WO2020221714A1 - Mélange pigment/fritte - Google Patents

Mélange pigment/fritte Download PDF

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Publication number
WO2020221714A1
WO2020221714A1 PCT/EP2020/061686 EP2020061686W WO2020221714A1 WO 2020221714 A1 WO2020221714 A1 WO 2020221714A1 EP 2020061686 W EP2020061686 W EP 2020061686W WO 2020221714 A1 WO2020221714 A1 WO 2020221714A1
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WO
WIPO (PCT)
Prior art keywords
sno
pseudobrookite
sio
layer
pigment
Prior art date
Application number
PCT/EP2020/061686
Other languages
German (de)
English (en)
Inventor
Jens Kersten
Cairon PLATZER
Emma ZHANG (Ke)
Sheng TANG (Thomson)
Robert BAI
Original Assignee
Merck Patent Gmbh
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 Merck Patent Gmbh filed Critical Merck Patent Gmbh
Priority to EP20723319.8A priority Critical patent/EP3963008A1/fr
Priority to CN202080032274.2A priority patent/CN113767152A/zh
Priority to KR1020217038391A priority patent/KR20220003011A/ko
Priority to JP2021564479A priority patent/JP2022540280A/ja
Publication of WO2020221714A1 publication Critical patent/WO2020221714A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
    • C09C1/0027—One layer consisting of at least one sub-stoichiometric inorganic compound
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/86—Glazes; Cold glazes
    • C—CHEMISTRY; METALLURGY
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
    • C09C1/003—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index comprising at least one light-absorbing layer
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
    • C09C1/003—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index comprising at least one light-absorbing layer
    • C09C1/0039—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index comprising at least one light-absorbing layer consisting of at least one coloured inorganic material
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
    • C09C1/003—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index comprising at least one light-absorbing layer
    • C09C1/0039—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index comprising at least one light-absorbing layer consisting of at least one coloured inorganic material
    • C09C1/0042—Sub-stoichiometric inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1087—Interference pigments characterized by the core material the core consisting of bismuth oxychloride, magnesium fluoride, nitrides, carbides, borides, lead carbonate, barium or calcium sulfate, zinc sulphide, molybdenum disulphide or graphite
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/301—Thickness of the core
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/302—Thickness of a layer with high refractive material
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    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/303—Thickness of a layer with low refractive material
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/305—Thickness of intermediate layers within the stack
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/307—Thickness of an outermost protective layer
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/308—Total thickness of the pigment particle
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    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/401—Inorganic protective coating
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    • C09C2210/00—Special effects or uses of interference pigments
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    • C09C2220/00—Methods of preparing the interference pigments
    • C09C2220/10—Wet methods, e.g. co-precipitation
    • C09C2220/106—Wet methods, e.g. co-precipitation comprising only a drying or calcination step of the finally coated pigment

Definitions

  • the invention relates to frits or frit mixtures with effect pigments for ceramic glazes which are stable above 900 ° C. and produce a so-called “liquid metal effect” in ceramic glazes.
  • Effect pigments are often used to decorate ceramic, metallic or glass-like materials.
  • the effect pigments are mixed with so-called glass frits / rivers and applied to the workpiece to be decorated using a medium.
  • the medium here depends on the type of application. For screen printing it can e.g. one
  • the medium is only used for application and is for the
  • Effect pigment one unit A composite layer is created consisting of effect pigments which are embedded in a continuous glass matrix.
  • Substrates for achieving glittering pearlescent luster or metallic effects in ceramic glazes are known, for example, from DE 10 2015 013 400 A1 and CN 101462895A.
  • High-gloss and non-glittering surfaces, as we know them from polished metals, are made possible by the rigid, platelet-shaped structure of the Effect pigments prevented.
  • the pigments are not completely plane-parallel to the surface of the glaze. The one from it
  • Suitable frits are those which have a precisely defined content of sodium oxide.
  • the effect pigment is dissolved during firing, whereby dissolving means that the metal oxides of the pigment form tiny crystals in a very aggressive medium, which change the refractive index of the glaze on its surface and are responsible for the so-called liquid metal effect.
  • the actual color bodies are therefore only during of the penetration formed in situ, as the pigments change during the
  • the subject of the invention is therefore an effect pigment / frit mixture that is characterized in that the frit contains 3-7% sodium oxide and the effect pigment is based on platelet-shaped substrates based on the
  • Oxides can be doped in amounts of £ 10% by weight based on layer (B),
  • n 3 1, 8 consisting of at least two colorless
  • Oxides can be doped in amounts of £ 10% by weight based on layer (E), and optionally
  • the glazes from the pigment / frit mixture according to the invention are abrasion-resistant and stable to detergents as well as those of the Cleaning of dishes with normal mechanical loads. In addition, they can be used in microwave ovens without any problems.
  • the pigment-frit mixture is suitable for decorating ceramic objects selected from the group of porcelain, bone china and earthenware, in particular porcelain stoneware tiles, stoneware tiles,
  • the pigment / frit mixture according to the invention consists of 20-70% by weight effect pigment and 30-80% by weight frit and optionally 0-10% by weight of one or more additives, the sum of pigment, frit and additives 100% results.
  • the pigment weight fraction in the effect pigment / frit mixture is preferably 20-70% by weight, very particularly preferably 25-60% by weight
  • the effect pigment is an essential component of the effect pigment / ZFring mixture according to the invention.
  • Suitable base substrates for the effect pigments of the invention are semitransparent and transparent platelet-shaped substrates.
