WO2023274610A1 - Vitre ayant un revêtement sol-gel contenant des nano-inclusions - Google Patents

Vitre ayant un revêtement sol-gel contenant des nano-inclusions Download PDF

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Publication number
WO2023274610A1
WO2023274610A1 PCT/EP2022/062429 EP2022062429W WO2023274610A1 WO 2023274610 A1 WO2023274610 A1 WO 2023274610A1 EP 2022062429 W EP2022062429 W EP 2022062429W WO 2023274610 A1 WO2023274610 A1 WO 2023274610A1
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WO
WIPO (PCT)
Prior art keywords
sol
shell
coating
oxide
nanoparticles
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PCT/EP2022/062429
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German (de)
English (en)
Inventor
Jan Hagen
Pauline GIRARD
Original Assignee
Saint-Gobain Glass France
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Filing date
Publication date
Application filed by Saint-Gobain Glass France filed Critical Saint-Gobain Glass France
Priority to EP22728418.9A priority Critical patent/EP4363386A1/fr
Priority to CN202280002272.8A priority patent/CN115812068A/zh
Priority to KR1020247002824A priority patent/KR20240025002A/ko
Publication of WO2023274610A1 publication Critical patent/WO2023274610A1/fr

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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
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • 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
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C03C2217/45—Inorganic continuous phases
    • C03C2217/452—Glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/465—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific shape
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials
    • C03C2217/477—Titanium oxide
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials
    • C03C2217/478—Silica
    • C—CHEMISTRY; METALLURGY
    • 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

Definitions

  • the invention relates to a coated pane, a method for its production and its use.
  • Sol-gel coatings as such are well known.
  • a solution with precursors (sol) is applied to a surface of a pane, where the precursors are condensed to form a gel, which remains on the pane surface after the solvent has been expelled.
  • sol-gel coatings include low cost and easy, wet-chemical handling.
  • sol-gel coatings are their properties can be adjusted comparatively easily, in particular by selecting the precursors and/or by inclusions, which can easily be added to the sol solution.
  • WO2008059170A2 discloses a sol-gel coating made of silicon oxide with nano inclusions in the form of pores (produced by thermally decomposed PMMA inclusions), hollow silicon oxide spheres or oil droplets.
  • the refractive index of the sol-gel layer can be adjusted (reduced) by said inclusions, so that the sol-gel coating can be used as an anti-reflective coating on a pane of glass.
  • the post-published WO2021209201 A1 discloses an optically high-index sol-gel coating which, in one embodiment, is formed by a sol-gel matrix made of silicon oxide with inclusions that increase the refractive index, in particular with titanium oxide inclusions.
  • sol-gel coatings whose properties can be adjusted over a wide range or with which multifunctional coatings can be realized.
  • So-called core-shell nanoparticles are known, which comprise a core and a shell made of different materials.
  • the refractive index of such nanoparticles is based essentially on so-called quantum confinement effects and can therefore be adjusted over a wide range, in particular by choosing their size.
  • the shell of the core-shell nanoparticles can be produced by atomic layer deposition (ALD).
  • ALD atomic layer deposition
  • Atomic layer deposition enables the production of high-quality shells with a precisely defined layer thickness. It has been shown in the literature that such an ALD shell can improve the chemical resistance of the nanoparticles (AW Weimer, Particle atomic layer deposition. Journal of Nanoparticle Research 21, 2019).
  • WO2015075229A1 discloses a porous anti-reflection coating with organic-inorganic hybrid core-shell nanoparticles, which are produced wet-chemically.
  • WO2011157820A1 and WO2013174754A2 also disclose sol-gel coatings with inclusions of wet-chemically produced core-shell nanoparticles.
  • the object of the present invention is to provide a pane with an improved sol-gel coating.
  • the properties of the sol-gel coatings, in particular their refractive index, should be adjustable precisely and reproducibly over a wide range.
  • the coating should also be mechanically stable and resistant to aging and be suitable as a multifunctional coating.
  • the coated pane of the invention comprises at least one transparent substrate and a sol-gel coating on a surface of the substrate.
  • the sol-gel coating contains a sol-gel matrix or is made up of or consists of a matrix formed according to the sol-gel principle (sol-gel matrix) which is provided with nano inclusions.
  • the nano inclusions can also be described as doping of the sol-gel matrix.
  • the sol-gel matrix is based on metal oxide or semimetal oxide formed or consists of metal oxide or semi-metal oxide. Semimetal oxide could also be referred to as semiconductor oxide.
  • the sol-gel matrix can contain process-related residues or additives, for example stabilizers or UV blockers.
  • the inclusions are in particular introduced into the sol-gel matrix by being added to the sol (preferably as a solution), so that they are enclosed by the sol-gel matrix during the condensation and drying of the sol-gel coating.
