WO2012113886A1 - Pigment lamellaire contenant de l'oxyde métallique, son procédé de fabrication et son utilisation comme pigment à effet et/ou comme substrat pour pigments à effet - Google Patents

Pigment lamellaire contenant de l'oxyde métallique, son procédé de fabrication et son utilisation comme pigment à effet et/ou comme substrat pour pigments à effet Download PDF

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Publication number
WO2012113886A1
WO2012113886A1 PCT/EP2012/053104 EP2012053104W WO2012113886A1 WO 2012113886 A1 WO2012113886 A1 WO 2012113886A1 EP 2012053104 W EP2012053104 W EP 2012053104W WO 2012113886 A1 WO2012113886 A1 WO 2012113886A1
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Prior art keywords
aluminum
aluminum alloy
oxide
pigment
range
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PCT/EP2012/053104
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German (de)
English (en)
Inventor
Michael GRÜNER
Dirk Schumacher
Günter KAUPP
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Eckart Gmbh
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Priority to EP12708100.8A priority Critical patent/EP2678393A1/fr
Publication of WO2012113886A1 publication Critical patent/WO2012113886A1/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
    • C09C1/0051—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 low and high refractive indices, wherein the first coating layer on the core surface has the low refractive index
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0254—Platelets; Flakes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/26—Aluminium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
    • A61K2800/436—Interference pigments, e.g. Iridescent, Pearlescent
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/65—Characterized by the composition of the particulate/core
    • A61K2800/651—The particulate/core comprising inorganic material
    • 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
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/62—L* (lightness axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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
    • C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
    • 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
    • C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
    • C09C2200/1058—Interference pigments characterized by the core material the core consisting of a metal comprising a protective coating on the metallic layer
    • 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
    • C09C2200/20—Interference pigments comprising a layer with a concentration gradient or a gradient of the refractive index
    • 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
    • C09C2220/00—Methods of preparing the interference pigments
    • C09C2220/10—Wet methods, e.g. co-precipitation

Definitions

  • Platelet-shaped metal oxide-containing pigment process for its preparation and use thereof as an effect pigment and / or as
  • the present invention relates to a platelet-shaped metal oxide-containing pigment having a metallic core of elemental aluminum and / or a
  • An aluminum alloy wherein the metallic core is present in a weight proportion in the range of 0 to 18 wt .-%, based on the total weight of metal oxide in the form of aluminum oxide and / or oxide of the aluminum alloy and aluminum and / or aluminum alloy.
  • the invention further relates to a process for the preparation of these pigments and their use.
  • Oxidized colored aluminum pigments with a content of metallic aluminum of not more than 90% by weight, based on the total weight, are produced according to EP 0 848 735 B1 by a controlled oxidation of conventional aluminum pigments.
  • a striking feature of these oxidized colored aluminum pigments is their excellent metallic luster and their very good hiding power.
  • Platelet-shaped aluminum oxide with a titanium oxide content of 0.1 to 4% by weight is known from EP 0 763 573 B1.
  • the preparation is carried out by a process in which from an aqueous solution of a water-soluble aluminum salt and a water-soluble titanium salt in the presence of an aqueous
  • the platelet-shaped aluminum oxide thus prepared has an average particle diameter of 5 to 60 .mu.m, a thickness of less than 1 pm and a
  • Form factor greater than 20 Particularly important in this process is the addition of the titanium salt, which causes twinning and agglomeration during the process
  • the amount of titanium salt added depends on the form, i. the particle diameter, thickness and aspect ratio of the desired product. At a content of more than 4 wt .-% titanium salt, the formation of platelet-shaped pigments is prevented.
  • the titanium salt, in the preparation of pearlescent pigments, is believed to facilitate the adhesion of the metal oxide on the platelet-shaped alumina substrate.
  • Aluminum oxide substrate with metals for example aluminum, titanium, chromium, nickel, silver, copper, gold or platinum, is described in EP 1 438 360 B1.
  • Molten salt For this purpose, hydrated aluminum oxide, which is doped with titanium oxide and phosphate, mixed with sodium sulfate in aqueous suspension and then dried, whereby a homogeneous powder is obtained. This powder is heated up to 1200 ° C. The resulting Aluminiumoxideinkristalle be separated after cooling from the soluble constituents.
  • platelet-shaped aluminas have a smooth surface and regular crystal forms. They do not tend to twinning and agglomeration during crystal growth.
  • WO 2006/101306 A1 and WO 2008/026860 A1 disclose platelet-shaped a-aluminum oxide crystals and processes for their preparation. These platelet-shaped ⁇ -alumina crystals are additional, in the case of WO
  • platelet-shaped ⁇ -aluminum oxide crystals find use, for example, as a substrate for pearlescent pigments, as described in WO 2008/026829 A1, or as fillers.
  • flaky ⁇ -alumina is heated mullite (3 Al2O3 ⁇ 2 S1O2) in the presence of a reactive fluoride salt such as Na 3 AIF 6 to 1 100 to 1200 ° C.
  • a reactive fluoride salt such as Na 3 AIF 6 to 1 100 to 1200 ° C.
