EP1633819A1 - Photostabilisierte effektpigmente - Google Patents

Photostabilisierte effektpigmente

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Publication number
EP1633819A1
EP1633819A1 EP04729647A EP04729647A EP1633819A1 EP 1633819 A1 EP1633819 A1 EP 1633819A1 EP 04729647 A EP04729647 A EP 04729647A EP 04729647 A EP04729647 A EP 04729647A EP 1633819 A1 EP1633819 A1 EP 1633819A1
Authority
EP
European Patent Office
Prior art keywords
metal
oxide
vanadium
photo
shaped
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Withdrawn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
EP04729647A
Other languages
German (de)
English (en)
French (fr)
Inventor
Ulrich Schoenefeld
Padma Kaviratna
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.)
Merck Patent GmbH
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
Publication of EP1633819A1 publication Critical patent/EP1633819A1/de
Withdrawn legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT 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
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0021Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27Zinc; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29Titanium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT 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
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0006Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black containing bismuth and vanadium
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT 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
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT 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
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62Metallic pigments or fillers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/03Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/50Sympathetic, colour changing or similar inks
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03Powdery paints
    • C09D5/033Powdery paints characterised by the additives
    • C09D5/035Coloring agents, e.g. pigments
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/36Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/41Organic pigments; Organic dyes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42Colour properties
    • A61K2800/43Pigments; Dyes
    • A61K2800/436Interference pigments, e.g. Iridescent, Pearlescent
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52Stabilizers
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/50Solid solutions
    • C01P2002/52Solid solutions containing elements as dopants
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/014Stabilisers against oxidation, heat, light or ozone
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT 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
    • C09C2200/00Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10Interference pigments characterized by the core material
    • C09C2200/1004Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT 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
    • C09C2200/00Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10Interference pigments characterized by the core material
    • C09C2200/102Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT 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
    • C09C2200/00Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10Interference pigments characterized by the core material
    • C09C2200/1087Interference 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT 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
    • C09C2200/00Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/301Thickness of the core
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT 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
    • C09C2200/00Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40Interference pigments comprising an outermost surface coating
    • C09C2200/401Inorganic protective coating
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT 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
    • C09C2200/00Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40Interference pigments comprising an outermost surface coating
    • C09C2200/402Organic protective coating
    • C09C2200/407Organosilicon materials, e.g. silanes, silicones
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT 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
    • C09C2200/00Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40Interference pigments comprising an outermost surface coating
    • C09C2200/402Organic protective coating
    • C09C2200/407Organosilicon materials, e.g. silanes, silicones
    • C09C2200/408Organosilicon materials, e.g. silanes, silicones comprising additional functional groups, e.g. –NH2, -C=C- or -SO3
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991Coated
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991Coated
    • Y10T428/2993Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

Definitions

  • the present invention relates to photostabilized effect pigments, one or more calcined and vanadium-containing oxide layers being applied to a substrate, alone or in a mixture with sulfates, borates or phosphates, processes for their preparation and their use in plastics, paints, paints, printing inks, cosmetics , Foils, in security printing, for laser marking, in heat protection or for seed coloring.
  • Plastic parts and layers of paint for outdoor applications are often exposed to extreme weather conditions and long-lasting intense light, which leads to an aging of the materials. This manifests itself in discoloration, embrittlement and reduced mechanical and chemical stability.
  • the causes for this are oxidative or photolytic decomposition of the binders or decomposition by the action of water in liquid form or water vapor.
  • the pigments used in particular pearlescent pigments containing titanium oxide layers, can also impair the resistance of the application media to the effects of light and weather. The reason for this is the special photoactivity of titanium dioxide layers, which accelerates the photolytic decomposition of the organic components of the application medium.
  • WO 98/58017 describes a composition containing a polyolefin, an antioxidant and a pearlescent pigment which is said to show a lower tendency to yellowing.
  • the antioxidant is an essential component of the mixture, which limits the applicability in application media, since the antioxidant has to be adapted to the other application components in order to avoid destruction of these compounds in the applications.