  • Preferred substrates are layered silicate flakes, SiC, TiC, WC, B 4 C, BN, graphite, iO 2 and Fe 2 O 3 flakes, doped or undoped Al 2 O 3 flakes, doped or undoped glass flakes , doped or undoped SiO 2 flakes, TiO 2 flakes, BiOCI and mixtures thereof.
  • natural and synthetic mica flakes, muscovite, talc and kaolin are particularly preferred.
  • synthetic mica fluorophlogopite or Zn phlogopite are preferably used as substrate.
  • the glass platelets can consist of all types of glass known to those skilled in the art, provided they are temperature-stable in the firing range used. Suitable glasses are, for example, quartz glass, A-glass, E-glass, C-glass, ECR-glass, waste glass, alkali borate glass, alkali silicate glass, borosilicate glass, Duran® glass, laboratory glass or optical glass.
  • the refractive index of the glass flakes is preferably 1.45-1.80, in particular 1.50-1.70. Particularly preferred are the
  • Glass substrates made of C glass, ECR glass or borosilicate glass.
  • Synthetic substrate wafers such as glass wafers, SiO 2 wafers,
  • Al 2 O 3 platelets can be doped or undoped. If they are doped, the doping is preferably Al, N, B, Ti, Zr, Si, In, Sn, or Zn or mixtures thereof. Furthermore, further ions from the group of transition metals (V, Cr, Mn, Fe, Co, Ni, Cu, Y, Nb, Mo, Hf, Sb, Ta, W) and ions from the group of lanthanides can serve as dopants.
  • transition metals V, Cr, Mn, Fe, Co, Ni, Cu, Y, Nb, Mo, Hf, Sb, Ta, W
  • ions from the group of lanthanides can serve as dopants.
  • the substrate is preferably undoped or doped with TiO 2 , ZrO 2 or ZnO.
  • the Al 2 O 3 platelets are preferably corundum.
  • Suitable Al 2 O 3 flakes are preferably doped or undoped a-Al 2 O 3 flakes, in particular a-Al 2 O 3 flakes doped with TiO 2 or ZrO 2 .
  • the proportion of doping is preferably 0.01-5% by weight, in particular 0.10-3% by weight, based on the substrate.
  • the size of the base substrates is not critical per se and can be tailored to the particular application.
  • the platelet-shaped substrates have a thickness between 0.05 and 5 mm, in particular between 0.1 and 4.5 mm.
  • Substrates of different particle sizes can also be used.
  • a mixture of mica fractions of N-mica (10-60 mm), F-mica (5-20 mm) and / or M-mica ( ⁇ 15 mm) is particularly preferred.
  • N and S fractions (10-130 mm) and F and S fractions (5-130 mm) are also preferred.
  • Typical examples of particle size distributions are:
  • D 1 0 1 - 50 mm, in particular 2-45 mm, most preferably 5-40 mm D 50: 7 - 275 mm, especially 10-200 mm, preferably 15-150 mm especially D 90 : 15-500 mm, in particular 25-400 mm, very particularly preferably 50-200 mm.
  • high refractive index means a refractive index of 3 1.8
  • low refractive index means a refractive index of ⁇ 1.8
  • Effect pigment is essential for the stability of the pigment and the optical properties.
  • the layer (A) is a high-index layer with a refractive index of n 3 1, preferably n 3 2.0.
  • the layer (A) can be colorless or absorbent in visible wave light.
  • Layer (A) preferably consists of metal oxides or metal oxide mixtures.
  • the metal oxide is preferably selected from the group TiO 2 , ZrO 2 , ZnO, SnO 2 , Cr 2 O 3 , Ce 2 O 3 , BiOCI, Fe 2 O 3 , Fe 3 O 4 , FeO (OH), Ti suboxides ( TiO 2 partially reduced with oxidation numbers of ⁇ 4 to 2 and lower oxides such as Ti 3 O 5 , Ti 2 O 3 up to TiO), titanium oxynitride and titanium nitride, CoO, CO 2 O 3 , Co 3 O 4 , VO 2 , V 2 O 3 , NiO, WO 3 , MnO, Mn 2 O 3 or mixtures of these
  • Layer (A) preferably consists of TiO 2 , Fe 2 O 3 , Cr 2 O 3 or SnO 2 .
  • the layer (A) preferably has a layer thickness of 1-15 nm
  • the pseudobrookit layers (B) and (E) can be the same or different.
  • the layers are preferably identical in composition.
  • the pseudobrookite layers preferably consist entirely of Fe 2 TiO 5 .
  • the Fe 2 TiO 5 can be slightly over or under stoichiometric due to slight variations in the Fe / Ti ratio and the resulting lattice vacancies.
  • the layers can be produced by simultaneous addition and precipitation of an Fe-containing and a Ti-containing salt solution or by co-precipitation from a single solution containing Fe and Ti salts.
  • the pseudobrookite layers should preferably consist of 100% crystalline pseudobrookite.
  • the oxides are preferably selected from the group Al 2 O 3 , Ce 2 O 3 , B 2 O 3 , ZrO 2 , SnO 2 , Cr 2 O 3 , CoO, Co 2 O 3 , Co 3 O 4 , Mn 2 O 3 .
  • Oxide mixture in the pseudobrookite layer is preferably not more than 5% by weight and is in particular in the range of 1-5% by weight, very particularly preferably 1-3% by weight, based on layer (B) or layer (E. ).