  • the fluoride salt reacts with mullite to form SiF 4 and a-alumina.
  • Produce a-alumina particles with a size of up to 15 pm in the longitudinal direction succeeds according to DE 43 13 358 A1 by sintering a liquid phase of alumina powder with additives that promote the formation of a-alumina platelets and control their grain growth.
  • Additives such as lithium, potassium, sodium or calcium oxide promote the formation of a-alumina platelets here.
  • the grain growth of the ⁇ -alumina platelets controls additives such as zirconium or hafnium oxide.
  • platelet-shaped alumina having a mean diameter of 0.5 to 25 pm and an aspect ratio of over 50 to 2000 described.
  • aluminum oxide platelets Due to their production, aluminum oxide platelets have a phosphorus content of 0.2 to 5.0% by weight, based on the total weight.
  • alumina platelets is phosphoric acid or phosphate in an amount of 0.1 to 3% by weight, calculated as P2O5.
  • P2O5 phosphoric acid or phosphate
  • Aluminum oxide platelets have an aspect ratio of 1:10 to 1: 100.
  • Platelet-shaped boehmite or aluminum hydroxide in a size of 2.5 to 15 pm and an aspect ratio of 100 to 350 is obtained according to JP 2003002641 A by the hydrothermal process in the presence of a (meth) acrylic acid monomer or polymer.
  • Fine platelet-shaped boehmite particles having an orthorhombic crystal structure and a flat-plate-grown crystal surface in which the aspect ratio (minor axis ratio to thickness) is from 3 to 100 are described in EP 0 563 653 A1.
  • the preparation is carried out by the hydrothermal treatment of aluminum hydroxide in water or an aqueous alkali solution at a temperature of at least 150 ° C and a pressure of at most 100 atm.
  • Aluminum hydroxide or aluminum sulfate which after grinding and classification has a particle size of 5 to 50 pm. While in WO 2009/028887 A2 melting in the presence of at least one salt, such as
  • Calcium carbonate is carried out in an electric furnace, are used in WO 2009/028888 A2 for heating microwaves.
  • Porous platelet-shaped metal oxides such as, for example, flaky aluminum oxide, with a specific surface area of from 10 to 3000 m 2 / g, a middle surface
  • Particle diameters of 5 to 500 ⁇ m, an average thickness of 0, 10 to 5 ⁇ m and an aspect ratio of 5 to 300 are described in EP 1 512 664 A1.
  • the preparation is carried out by applying a colloidal solution containing
  • porous platelet-shaped metal oxides are suitable as fillers in, for example, cosmetic formulations, where they include, inter alia, as
  • Carrier material can serve for other auxiliaries.
  • a process for producing platelet-shaped metal oxides such as
  • platelet-shaped aluminum oxide or platelet-shaped titanium dioxide is known from EP 0 236 952 B1.
  • a smooth surface is covered with a dispersion
  • Platelet-shaped aluminum oxide with a tin oxide content of 0.1 to 1.0% by weight is described in JP 2005082441A.
  • a platelet-shaped ⁇ -alumina having a surface roughness Ra of 1 nm to 5 0 10 ⁇ 2 nm is known from JP 2003192338 A.
  • Platelet-shaped ⁇ -alumina having an average particle size of 0.5 to 20 ⁇ m, an average thickness of 0.03 to 0.35 ⁇ m and an aspect ratio of 15 to 20 is described in JP 2008088317 A. After coating with 30 to 50 wt .-% titanium dioxide, the platelet-shaped ⁇ -alumina for no
  • Pearlescent pigments have a typical shine.
  • Metal oxide coated flaky alumina having an aspect ratio of 10 to 50, a diameter of 2 to 20 pm, a brightness (L) of a range of 50 to 80, a and b values ranging from -15 to 15 and -25, respectively to 20 is known from WO 2008/020665 A1.
  • Particle size and aspect ratio should be obtained gloss reduced pigments for use in cosmetic formulations.
  • the object of the present invention is to provide platelet-shaped metal oxide-containing pigments which can be used both as an effect pigment and as a substrate for effect pigments. Furthermore, a simple and reliable method for producing these platelet-shaped metal oxide-containing pigments which can be used both as an effect pigment and as a substrate for effect pigments. Furthermore, a simple and reliable method for producing these platelet-shaped metal oxide-containing pigments which can be used both as an effect pigment and as a substrate for effect pigments. Furthermore, a simple and reliable method for producing these platelet-shaped
  • metal oxide-containing pigments are provided.
  • the object underlying the invention was achieved by providing platelet-shaped metal oxide-containing pigment, wherein the metal oxide-containing pigment has a metallic core of elemental aluminum and / or an aluminum alloy, wherein the metallic core in a weight proportion from a range of 0 to 18 wt .-%, based on the total weight of metal oxide in the form of aluminum oxide and / or oxide of the aluminum alloy and aluminum and / or aluminum alloy, wherein the aluminum and / or the aluminum alloy one of alumina and / or the oxide of
  • Aluminum alloy coated core forms, with the proviso that the
  • Aluminum alloy has an aluminum content of at least 60 wt .-%, based on the total weight of the aluminum alloy.