  • DE 2 545 243 describes a method for producing a titanium dioxide pigment with increased photochemical stability by adding water-containing titanium dioxide to metal ions from the group of vanadium, copper and / or manganese and then calcining at 600 to 1100 ° C. This process is limited to pure titanium dioxide pigments, which limits the range of applications for paints, varnishes or plastics.
  • photostabilized effect pigments with improved application properties, which can be used without restriction in all common application media and applications, without showing changes in the properties of the effect pigments.
  • the photostabilized effect pigments should be easily and inexpensively accessible, which means that the effort for their production should be low.
  • This complex object is achieved according to the present invention by a photostabilized effect pigment, one on a substrate or more calcined and vanadium-containing oxide layers, applied alone or in a mixture with sulfates, borates or phosphates.
  • the effect pigments according to the invention are notable for improved photostability, are easily accessible and can be incorporated into all conceivable application media and applications. They are chemically stable and inert and, in combination with the photostability, show the usual features of effect pigments, e.g. Gloss, color strength or variety of colors.
  • the pigments according to the invention can be produced in a simple process with a wide selection of substrates, and, depending on the embodiment, the process for producing the pigments according to the invention can be integrated directly into the production process of the effect pigments. This means less expenditure on equipment and allows better control of the desired pigment properties, e.g. Shine, color or opacity.
  • the addition of further photostabilizers to formulations or applications can be reduced or even dispensed with entirely, which likewise reduces the production outlay for these formulations and applications.
  • the substrate consists of a platelet-shaped, spherical or needle-shaped carrier and / or a layer coated with one or more transparent, semi-transparent and / or opaque layers containing metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides, metal oxynitrides or mixtures of these materials platelet-shaped, spherical or acicular carriers.
  • Substrates based on platelet-shaped supports are particularly preferably used.
  • platelet-shaped Ti0 2 synthetic or natural mica, glass platelets, metal platelets, platelet-shaped SiO 2 , Al 2 0 3 or platelet-shaped iron oxide.
  • the metal platelets can consist of aluminum, titanium, bronze, steel or silver, preferably aluminum and / or titanium.
  • the metal platelets can be passivated by appropriate treatment. In a preferred one
  • the carrier can be coated with one or more transparent, semitransparent and / or opaque layers containing metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides, metal oxynitrides or mixtures of these materials.
  • Metal nitride, metal oxynitride layers or the mixtures thereof can be low (refractive index ⁇ 1.8) or high refractive index (refractive index> 1.8).
  • Suitable metal oxides and metal oxide hydrates are all metal oxides or metal oxide hydrates known to the person skilled in the art, such as, for. B. aluminum oxide, aluminum oxide hydrate, silicon oxide, silicon oxide hydrate, iron oxide, tin oxide, cerium oxide, zinc oxide, zirconium oxide, chromium oxide, titanium oxide, in particular titanium dioxide, titanium oxide hydrate and mixtures thereof, such as e.g. Ilmenite or pseudobrookite.
  • the titanium suboxides can be used as metal suboxides.
  • Suitable metals are e.g. Chromium, aluminum, nickel, silver, gold, titanium, copper or alloys, as
  • Metal fluoride is suitable, for example, magnesium fluoride.
  • the nitrides or oxynitrides of the metals titanium, zirconium and / or tantalum can be used as metal nitrides or metal oxynitrides.
  • Metal oxide, metal, metal fluoride and / or metal oxide hydrate layers are preferred and very particularly preferably metal oxide and / or
  • Metal oxide hydrate layers applied to the carrier Furthermore, multilayer structures made of high and low refractive metal oxide, metal oxide hydrate, metal or metal fluoride layers can also be present, with high and low refractive layers alternating. Layer packages consisting of a high and a low refractive index layer are particularly preferred, it being possible for one or more of these layer packages to be applied to the support.
  • the order of high and low-index layers can be adapted to the carrier in order to include the carrier in the multilayer structure.
