EP2718240A1 - Matériau de revêtement pour un substrat en verre ou en vitrocéramique ainsi que substrat en verre ou en vitrocéramique enduit - Google Patents

Matériau de revêtement pour un substrat en verre ou en vitrocéramique ainsi que substrat en verre ou en vitrocéramique enduit

Info

Publication number
EP2718240A1
EP2718240A1 EP12733590.9A EP12733590A EP2718240A1 EP 2718240 A1 EP2718240 A1 EP 2718240A1 EP 12733590 A EP12733590 A EP 12733590A EP 2718240 A1 EP2718240 A1 EP 2718240A1
Authority
EP
European Patent Office
Prior art keywords
coating material
glass
particles
coating
sol
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Withdrawn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
EP12733590.9A
Other languages
German (de)
English (en)
Inventor
Matthias Bockmeyer
Andrea Anton
Matthias SEYFARTH
Vera Breier
Silke Knoche
Angelina Milanovska
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.)
Schott AG
Original Assignee
Schott AG
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 Schott AG filed Critical Schott AG
Publication of EP2718240A1 publication Critical patent/EP2718240A1/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Withdrawn legal-status Critical Current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
    • C03C17/006—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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
    • C03C1/008—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route for the production of films or coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • 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
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • 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
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C03C17/326—Epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • 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
    • C03C2203/00—Production processes
    • C03C2203/20—Wet processes, e.g. sol-gel process
    • C03C2203/26—Wet processes, e.g. sol-gel process using alkoxides
    • C03C2203/27—Wet processes, e.g. sol-gel process using alkoxides the alkoxides containing other organic groups, e.g. alkyl groups
    • 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
    • C03C2203/00—Production processes
    • C03C2203/20—Wet processes, e.g. sol-gel process
    • C03C2203/26—Wet processes, e.g. sol-gel process using alkoxides
    • C03C2203/27—Wet processes, e.g. sol-gel process using alkoxides the alkoxides containing other organic groups, e.g. alkyl groups
    • C03C2203/28—Wet processes, e.g. sol-gel process using alkoxides the alkoxides containing other organic groups, e.g. alkyl groups functional groups, e.g. vinyl, glycidyl
    • 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
    • C03C2203/00—Production processes
    • C03C2203/20—Wet processes, e.g. sol-gel process
    • C03C2203/30—Additives
    • 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
    • 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
    • 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
    • C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
    • 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
    • C03C2218/119—Deposition methods from solutions or suspensions by printing
    • 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
    • Y10T428/24997—Of metal-containing material
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31609—Particulate metal or metal compound-containing
    • Y10T428/31612—As silicone, silane or siloxane

Definitions

  • the invention relates to a coating material for glass or glass ceramic substrates, which in particular for
  • Invention a composite material coated with the coating material.
  • Glass-ceramic substrates are used, for example, for coating cooktops, for coating thermally stressed substrates and for coating bullet-proof
  • Washers in particular for vehicles, used.
  • the layers are both thermally stable during a bending process, as he for example
  • Vehicle glazing is used, as well as meet the thermal requirements of a coated substrate for cooktops (induction, gas and IR radiation).
  • the layers should provide sufficiently opaque color locations.
  • black and white color schemes should be able to be provided.
  • the invention is based on the object, at least to reduce the disadvantages of the prior art.
  • a screen-printable Beschichungsmaterial is to be made available, which is thermally stable and neither tends to cracks or delamination.
  • the object of the invention is already by a
  • the invention relates to a coating material for
  • Coating of glass or glass ceramic substrates is in particular formed as a paint or varnish and is. in the following therefore also referred to simply as "color”.
  • the coating material is used in particular for
  • temperature-loaded ceramic substrates such as hobs, kitchen appliances, stove and fireplace panes used.
  • coating material in particular decorative coatings can be applied, for example as a cooking surface boundary, operating inscription, etc.