  • the layers (B) and (E) each have independent of one another
  • Layer thicknesses preferably in the range of 60-120 nm, in particular 70-110 nm, and very particularly preferably 80-100 nm.
  • layers (B) and (E) are separated from one another by a separation layer (C) and a separation layer (D).
  • the distance between layers (B) and (E) should preferably be 40-100 nm, in particular 45-90 nm and very particularly preferably 50-80 nm.
  • the silicate layer can be doped with further alkaline earth or alkali ions.
  • Layer (C) is preferably a “silicate” layer.
  • Layer (C) very particularly preferably consists of doped or undoped SiO 2 .
  • Layer (C) preferably has a layer thickness of 40-90 nm
  • the high-index coating of layer (D) with a refractive index of n 3 1.8, preferably n 3 2.0, consists of at least two colorless metal oxide layers.
  • Layer (D) preferably consists of 2 or 3 colorless metal oxide layers. The metal oxides are preferred
  • the coating of the layer (D) preferably consists of the
  • the coating of layer (D) preferably has layer thicknesses of 10-25 nm, in particular 11-21 nm and very particularly preferably 12-17 nm. The sum of all layer thicknesses of the individual metal oxide layers
  • Pseudobrookit layers (B) and (E) contribute if the total layer thickness of the layers (C) and (D) do not exceed the thickness range of 120 nm and are preferably in the range 50-115 nm, in particular 51-91 nm and very particularly preferably 62-77 nm. If the layer (A) or (D) consists of iO 2 , the iO 2 can be in the rutile or anatase modification.
  • Particularly preferred effect pigments have the following structure: substrate + iO 2 + pseudobrookite + SiO 2 + SnO 2 + iO 2 + SnO 2 +
  • the metal oxide layer (s) are preferably applied wet-chemically, with those developed for the production of pearlescent pigments
  • Such methods are e.g. B. described in U.S. 3087828, U.S. 3087829, U.S. 3553001, DE 14 67 468, DE 19 59 988, DE 20 09 566, DE 22 14 545, DE 22 15 191, DE 22 44 298, DE 23 13 331, DE 25 22 572, DE 31 37 808, DE 31 37 809, DE 31 51 343, DE 31 51 354, DE 31 51 355, DE 32 11 602, DE 32 35 017, DE 196 18 568, EP 0 659 843, or in other patent documents and other publications known to the person skilled in the art.
  • the substrate platelets are suspended in water and one or more hydrolyzable metal salts are added at a pH value suitable for flydrolysis, which is selected so that the Metal oxides or metal oxide hydrates are precipitated directly on the platelets without secondary precipitation occurring.
  • the pH is usually kept constant by adding a base and / or acid at the same time.
  • the effect pigments are then separated off, washed and dried and, if necessary, calcined, it being possible for the calcination temperature to be optimized with regard to the particular coating present.
  • the annealing temperatures are between 250 and 1000 ° C, preferably between 350 and 900 ° C. If desired, after the application of individual coatings, the pigment can be separated off, dried and, if necessary, calcined in order then to be resuspended again for the precipitation of the further layers.
  • the coating can also be carried out in a fluidized bed reactor by gas phase coating, e.g. the methods proposed in EP 0 045 851 and EP 0 106 235 for the production of pearlescent pigments can be used accordingly.
  • the hue of the pigments can be varied within wide limits by different choices of the amounts of coating or the resulting layer thicknesses.
  • the fine-tuning for a certain color shade can be achieved beyond the pure choice of quantity by approaching the desired color with a visual or measurement technique.
  • the layer (F) is preferably a layer made of SnO 2.
  • Coating (s) in this patent application are understood to mean the complete covering / covering of the platelet-shaped substrates.
  • the optimal orientation of the color bodies in the glaze is supported by the frit containing Na 2 O.
  • the effect increases with increasing pigment concentration from 3 30% by weight to 3 50% by weight up to 3 70% by weight.
  • Frit melt Temperature stability as well as stability to chemically highly reactive medium (the frit melt) play a decisive role in the use of the pigment / frit mixture.
  • the use of frits containing Na 2 O significantly increases the temperature stability.
  • the Na 2 O proportion in the frit is 3 to 7% by weight, in particular 4 to 6.5% by weight, and very particularly preferably 5 to 6% by weight, based on the frit.
  • suitable commercially available frits contain common constituents such as Al 2 O 3 , SiO 2 , B 2 O 3 , TiO 2 , ZrO 2 , Sb 2 O 3 , P 2 O 5 , Hf 2 O, Fe 2 O 3 , ZnO, PbO, alkali oxides such as Li 2 O, K 2 O, alkaline earth oxides such as CaO, BaO, MgO, SrO, and oxides of rare earths.
  • Preferred fries included - (Na 2 O + K 2 O + Li 2 O) £ 10 wt.%
  • the frit mixtures 0-10% by weight can be used as additional components
  • Contain additives based on the pigment / frit mixture e.g. inorganic color pigments clay, kaolin, bentonite or organic
  • Substances e.g. to adjust the stability of the glaze slip.
  • the particles of the frits preferably have particle sizes of 1-20 mm, in particular 3-15 mm and very particularly preferably 5-12 mm.
  • Suitable frits / flows with an Na 2 O content in the range from 3 to 7% by weight, based on the frit, are commercially available, for example from Ferro, Sicer or Zschimmer & Schwarz. As an example, without restricting the number of frits / flows that can be used,
  • Sicer STDA450-76AT Torrecid EPS06321A, Ferro 10191 1, 101915, 101600, 101650 840, Sicer -SM1 12 / SM1 14 / SM140.