  • the metal oxide, metal oxide hydrate, metal suboxide, metal, metal fluoride, metal nitride, metal oxynitride layers can be mixed or doped with colorants or other elements. As
  • Colorants or other elements are suitable, for example, organic or inorganic color pigments such as colored metal oxides, e.g. Magnetite, chromium oxide or color pigments such as Berlin blue, ultramarine, bismuth vanadate, thenards blue, or organic color pigments such as Indigo, azo pigments, phthalocyanines or carmine red or
  • organic or inorganic color pigments such as colored metal oxides, e.g. Magnetite, chromium oxide or color pigments such as Berlin blue, ultramarine, bismuth vanadate, thenards blue
  • organic color pigments such as Indigo, azo pigments, phthalocyanines or carmine red or
  • Elements such as Yttrium or antimony, photostabilized effect pigments containing these layers show, in addition to photostability, a wide range of colors in relation to their body color and can in many cases show an angle-dependent change in color (color flop) due to interference.
  • the outer layer on the carrier is a high-index metal oxide.
  • This outer layer can additionally be part of a layer package on the above-mentioned layer packages or in the case of high-index supports and, for example, of T1O 2 , titanium suboxides, Fe 2 0 3 , Sn0 2) ZnO, ZrO 2 , Ce 2 0 3 , CoO, Co 3 0 4 , V 2 O 5 , Cr 2 O 3 and / or mixtures thereof, such as, for example, llmenite or pseudobrookite. TiO 2 is particularly preferred.
  • the embodiment is titanium oxide or a substrate containing titanium oxide on the basis of a support coated with one or more transparent, semitransparent and / or opaque layers containing metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides, metal oxynitrides or mixtures of these materials.
  • the outer layer preferably contains one or more transparent, semi-transparent and / or opaque layers containing metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides, metal oxynitrides or mixtures of these materials coated platelet-shaped, spherical or acicular carrier titanium oxide.
  • substrates in particular are distinguished by a high photoactivity caused by the titanium oxide, which can have a disadvantageous effect on the stability of the application medium surrounding the pigment, such as, for example, the plastic.
  • substrates in particular can be photostabilized, which facilitates their applicability in numerous applications.
  • Substrates based on platelet-shaped carriers and / or a platelet-shaped carrier coated with one or more metal oxide, metal or metal fluoride layers generally have a thickness between 0.05 and 5 ⁇ m, in particular between 0.1 and 4.5 ⁇ m.
  • the extension in length or width is usually between 1 and 250 ⁇ m, preferably between 2 and 200 ⁇ m and in particular between 2 and 100 ⁇ m.
  • Substrates made of a spherical carrier and / or a spherical carrier coated with one or more metal oxide, metal or metal fluoride layers generally have average diameters of 10 nm to 100 ⁇ m, preferably between 500 nm and 50 ⁇ m and in particular between 1 and 20 ⁇ m on.
  • the thickness of the metal oxide, metal oxide hydrate, metal suboxide, metal, metal fluoride, metal nitride, metal oxynitride layers or a mixture thereof is usually 3 to 300 nm and in the case of the metal oxide, metal oxide hydrate, metal suboxide, metal fluoride, metal nitride , Metal oxynitride layers or a mixture thereof, preferably 20 to 200 nm.
  • the thickness of the metal layers is preferably 4 to 50 nm.
  • the oxides of Al, Ca, Sr, Zn, Si, Zr, Ce, Ti or mixtures thereof are suitable, preferably TiO 2 , Al 2 O. 3 , Ce O 3 , ZnO, ZrO and / or SiO 2 are used. Mixtures of the above are particularly preferred
  • Oxides are used, ZnO being a particularly suitable mixture component of the oxide layer or oxide layers. Layers of these oxides are characterized by high transparency, lack of or little inherent color and high gloss, so that the coloristic properties of the substrates are not changed. Furthermore, these materials result in anhydrous and chemically inert surfaces after calcining.
  • the oxide layer containing vanadium can be integrated into the multi-layer structure, which makes it easier to manufacture.