  • the object underlying the invention was further achieved by providing a method for producing a platelet-shaped metal oxide-containing
  • Aluminum alloy in a range of 0 to 18 wt .-%, based on the Total weight of metal oxide in the form of alumina and / or the oxide of the aluminum alloy and aluminum and / or the aluminum alloy is located.
  • the object underlying the invention is also obtainable by providing a platelet-shaped metal oxide-containing pigment according to the
  • platelet-shaped metal oxide-containing pigment with a content of elemental aluminum and / or an aluminum alloy within a range from 3 to 18% by weight, preferably from a range from 4 to 15% by weight,
  • the object underlying the invention by the use of platelet-shaped metal oxide-containing pigment having a content of elemental aluminum and / or an aluminum alloy from a range of 0 to less than 3 wt .-%, based on the total weight of metal oxide in the form of
  • the pigments according to the invention can be obtained with a well-defined composition, starting from metallic platelets with or made of aluminum and / or with or from an aluminum alloy with defined proportions, wherein the proportion of aluminum at least 60 wt. %, based on the total weight of the
  • the platelet-shaped aluminum oxide platelets are produced, for example, from melts or colloidal solutions.
  • the invention one starts from a platelet-shaped metal substrate.
  • the plate-shaped metal substrates can be obtained by strain-milling aluminum grit or aluminum alloy grit, for example, in a ball mill. About the grinding time, the thickness distribution of the
  • platelet-shaped pigments can be adjusted. If desired, size classification can also be made with respect to the diameter of the platelet-shaped pigments.
  • substrates with defined thickness distribution, defined size distribution in relation to the diameter and defined composition can be used in the method according to the invention.
  • a defined content of aluminum and / or aluminum alloy in the pigments can be adjusted.
  • the inventive method is characterized by simplicity and reliability in terms of the properties of
  • aluminum effect pigments with particularly rounded edges which are also referred to as silver dollars, aluminum effect pigments produced by PVD processes or pigments according to EP 1 613 702 B1 or EP 2 102 294 A2.
  • the platelet-shaped metal oxide-containing pigments produced by the process according to the invention differ structurally from those conventionally used known aluminum oxide platelets.
  • the platelet-shaped pigments according to the invention can be present in amorphous or partially crystalline form.
  • the metal substrates are aluminum and / or
  • the porous surface of the oxidized aluminum and / or aluminum alloy platelets can be identified, for example, by means of scanning electron images.
  • aluminum and / or aluminum alloy plates which were produced by conventional wet grinding or PVD processes and in which a natural oxide layer has formed, is in the
  • oxidized metallic platelets in particular aluminum and / or aluminum alloy platelets to recognize a much rougher surface.
  • an alumina wafer obtained by crystal growth does not have the porous surface structure of the oxidized aluminum and / or aluminum alloy flakes of the present invention.
  • BET specific surface area increases at least by a factor of 2.5, preferably by at least a factor of 2.7, more preferably by at least a factor of 10 and most preferably at least by a factor of 15.
  • BET values of the oxidized aluminum and / or Aluminum alloy flakes are preferably in a range of 50 to 500 m 2 / g, more preferably in a range of 75 to 400 m 2 / g and in total
  • the porosity of the alumina / hydroxide layer causes a subsequent coating applied thereto to be first filled, at least in part, into the pores to form a mixed layer. This results in a
  • the refractive index thus varies between the refractive index of the pure
  • the formation of the mixed layer causes a strong anchoring of the coating on the oxidized aluminum and / or aluminum alloy platelets and thus a high mechanical resistance of the resulting effect pigment or provided with a protective layer oxidized aluminum and / or
  • Aluminum hydroxide layer or the oxide layer of the aluminum alloy also as an interference color line. Be oxidized aluminum and / or
  • the aluminum oxide substrate or the substrate consisting of the oxide of the aluminum alloy has cavities and / or fissures that result from the wet-chemical oxidation. Therefore distinguish the flake-form alumina produced by the process according to the invention differs from the alumina known from the prior art, on the one hand, by a rough, fissured surface and, on the other hand, by a
  • the cavities have average diameters from a range of 20 nm to 40 nm,
  • the proportion of elemental aluminum and / or the aluminum alloy is in a range of 3 to 18 wt .-%, preferably in a range of 4 to 15 wt .-%, based on the total weight of aluminum oxide and / or the oxide of the aluminum alloy and elemental aluminum and / or the aluminum alloy.
  • Aluminum alloy in a range of 6 to 14 wt .-%, even more preferably in a range of 7 to 13 wt .-%, even more preferably in a range of 8 to 12 wt .-%, each based on the total weight of aluminum oxide and / or oxide of the aluminum alloy and elemental aluminum and / or the
  • Aluminum alloy also has a range of 9 to 1 1% by weight, based on the total weight of aluminum oxide and / or oxide of the very suitable
  • Aluminum alloy platelets have an aspect ratio, i. a ratio of average diameter to mean thickness of the platelets, from a range of 50 to 2000, more preferably from a range of 55 to 1500, more preferably from a range of 60 to 1000, and most preferably from a range of 62 to 500.