  • Another field of application is in particular special glasses and glass ceramics with a low coefficient of thermal expansion.
  • the invention is used for safety discs.
  • One application is the coating of
  • a vehicle window is generally bent three-dimensionally and has a coating at the edge in the area in which the windows are glued to the body, which is usually formed black.
  • the coating material or the paint of the invention should be processable in particular by means of a screen printing process.
  • the coating material comprises a sol-gel lacquer system, wherein a substance is present under a sol-gel lacquer system
  • the coating material is in particular formed as a one-component paint, so it is storage stable over at least several weeks, in particular, greater than 3 months, especially 6 months.
  • the coating material does not gel and remains liquid or processable.
  • the viscosity of a processable is preferably from 150 to 125,000 mPas, preferably from 200 to 7,000 mPas, very particularly preferably from 250 to 3,000 mPas.
  • the viscosity of the screen printing ink is between 200 and 1000 mPas.
  • the coating material further comprises pigments with which the color of the Be Anlagenungsmateriais is determined.
  • pigments with which the color of the Be Anlagenungsmateriais is determined.
  • black pigments are provided.
  • the coating material but pigments in
  • the coating material comprises
  • Main extension direction at least twice, preferably three times, is as large as the size along the smallest dimension of the particle, which in turn applies on average for the particles used.
  • particles with a chain morphology are secondary particles, which consists of a
  • Consist of a plurality of juxtaposed smaller primary particles may be at least partially branched.
  • spherical primary particles (diameter of about 15 nm in the SEM) show a diameter of 38 nm with a standard deviation of about 14 'nm.
  • the coating material is preferably semitransparent or opaque.
  • An opaque embodiment is understood to mean a coating which is opaque to the human eye, whereas a semi-transparent coating is understood to mean a coating which, although having a clearly visible color impression, is hidden behind the, for example, illuminated displays
  • the sol-gel material used is in particular a sol-gel hybrid polymer lacquer system.
  • the pigments are preferably in the form of particles having a size smaller than 2 ⁇ m, preferably as particles smaller than 200 nm, very particularly as nanoparticles smaller than or equal to 100 nm
  • silicon oxide particles are preferably used.
  • the mass ratio of sol-gel particles in one embodiment of the invention is 10: 1 to 1: 1, preferably 5: 1 to 2: 1.
  • the absorbent pigments in one embodiment of the invention have a size of from 1 to 200 nm, preferably from 5 to 100 nm and more preferably from 10 to 50 nm.
  • the invention further relates to a
  • the coating material has the following mass-related composition: - 14 to 25%, preferably 15 to 22%, especially
  • a composite material which has the following composition by mass:
  • An organic crosslinking can be induced both thermally and photochemically.
  • crosslinking via hydrolysis and condensation reactions may also be thermally induced.
  • a composite material which has the following composition by mass:
  • the invention therefore relates in particular to a
  • pigmented hydride polymer based ink comprising chain and / or fibrous Si0 2 nanoparticles.
  • the color consists of a sol-gel hydrolyzate
  • Nanoparticles optionally organic crosslinker,
  • inorganic pigments high boiling solvent, initiators and additives.
  • the viscosity of a paint according to the invention is preferably from 150 to 125,000 mPas, preferably from 200 to 7,000 mPas, very particularly preferably from 250 to 3,000 mPas.
  • metal alkoxides are preferably used, in particular alkoxysilanes, for example TEOS (tetraethoxysilane) or TMOS (tetramethoxysilane).
  • alkoxysilanes for example TEOS (tetraethoxysilane) or TMOS (tetramethoxysilane).
  • OR1 organic radical, in particular methylate, ethylate, propylate, Butylate, sec. Butylate, in combination with an alkoxysilane, which is an organically crosslinkable
  • a further organosilane is used, for example Si (OR1) 3 R2, Si (OR1) 2 R2 2 , where R2 is methyl, phenyl, ethyl, aminopropyl, mercapto, for example MTEOS
  • Alkoxysilanes functionalized with organically crosslinkable monomers may be, for example: GPTES (3-glycidyloxypropyltriethoxysilane), MPTES
  • the T (tertiary) to Q (quaternary) group ratio is preferably 3: 1 to 5: 1, preferably 3.5: 1 to 4.5: 1.