  • the outer layer of a multilayer pigment can contain a vanadium
  • Titanium oxide layer which in addition to increasing the photostability also influences the optical properties of the pigment, e.g. through interference.
  • the vanadium content of the vanadium-containing oxide layer is 0.002 to 0.2% by weight, calculated as V 2 O5 and based on the total pigment, preferably 0.01 to 0.1% by weight.
  • the vanadium concentration in the vanadium-containing oxide layer can increase or decrease in the form of a gradient in the direction of the surface of the vanadium-containing oxide layer.
  • the vanadium concentration in the vanadium-containing oxide layer preferably increases in the direction of the surface of the vanadium-containing oxide layer. This can further increase the photostability of the pigments, since the photoactivity of the surface of the pigment which is in contact with the application medium is reduced particularly strongly.
  • the amount of vanadium required can be reduced in this way, which is a possible change in the color and gloss properties of the pigment prevented.
  • an organic coating can additionally be applied to the calcined oxide layer containing vanadium, which additionally stabilizes the pigments according to the invention against further weather influences.
  • This enables the use of the pigments according to the invention e.g. in paints for outdoor applications that, in addition to photostability, also require high resistance to moisture.
  • the applied organic coating can also act as a coupling reagent to the surrounding medium of the formulation or application and thus the application properties such as improve dispersibility.
  • the organic coating can consist of organosilanes, aluminates, titanates and / or zirconates of the general formula
  • R alkyl, phenyl or hydrogen
  • B organic, at least bifunctional group (alkylene, alkyleneoxyalkylene)
  • the coupling reagents consist of an anchor group (X4- n -mZ) that binds to the surface, at least one hydrophobic group (R, B) and one or more functional groups (Y).
  • the anchor group preferably consists of alkoxysilanes which can be converted into corresponding hydroxyl groups by hydrolytic reaction conditions. The latter can bind to the calcined and vanadium-containing metal oxide surface and cause anchoring via oxygen bridges.
  • mixtures of different coupling reagents can be used, which can be applied as a mixture or individually.
  • the organic coating can be adapted to the medium used.
  • additional bonds between pigment and medium can be generated via the coupling reagent by reaction of the functional groups with corresponding functionalities in the application media.
  • the surface of the pigments according to the invention is modified with a combination of organic functionalities adapted to the feed medium.
  • the use of mixtures of different coupling agents within the organic coating is also suitable for this.
  • the hydrophobicity of the pigment surface can be adjusted by integrating alkyl-containing coupling reagents such as alkyl silanes.
  • organosilanes In addition to the organosilanes, the use of their hydrolysates and homogeneous and heterogeneous oligomers and / or polymers is also preferred, which can also be used as an organic coating, either alone or in combination with silanes, zirconates, aluminates, zirconium aluminates and / or carboxyzirconium aluminates.
  • An organic coating with mixtures of different coupling reagents, in particular with functional groups Y that differ from one another, is particularly preferred, which ensures a particular range of applications.
  • organosilanes are propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, n-octyltrimethoxysilane, i-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, dodecyltrimethoxysilanilysilane As oligomeric, alcohol-free
  • Organosilane are, among others, those sold under the trade name "Dynasylan ®" by the company. Sivento products, such. As Dynasylan HS 2926, Dynasylan HS 2909, Dynasylan HS2907, Dynasylan HS 2781, Dynasylan HS 2776, Dynasylan HS 2627. In addition, oligomeric vinylsilane and aminosilane hydrolyzate are suitable as organic coatings. Functionalized organosilanes are, for example, 3-aminopropyltrimethoxysilane, 3-
  • Ureidopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-methacryloxytrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-isocyanatopropyltrimethoxysilane are preferred.
  • Examples of polymeric silane systems are described in WO 98/13426 and are described, for. B. from Sivento under the trademark Hydrosil ® .
  • the organic coating has a positive influence on the surface properties of the calcined oxide layers containing vanadium.
