fr) 2021-03-24 2023-12-29 Saint Gobain Vitrage de vehicule et dispositif avec systeme de vision proche infrarouge associe
CN114716153B (zh) * 2022-04-14 2023-06-02 常州亚玛顿股份有限公司 一种增透防眩光镀膜玻璃

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3616133A1 (de) * 1985-09-25 1987-11-19 Merck Patent Gmbh Kugelfoermige sio(pfeil abwaerts)2(pfeil abwaerts)-partikel
DE3534143A1 (de) * 1985-09-25 1987-04-02 Merck Patent Gmbh Kugelfoermige sio(pfeil abwaerts)2(pfeil abwaerts)-partikel
US4830879A (en) * 1986-09-25 1989-05-16 Battelle Memorial Institute Broadband antireflective coating composition and method
JP2716330B2 (ja) * 1992-11-13 1998-02-18 セントラル硝子株式会社 低反射ガラスおよびその製法
DE19642419A1 (de) * 1996-10-14 1998-04-16 Fraunhofer Ges Forschung Verfahren und Beschichtungszusammensetzung zur Herstellung einer Antireflexionsbeschichtung
EP0897898B1 (fr) * 1997-08-16 2004-04-28 MERCK PATENT GmbH Méthode de déposition de couches optiques
DE19828231C2 (de) * 1997-08-16 2000-09-07 Merck Patent Gmbh Verfahren zur Abscheidung poröser optischer Schichten
DE19918811A1 (de) * 1999-04-26 2000-11-02 Fraunhofer Ges Forschung Vorgespanntes, mit einer wischfesten, porösen SiO¶2¶-Antireflex-Schicht versehenes Sicherheitsglas u. Verfahren z. d. Herstellung
EP1167313B1 (fr) * 1999-12-13 2015-09-23 Nippon Sheet Glass Co., Ltd. Article en verre a faible reflexion
DE10051724A1 (de) * 2000-10-18 2002-05-02 Flabeg Gmbh & Co Kg Thermisch vorgespanntes Glas mit einer abriebfesten, porösen SiO¶2¶-Antireflexschicht
DE10051725A1 (de) * 2000-10-18 2002-05-02 Merck Patent Gmbh Wäßrige Beschichtungslösung für abriebfeste SiO2-Antireflexschichten
DE10052075A1 (de) * 2000-10-19 2002-05-02 Thomas Bein Poröse Schichten und ein Verfahren zu deren Herstellung mittels Spin-Coating
ES2289154T3 (es) * 2001-09-21 2008-02-01 Merck Patent Gmbh Nuevo sol hibrido para la obtencion de capas antirreflectantes de sio2, resistentes a la abrasion.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03027034A2 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011157820A1 (fr) 2010-06-18 2011-12-22 Dsm Ip Assets B.V. Revêtement d'oxyde inorganique
WO2012107392A1 (fr) 2011-02-11 2012-08-16 Dsm Ip Assets B.V. Procédé de dépôt de couche antireflet sur un substrat
WO2013174754A2 (fr) 2012-05-22 2013-11-28 Dsm Ip Assets B.V. Composition et procédé pour la formation d'un revêtement d'oxyde inorganique poreux
WO2014023716A1 (fr) 2012-08-09 2014-02-13 Dsm Ip Assets B.V. Processus et appareil de revêtement au rouleau

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US20040258929A1 (en) 2004-12-23
JP2005503317A (ja) 2005-02-03
JP4435566B2 (ja) 2010-03-17
US7575809B2 (en) 2009-08-18
DE10146687C1 (de) 2003-06-26
WO2003027034A2 (fr) 2003-04-03
WO2003027034A3 (fr) 2003-11-13
AU2002362546A1 (en) 2003-04-07

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