  • the sol-gel precursor contains no M and or D groups.
  • the preparation of the hydrolyzate is carried out by the targeted reaction of the monomers with H 2 0 .. This is preferably carried out in the presence of an acid, in particular HCl,
  • the aqueous hydrolysis solution preferably has a pH of less than 4, most preferably less than 2.5.
  • the hydrolysis can also be carried out in an alkaline environment, in particular using NH 3 .
  • the hydrolysis is carried out with an aqueous nanoparticle dispersion.
  • the degree of crosslinking of the hydrolyzate can via the
  • the degree of crosslinking is preferably 5-70%, particularly preferably 11-50%, very particularly preferably 15-35%.
  • the degree of crosslinking can be determined by the method of 29 Si NMR spectroscopy known to the person skilled in the art.
  • the proportion of TO groups is preferably> 15% and that of the Tl groups is preferably> 35%.
  • the viscosity of the hydrolyzate is preferably 5 to 30 mPas, preferably 9 to 25 mPas.
  • Solvent for example ethanol, of the hydrolyzate used is preferably below 10% by mass.
  • the particles with chain and / or fibrous morphology are preferably over a
  • Liquid phase synthesis process in particular sol-gel-based alkaline catalyzed process or
  • Stöberrea manufactured.
  • a nonaqueous solvent is used.
  • the fibrous nanoparticles are produced via a hydrothermal process and / or a fiber spinning process and / or gas-phase-based processes.
  • fibrous particles are used which have been produced by electrospinning.
  • the boiling point is preferably more than 90 ° C, most preferably more than 110 ° C.
  • Preferred solvents are ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, methyl isobutyl ketones,
  • the viscosity of the nanoparticle-containing dispersion in one embodiment of the invention is 300-1500 mPas, preferably 400-700 mPas.
  • the nanoparticles can have an average size of 3 to 300 nm, a diameter of 3 to 70 nm and a length of 50 to 300 nm, preferably 70 to 150 nm.
  • Size and anisotropy can be determined by means of a
  • Rasterelektonenmikroskop be determined. Ten randomly selected particles are measured and entered
  • cationic and / or anionic and / or neutral surfactants used.
  • Coating material organic crosslinkers having a plurality of organic crosslinkable groups in particular epoxides or acrylates may be added, for example bis-epoxide or bismethacrylate.
  • Coating composition polyfunctional organic monomers and / or organosilanes. These monomers preferably have 2 or 3 or 4 organically crosslinkable
  • Preferred substances of this group are bismethacrylates, bisepoxides, bismethacrylate silanes, bisepoxy silanes,
  • Crosslinking agent may be 35: 1 - 10: 1, preferably 25: 1 - 15: 1, amount.
  • the following substances or mixtures thereof are particularly preferred: 3,4-epoxycyclohexanecarboxylate or
  • Ethylene glycol dimethacrylate polyethylene glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethacrylate,
  • pigments are preferably inorganic
  • These absorption pigments are preferably in nanoscale form having a primary particle size of 2 to 5000 nm,
  • TiN and ZrN and / or TiC and ZrC or oxidic pigments for example, TiN and ZrN and / or TiC and ZrC or oxidic pigments such as
  • the coating solution To initiate the crosslinking reaction of the organic functional groups, the coating solution
  • thermally activated starters may be added. These may be, for example, aluminum acetylacetonate or methylimidazole.
  • the coating solution UV activatable initiators such as iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -, hexafluorophosphate (1-) or
  • Irgacure 186® are added.
  • adhesion promoters may be added to the coating material. These may be, for example, amino and / or mercaptosilanes. For example, this may be 3-aminopropyltriethoxysilane or 3-mercaptopropyltrimethoxysilane.