  • the surfaces coated with the organic coating are more hydrophobic and less polar than the untreated oxide surfaces and are therefore better wettable by binders and organic solvents. This results in better compatibility of the pigments according to the invention with the binder systems used in the application, in particular paints.
  • the organic coating also inhibits because of its steric shielding of the pigment surface the agglomeration of the pigment particles and thus improves their dispersibility.
  • the object of the present invention is achieved by a method for producing photo-stabilized effect pigments, with a
  • One or more hydroxide, oxide hydrate and / or oxide layers containing vanadium are applied alone or in a mixture with sulfates, phosphates and / or borates and the pigment obtained is then calcined.
  • the method according to the invention can be carried out in a one-step production process and is therefore inexpensive and simple. In the case of multilayer substrates, the method according to the invention can be directly integrated into the pigment production process.
  • Hydroxide, oxide hydrate and / or oxide layers can be carried out both wet-chemically and via sol-gel processes; the precipitation is preferably carried out wet-chemically.
  • the corresponding vanadium-containing oxides, hydroxides and / or oxide hydrates are coated.
  • the substrates are suspended in a solvent or solvent mixture, preferably water, and solutions with the metal salts suitable for the formation of hydroxide, hydrated oxide and / or oxide layers and one or more vanadium compounds are added.
  • the pH value required for the precipitation of the respective hydroxide, oxide hydrate and / or oxide is set and optimized professionally.
  • the vanadium compounds can be introduced at any time and in any form into the coating with the hydroxide, hydrated oxide and / or oxide layers, for example in solid form or as a solution of one or more vanadium compounds.
  • the vanadium compounds are preferably added in the form of a solution, this being done via the Solutions of the metal salts suitable for the formation of the hydroxide, oxide hydrate and / or oxide layers and / or by means of the auxiliary solutions required in the coating process when setting the coating parameters, such as pH value or amount of solvent.
  • the vanadium compounds are preferably added via the auxiliary solutions required for controlling the pH, the auxiliary solutions preferably being aqueous solutions of acids or bases, such as, for example, hydrochloric acid or sodium hydroxide solution.
  • the vanadium compound can be introduced into the hydroxide, oxide hydrate and / or oxide layer such that the vanadium concentration in the layer increases or decreases in the form of a gradient in the direction of the surface of the layer containing vanadium.
  • the gradient formation is controlled via the time and the speed of the vanadium addition. For example, if the vanadium concentration is to increase toward the surface, this can be done, for example, by adding the vanadium compounds in a targeted manner at the end of the application of the hydroxide, oxide hydrate and / or oxide layer to the substrate.
  • the vanadium compounds can be introduced in the auxiliary solution necessary for controlling the pH, with which the precipitation of the hydroxide, oxide hydrate and / or oxide layer is completed.
  • the desired size of the gradient can be set by controlling the speed of the addition. All other possibilities of gradient control conceivable in connection with this invention are within the knowledge of the person skilled in the art.
  • Suitable vanadium compounds are in principle all vanadium compounds of various oxidation levels that are soluble in a solvent or solvent mixture, for example vanadium (IV) or vanadium (V) compounds.
  • Vanadyl (IV) salts for example vanadyl chloride or vanadyl sulfate, vanadates or Solutions of vanadium (V) oxide, especially sodium metavanadate, are used.
  • the corresponding halides, nitrates and / or sulfates are suitable as metal salts for the formation of the hydroxide, oxide hydrate and / or oxide layers; the corresponding halides and / or nitrates are preferably used.
  • the sulfates, phosphates and / or borates can be co-precipitated together with the oxides, hydroxides and / or oxide hydrates from suitable metal salts and from corresponding sulfate, phosphate or borate sources.
  • Suitable sulfate sources are sulfuric acid and all soluble sulfates such as.
  • sodium sulfate, potassium sulfate or lithium sulfate as phosphate sources phosphoric acid or all soluble phosphates such as. B. sodium phosphate, disodium hydrogen phosphate or potassium phosphate and as borate sources all soluble borates such as. B. sodium borate or sodium diborate.