  • the wet-chemically oxidized aluminum and / or aluminum alloy platelets clearly differ in their optical appearance from the aluminum and / or aluminum alloy platelets used as starting material.
  • the pigments according to the invention have an extremely low content elemental or metallic aluminum or on aluminum alloy, so that the typical metallic luster is lost and the oxidized aluminum or
  • Aluminum alloy platelets have a dark silk gloss.
  • Aluminum alloy the content of aluminum being at least 60% by weight, based on the total weight of the alloy, of a range of from 3 to 15% by weight, based on the total weight of aluminum oxide and / or oxide of the aluminum alloy and aluminum and / or aluminum alloy, a metallic core with an average thickness of preferably ⁇ 25 nm, more preferably ⁇ 22 nm, even more preferably ⁇ 18 nm, even more preferably ⁇ 15 nm, is still present in the oxidized aluminum and / or aluminum alloy plate , At a thickness of ⁇ 20 nm, the metallic core is partially transparent, resulting in partial transparency of the oxidized aluminum and / or aluminum alloy platelets. Due to this partial transparency, the oxidized aluminum and / or aluminum alloy plate has a dark body color. The light falling on the pigment is separated from the partially transparent aluminum and / or
  • Aluminum alloy layer absorbs, which is why the dark body color arises.
  • the metallic core need not be continuous, but can also be clustered, i. fragmented.
  • the oxidized aluminum and / or aluminum alloy platelets can therefore be used as effect pigments without further postcoating and without additional size classification.
  • Protective layer or surface modification provided and / or with at least an optically active layer are coated. If the at least one optically active layer has a refractive index of> 1.8, the above-mentioned interference phenomena can be enhanced.
  • the oxidized aluminum and / or aluminum alloy platelets according to the invention are the result of a controlled-running wet-chemical
  • the oxidation is carried out in an oxidizing agent-containing organic solvent.
  • Oxidationsm ittel preferably water is used.
  • other or further Oxidationsm means, such as peroxides such as
  • Hydrogen peroxide can be used.
  • the starting material to be used aluminum and / or
  • Aluminum alloy flakes are preferably stirred in an aqueous organic solvent, for example a mixture of water and at least one water-miscible solvent, at a pH in the range from 7 to 12 between room temperature and the boiling point of the solvent mixture.
  • an aqueous organic solvent for example a mixture of water and at least one water-miscible solvent
  • oxidized aluminum and / or aluminum alloy platelets can be adjusted.
  • the wet-chemical oxidation can, depending on the desired degree of oxidation of the aluminum or aluminum alloy platelets during the
  • Hydrogen evolution for example, quenched by the addition of a silane, or stopped by filtration of the suspension.
  • the proportion of water in the solvent mixture to be used for the controlled wet-chemical oxidation is preferably in a range from 10 to 89% by weight, preferably in a range from 20 to 75% by weight, based on the weight of the solvent mixture. Based on the weight of the used
  • the water content is preferably in a range of 20 to 500 wt .-%, more preferably in a range of 25 to 355 wt .-%.
  • the proportion of water is preferably at the desired content of metallic aluminum and / or at Aluminum alloy adapted in the oxidized aluminum or aluminum alloy plate.
  • the reaction can become uncontrollable and agglomerates can form.
  • Particularly suitable water-miscible solvents are alcohols, ketones or glycols, such as, for example, ethanol, isopropanol, isobutanol, methoxypropanol, acetone or butylglycol.
  • the solvent mixture may optionally contain aliphatic or aromatic amines, such as, for example, 2-aminoethanol,
  • Ammonia triethylamine, diethylamine, dimethylamine, n-butylamine, isobutylamine, tert-butylamine or pyridine.
  • the controlled wet chemical oxidation is preferably carried out at a temperature in the range of 20 to 140 ° C.
  • the metallic core of elemental aluminum and / or the aluminum alloy is platelet-shaped.
  • the metallic core has holes and / or is subdivided into fragments.
  • the fragments are substantially within an area in the pigment that is substantially parallel to the outer surfaces.
  • the elemental or metallic aluminum and / or the aluminum alloy in the inventive metal oxide-containing pigments form a continuous surface or an area with holes or openings or fragmented.
  • Aluminum alloy plate the surface of the metallic plate or metallic core is heavily roughened and rugged, but may still be formed throughout. According to the invention it is particularly preferred if the
  • metallic core has holes or openings. In these holes or openings, the oxidation of the metallic core is locally completed, so that the metallic core of the aluminum and / or
  • Aluminum alloy plate has openings made of aluminum oxide and / or the oxide of the aluminum alloy.
  • fragments of elemental aluminum and / or aluminum alloy which no longer have to be connected to each other, thus can be present separately. These fragments can be formed flat. In a very strong oxidation, the flat character of the fragments is lost.
  • the fragments of aluminum and / or aluminum alloy platelets are produced by wet chemical oxidation, the fragments lie in an area within the metal oxide-containing pigment.