  • the element mainly consists of this material, in particular essentially of this material in addition to any impurities or dopings.
  • the proportion of the material is more than 50% by weight, preferably more than 70% by weight, very particularly preferably more than 90% by weight. Based on metal oxides or semi-metal oxides as materials of the nano inclusions (shell or core), the proportion is more than 99% by weight in particular.
  • the nano-inclusions comprise a core and a shell, which is arranged around the core and encloses it.
  • Core and shell are made of different materials.
  • the nano inclusions can therefore be understood as core-shell nanoparticles.
  • the shell is produced on the core by atomic layer deposition (ALD).
  • Sol-gel coatings can be produced inexpensively. They are easy to apply wet-chemically to the substrate, either over the entire surface or only in certain areas. They can be used in many different ways and their properties can be easily controlled, for example by the choice of the material of the sol-gel matrix and/or any inclusions). This circumstance is used within the scope of the invention by the nano inclusions according to the invention, which have a shell produced by atomic layer deposition. The nano inclusions can, for example, influence the optical properties of the coating and/or increase its chemical or mechanical stability. Better storage or connection to the matrix can be achieved through the shell.
  • the nano inclusions enable a very flexible adjustment of the refractive index over a large range, since the refractive index of the nano inclusions is based on quantum effects (quantum confinement). These quantum effects result from the electronic interaction between the shell and the core and are influenced by the choice of materials and the size of the core and the shell.
  • Atomic layer deposition enables the shell to be produced with a very precisely defined layer thickness, so that the properties can be set precisely and reproducibly.
  • atomic layer deposition leads to very dense layers, which on the one hand ensures high chemical and mechanical stability and on the other hand leads to the desired properties being achieved even with a comparatively small layer thickness.
  • the shell is produced by means of atomic layer deposition, for example by means of high-resolution transmission electron microscopy (HRTEM, High Resolution Transmission Electron Microscopy).
  • HRTEM high-resolution transmission electron microscopy
  • the atomic layer deposition leads to an ideally uniform formation of the shell, also at the atomic level, which results in an almost perfectly constant layer thickness of the shell, which cannot be achieved with other coating processes.
  • the shell follows the contour of the surface of the core almost perfectly and is ideally concentric with it, for example in the case of a spherical core.
  • the thickness of the sol-gel coating is preferably from 30 nm to 500 nm, particularly preferably from 50 nm to 150 nm.
  • the sol-gel matrix is based on silicon oxide (S1O2) or consists of S1O2.
  • Si0 2 sol-gel coatings have been well researched and can be produced in high quality.
  • S1O2 has a refractive index that is similar to that of typical substrates (especially soda-lime glass panes or plastic panes made of PMMA or polycarbonate).
  • Si0 2 sol-gel coatings are therefore optically compatible with such substrates.
  • Anti-reflection properties can be produced by such a coating, in particular by a specifically adjusted porosity or other inclusions that lower the refractive index.
  • other sol-gel matrices can also be used, for example those based on T1O2, in order to produce an optically highly refractive layer.
  • the nano-inclusions are core-shell nanoparticles, with the shell (“shell”) being produced by atomic layer deposition on the core (“core”).
  • the nano-inclusions may alternatively be hollow particles formed by the shell surrounding a cavity (pore) forming the core.
  • a polymeric nanoparticle can be provided with the shell by atomic layer deposition, the coated nanoparticle can be embedded in the coating and the polymeric core can then be removed thermally or by means of a solvent.
  • Nano inclusions or nanoparticles are understood to mean particles which have sizes in the nanometer range, ie from 1 nm to less than 1000 nm (1 pm).
  • the nano inclusions or nanoparticles are preferably formed spherically, ie have an essentially circular cross section.
  • the nano inclusions or nanoparticles can also have other cross sections, for example an elliptical, oval or elongated cross section (ellipsoid or ovoid nanoparticles).
  • the proportion by volume of the nano inclusions in the sol-gel coating is preferably between 10% and 90%, particularly preferably below 80%, very particularly preferably less than 70% or less than 60%.
  • the nano inclusions can be formed in different ways, depending on the intended use in the application - this applies to the material of the core and the shell as well as to the combinations thereof.
  • Both the core and the shell are preferably formed from dielectric materials.
  • Dielectric materials within the meaning of the invention have, in particular, an electrical conductivity (reciprocal of the specific resistance) of less than 10 4 S/m.
  • the core is designed as a pore, ie as a type of void (in particular gas, air or vacuum-filled) in the sol-gel matrix.
  • the refractive index of the sol-gel coating can be adjusted by pores, in particular it can be reduced in comparison to the refractive index of the sol-gel matrix. This allows the coating to be provided with anti-reflective (anti-reflective) properties.