  • the pigment-frit mixture is suitable for decorating ceramic objects on the basis of porcelain, bone china and earthenware.
  • Suitable workpieces for the pigment / frit mixture according to the invention are specified in the table below: unfired, pre-glazed with engobe, burned, burned
  • the pigment / frit mixture according to the invention can be applied to the workpiece, for example by
  • decoration powder e.g. grit Vetrosa
  • decoration powder e.g. grit Vetrosa
  • pre-printed glue then sprinkled with decoration powder and finally vacuumed or blown.
  • a particularly pronounced liquid metal effect is achieved when the frit used in the pigment-frit mixture or a frit similar in composition and melting behavior is applied as an intermediate layer (so-called "underlay") between the ceramic or glaze and the pigment-frit mixture. Both layers, underlay and mixture of pigment and frit, are applied separately, but then baked together. Underlay and pigment-frit mixture can for example by
  • Spray application can be applied to the glazed or unglazed ceramic surface.
  • the total layer thicknesses measured after firing are
  • the baking temperatures vary with the frits used. Typical stoving temperatures for the pigment-frit mixture according to the invention are in the range of 950.degree. C. and 1150.degree.
  • stable inorganic color pigments or color pigments can be added to the pigment / frit mixture according to the invention.
  • the proportion of color pigments is 0-30% by weight, in particular 0-15% by weight and very particularly preferably 0-10% by weight, based on the pigment / frit mixture.
  • Suitable and stable color pigments are, for example, green chromium oxide pigments, black spinel pigments, yellow-brown rutile pigments, cadmium red and yellow, cobalt blue pigments.
  • Such color pigments are commercially available, for example, from Ferro and Shepard.
  • Pigment / frit mixture are characterized by a particularly high gloss in combination with low sparkle values and show the
  • the invention also relates to the use of the pigment / frit mixture according to the invention for ceramic glazes on fired or unfired bricks, floor and wall tiles for indoor or outdoor use
  • the invention thus also relates to formulations comprising the effect pigment / frit mixture according to the invention.
  • the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution.
  • the pH is raised to 7.5 and at this pH 650 ml of sodium water glass solution (13% by weight SiO 2 ) are slowly metered in, the pH being constant with 10% hydrochloric acid is held.
  • the pH is lowered to 1.8 with 10% hydrochloric acid and a solution of 5 g SnCl 4 ⁇ 5 H 2 O and 41 ml hydrochloric acid (20%) is metered in.
  • 105 ml of TiCl 4 solution 400 g / l TiCl 4
  • a solution consisting of 5 g SnCl 4 ⁇ 5 H 2 O and 41 ml hydrochloric acid (20%) is then added again.
  • the pH is kept constant at 1.8 with 32% sodium hydroxide solution.
  • the pH is then adjusted to 2.8 again using sodium hydroxide solution.
  • the coated mica substrate is filtered off, washed and dried at 110 ° C. for 16 h.
  • the effect pigment obtained is calcined at 850 ° C. for 0.5 h and sieved.
  • Example 2 A temperature-stable golden multilayer pigment with high brilliance is obtained.
  • the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution.
  • the pH is raised to 7.5 and at this pH 650 ml of sodium water glass solution (13% by weight SiO 2 ) are slowly metered in, the pH being constant with 10% hydrochloric acid is held.
  • the pH is lowered to 1.8 with 10% hydrochloric acid and a solution of 5 g SnCl 4 ⁇ 5 H 2 O and 41 ml hydrochloric acid (20%) is metered in.
  • 105 ml of TiCl 4 solution 400 g / l TiCl 4
  • mice substrate was filtered off, washed and dried at 110 ° C. for 16 h.
  • the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution.
  • the pH is raised to 7.5 and at this pH 650 ml of sodium waterglass solution (13% by weight SiO 2 ) are slowly metered in, the pH being kept constant with 10% hydrochloric acid .
  • the pH is lowered to 1.8 with 10% hydrochloric acid and a solution of 5 g SnCl 4 ⁇ 5 H 2 O and 41 ml hydrochloric acid (20%) is metered in.
  • 105 ml of TiCl 4 solution 400 g / l TiCl 4
  • mice substrate is filtered off, washed and dried at 110 ° C. for 16 h.
  • the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution.
  • the pH is raised to 7.5 and at this pH 650 ml of sodium waterglass solution (13% by weight SiO 2 ) are slowly metered in, the pH being kept constant with 10% hydrochloric acid .
  • the pH is lowered to 1.8 with 10% hydrochloric acid and a solution of 5 g SnCl 4 ⁇ 5 H 2 O and 41 ml hydrochloric acid (20%) is metered in.
  • 105 ml of TiCl 4 solution 400 g / l TiCl 4
  • the pH is kept constant at 1.8 with 32% sodium hydroxide solution.
  • the pH is then adjusted to 2.8 again using sodium hydroxide solution.
  • the effect pigment is calcined at 850 ° C. for 0.5 h and sieved.
  • a temperature-stable golden multilayer pigment with a very strong glitter effect is obtained.