  • the fragments lie in an area within the metal oxide-containing pigment.
  • the fragments of the invention When the pigments of the invention are arranged planar, then the fragments lie substantially in a central plane of the pigment. If the metal oxide-containing pigments should be bent, then the fragments lie within a central area in the pigment that corresponds to the bending of the pigment
  • metal oxide-containing pigment follows, so that the fragment-containing surface in the
  • the metallic core has an average thickness ranging from 2 nm to 25 nm. Further, it is preferable that the average thickness is in a range of 4 nm to 22 nm, more preferably 6 nm to 21 nm, still more preferably 8 nm to 18 nm, still more preferably 10 nm to 16 nm preferably from 12 nm to 15 nm.
  • the metallic core By average thickness of the metallic core is meant both the thickness of a continuous metallic layer of aluminum and / or aluminum alloy, a metallic layer of aluminum and / or aluminum alloy with holes or openings or a layer with fragments of aluminum and / or aluminum alloy.
  • the mean layer thickness of the aluminum oxide and / or the aluminum alloy oxide is in a range from 5 nm to 500 nm, preferably from 10 nm to 400 nm.
  • a very suitable average layer thickness is in the range from 12 nm to 300 nm.
  • the details of this layer thickness are the sum of the layer thicknesses of aluminum oxide and / or the oxide of the aluminum alloy of the two layers, which are applied on both sides to the surfaces of the metallic core.
  • the average thicknesses of the respective single layer on the top and the bottom of the pigment in a range of 2.5 nm to 250 nm, preferably in a range of 5 nm to 200 nm, more preferably in a range of in each case 6 nm to 150 nm. If no metallic core is present in the metal oxide-containing pigments, the aforementioned average layer thickness in the range from 5 nm to 500 nm is the total layer thickness of the
  • the average thickness of the metallic core and the average layer thickness of the aluminum oxide and / or the oxide of the aluminum alloy are determined by means of scanning electron micrographs of cross sections. To obtain statistically secured values, at least 100 pigment particles are counted.
  • the proportion of aluminum in the aluminum alloy is in a range from 70 to 99% by weight, preferably in a range from 80 to 98% by weight, more preferably in a range from 85 to 95% by weight. -%, in each case based on the total weight of the aluminum alloy.
  • the aluminum alloy contains silicon, magnesium, zinc, titanium, cobalt, copper and / or iron.
  • the aluminum alloy may contain silicon, magnesium, zinc and / or titanium each in a range of 0 to 20 wt%, preferably each in a range of 1 to 10 wt%, each based on the total weight of the alloy.
  • the aluminum alloy cobalt, copper and / or iron in each case in a range of 0 to 5 wt .-%, preferably in each case in a range of 1 to 3 wt .-%, each based on the total weight of the alloy.
  • the aluminum preferably has a purity of at least 98 wt .-%, preferably of at least 99 wt .-%, more preferably of at least 99.9 wt .-%, on. Also in the case of aluminum alloy pigments, the aluminum alloy preferably has a purity of at least 98% by weight, preferably at least 99% by weight.
  • Aluminum alloy platelets which are then oxidized according to the invention used.
  • Aluminum alloy platelets by, for example, iron, zinc, copper, vanadium, chromium, nickel, cobalt, silicon, manganese and / or titanium is preferably less in total as 1 wt .-%, more preferably less than 0.1 wt .-%, most preferably less than 0.01 wt .-%, each based on the total weight of the aluminum or aluminum alloy platelets.
  • the heavy metal content was determined according to the leaching method.
  • the corresponding pigments were heated to boiling in 0.5 M HCl and the extract was analyzed by means of graphite atomic absorption spectrometry (type 240 Z, Varian.) Or by inductively coupled plasma optical emission spectrometry (type CIROS, Spectro).
  • the content of elemental aluminum and / or the aluminum alloy in the oxidized aluminum and / or aluminum alloy plate is in a range of 0 to less than 3 wt .-%, preferably in a range of 0.1 to 2 %
  • the oxidized aluminum and / or aluminum alloy platelets preferably have an average particle size D 50 from a range of 2 ⁇ m 50 pm.
  • Aluminum and / or aluminum alloy flake is preferably in a range of 50 m 2 / g to 500 m 2 / g. More preferably, the BET surface area of the largely, preferably completely, oxidized aluminum and / or
  • Aluminum alloy plate in a range from 75 m 2 / g to 400 m 2 / g, more preferably at 100 m 2 / g to 350 m 2 / g and most preferably at 105 m 2 / g to 300 m 2 / g.
  • Aluminum alloy platelets are therefore suitable as a transparent substrate for the coating with at least one optically active layer and optionally a protective layer.
  • Aluminum alloy flakes can also be used as fillers in
  • Aluminum alloy platelets may optionally be provided with at least one protective layer.
  • a surface modification is conceivable, which facilitates, for example, the incorporation into a surrounding medium.
  • Aluminum alloy platelets at less than 3 wt .-%, based on the
  • Aluminum alloy is less than 1000 nm, preferably less than 300 nm, more preferably less than 260 nm, most preferably less than 200 nm.