  • refractive indices are generally given in relation to a wavelength of 550 nm.
  • the refractive index can, for example, by means ellipsometry can be determined. Ellipsometers are commercially available, for example from Sentech.
  • the core is formed from a polymer or is based on a polymer or consists of a polymer.
  • the refractive index of the coating can also be adjusted by inclusions with such a core.
  • the stability and mechanical properties of the coating can sometimes be improved.
  • Polymethyl methacrylate (PMMA) is particularly preferred because of its suitable refractive index and its good availability and ease of handling.
  • PMMA polymethyl methacrylate
  • Polymeric cores can also act as a precursor to a pore if, after being incorporated into the sol-gel matrix, the core is thermally decomposed as part of a temperature treatment or is dissolved out by a solvent.
  • PMMA for example, polycarbonates, polyesters, polystyrenes or copolymers of methyl (meth)acrylates and (meth)acrylic acid are also suitable for this purpose.
  • the core is formed from metal oxide or semi-metal oxide or is based on metal oxide or semi-metal oxide or consists of metal oxide or semi-metal oxide.
  • Silicon oxide (SiC> 2 ) is particularly preferred.
  • the refractive index of the coating can also be adjusted, where—if the sol-gel matrix is also made of SiO 2 , the effect is primarily based on the shell and good optical compatibility with the matrix due to the SiO 2 core is ensured.
  • Titanium oxide (T1O 2 ), aluminum oxide (Al 2 O 3 ), zirconium oxide (Zr0 2 ) or hafnium oxide (Hf0 2 ) is also particularly preferred. This also makes it possible to adjust the refractive index of the coating—if the sol-gel matrix is made of S1O 2 , in particular to increase it.
  • the coating can be provided with photocatalytic, self-cleaning properties by T1O 2 .
  • the core is designed as a hollow particle, ie as a shell around an (in particular air-filled) empty space.
  • the hollow particle is formed from metal oxide or semi-metal oxide or based on metal oxide or semi-metal oxide, for example from S1O 2 or T1O 2 .
  • S1O 2 - Hollow particles are commercially available and can easily be purchased.
  • the empty space forms a pore in the sol-gel matrix, which in turn allows its refractive index to be adjusted, with the SiC>2 cladding ensuring good optical compatibility with the sol-gel matrix, at least if it is also made of SiO2 is.
  • hollow particle cores can also be used for other purposes, for example for generating scattering surfaces on the substrate, which serve, for example, for light extraction.
  • the formation of the core as a pore, made of metal oxide or semi-metal oxide (in particular S1O2 and T1O2) or as hollow particles made of metal oxide or semi-metal oxide (in particular S1O2 and T1O2) is particularly preferred.
  • Very particularly preferred materials for the core are S1O2, pores and SiO 2 hollow particles because of their wide range of possible uses.
  • the core preferably has a size of 10 nm to 500 nm, particularly preferably from 10 nm to 150 nm, very particularly preferably from 50 nm to 100 nm. Good results can be achieved in this way, in particular as regards the incorporation of the nanoparticles in the sol -Gel- matrix and the adjustment of its refractive index.
  • the size is understood to mean the maximum expansion of the core that occurs along a spatial dimension, ie, in the case of spherical nanoparticles, their diameter.
  • the size of at least 80% of all cores is preferably in the specified ranges, particularly preferably all cores.
  • the shell of the nano-incorporation preferably has a refractive index of greater than 1.5, particularly preferably greater than 1.7, in particular greater than 1.9. This is particularly advantageous if an increase in the refractive index of the sol-gel matrix is to be achieved by the nano inclusions. But even if this is not the case, a slight increase in the refractive index due to the material of the shell can be acceptable if, for example, a significant improvement in the mechanical properties can be achieved as a result.
  • the shell is formed from or is based on metal oxide or semi-metal oxide or consists of metal oxide or semi-metal oxide.
  • Suitable metal oxides or semi-metal oxides are, for example, silicon oxide (S1O2), aluminum oxide (AI2O3) or transition metal oxides, in particular titanium oxide (T1O2), Zirconium oxide (Zr0 2 ) or hafnium oxide (Hf0 2 ).
  • T1O2 titanium oxide
  • Zr0 2 Zirconium oxide
  • Hf0 2 hafnium oxide
  • the other metal oxides mentioned can bring about, for example, an increase in the refractive index, for example in order to provide the coating with reflective properties.
  • the coating can also be provided with photocatalytic, self-cleaning properties by means of a Ti0 2 shell. Shells made of S1O2 or T1O2 are particularly preferred.
  • the shell can alternatively also be made of or based on nitrides.