  • the proportion of the coupling agent silanes can be between 1:30 and 1:10, preferably between 1:20 and 1:15, with respect to the further alkoxysilanes.
  • Coating material one or more amino functionalized silanes added.
  • Preferred amino-functionalized silanes are 3-aminopropyltrimethoxysilane, [3- (methylamino) propyl] trimethoxysilane, [3- (phenylamino) propyl] trimethoxysilane, [3- (diethylamino) propyl] trimethoxysilane, 3- [2- (2- Aminoethylamino) ethylamino] propyltrimethoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine, 1- [3-
  • the coating solution is preferred.
  • additives can constitute up to 5% by mass, preferably up to 2% by mass, of the coating solution and are referred to, for example, as deaerators, defoamers, levelers, and dispersing reagents. You can
  • EVONIC TEGO
  • these are pure and / or organically modified low molecular weight polysiloxanes, organic polymers, fluorine-functionalized polymers, Polyether-modified polymers, polysiloxanes and / or polyacrylates and basic and acidic fatty acid derivatives.
  • the dried and cured hydride polymer layer produced from the coating material consists of an organic and inorganic crosslinked sol-gel material, nanoparticles, optionally organic crosslinker,
  • the coating material according to the invention can be used both as a dried and / or cured lacquer as well as baked on the substrate, wherein organic.
  • Components of the coating material are at least partially removed. Under a branding in the sense of
  • the invention is understood to mean a thermal treatment in which organic components are decomposed.
  • the dried and / or cured layer contains an organic-inorganic network with chain-like
  • the pigmented layer (mass fraction less than 25%, preferably less than 15%) consists of an inorganic oxidic binder, crosslinked sol-gel material and inorganic
  • Nanoparticles and inorganic pigments are nanoparticles and inorganic pigments.
  • the organic degree of crosslinking of the dried but not baked layer is preferably greater than 30%, very particularly preferably greater than 50%.
  • the hardened layer (170 ° C., lh) in the N 2 sorption preferably exhibits a multipoint BET surface area of less than 10 m 2 / g, preferably less than 5 m 2 / g.
  • the oxide decomposition products of the sol-gel hydrolyzate are part of the skeleton-forming material consisting of
  • silicon-based sol-gel precursors result in Si0 2 .
  • Zr0 2 can be formed from Zr-based sol-gel precursors and from Al-based sol-gel precursors A1 2 0 3 and / or their mixed oxides.
  • the invention designed as a color
  • Coating material is particularly useful for the production of inorganic porous decorative layers
  • Special glass such as borosilicate glass and lithium-aluminum-silicate (LAS) - used glass ceramic.
  • LAS lithium-aluminum-silicate glass-ceramic: Li 2 0-Al 2 0 3 -Si0 2
  • LAS lithium-aluminum-silicate glass-ceramic: Li 2 0-Al 2 0 3 -Si0 2
  • high-quartz mixed crystals and / of the keatite mixed crystals as predominant
  • high temperature stable layers with a transmission less than 5%, preferably less than 3%, especially
  • preferably less than 0.5% can be produced.
  • non-platelet pigments can be used for coloring.
  • the temperature stability of the matrix used is preferably above 1000 ° C and the temperature stability of the inorganic coating is therefore usually dependent on the thermal stability of the pigments used. This advantage is achieved significantly by the use of a high proportion of more than 11% of chain-shaped and / or fibrous nanoparticles (preferably Si0 2 ).
  • the inventors have found that the chain-shaped nanoparticles have the internal cohesion of the inorganic
  • the coating material can be used as a paint for the production of decorative layers for white goods or vehicle glazes based on special glasses.
  • a coating material according to the invention in particular formed as a paint, can be produced, for example, as follows:
  • Rotary evaporator removes the solvent and obtain the so-called hydrolyzate.