  • boehmite is essentially formed in the wet-chemical oxidation of aluminum platelets
  • the oxidized aluminum and / or aluminum alloy platelets may be provided with at least one optically active layer and / or optionally a protective layer. These layers may be metal oxides, metal oxide hydrates,
  • the above-mentioned materials can be present either as separately separate layers or also side by side in the same layer.
  • the optically active layer used is preferably metal oxides, metal oxide hydrates, metal hydroxides and / or mixtures thereof.
  • the protective layer may comprise or preferably consist of one or two metal oxide layers of the elements Si, Al or Ce.
  • a silicon oxide layer preferably SiO 2 layer, is applied as outermost metal oxide layer.
  • particularly preferred is an order in which first a cerium oxide layer is applied, which then follows a Si0 2 layer, as described in EP 1 682 622 B1, the content of which is hereby incorporated by reference
  • Coating may either completely encase the substrate, be only partially on the substrate, or cover only its top and / or bottom surfaces.
  • the pigment is additionally coated with at least one high refractive index metal oxide layer.
  • this is preferably a high-index layer whose refractive index is n> 1, 8, preferably n> 1, 9 and more preferably n > 2.0 is.
  • Suitable high-index layers are, for example, metal oxides, such as titanium oxide, preferably titanium dioxide (TIO 2), iron oxide, preferably iron (III) oxide (Fe 2 O 3 ) and / or iron (II / III) oxide (Fe 3 O 4 ), zinc oxide, preferably ZnO, tin oxide,
  • metal oxides such as titanium oxide, preferably titanium dioxide (TIO 2), iron oxide, preferably iron (III) oxide (Fe 2 O 3 ) and / or iron (II / III) oxide (Fe 3 O 4 ), zinc oxide, preferably ZnO, tin oxide,
  • Calcium titanate CaTiOs
  • iron titanates such as ilmenite (FeTiOs), pseudobrookite (Fe 2 TiO 5) and / or pseudorutile (Fe 2 Ti 3 O 9)
  • metals such as molybdenum, iron, tungsten, chromium, cobalt, nickel, silver, Palladium, platinum, their mixtures and / or alloys, doped metal oxides, such as titanium dioxide and / or
  • Zirconia colored with selectively absorbing colorants and / or mixtures thereof can be used.
  • the latter coloring of non-absorbing high-index metal oxides can e.g. by incorporation of colorants in the
  • Metal oxide layer by doping with selectively absorbing metal cations or colored metal oxides such as iron (III) oxide or by coating the
  • Metal oxide layer with a colorant-containing film take place.
  • the high-index layer preferably comprises metal oxides, metal hydroxides and / or metal oxide hydrates. Particular preference is given to using metal oxides. Very particular preference is given to using titanium dioxide and / or iron oxide and also their mixed oxides, for example ilmenite, pseudobrookite or pseudorutil.
  • the titanium dioxide When coated with titanium dioxide, the titanium dioxide may be in the rutile or anatase crystal modification.
  • the rutile form can be obtained, for example, by applying, for example, a layer of tin dioxide to the platelet-shaped substrate to be coated before applying the titanium dioxide layer. On this layer of tin dioxide, titanium dioxide crystallizes in the rutile modification.
  • the tin dioxide may be present as a separate layer, wherein the layer thickness may be a few nanometers, for example less than 10 nm, more preferably less than 5 nm, even more preferably less than 3 nm.
  • the tin dioxide can also be present at least partially in admixture with the titanium dioxide.
  • metal oxide-containing pigments also have a multilayer coating structure comprising metal oxides, metal hydroxides, metal suboxides and / or metal oxide.
  • preference is given to a layer sequence in which at least one high-index layer and at least one low-index layer are arranged in an alternating manner on a substrate. In the alternating arrangement, it is also possible that one or more high-index layers are arranged directly above one another and subsequently one or more low-refractive layers are arranged directly above one another.
  • the high refractive index layer (s) may be selected from those already mentioned.
  • Examples of low-refraction layers having a refractive index of n ⁇ 1.8, preferably n ⁇ 1.7, and more preferably n ⁇ 1.6 include metal oxides such as silicon oxide, preferably silicon dioxide (S1O2), aluminum oxide, preferably Al 2 O 3, boron oxide, preferably boron (III) oxide (B 2 O 3), metal fluorides such as magnesium fluoride, preferably MgF 2 , aluminum fluoride, preferably AIF 3 , cerium fluoride, preferably cerium (III) fluoride (CeF 3 ), calcium fluoride, preferably CaF 2 , metal oxide hydrates such as Alumina hydrate AIOOH, silica hydrate, and / or mixtures thereof.
  • metal oxides such as silicon oxide, preferably silicon dioxide (S1O2), aluminum oxide, preferably Al 2 O 3, boron oxide, preferably boron (III) oxide (B 2 O 3
  • metal fluorides such as magnesium fluoride, preferably MgF 2 , aluminum fluoride
  • the low refractive index layer comprises silicon dioxide.
  • the metal oxide-containing pigments according to the invention can be coated with a protective layer applied thereon.