  • Example 5 100 g of SiO 2 flakes with a particle size of 10-40 mm are in 2 l
  • Demineralized water heated to 80 ° C with stirring. After reaching 44 g of TiCl 4 solution (400 g / l of TiCl 4 ) are metered in at pH 1.8 at pH 1.8, the pH being kept constant with 32% sodium hydroxide solution. The pH value is then adjusted to 2.8 using sodium hydroxide solution and at this pH value and 75 ° C, 600 ml of an aqueous FeCl 3 solution (w (Fe) 7%) and 462 ml of an aqueous TiCl 4 - Solution (200 g TiCl 4 / l) added. During the entire addition time, the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution.
  • the pH is then adjusted to 2.8 again using sodium hydroxide solution.
  • TiCl 4 solution 200 g TiCl 4 / l
  • the SiO 2 flakes coated in this way are filtered off, washed and dried at 110 ° C. for 16 h.
  • the effect pigment is calcined at 850 ° C. for 0.5 h and sieved.
  • a temperature-stable golden multilayer pigment with high brilliance and good hiding power is obtained.
  • the pH is kept constant by simultaneous dropwise addition of a 32% sodium hydroxide solution.
  • the pH is raised to 7.5 and at this pH 650 ml sodium water glass solution (13% by weight SiO 2 ) are slowly metered in, the pH being kept constant with 10% hydrochloric acid becomes.
  • the pH is lowered to 1.8 with 10% hydrochloric acid and a
  • Solution of 5 g SnCl4x 5 H 2 O and 41 ml hydrochloric acid (20%) are metered in.
  • 105 ml of TiCl 4 solution (400 g / l TiCl 4) are now slowly metered in.
  • a solution consisting of 5 g SnCl 4 ⁇ 5 H 2 O and 41 ml hydrochloric acid (20%) is then added again.
  • the pH is kept constant at 1.8 with 32% sodium hydroxide solution.
  • the pH value is then adjusted to 2.8 again using sodium hydroxide solution.
  • mice substrate is filtered off, washed and dried at 110 ° C. for 16 h. Finally, the effect pigment obtained in this way is calcined at 850 ° C. for 0.5 h and sieved. A temperature-stable golden multilayer pigment with high brilliance and moderate hiding power is obtained.
  • the talc flakes coated in this way are filtered off, washed and dried at 110 ° C. for 16 h. Finally, the effect pigment obtained in this way is calcined at 850 ° C. for 0.5 h and sieved.
  • a temperature-stable golden multilayer pigment with high hiding power is obtained.
  • the pH value is increased by simultaneous dropwise addition of a 32% sodium hydroxide solution kept constant.
  • the pH is raised to 7.5 and at this pH 650 ml of sodium water glass solution (13% by weight SiO 2 ) are slowly metered in, the pH being constant with 10% hydrochloric acid is held.
  • the pH is lowered to 1.8 with 10% hydrochloric acid and a solution of 5 g SnCl 4 ⁇ 5 H 2 O and 41 ml hydrochloric acid (20%) is metered in.
  • 105 ml of TiCl 4 solution 400 g / l TiCl 4
  • a solution consisting of 5 g SnCl 4 ⁇ 5 H 2 O and 41 ml hydrochloric acid (20%) is then added again.
  • the pH is kept constant at 1.8 with 32% sodium hydroxide solution. in the
  • the pH is then adjusted to 2.8 again using sodium hydroxide solution.
  • the coated mica substrate is filtered off, washed and dried at 110 ° C. for 16 h.
  • the effect pigment is calcined at 850 ° C. for 0.5 h and sieved.
  • a temperature-stable golden multilayer pigment with a strong glitter effect is obtained.
  • Stoneware / well-tiles porcelain (e.g. hard porcelain, soft porcelain,
  • the decoration can be in addition to the ceramic color
  • underlay one or more forms
  • the latter can produce interesting effects (relief printing).
  • the degree of gloss of the pigmented glaze can be influenced by choosing the underlay.
  • the points AE do not necessarily have to be given in the application; depending on the case, points are skipped or replaced. In general, to achieve the effect described, the individual points AE can be combined as desired and / or used twice. All combinations from AE (tables) can produce the liquid metal effect with the effect pigments according to Examples 1-8. The possible combinations are shown schematically in Fig. 3. In addition to the effect pigments of Examples 1 to 8, the following commercially available effect pigments in the combinations of AE are also tested analogously:
  • BASF BASF shiny gold
  • Screen printing - example A1 Screen printing application with underlay, indirect
  • Decorative paste printed congruently on the underlay layer This is followed by intermediate drying again at 0-40 ° C until it is smudge-proof. Then a cover coat (Ferro 80 450) is printed over and dried again at 0-40 ° C until it is smudge-proof.
  • the finished decal is removed with the help of water and applied to Fine China (plate from Villeroy & Boch) and finally baked at 1060 ° C. with a holding time of 3 minutes.
  • Screen printing - example A2 Screen printing application with underlay, directly on porcelain stoneware tile
  • the underlay layer is preprinted onto the porcelain stoneware tile and dried at 0-40 ° C until it is smudge-proof.
  • the decor paste is then printed onto the underlay layer in an overlapping manner. It is then dried again at 0-40 ° C. until it is smudge-proof. Finally, it is baked in at 1050 ° C with a holding time of 10 minutes.
  • the overlapping printing of the decorative layer on the underlay layer results in relief effects that contain matt and glossy areas.
  • Screen printing - example A3 Screen printing application with pre-fired underlay, directly on stoneware tile
  • the underlay layer is preprinted onto the stoneware tile and dried at 0-40 ° C until it is smudge-proof. Then baked at 1050 ° C with a holding time of 10 minutes.