  • Chain-shaped nanoparticles 1 1:
  • Spherical diameter of 15 nm) in isopropanol are mixed with 428 g of diethylene glycol monoethyl ether.
  • Chain-shaped nanoparticles 2 are chain-shaped nanoparticles 2:
  • Hybrid polymer color 1
  • Diethylene glycol monoethyl ether is 30 g of a
  • nanoscale ( ⁇ 100 nm) black pigment manganese ferrite spinel
  • 0.4 g of a flow-promoting paint additive is added.
  • the color is stirred homogeneously by means of a dissolver disc.
  • Hybrid polymer color 2
  • the color is stirred homogeneously by means of a dissolver disc.
  • Color 3 To 18 g of hydrolyzate 1 and 55 g of chain-shaped nanoparticles 1 are added 38 g of a nanoscale (30 nm) black pigment (CoFe204 spinel). Subsequently, 0.5 g of a foam-preventing paint additive is added.
  • a nanoscale (30 nm) black pigment CoFe204 spinel
  • the color is stirred homogeneously by means of a dissolver disc.
  • the color is stirred homogeneously by means of a dissolver disc.
  • the color is stirred homogeneously by means of a dissolver disc.
  • the hydride polymer ink 1 is printed on a transparent lithium-aluminum-glass-ceramic (LAS) glass-ceramic with a coefficient of expansion of 0 +/- 0.3 10-6 / K by means of a sieve 140 and then dried at 170 ° C. for 1 h.
  • LAS lithium-aluminum-glass-ceramic
  • the layer thickness is about 2.8 pm.
  • the Hydridpolymer case 4 by means of a 140 sieve it on a transparent lithium - aluminum glass ceramic (LAS) printed glass-ceramic having an expansion coefficient of 0 +/- 0.3 10 "6 / K and then at 170 ° C for 1 h dried.
  • LAS transparent lithium - aluminum glass ceramic
  • the layer thickness is about 3.0 ⁇ .
  • the hydride polymer paint 1 by means of a 140 sieve on a Borofloat glass substrate (SCHOTT AG) with a
  • the layer thickness is about 2.8 pm.
  • the coated substrate is then bent three-dimensionally with other substrates in the composite at about 590 ° C.
  • the coating does not melt and does not adhere to the other substrates in contact.
  • the coating does not burst.
  • the hydride polymer color 5 is coated by means of a 140 sieve on a Borofloat glass substrate (SCHOTT AG) with a
  • the layer thickness is about 2.8 pm.
  • the coated substrate is then bent three-dimensionally with other substrates in the composite at about 590 ° C.
  • the coating does not melt and does not adhere to the other substrates in contact.
  • the coating does not burst.
  • Fig. 1 shows schematically a composite material 1 produced according to the invention, which is a glass or
  • Glass-ceramic substrate 2 comprises.
  • Coating material 3 which is formed as a varnish applied by means of a screen printing process.
  • the coating material 3 can only be dried and cured. Further, the coating material 3 is resistant to high temperatures, during the burning of the
  • Coating material 3 are mainly removed.
  • Coating material be explained in more detail.
  • Fig. 2 shows by way of example the essential steps for the preparation of a hydrolyzate for forming a sol-based matrix.
  • a mixture of a silane with at least one organic crosslinkable substance and a tetravalent alkoxysilane is prepared.
  • one or more further organosilane monomers or organosilanol oligomers may be added.
  • Catalyst with a pH value of less than 4 becomes an inorganic condensation degree of 10 to 40%
  • an aqueous dispersion with oxidic nanoparticles can be used. These nanoparticles " can form an additional filler in the sol-gel matrix.
  • the coating material contains chain-shaped nanoparticles whose. Referring to Fig. 3
  • the chain-shaped nanoparticles which are produced for example by means of a Stöbervones, are provided in the form of a dispersion with a low-boiling solvent such as isopropanol.
  • Stabilization additive can be added.