  • the protective layer can increase the light, weather and / or chemical stability of these metal oxide-containing pigments or as a post-coating which enhances the handling of the metal oxide-containing pigments
  • the protective layer can furthermore be modified organochemically on the surface.
  • one or more silanes may be applied to this outer protective layer.
  • the silanes may be alkylsilanes having branched or unbranched alkyl radicals having 1 to 24 carbon atoms, preferably 6 to 18 carbon atoms.
  • the surface of the pigment is additionally modified organically-chemically.
  • the silanes may also be organofunctional silanes which allow a chemical attachment to a plastic, a binder of a paint or a paint, etc.
  • Organofunctional silanes which have suitable functional groups are commercially available and are manufactured, for example, by Evonik and marketed under the trade name "Dynasylan.” Further products can be obtained from the company Momentive (Silquest-Silane) or from Wacker, For example, standard and ⁇ -silanes from the GENIOSIL product group, related.
  • Examples of these are 3-methacryloxypropyltrimethoxysilane (Dynasylan MEMO, Silquest A-174NT), vinyltri (m) ethoxysilane (Dynasylan VTMO or VTEO, Silquest A-151 or A-171), methyltri (m) ethoxysilane (Dynasylan MTMS or MTES ), 3- Mercaptopropyltrimethoxysilane (Dynasylan MTMO; Silquest A-189), 3-glycidoxypropyltrimethoxysilane (Dynasylan GLYMO, Silquest A-187), tris [3- (trimethoxysilyl) propyl] isocyanurate (Silquest Y-1 1597), bis [3- (triethoxysilyl) propyl ) tetrasulfide (Silquest A-1289), bis [3- (triethoxysilyl) propyl disul
  • organofunctional silanes preference is given to 3-methacryloxypropyltrimethoxysilane (Dynasylan MEMO, Silquest A-174NT), vinyltri (m) ethoxysilane
  • Methacryloxymethyltri (m) ethoxysilane (GENIOSIL XL 33, XL 36),
  • aqueous prehydrolysates commercially available from Degussa. These include u.a. aqueous aminosiloxane (Dynasylan Hydrosil 1 151), aqueous amino / alkyl functional siloxane (Dynasylan Hydrosil 2627 or 2909), aqueous diaminofunctional siloxane (Dynasylan Hydrosil 2776), aqueous, aqueous epoxyfunctional siloxane (Dynasylan Hydrosil 2926), amino / alkyl functional oligosiloxane (Dynasylan 1 146), vinyl- / alkyl-functional
  • Oligosiloxane (Dynasylan 6598), oligomeric vinylsilane (Dynasylan 6490) or oligomeric short-chain alkyl-functional silane (Dynasylan 9896).
  • the organofunctional silane mixture contains at least one amino-functional silane in addition to at least one silane without a functional bond group.
  • the amino function is a functional group which, with most of the groups present in binders, has one or more chemical groups
  • the following compounds are preferably used for this purpose: 3-aminopropyltrimethoxysilane (Dynasylan AMMO, Silquest A-1110), 3-aminopropyltriethoxysilane (Dynasylan AMEO), [3- (2-aminoethyl) aminopropyl] trimethoxysilane (Dynasylan DAMO, Silquest A-1 120), [3- (2-aminoethyl) aminopropyl] triethoxysilane, triaminofunctional trimethoxysilane (Silquest A-1 130), bis (gamma-trimethoxysilylpropyl) amine (Silquest A-1 170), N-ethyl-gamma-aminoisobutyltrimethoxysilane ( Silquest A-Link 15), N-phenyl-gamma-aminopropyltrimethoxysilane (Silquest Y-9669), 4-amino
  • the silane without a functional linking group is an alkylsilane.
  • the alkylsilane preferably has the formula R (4- Z ) Si (X) z.
  • z is an integer from 1 to 3
  • R is a substituted or unsubstituted, unbranched or branched alkyl chain having 10 to 22 carbon atoms
  • X is a halogen and / or alkoxy group.
  • R may also be cyclically connected to Si, in which case z is usually 2.
  • organic-chemical modifiers such as, for example, substituted or unsubstituted alkyl radicals, polyethers, thioethers, siloxanes, etc., and mixtures thereof can be arranged on or on the surface of the metal oxide-containing pigments or effect pigments based thereon .
  • inorganic-chemical modifiers e.g., Al 2 O 3 or ZrO 2 or mixtures thereof
  • can increase the dispersibility and / or compatibility in the respective application medium are applied to the pigment surface.
  • the surface modification for example, the hydrophilicity or
  • Hydrophobicity of the pigment surface can be changed and / or adjusted.
  • Nonleafing properties of the inventive metal oxide-containing pigments or effect pigments based thereon are changed and / or adjusted.
  • Leafing is understood to mean that the metal oxide-containing pigments according to the invention or effect pigments based thereon are arranged in an application medium, for example a lacquer or an ink, at or in the vicinity of the boundary or surface of the application medium.