  • the decor paste is then printed onto the pre-fired underlay layer in an overlapping manner. It is then dried again at 0-40 ° C. until it is smudge-proof. Finally, it is baked in at 1050 ° C with a holding time of 10 minutes.
  • the overlapping printing of the decorative layer on the underlay layer results in relief effects that contain matt (without underlay) and glossy areas (with underlay).
  • Screen printing - example A4 indirect screen printing application with underlay on an extra sliding image
  • the decor paste is printed on a transfer paper and dried at 0-40 ° C until it is smudge-proof. Then a cover coat (Ferro 80 450) is printed over and dried again at 0-40 ° C until it is smudge-proof.
  • the finished decal with underlay is removed with the help of water and applied to hard porcelain.
  • the finished decal with decorative paint is removed with the help of water and transferred to the applied underlay applied to the hard porcelain and finally fired at 1115 ° C with a holding time of 3 minutes.
  • a pre-fired biscuit tile is coated with an engobe and then glazed with an underlay. After that there is a screen printing
  • the coated, glazed and printed tile is then fired at 1090 ° C. for a holding time of 8 minutes.
  • An unfired tile is coated with an engobe and
  • the coated, glazed and printed tile is then fired at 1090 ° C. for a holding time of 8 minutes.
  • Rotocolor - Example A7 unfired tiles (green goods) with engobe and direct Rotocolor application on unfired glaze Material:
  • the coated, glazed and printed tile is then fired at 1090 ° C. for a holding time of 8 minutes.
  • Rotocolor - Example 8 unfired tile (green goods) with engobe and direct Rotocolor application on unfired glaze with
  • the coated, glazed and double-printed tile is then fired at 1100 ° C. for a holding time of 8 minutes.
  • Rotocolor - Example A9 pre-fired tile (biscuit) with engobe and direct Rotocolor application on unfired glaze with
  • Spray application - example A10 unfired tile (green goods) with engobe and spray application with effect glaze
  • Pigment / frit mixture are characterized by a particularly high gloss in combination with low sparkle values and show the
  • the shine is achieved with a Rhopoint IQ mini 2.0.
  • the liquid metal glazes are characterized by the following gloss values:
  • the fired effect glazes are characterized by a particularly high gloss in combination with low sparkle values.
  • the gloss is determined with a Rhopoint IQ mini 2.0 (goniophotometer).
  • the liquid metal glazes are characterized by the following gloss values:
  • the sparkle is determined with a BYK mac measuring device.
  • the sparkle is below the measurable range in the lighting angles of 45 ° and 75 °. Unevenness in the glaze surface can lead to measured values of up to 2 (Sa and Si) at an angle of 15 °. The SG value is then also 0.

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Abstract

L'invention concerne des frittes ou des mélanges de frittes avec des pigments à effets pour les glaçures céramiques qui sont stables au-dessus de 1000 °C et produisent un effet dit de métal liquide dans les glaçures.
PCT/EP2020/061686 2019-04-30 2020-04-28 Mélange pigment/fritte WO2020221714A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP20723319.8A EP3963008A1 (fr) 2019-04-30 2020-04-28 Mélange pigment/fritte
CN202080032274.2A CN113767152A (zh) 2019-04-30 2020-04-28 颜料/玻璃料的混合物
KR1020217038391A KR20220003011A (ko) 2019-04-30 2020-04-28 안료/프릿 혼합물
JP2021564479A JP2022540280A (ja) 2019-04-30 2020-04-28 顔料／フリット混合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102019003073.7 2019-04-30
DE102019003073.7A DE102019003073A1 (de) 2019-04-30 2019-04-30 Pigment/Fritten-Gemisch

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WO2020221714A1 true WO2020221714A1 (fr) 2020-11-05

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JP (1) JP2022540280A (fr)
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WO (1) WO2020221714A1 (fr)

Citations (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3087828A (en) 1961-06-28 1963-04-30 Du Pont Nacreous pigment compositions
US3087829A (en) 1961-06-28 1963-04-30 Du Pont Micaceous pigment composition
DE1467468A1 (de) 1961-06-28 1968-12-12 Du Pont Glimmerschuppenpigment
US3553001A (en) 1969-01-02 1971-01-05 Merck Ag E Process for coating titanium dioxide on solid materials