  • Hydrolyzate which was prepared according to FIG. 2 was submitted. Then be added to the chain-like nanoparticles' in high-boiling solvents according to the preparation of FIG. 3.
  • organic crosslinkers, additives and starters are added and the hybrid polymer paint is ready.
  • FIG. 1 An exemplary processing of the coating material is shown in FIG.
  • the coating material in the form of
  • the coating material is dried and / or an organic crosslinking is carried out. This can already be done at room temperature or at a temperature up to 250 ° C.
  • the coating material is in preferred
  • a s either used as a cooking surface or for vehicle glazing, which at a temperature is bent between 500 to 700 ° C, wherein
  • the coating material was already applied before bending the disc.
  • Fig. 6 shows a table with a composition of the hybrid polymer lacquer according to the invention in a simple as well as in preferred and particularly preferred
  • the hybrid polymer lacquer has, on the one hand, binder components which comprise a sol-gel hydrolyzate, nanoparticles and organic crosslinkers.
  • the hybrid polymer varnish comprises a high boiling solvent.
  • starters and additives may be added in the amount mentioned in FIG.
  • Fig. 7 shows schematically examples of the morphology of the chain-shaped and fibrous nanoparticles used.
  • Secondary particles formed which can reach a length of well over 100 nm.
  • fibrous nanoparticles may also be used.
  • FIGS. 8 and 9 show SEM images of dried chain-shaped Si0 2 nanoparticles.
  • the primary particle size is about 15 nm and the chain length is at values of 39-89 nm.
  • Primary particle size of about 15 nm.
  • the measured particle size is about 38 nm with a relatively small scattering
  • Differences from SEM to DLS - Particle size measurements are due, among other things, to the fact that DLS measures the average hydrodynamic radius of the particles.
  • Fig. 11 shows the DLS measurement of a highly diluted alcoholic dispersion with predominantly
  • the particles show a chain-like. Morphology in SEM at a primary particle size of about 15 nm and a mean chain length of 120 nm.
  • Scattering is (standard deviation: about 71 nm.
  • Chain-shaped geometry is therefore primarily evident in the large range of the measured values.
  • Fig. 12 shows schematically the essential components of a hybrid polymer layer according to the invention after drying at a temperature between 140 and 250 ° C.
  • the solvent has now been largely removed so that the now cross-linked organic and inorganic components of the coating material are left over.
  • Fig. 13 shows schematically the pore volume
  • Nitrogen adsorption was determined.
  • crosslinked coating material is substantially dense, thus having no microporous or mesoporous structures.
  • Fig. 14 shows schematically the viscosity (y-axis), wherein the time in weeks is plotted on the y-axis of two embodiments of the invention. It can be seen that the viscosity is still above 20,000 mPa s after an initial, partially significant decrease within the first two weeks even after eight weeks.
  • Fig. 15 shows the composition of
  • the coating consists of oxidic components, which are predominantly transparent oxidic
  • the coating has a high inorganic content
  • FIG. 16 shows a BET nitrogen adsorption porosimetry measurement on scraped-off layer components of FIG
  • the layer shows a clearly micro- and mesoporous structure.
  • a bimodal pore distribution can be recognized. They are both
  • Micropores (about lnm radius) and mesopores with a radius of 3 - 5 nm determinable.
  • the mesopore volume is
  • the surface volume of the pores has only compared to that dried layer increased to more than 50 to 100 times the value.
  • 17 shows the color of an exemplary layer in the Lab color space, on the one hand after drying on the other after firing.
  • the values for a and b vary only slightly by 0. Furthermore, the L value is preferably below 30 even after the penetration, at least in one exemplary embodiment.
  • the layer is therefore black.
  • Fig. 18 shows the transmission characteristic, wherein the
  • Transmission in% is plotted on the y-axis.
  • the transmission is less than 0.5%.
  • the layer is therefore opaque.