  • the amount of sulfates, phosphates and / or borates and the precipitation conditions, such as. B. pH or temperature can be optimized in a professional manner.
  • the pigments obtained in this way are then calcined.
  • the calcination can take place at temperatures of 300-900 ° C, preferably at 600-900 ° C.
  • the precipitated oxides, hydroxides and / or oxide hydrates are dewatered, converted into the corresponding oxides and compressed.
  • an organic coating can additionally be applied to the calcined oxide layer containing vanadium, which additionally stabilizes the pigments according to the invention against further weather influences.
  • Coating takes place in solution at temperatures above 60 ° C, preferably above 70 ° C.
  • solvents organic solvents, water or mixtures thereof, water is preferably used.
  • the reaction time required for applying the organic coating is at least 5 minutes, preferably over a period of 10 to 90 minutes, but can also be extended as desired.
  • the pigment obtained is worked up and isolated by methods known to those skilled in the art, e.g. B. by filtration, drying and screening.
  • the photostabilized effect pigments according to the invention are notable for good application properties.
  • the calcination dehydrates and densifies the oxide layers, which leads to a reduction in the porosity of the pigment surface. Less water can be absorbed on the compacted surface and thus the disadvantageous effects of water adsorbed in the boundary layer in the lacquer can be reduced.
  • the calcination also removes water chemically bound in the form of hydroxides or oxide hydrates. This has advantages when using the pigments in plastics, since water present in thermoplastic polymers such as in polyesters, can lead to hydrolytic decomposition of the polymer at higher temperatures.
  • the photostabilized effect pigments described here are suitable for one
  • the invention thus furthermore relates to the use of the photostabilized agents according to the invention Effect pigments for pigmenting plastics, lacquers, such as hydraulic lacquers or powder lacquers, paints, printing inks, cosmetic formulations, paper, ceramic materials, glasses, foils, in security printing, in the agricultural sector, for example in seed coloring, for laser marking of, for example, paper or plastics, in Thermal protection and for the production of pigment preparations such as pearlets, pastes and pastes as well as dry preparations such as pellets, granules, chips etc, which are preferably used in printing inks and varnishes.
  • the toxicity of the materials used plays a role, e.g. in cosmetic
  • vanadium (IV) compounds for producing the vanadium-containing oxide layers is preferred.
  • the pigments according to the invention can be used in a large number of the known binders used in color systems and can be used both in aqueous and in solvent-based systems.
  • the pigments can be incorporated into the respective application media by all methods known to the person skilled in the art.
  • the effect pigments according to the invention are particularly suitable for products and formulations of decorative cosmetics, such as, for example, nail polishes, coloring powders, lipsticks or eyeshadows, soaps, toothpastes, etc.
  • decorative cosmetics such as, for example, nail polishes, coloring powders, lipsticks or eyeshadows, soaps, toothpastes, etc.
  • the pigments according to the invention can also be used in the formulations with any type of cosmetic raw and auxiliary materials can be combined. These include oils, fats, waxes, film formers, preservatives and auxiliary substances that determine general application properties, such as thickeners and rheological additives such as bentonites, hectorites, silicon dioxide, calcium silicates, gelatin, high-molecular carbohydrates and / or surface-active additives, etc.
  • Formulations containing pigments according to the invention can be of the lipophilic, hydrophilic or hydrophobic type.
  • the pigments according to the invention can each contain only one of the two phases or can be distributed over both phases.
  • the pH values of the aqueous formulations can be between 1 and 14, preferably between 2 and 11 and particularly preferably between 5 and 8. There are no limits to the concentrations of the pigments according to the invention in the formulation. Depending on the application, they can be between 0.001 (rinse-off products, e.g. shower gels) - 100% (e.g. gloss effect articles for special applications when using effect pigments as a substrate).
  • the pigments according to the invention can also be combined with cosmetic active ingredients. Suitable active ingredients are e.g. Insect repellents, UV A / BC protective filters (e.g. OMC, B3, MBC), anti-aging ingredients, vitamins and their derivatives (e.g.