DE1959988A1 (de) 1969-11-29 1971-06-16 Ford Werke Ag Fahrzeugtuer mit Seitenschutz,insbesondere fuer Personenkraftwagen
DE2009566B1 (de) 1970-02-28 1971-11-11 Merck Patent Gmbh Verfahren zur Herstellung von Titandioxid- bzw. Titandioxidaquatüberzügen
DE2214545A1 (de) 1971-03-26 1972-10-05 E.I. Du Pont De Nemours And Co., Wilmington, Del. (V.St.A.) Perlmuttpigmente und deren Herstellung
DE2215191A1 (de) 1971-03-30 1972-10-12 E I du Pont de Nemours and Co , Wilmington, Del (V St A) Verbesserte Pigmente
DE2244298A1 (de) 1972-09-09 1974-03-28 Merck Patent Gmbh Perlglanzpigmente und verfahren zu ihrer herstellung
DE2313331A1 (de) 1973-03-17 1974-09-19 Merck Patent Gmbh Eisenhaltige glimmerschuppenpigmente
DE2522572A1 (de) 1975-05-22 1976-12-09 Merck Patent Gmbh Rutilhaltige perlglanzpigmente
EP0045851A1 (fr) 1980-08-08 1982-02-17 BASF Aktiengesellschaft Procédé pour la fabrication de pigments micacés en forme d'écailles recouvertes d'oxydes métalliques et leur utilisation
US4353991A (en) 1981-04-13 1982-10-12 Ferro Corporation Glass composition and method of manufacture and article produced therefrom
GB2096592A (en) 1981-03-19 1982-10-20 Takahashi Yuichiro Ground strengthening composition
DE3137808A1 (de) 1981-09-23 1983-03-31 Merck Patent Gmbh, 6100 Darmstadt Perlglanzpigmente mit verbesserter lichtechtheit, verfahren zur herstellung und verwendung
DE3137809A1 (de) 1981-09-23 1983-03-31 Merck Patent Gmbh, 6100 Darmstadt "perlglanzpigmente, ihre herstellung und ihre verwendung"
DE3151354A1 (de) 1981-12-24 1983-07-07 Merck Patent Gmbh, 6100 Darmstadt Perlglanzpigmente, verfahren zu ihrer herstellung und ihre verwendung
DE3151355A1 (de) 1981-12-24 1983-07-07 Merck Patent Gmbh, 6100 Darmstadt "perlglanzpigmente mit verbesserter lichtbestaendigkeit, ihre herstellung und verwendung"
DE3151343A1 (de) 1981-12-24 1983-07-07 Merck Patent Gmbh, 6100 Darmstadt Perlglanzpigmente mit verbesserter lichtbestaendigkeit, ihre herstellung und ihre verwendung
EP0090259A1 (fr) 1982-03-26 1983-10-05 MERCK PATENT GmbH Procédé d'hydrophobisation de pigments nacrés
DE3211602A1 (de) 1982-03-30 1983-10-13 Merck Patent Gmbh, 6100 Darmstadt Verfahren zur herstellung von perlglanzpigmenten mit verbesserten glanzeigenschaften
DE3235017A1 (de) 1982-09-22 1984-03-22 Merck Patent Gmbh, 6100 Darmstadt Perlglanzpigmente
EP0106235A1 (fr) 1982-10-08 1984-04-25 BASF Aktiengesellschaft Procédé de préparation de pigments à effet de nacre recouverts d'oxyde métallique
DE3334598A1 (de) 1983-09-24 1985-04-18 Merck Patent Gmbh Witterungsbestaendige perlglanzpigmente
EP0419843A1 (fr) 1989-09-28 1991-04-03 Degussa Aktiengesellschaft Procédé et moyen de fabrication d'un décor en relief sur des surfaces céramiques
EP0634459A2 (fr) 1993-07-16 1995-01-18 MERCK PATENT GmbH Formulations
EP0659843A2 (fr) 1993-11-25 1995-06-28 MERCK PATENT GmbH Pigment non brillant
WO1996032446A1 (fr) 1995-04-10 1996-10-17 Merck Patent Gmbh Agent de traitement de surface, pigment de type plaquette a surface traitee et leurs procedes de fabrication
US5571851A (en) 1994-01-28 1996-11-05 J.M. Huber Corporation Reinforcing fillers for plastics systems
DE19618569A1 (de) 1996-05-09 1997-11-13 Merck Patent Gmbh Mehrschichtige Interferenzpigmente
DE19618568A1 (de) 1996-05-09 1997-11-13 Merck Patent Gmbh Metalloxidbeschichtete Titandioxidplättchen
US5759255A (en) 1996-02-07 1998-06-02 Engelhard Corporation Pearlescent pigment for exterior use
US5783506A (en) 1997-01-31 1998-07-21 Engelhard Corporation Ceramic glaze including pearlescent pigment
WO1999057204A1 (fr) 1998-05-06 1999-11-11 Eckart-Werke Standard Bronzepulver-Werke Carl-Eckart Gmbh & Co. Pigments a effet recouverts d'auxiliaires d'orientation reactifs
WO2001092425A2 (fr) 2000-05-26 2001-12-06 Engelhard Corporation Films en polymere composite hydroxyde-organique a metal lie sur substrats de particules
CN101462895A (zh) 2009-01-01 2009-06-24 江门市道氏标准制釉股份有限公司 一种金黄色的金属光泽釉及其制备方法
US20170107379A1 (en) * 2015-10-19 2017-04-20 Merck Patent Gmbh Pigment/frit mixtures

Patent Citations (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3087828A (en) 1961-06-28 1963-04-30 Du Pont Nacreous pigment compositions
US3087829A (en) 1961-06-28 1963-04-30 Du Pont Micaceous pigment composition
DE1467468A1 (de) 1961-06-28 1968-12-12 Du Pont Glimmerschuppenpigment
US3553001A (en) 1969-01-02 1971-01-05 Merck Ag E Process for coating titanium dioxide on solid materials
DE1959988A1 (de) 1969-11-29 1971-06-16 Ford Werke Ag Fahrzeugtuer mit Seitenschutz,insbesondere fuer Personenkraftwagen