  • nitrides examples are silicon nitride (S13N4) or aluminum nitride (AIN). This can be application-specifically advantageous with regard to, for example, the surface properties of the nano inclusions and/or the attachment of the shell to the core.
  • the selection of the material of the shell is of course made under the stipulation that it must differ from the material of the core.
  • the oxides and nitrides used in the context of the present invention do not necessarily have to be stoichiometric, but can alternatively also be substoichiometric or superstoichiometric. This applies equally to the core and the shell of the nano inclusions and to the sol-gel matrix.
  • the shell of the nano inclusions is preferably formed stoichiometrically, which is possible precisely and reproducibly by depositing complete monolayers during atomic layer deposition.
  • the shell preferably has a layer thickness of 1 nm to 100 nm, particularly preferably from 2 nm to 20 nm, in particular from 5 nm to 15 nm.
  • a layer thickness refers, unless otherwise stated, to the geometric thickness of a layer, not to the optical thickness, which results from the product of the geometric thickness and the refractive index.
  • the sol-gel coating according to the invention can be used for a wide range of applications and can thereby fulfill a wide range of functions.
  • the sol-gel coating can be, for example: an anti-reflective coating: these are in particular coatings that have a lower refractive index than the substrate.
  • they can be realized by a SiC>2 matrix whose refractive index is reduced by pores (pores as cores of the nano-inclusions or hollow particles, in particular SiC>2 hollow particles as cores of the nano-inclusions).
  • the refractive index depends on the pore size and the density of the pores.
  • the proportion of the pore volume in the total volume is preferably between 10% and 90%, particularly preferably below 80%, very particularly preferably less than 60%.
  • S1O2 is particularly preferred as a shell in order to optimize the connection of the pores or hollow particles to the SiC matrix. But all other materials mentioned are conceivable for the shell, especially if the
  • Coating should be equipped with additional properties a reflection-increasing coating: these are in particular coatings that have a higher refractive index than the substrate. They can be achieved, for example, by using a sol-gel matrix with a high refractive index (especially T1O2, ZrÜ2 or Hf0 2 ) or by using a Si0 2 matrix that contains nano inclusions that increase the refractive index (especially T1O2, ZrÜ2 or Hf0 2 as a shell or core of the nano-inclusions).
  • a hydrophilic or hydrophobic coating i.e. a coating that affects the usage behavior of the substrate surface.
  • a sun protection coating i.e. a coating which electromagnetic
  • a photocatalytic coating reflects or absorbs radiation in the infrared and/or ultraviolet range: such coatings are capable of decomposing organic deposits and therefore have self-cleaning properties.
  • the photocatalytic properties are achieved in particular by using PO2 as the material for the sol-gel matrix or the shell or the core of the nano-inclusions.
  • a light-scattering coating the coated area of the substrate surface is thereby provided with strong light-scattering properties. This can be used, for example, to couple out light, which is coupled into the substrate via the side edge and propagates there by total reflection, out of the substrate for lighting purposes or for generating a display.
  • a decorative coating especially colored coating.
  • the reflection color can be adjusted by the refractive index of the sol-gel coating and any optical interference effects.
  • multifunctional coatings can be realized, in particular those that fulfill several of the functions mentioned above . Examples include: anti-reflective coatings with photocatalytic properties anti-reflective coatings with hydrophobic properties photocatalytic coatings with hydrophobic properties anti-reflective coatings with sun protection - colored anti-reflective coatings.
  • the preferred materials described above for the core and shell of the nano inclusions can in principle be combined with one another as desired. Particularly preferred combinations are, for example: - core: pore, shell: S1O2: such nano-inclusions can reduce the
  • Refractive index of the sol-gel coating can be used. They can also increase mechanical and chemical resistance and reduce fingerprint visibility.
  • the Si0 2 shell improves the connection of the inclusions to the matrix. They can be generated in particular by nanoparticles with a polymer core (preferably PMMA core) and a SiO 2 shell, the core being thermally decomposed or dissolved out after coating.
  • Sun protection coatings can also be realized with it. They can be generated in particular by nanoparticles with a polymer core (preferably PMMA core) and a TiO 2 shell, the core being thermally decomposed or dissolved out after coating.
  • Core S1O2
  • shell PO2: such nano-inclusions can be used for example for reflection-enhancing coatings, especially in the case of a
  • the Si0 2 shell improves the connection to the matrix.
  • the sol-gel coating can be arranged over the entire surface of the substrate. However, it is also possible that the sol-gel coating is only arranged on one or more areas of the surface, while other areas are uncoated. For example, the coating can be applied over the entire surface with the exception of a peripheral edge area, which is uncoated, so that the central transparent area of the substrate is completely covered by the coating. In particular, at least 80% of the substrate surface is provided with the coating. This is particularly advantageous if the coating is intended to provide the substrate with largely homogeneous properties overall, for example as an anti-reflective coating, hydrophilic or hydrophobic coating, sun protection coating and/or self-cleaning coating.