  • vitamins A, C, E etc. vitamins A, C, E etc.
  • self-tanners e.g. DHA, erytrolosis etc.
  • others cosmetic active ingredients such as Bisaboloi, LPO, ectoin, emblica, allantoin, bioflavanoids and their derivatives.
  • the effect pigments according to the invention are particularly suitable for use in plastics, for example in agricultural foils, infrared-reflecting foils and disks, gift foils, plastic containers and moldings, for all applications known to the person skilled in the art, since the photostability of the effect pigments according to the invention, in particular in plastics, in order to extend the shelf life of them Leads products.
  • All common plastics are suitable as plastics for incorporating the effect pigments according to the invention, for example duromers or thermoplastic plastics.
  • the description of the possible uses and the plastics, processing methods and additives that can be used can be found, for example, in RD 472005 or in R. Glausch, M. Kieser, R. Maisch, G. Pfaff, J.
  • binders in particular water-soluble types, are suitable for the production of the printing inks, e.g. based on acrylates, methacrylates, polyesters, polyurethanes, nitrocellulose, ethyl cellulose, polyamide, polyvinyl butyrate, phenolic resins, maleic resins, starch or polyvinyl alcohol.
  • the lacquers can be water- or solvent-based lacquers, the selection of the lacquer components being subject to the general knowledge of the person skilled in the art.
  • the pigments of the invention are preferably used in paints such as in car paints or water-based paints that are suitable for all indoor and outdoor applications due to the special stability of the pigments.
  • Powder coating formulations allow the effect pigments according to the invention to be easily incorporated even without further organic coating and, in these applications, have a bright, metallic luster with a pronounced sparkle or glitter effect.
  • the so-called superdurable powder coatings When used in outdoor applications, the occurrence of chalking and graying is greatly delayed or largely avoided with highly weather-stable formulations, the so-called superdurable powder coatings.
  • silane-based weather stabilizations known from the prior art, there are often incompatibilities with the powder coating matrix, in particular in the area of so-called dry blending, which is often expressed in strong pigment associations in the baked powder coating layer. This disorder is in the invention
  • plastics, lacquers, paints, printing inks, cosmetic formulations, paper, ceramic materials, glasses, foils, seeds, pigment preparations and dry preparations containing one or more of the photostabilized effect pigments according to the invention are also an object of the present invention.
  • the pigment samples were worked into a plastic matrix and the extent of the reduction from Pb 2+ to Pb was determined visually.
  • the gray color is assessed according to ISO 105-Part A 02 (corresponds to DIN 54 001).
  • the test scale ranges from 5 (very good) to 1 (very bad).
  • the pigment is washed off from the supernatant by filtration. After drying at 120 ° C, the pigment is calcined at 800 ° C for 45 min and the effect pigment obtained is freed from coarse fractions by sieving (mesh size 63 ⁇ m) with blue interference color.
  • Example 1 The vanadium-containing pigment is produced as in
  • Example 2 The base pigment suspension is prepared as in
  • Comparative Example 1 described. The pH is then adjusted to 6.5 with sodium hydroxide solution. A solution of 3.35 g of zinc chloride in 60 ml of water is added within one hour, the pH being kept constant with 5% sodium hydroxide solution in which 53 mg of sodium vanadate has been dissolved. The pigment is worked up as described in Comparative Example 1. The pigment therefore contains 2% zinc oxide and 0.025%
  • Vanadium oxide based on the total weight.
  • the pigment suspension is generally prepared as described in Comparative Example 1. Following the assignment, the pH of the suspension is adjusted to 5.0 with sodium hydroxide solution. A solution of 9.5 g of aluminum chloride * 6 H 2 O in 100 ml of water is added over the course of an hour, the pH being kept constant with 5% sodium hydroxide solution in which 100 mg of vanadium (V) oxide has been dissolved.
  • the pigment is worked up as described in Comparative Example 1. The pigment therefore contains 2% aluminum oxide and 0.1% vanadium oxide, based on the total weight. The body color of the pigment is yellowish. The photoactivity of this pigment is rated 3-4.