  • the invention has made it possible to provide a screen-printable coating system for glass or glass-ceramic substrates, in which even high-temperature stress does not crack and does not detach.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Composite Materials (AREA)
  • Dispersion Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Surface Treatment Of Glass (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un matériau de revêtement, lequel comprend un système de peinture sol-gel, des pigments ainsi que des nanoparticules en forme de chaîne ou fibreuses. Le système de peinture est stable à haute température et est approprié à un substrat en verre ou en vitrocéramique présentant de faibles coefficients de dilatation thermique.
EP12733590.9A 2011-06-06 2012-06-06 Matériau de revêtement pour un substrat en verre ou en vitrocéramique ainsi que substrat en verre ou en vitrocéramique enduit Withdrawn EP2718240A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201110050872 DE102011050872A1 (de) 2011-06-06 2011-06-06 Semitransparentes Beschichtungsmaterial
PCT/EP2012/002418 WO2012167932A1 (fr) 2011-06-06 2012-06-06 Matériau de revêtement pour un substrat en verre ou en vitrocéramique ainsi que substrat en verre ou en vitrocéramique enduit

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EP2718240A1 true EP2718240A1 (fr) 2014-04-16

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EP12716339.2A Pending EP2718239A1 (fr) 2011-06-06 2012-04-13 Matériau de revêtement semi-transparent
EP12733590.9A Withdrawn EP2718240A1 (fr) 2011-06-06 2012-06-06 Matériau de revêtement pour un substrat en verre ou en vitrocéramique ainsi que substrat en verre ou en vitrocéramique enduit

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EP (2) EP2718239A1 (fr)
JP (1) JP2014522370A (fr)
CN (1) CN103596895A (fr)
DE (1) DE102011050872A1 (fr)
WO (2) WO2012167977A1 (fr)

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DE102013110783A1 (de) * 2013-09-30 2015-04-02 Schott Ag Teilweise beschichtete Verbundglasscheibe sowie Verfahren zu deren Herstellung und Beschichtung für eine Verbundglasscheibe
CN104087157B (zh) * 2014-06-25 2016-02-17 上海宜瓷龙新材料股份有限公司 一种用于公共场合装饰墙的陶瓷涂料
US10457562B2 (en) 2015-03-27 2019-10-29 Trent University Anti-corrosion sol-gel material
CN104987834B (zh) * 2015-06-24 2017-07-11 慧智科技（中国）有限公司 耐刮擦玻璃涂层
ES2597749B1 (es) * 2015-07-20 2017-12-26 Bsh Electrodomésticos España, S.A. Componente de aparato doméstico que comprende un elemento base con un recubrimiento funcional
AU2016343719B2 (en) * 2015-10-30 2021-03-04 Corning Incorporated Glass articles with mixed polymer and metal oxide coatings
US10131802B2 (en) 2015-11-02 2018-11-20 Metashield Llc Nanosilica based compositions, structures and apparatus incorporating same and related methods
ES2629062B1 (es) * 2015-12-22 2018-06-08 Bsh Electrodomésticos España, S.A. Proceso para fabricar un componente de aparato doméstico
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FR3057576B1 (fr) * 2016-10-14 2020-06-19 Etablissements Tiflex Nouvelle encre sol-gel destinee a l’impression par serigraphie
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DE102017127624A1 (de) 2017-11-22 2019-05-23 Schott Ag Beschichtetes Glas- oder Glaskeramik-Substrat, Beschichtung umfassend geschlossene Poren sowie Verfahren zur Beschichtung eines Substrats
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Also Published As

Publication number Publication date
DE102011050872A1 (de) 2012-12-06
WO2012167977A1 (fr) 2012-12-13
EP2718239A1 (fr) 2014-04-16
US9758425B2 (en) 2017-09-12
JP2014522370A (ja) 2014-09-04
US20150037563A1 (en) 2015-02-05
CN103596895A (zh) 2014-02-19
US20150024145A1 (en) 2015-01-22
WO2012167932A1 (fr) 2012-12-13

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