  • the coating for example a camera or sensor area that is to be provided with specific properties
  • the coating is applied to the substrate in the form of a pattern.
  • the wet-chemical sol-gel process enables both full-surface and area-specific coating in a simple manner.
  • the substrate is designed as a glass pane or plastic pane.
  • a pane is a largely rigid, at most elastically flexible, plate-like or layer-like object.
  • the substrate is preferably made of soda-lime glass, as is customary for window panes.
  • other types of glass are also conceivable, for example borosilicate glass, quartz glass or aluminosilicate glass.
  • the substrate is preferably formed from or based on PMMA or polycarbonate (PC).
  • the thickness of the substrate can be freely selected depending on the application. Typical thicknesses for window panes in the field of architecture or vehicles are, for example, from 0.5 mm to 5 mm, preferably from 1.0 mm to 2.5 mm.
  • the substrate is transparent. This is understood to mean a substrate which enables the see-through, which can therefore be used in particular as a window pane.
  • the substrate can certainly be tinted or colored, as is customary in particular in the case of many vehicle windows.
  • the light transmission of the substrate in the visible spectral range from 400 nm to 800 nm is preferably at least 10%, particularly preferably at least 30%, more particularly at least 50% and especially at least 70%. These values relate to the total proportion of the transmitted radiation in the total radiation that hits the substrate in the specified spectral range with an angle of incidence of 0° to the surface normal.
  • the coated pane is preferably intended as a window pane, in particular as a window pane in buildings, interiors or vehicles.
  • the invention also includes a method of making a coated pane according to the invention, wherein at least:
  • the nanoparticles are provided with a shell by atomic layer deposition
  • the sol is condensed to form a sol-gel coating, the metal oxide or semi-metal oxide precursors forming a sol-gel matrix provided with nano-inclusions comprising a core formed from the nanoparticles is, as well as the shell arranged around the core.
  • the process steps do not necessarily have to be carried out in the specified order unless this is technically necessary. It is thus necessary for the nanoparticles to be provided with the shell (method step b) before they are added to the sol (method step d). It is also necessary for the nanoparticles provided with the shell to be added to the sol (method step d) before this is applied to the substrate surface (method step e). It is also necessary for the sol to be applied to the substrate surface (method step e) before it is condensed to form the sol-gel coating (method step f). However, whether the nanoparticles are first provided with the shell (method step b) and then the sol is prepared with the precursors (method step c) or vice versa is irrelevant.
  • the nanoparticles provided with the shell are typically long-term stable and can therefore be stored, so that the coating of the nanoparticles (method step b) is not immediate must take place before the preparation of the sol (method step c). For example, larger quantities of the coated nanoparticles can be produced and stored in advance and used as needed in the sol-gel coating.
  • the nanoparticles are provided with the shell by means of atomic layer deposition.
  • Atomic layer deposition is an efficient process for depositing everything from thin layers to atomic monolayers.
  • the components (atoms) of the material to be deposited are chemically bound to a carrier gas (so-called precursors or reactants).
  • precursors or reactants are used to react the respective precursor.
  • the reaction chamber is then emptied and filled with the next precursor. In this way, alternating layers of the components of the coating are applied one after the other.
  • Suitable reactants for producing ALD coatings from a metal oxide are, for example, the corresponding methyl metal compound or the corresponding metal chloride on the one hand and water vapor on the other hand.
  • the methyl metal compound (or the metal chloride) serves as the source of the metal and the water vapor as the source of the oxygen.
  • some methyl groups are split off and the metal with the remaining methyl groups is chemically bonded to the substrate, for example via free OH groups on the surface of the object to be coated or the layer deposited from water vapor underneath.
  • the reaction chamber is then filled with steam. During the subsequent reaction, OH groups replaced the methyl groups of the underlying metal layer.
  • a characteristic of ALD is the self-limiting character of the partial reactions: the reactant does not react with itself or ligands of itself, which limits the layer growth of a partial reaction to a maximum of one monolayer for any length of time and amount of gas. In this way, very dense layers with a precisely adjusted layer thickness can be produced. Since the gas is evenly distributed in the reaction chamber, the objects are completely coated regardless of their geometric shape, apart from that from any supporting surfaces. ALD coatings of a semi-metallic oxide can also be produced, substituting semi-metallic for metal in the above description.
  • the atomic layers of the shells are typically deposited on the cores in portions (batch processing), not in a continuous process.
  • a certain quantity of nanoparticles is introduced into a reaction container, where it is simultaneously coated with the shell and then removed. Such reactions are typically carried out in a so-called "batch reactor”.