  • the pigment suspension is generally prepared as described in Comparative Example 1. During the first 75% of the occupancy, the pH is kept constant with 32% sodium hydroxide solution. 64 mg of sodium vanadate are dissolved in the sodium hydroxide solution, which is used for the remaining coating. The pigment is worked up as described in Comparative Example 1.
  • the pigment therefore contains a calculated 0.025% vanadium oxide based on the total weight. Due to the manufacturing conditions, the doping takes place in the form of a gradient and primarily in the outer TiO 2 layer.
  • the photoactivity of this pigment is rated 3-4.
  • Example 6 The vanadium-containing pigment is produced as in
  • Vanadyl (IV) sulfate can be dissolved.
  • the pigment therefore contains a doping of 0.03% vanadium (calculated as V 2 O 5 ) based on the total weight.
  • the photoactivity of this pigment is rated 3.

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  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
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EP04729647A 2003-05-21 2004-04-27 Photostabilisierte effektpigmente Withdrawn EP1633819A1 (de)

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WO2006063949A1 (en) * 2004-12-15 2006-06-22 Ciba Specialty Chemicals Holding Inc. Process of using microwave deposition of metal oxide onto an organic substrate
US7842130B2 (en) * 2005-08-22 2010-11-30 Basf Corporation Complex inorganic effect materials
JP5068979B2 (ja) * 2006-11-07 2012-11-07 日揮触媒化成株式会社 歯科用充填材、その製造方法および歯科用複合材料
JP2009078955A (ja) * 2007-09-27 2009-04-16 Okuno Chem Ind Co Ltd 無鉛セラミックカラー組成物
CN101168625B (zh) * 2007-11-28 2012-02-15 四川大学 智能控温功能型云母钒珠光颜料及其制备
CN101168624B (zh) * 2007-11-28 2012-02-15 四川大学 多层结构智能控温功能型云母珠光颜料及其制备
DE102008047572A1 (de) * 2008-09-16 2010-04-15 Eckart Gmbh Metalleffektpigmentpräparation in kompaktierter Form, Verfahren zu deren Herstellung und Verwendung derselben
WO2011095326A1 (de) * 2010-02-04 2011-08-11 Merck Patent Gmbh Effektpigmente
CN103221197A (zh) * 2010-08-02 2013-07-24 裕克施乐股份公司 用于制造染色的纤维复合材料的方法和该纤维复合材料以及由此制造的成型件
CN102029113B (zh) * 2010-11-09 2012-09-26 中国海洋石油总公司 一种味精工业废水处理膜清洗剂的制备方法
DE102012017710A1 (de) * 2012-09-07 2014-03-13 Polysecure Gmbh Werkstück oder Werkstoff mit inertem Markersystem
US9168393B2 (en) 2013-03-13 2015-10-27 Johnson & Johnson Consumer Inc. Pigmented skin-care compositions
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US9168394B2 (en) 2013-03-13 2015-10-27 Johnson & Johnson Consumer Inc. Pigmented skin-care compositions
US9320687B2 (en) 2013-03-13 2016-04-26 Johnson & Johnson Consumer Inc. Pigmented skin-care compositions
CN103254664A (zh) * 2013-05-14 2013-08-21 四川大学 一种二氧化钒包覆云母的智能控温型粉体的制备方法
US9881714B2 (en) 2014-06-19 2018-01-30 Saint-Gobain Performance Plastics Corporation Laser-markable insulation material for wire or cable assemblies
US10256009B2 (en) 2014-06-19 2019-04-09 Saint-Gobain Performance Plastics Corporation Laser-markable insulation material for wire or cable assemblies
TR201816042T4 (tr) * 2014-12-19 2018-11-21 Eckart Gmbh Yüksek renk koyuluğuna ve yüksek parlaklığa sahip absorbe edici etki pigmentleri, üretimlerine yönelik yöntem ve kullanımları.
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