DE2009566B1 (de) 1970-02-28 1971-11-11 Merck Patent Gmbh Verfahren zur Herstellung von Titandioxid- bzw. Titandioxidaquatüberzügen
DE2214545A1 (de) 1971-03-26 1972-10-05 E.I. Du Pont De Nemours And Co., Wilmington, Del. (V.St.A.) Perlmuttpigmente und deren Herstellung
DE2215191A1 (de) 1971-03-30 1972-10-12 E I du Pont de Nemours and Co , Wilmington, Del (V St A) Verbesserte Pigmente
DE2244298A1 (de) 1972-09-09 1974-03-28 Merck Patent Gmbh Perlglanzpigmente und verfahren zu ihrer herstellung
DE2313331A1 (de) 1973-03-17 1974-09-19 Merck Patent Gmbh Eisenhaltige glimmerschuppenpigmente
DE2522572A1 (de) 1975-05-22 1976-12-09 Merck Patent Gmbh Rutilhaltige perlglanzpigmente
EP0045851A1 (fr) 1980-08-08 1982-02-17 BASF Aktiengesellschaft Procédé pour la fabrication de pigments micacés en forme d'écailles recouvertes d'oxydes métalliques et leur utilisation
GB2096592A (en) 1981-03-19 1982-10-20 Takahashi Yuichiro Ground strengthening composition
US4353991A (en) 1981-04-13 1982-10-12 Ferro Corporation Glass composition and method of manufacture and article produced therefrom
US4353991B1 (fr) 1981-04-13 1986-05-13
DE3137808A1 (de) 1981-09-23 1983-03-31 Merck Patent Gmbh, 6100 Darmstadt Perlglanzpigmente mit verbesserter lichtechtheit, verfahren zur herstellung und verwendung
DE3137809A1 (de) 1981-09-23 1983-03-31 Merck Patent Gmbh, 6100 Darmstadt "perlglanzpigmente, ihre herstellung und ihre verwendung"
DE3151354A1 (de) 1981-12-24 1983-07-07 Merck Patent Gmbh, 6100 Darmstadt Perlglanzpigmente, verfahren zu ihrer herstellung und ihre verwendung
DE3151355A1 (de) 1981-12-24 1983-07-07 Merck Patent Gmbh, 6100 Darmstadt "perlglanzpigmente mit verbesserter lichtbestaendigkeit, ihre herstellung und verwendung"
DE3151343A1 (de) 1981-12-24 1983-07-07 Merck Patent Gmbh, 6100 Darmstadt Perlglanzpigmente mit verbesserter lichtbestaendigkeit, ihre herstellung und ihre verwendung
EP0090259A1 (fr) 1982-03-26 1983-10-05 MERCK PATENT GmbH Procédé d'hydrophobisation de pigments nacrés
DE3211602A1 (de) 1982-03-30 1983-10-13 Merck Patent Gmbh, 6100 Darmstadt Verfahren zur herstellung von perlglanzpigmenten mit verbesserten glanzeigenschaften
DE3235017A1 (de) 1982-09-22 1984-03-22 Merck Patent Gmbh, 6100 Darmstadt Perlglanzpigmente
EP0106235A1 (fr) 1982-10-08 1984-04-25 BASF Aktiengesellschaft Procédé de préparation de pigments à effet de nacre recouverts d'oxyde métallique
DE3334598A1 (de) 1983-09-24 1985-04-18 Merck Patent Gmbh Witterungsbestaendige perlglanzpigmente
EP0419843A1 (fr) 1989-09-28 1991-04-03 Degussa Aktiengesellschaft Procédé et moyen de fabrication d'un décor en relief sur des surfaces céramiques
DE3932424C1 (fr) 1989-09-28 1991-06-06 Degussa Ag, 6000 Frankfurt, De
EP0634459A2 (fr) 1993-07-16 1995-01-18 MERCK PATENT GmbH Formulations
EP0659843A2 (fr) 1993-11-25 1995-06-28 MERCK PATENT GmbH Pigment non brillant
US5571851A (en) 1994-01-28 1996-11-05 J.M. Huber Corporation Reinforcing fillers for plastics systems
WO1996032446A1 (fr) 1995-04-10 1996-10-17 Merck Patent Gmbh Agent de traitement de surface, pigment de type plaquette a surface traitee et leurs procedes de fabrication
US5759255A (en) 1996-02-07 1998-06-02 Engelhard Corporation Pearlescent pigment for exterior use
DE19618569A1 (de) 1996-05-09 1997-11-13 Merck Patent Gmbh Mehrschichtige Interferenzpigmente
DE19618568A1 (de) 1996-05-09 1997-11-13 Merck Patent Gmbh Metalloxidbeschichtete Titandioxidplättchen
US5783506A (en) 1997-01-31 1998-07-21 Engelhard Corporation Ceramic glaze including pearlescent pigment
WO1999057204A1 (fr) 1998-05-06 1999-11-11 Eckart-Werke Standard Bronzepulver-Werke Carl-Eckart Gmbh & Co. Pigments a effet recouverts d'auxiliaires d'orientation reactifs
WO2001092425A2 (fr) 2000-05-26 2001-12-06 Engelhard Corporation Films en polymere composite hydroxyde-organique a metal lie sur substrats de particules
CN101462895A (zh) 2009-01-01 2009-06-24 江门市道氏标准制釉股份有限公司 一种金黄色的金属光泽釉及其制备方法
US20170107379A1 (en) * 2015-10-19 2017-04-20 Merck Patent Gmbh Pigment/frit mixtures
DE102015013400A1 (de) 2015-10-19 2017-04-20 Merck Patent Gmbh Pigment/Fritten-Gemisch

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J.J. PONJEE, PHILIPS TECHNICAL REVIEW, vol. 44, no. 3, pages 81 ff
P.H. HARDINGJ.C. BERG, J. ADHESION SCI. TECHNOL., vol. 11, no. 4, pages 471 - 493

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EP3963008A1 (fr) 2022-03-09

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