  • the nanoparticles are preferably selected or chemically functionalized by surface groups in such a way that they are soluble in a solvent.
  • the solvent can preferably be water, an alcohol or a water-alcohol mixture.
  • the nanoparticles are provided dissolved in the solvent. Then the solvent is evaporated.
  • the nanoparticles are then shelled by atomic layer deposition and then redissolved in a solvent, which may be the same solvent in which the nanoparticles were provided. Of course, the shell must also be selected or chemically functionalized after the atomic layer deposition in such a way that it ensures the solubility of the coated nanoparticles.
  • the solution with the nanoparticles can then be added to the sol (method step d).
  • the sol is a solution containing the precursors for the sol-gel matrix dissolved in a solvent.
  • these are metal oxide precursors or semimetal oxide precursors from which the metal oxide or semimetal oxide matrix can be formed.
  • the metal oxide precursors can be present, for example, as organometallic compounds, as metal alcoholates or as metal carboxylates.
  • the analogous compounds can be used as semimetal oxide precursors, substituting semimetal for metal.
  • the metal or semimetal (for example the metal alcoholate or metal carboxylate) is stabilized by ligands in the form of a chemical complex, as a result of which the reactivity can be reduced and the resistance of the sol to atmospheric moisture can be improved.
  • 2,4-Diketones are customary as ligands.
  • the solvent is preferably water, alcohol (particularly ethanol) or a water-alcohol mixture.
  • the sol can contain thickeners, for example cellulose derivatives (such as methyl cellulose or ethyl cellulose) or polyacrylic acids, in order to adjust the viscosity of the sol. It is possible that the solvent or thickening agent also acts as a complexing agent for the metal oxide or semi-metal oxide precursors if suitably chosen. In this case, additional ligands do not have to be added specifically.
  • the sol can also contain typical additives as are customary in the field of sol-gel technology and are known to those skilled in the art.
  • the sol contains silicon oxide precursors in the solvent.
  • the precursors are preferably silanes, in particular tetraethoxysilanes or methyltriethoxysilane (MTEOS).
  • silicates can also be used as precursors, in particular sodium, lithium or potassium silicates, for example tetramethyl orthosilicate, tetraethyl orthosilicate (TEOS), tetraisopropyl orthosilicate, or organosilanes of the general form R 2 n Si(OR 1 ) 4-n .
  • R 1 is preferably an alkyl group
  • R 2 is an alkyl, epoxy, acrylate, methacrylate, amine, phenyl or vinyl group
  • n is an integer from 0 to 2. Silicon halides or alkoxides can also be used will.
  • the precursors can optionally already mature in solution. Ripening may involve hydrolysis of the precursors and/or partial aggregation by (partial) reaction (particularly polycondensation) between the precursors.
  • the concentration of the precursors in the sol is preferably from 0.1% by weight to 20% by weight, particularly preferably from 2% by weight to 10% by weight.
  • the coated nanoparticles are added to the sol.
  • the nanoparticles and the sol-gel precursors are mixed in a solvent.
  • the solution of coated nanoparticles is mixed with the sol.
  • the precursors are added directly to the solution of the nanoparticles, ie the sol is produced directly from this. In this case, the provision of the sol and the addition of the nanoparticles would be realized in one step.
  • the sol together with the coated nanoparticles dissolved therein, that is to say provided with the shell, is then applied to the substrate surface, in particular by Wet-chemical methods, for example by dip coating (cf/p coating), centrifugal coating (spin coating), flow coating (flow coating), by application using rollers or brushes, by spray coating (spray coating) or by printing methods, for example by tampon printing (pad printing) or Screen printing.
  • Wet-chemical methods for example by dip coating (cf/p coating), centrifugal coating (spin coating), flow coating (flow coating), by application using rollers or brushes, by spray coating (spray coating) or by printing methods, for example by tampon printing (pad printing) or Screen printing.
  • This can be followed by drying, with the solvent being evaporated. This drying can take place at ambient temperature or by means of separate heating (for example at a temperature of up to 120° C.).
  • the surface is typically cleaned by methods known in the art.
  • the sol is then condensed to form the sol-gel coating according to the invention.
  • This preferably takes place by means of a temperature treatment, preferably at at least 400.degree. This can be carried out as a separate temperature treatment.
  • the heat treatment can be carried out as part of a glass bending process, typically at temperatures of 600°C to 700°C.
  • the precursors have UV-crosslinkable functional groups (for example methacrylate, vinyl or acrylate groups)
  • the condensation can comprise a UV treatment instead of or in addition to the heat treatment.
  • suitable precursors e.g. silicates
  • the condensation can comprise an IR treatment.
  • drying can optionally be carried out beforehand, with solvent evaporating and the concentration of the precursors being reduced as a result.
  • This drying can take place at ambient temperature or by means of separate heating (for example at a temperature of up to 120° C.).
  • the sol-gel matrix is formed from the metal oxide or semimetal precursors.
  • crosslinking processes typically take place among the precursors, with the precursors initially combining to form aggregates (aggregation, typically by hydrolysis of the precursors and polycondensation reactions among them) and these then being crosslinked to form a gel (gelation).
  • the aggregation can also take place partially in solution before it is applied to the disc surface (maturation).
  • the sol-gel matrix is provided with the nano inclusions, which comprise the core formed from the nanoparticles and the shell arranged around the core.
  • the core of the nano-incorporations according to the invention is formed from the nanoparticles. This does not necessarily mean chemical or mechanical conversion, although such conversion is optionally possible, as will become clear from the two preferred embodiments described below.
  • the nanoparticles remain in the sol-gel coating after they have been created as the core of the nano-inclusions.
  • the nanoparticles of the sol thus form the core of the inclusions of the sol-gel coating without any transformation.
  • the nanoparticles can preferably be formed from a polymer or based on a polymer (for example polycarbonates, polyesters or polystyrenes, or copolymers of methyl (meth)acrylates and (meth)acrylic acid, preferably PMMA), from or based on metal oxide or semimetal oxide (preferably S1O2 or T1O2) or as hollow particles made of or based on metal oxide or semimetal oxide (preferably S1O2).
  • a polymer for example polycarbonates, polyesters or polystyrenes, or copolymers of methyl (meth)acrylates and (meth)acrylic acid, preferably PMMA
  • metal oxide or semimetal oxide preferably S1O2 or T1O2
  • the nanoparticles of the sol are precursors of the core of the nano-inclusions. This is particularly true when the core of the nano-intercalation is intended to be a pore.
  • the nanoparticles act as pore formers and are preferably made of or based on a polymer, for example made of or based on PMMA, polycarbonates, polyesters or polystyrenes or copolymers of methyl (meth)acrylates and (meth)acrylic acid, PMMA being particularly preferred is preferred.
  • the nanoparticles are decomposed to form pores as the core of the nano-inclusions.
  • the shell of the nanoparticles remains as a shell around the pore.
  • the nanoparticles are preferably decomposed thermally by a temperature treatment at at least 400°C, preferably at least 500°C.
  • the polymeric nanoparticles are in particular charred (carbonized).
  • a separate tempering step can be provided for this purpose, which follows the condensation of the sol-gel matrix.
  • thermally decomposing the polymeric nanoparticles it is also possible to remove them from the coating using solvents.
  • the corresponding polymer must be soluble in the solvent, for example tetrahydrofuran (THF) can be used in the case of PMMA nanoparticles.
  • THF tetrahydrofuran
  • the substrate with the sol-gel coating according to the invention can be supplied to its final destination as such.
  • the coated pane must first be thermally prestressed and/or subjected to a bending process.
  • the coated pane (flat or curved) can be laminated with another pane via a thermoplastic intermediate layer, for example a PVB film, to form a composite pane. It is also possible to connect the coated pane to one or more other panes using spacers to form an insulating glass unit.
  • the invention also includes the use of a coated pane according to the invention in buildings or in means of transportation for traffic on land, in the air or on water.
  • the pane is preferably used outside of buildings as a window pane, glass door or facade element, inside buildings as a window pane of rooms, glass door or partition pane or as a vehicle pane (for example as a roof pane, side pane, rear pane or windshield of a vehicle, in particular a motor vehicle) or as a Part thereof, for example as part of a composite pane or insulating glass unit.
  • a vehicle pane for example as a roof pane, side pane, rear pane or windshield of a vehicle, in particular a motor vehicle
  • Part thereof for example as part of a composite pane or insulating glass unit.
  • the invention is explained in more detail below with reference to a drawing and exemplary embodiments.
  • the drawing is a schematic representation and not to scale. The drawing does not limit the invention in any way.
  • Fig. 2 shows a cross section through a nano-incorporation of the disc from Figure 1.
  • FIG. 1 shows a cross section through an embodiment of the coated pane according to the invention. It comprises a substrate 1 with a sol-gel coating 2.
  • the substrate 1 is, for example, a 2.1 mm thick pane made of soda-lime glass, which is provided as a vehicle pane (for example as part of a laminated windshield).
  • the substrate 1 can form the inner pane of the windshield, for example, and can be connected via the surface opposite the sol-gel coating 2 via a PVB film to an outer pane, which is also a 2.1 mm thick soda-lime glass pane, for example.
  • the sol-gel coating 2 includes a sol-gel matrix 3, for example made of S1O2.
  • the sol-gel matrix 3 was produced using the sol-gel process.
  • the sol-gel matrix 3 includes nano inclusions 4 through which the properties of the sol-gel coating 2 can be adjusted in a targeted manner.
  • FIG. 2 schematically shows a cross section through a nano-incorporation 4. It comprises a spherical core 4a surrounded by a shell 4b.
  • the shell 4b is produced by atomic layer deposition.
  • the core 4a has a diameter of about 70 nm, for example, and the shell 4b has a layer thickness of about 10 nm.
  • the core 4a and the shell 4b are chosen according to the intended application in order to provide the sol-gel coating 2 with the required properties.
  • the core can be made of S1O2 and the shell of T1O2. Due to the Si0 2 core, the nano-intercalation 4 is optically compatible with the Si0 2 matrix.
  • the refractive index of the sol-gel coating 2 is increased by the Ti0 2 shell and, on the other hand, it is provided with photocatalytic properties.
  • the core 4a can be designed as a cavity (pore), for example, and the shell 4b can be made of SiO2.
  • the pores are preferably produced in that in the sol-gel coating a PMMA nanoparticle with the shell 4b produced by atomic layer deposition is added to the sol and this PMMA nanoparticle is thermally decomposed after coating, whereby the pore is formed as the core 4a.
  • a shell of PO2 gives the anti-reflective coating additional photocatalytic properties.
  • Nano inclusions of the sol-gel coating 2 (4a) Core of nano inclusions 4

Abstract

L'invention concerne une vitre revêtue comprenant : un substrat transparent (1) ; un revêtement sol-gel (2) sur une surface du substrat (1), ledit revêtement sol-gel (2) contenant une matrice sol-gel (3) à base d'oxyde métallique ou d'oxyde semi-métallique et pourvue de nano-inclusions (4), les nano-inclusions (4) comprenant un noyau (4a) et une enveloppe (4b) autour du noyau (4b), l'enveloppe (4b) étant produite par dépôt de couche atomique (ALD).
PCT/EP2022/062429 2021-06-29 2022-05-09 Vitre ayant un revêtement sol-gel contenant des nano-inclusions WO2023274610A1 (fr)

Priority Applications (3)

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EP22728418.9A EP4363386A1 (fr) 2021-06-29 2022-05-09 Vitre ayant un revêtement sol-gel contenant des nano-inclusions
CN202280002272.8A CN115812068A (zh) 2021-06-29 2022-05-09 具有包含纳米嵌入物的溶胶-凝胶涂层的玻璃板
KR1020247002824A KR20240025002A (ko) 2021-06-29 2022-05-09 나노 함유물이 포함된 졸-겔 코팅 판유리

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EP21182237.4 2021-06-29

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008059170A2 (fr) 2006-11-14 2008-05-22 Saint-Gobain Glass France Couche poreuse, son procede de fabrication et ses applications
WO2011157820A1 (fr) 2010-06-18 2011-12-22 Dsm Ip Assets B.V. Revêtement d'oxyde inorganique
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
WO2015075229A1 (fr) 2013-11-22 2015-05-28 Dsm Ip Assets B.V. Procédé de fabrication d'une composition de revêtement antiréfléchissant et revêtement poreux constitué de cette composition
WO2021209201A1 (fr) 2020-04-16 2021-10-21 Saint-Gobain Glass France Ensemble de projection pour un affichage tête haute (hud) avec un rayonnement à polarisation en p

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008059170A2 (fr) 2006-11-14 2008-05-22 Saint-Gobain Glass France Couche poreuse, son procede de fabrication et ses applications
WO2011157820A1 (fr) 2010-06-18 2011-12-22 Dsm Ip Assets B.V. Revêtement d'oxyde inorganique
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
WO2015075229A1 (fr) 2013-11-22 2015-05-28 Dsm Ip Assets B.V. Procédé de fabrication d'une composition de revêtement antiréfléchissant et revêtement poreux constitué de cette composition
WO2021209201A1 (fr) 2020-04-16 2021-10-21 Saint-Gobain Glass France Ensemble de projection pour un affichage tête haute (hud) avec un rayonnement à polarisation en p

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A. W. WEIMER: "Particle atomic layerdeposition", JOURNAL OF NANOPARTICLE RESEARCH, 2019, pages 21
L. ZHANG ET AL.: "Mechanical properties of atomic layerdeposition-reinforced nanoparticle thin films", NANOSCALE, September 2012 (2012-09-01)
WEIMER ALAN W: "Particle atomic layer deposition", JOURNAL OF NANOPARTICLE RESEARCH, SPRINGER NETHERLANDS, DORDRECHT, vol. 21, no. 1, 4 January 2019 (2019-01-04), pages 1 - 42, XP036666140, ISSN: 1388-0764, [retrieved on 20190104], DOI: 10.1007/S11051-018-4442-9 *

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