  • the surface modifiers may also have reactive chemical groups such as acrylate, methacrylate, vinyl, isocyanate, cyano, epoxy, hydroxy, amino groups or mixtures thereof. These chemically reactive groups allow a chemical attachment, in particular formation of covalent bonds, to the application medium or components of the Application medium, such as binders. As a result, for example, the chemical and / or physical properties of cured paints, inks or printing inks such as resistance to environmental influences such as moisture, sunlight, UV resistance, etc., or against mechanical influences, such as scratches, etc., can be improved.
  • reactive chemical groups such as acrylate, methacrylate, vinyl, isocyanate, cyano, epoxy, hydroxy, amino groups or mixtures thereof.
  • Application medium or components of the application medium can be any suitable application medium or components of the application medium.
  • the invention thus also relates to effect pigments which are based on oxidized aluminum and / or aluminum alloy platelets and are optionally coated with at least one optically active layer and / or at least one protective layer.
  • Effect pigment and / or serve as a substrate for effect pigments is of the respective content of metallic aluminum and / or the respective content of
  • the wet-chemically oxidized aluminum and / or aluminum alloy platelets can be used without further size classification with at least one optically active
  • this fine fraction could, for example, lead to undesired scattering light effects. Furthermore, a different coating speed of the fines and the remaining oxidized aluminum and / or aluminum alloy platelets could
  • Size classification may be done before or after coating the oxidized aluminum and / or aluminum alloy platelets.
  • the oxidized aluminum and / or aluminum alloy platelets can also be sized according to size if they are not coated with an optically active layer.
  • Aluminum alloy platelets are preferably selected to correspond to the oxidized aluminum and / or aluminum alloy platelets to be coated. Alternatively, too much oxidized aluminum or
  • Aluminum alloy platelets prior to coating with at least one optically active layer and / or protective layer to the desired particle size e.g. be reduced by ball mill, jet or stirred ball mill, muller or dissolver.
  • the crushing can be a size classification
  • oxidized aluminum and / or aluminum alloy platelets are coated and / or classified according to size depends on the desired visual appearance and intended use:
  • Oxidized aluminum and / or aluminum alloy platelets containing less than 3% by weight of metallic aluminum and / or aluminum alloy, based on the total weight of oxidised aluminum or aluminum alloy
  • Aluminum alloy platelets may be coated without further coating, e.g. be used as a filler in cosmetic formulations.
  • the oxidized aluminum or aluminum alloy platelets may be a
  • ⁇ Are oxidised aluminum and / or aluminum alloy platelets with a content of metallic aluminum and / or aluminum alloy of less than 3 wt .-%, based on the total weight of the oxidized aluminum and / or aluminum alloy platelets, with at least one optically active layer and / or coated a protective layer, the respective coating can be done due to the low aluminum content in the aqueous medium.
  • the oxidized aluminum and / or aluminum alloy platelets should be used before the
  • Coating with at least one optically active layer are classified by size.
  • Metal hydroxides or metal oxide hydrates, the oxidized aluminum and / or aluminum alloy platelets are suspended in water and mixed with one or more hydrolyzable metal salts or a water glass solution at a suitable pH for the hydrolysis.
  • the pH is chosen so that the metal oxides, metal hydroxides or metal oxide hydrates are precipitated directly on the substrate to be coated.
  • the pH is
  • the annealing temperature can be optimized with respect to the particular coating present.
  • the annealing temperatures are in a range between 500 and 1000 ° C, preferably in a range between 600 and 900 ° C.
  • the effect pigments can each be separated off after the individual coatings, dried and, if appropriate, calcined, in order then to precipitate the other
  • silicon dioxide layer to be present in such a multi-layered structure, this can be achieved either by adding a potassium or sodium waterglass solution at a suitable pH or via sol-gel methods starting from alkoxysilanes, e.g. Tetraethoxysilane be applied.
  • Aluminum alloy platelets and a preferred aspect ratio in the range of 50 to 2,000, can be used without further coating
  • Effect pigment can be used. After the wet-chemical oxidation, a size classification and optionally a calcination can be carried out.
  • ⁇ Will be oxidized aluminum and / or aluminum alloy platelets containing metallic aluminum and / or aluminum alloy from a range of 3 to 15 wt .-%, based on the total weight of the oxidized aluminum and / or aluminum alloy platelets, and a preferred aspect ratio provided a region 50 to 2000 with at least one optically active layer and / or a protective layer, the coating is due to the high aluminum and / or aluminum alloy content
  • the resulting effect pigments can be calcined at less than 600 ° C. under inert gas.
  • Aluminum alloy platelets may be made before or after their coating.
  • Aluminum alloy platelets can be determined as follows:
  • the platelet-shaped metal oxide-containing pigments are dissolved in 15% strength by weight sodium hydroxide solution.
  • the resulting hydrogen is collected in a gas burette and calculated the metal content gas volumetric.
  • volume-averaged size distribution function as determined by
  • Laser diffraction methods indicates that 10%, 50% and 90% of the metal oxide-containing pigments or the effect pigments based thereon have a diameter which is equal to or less than the value specified in each case.
  • the size distribution curve of the metal oxide-containing pigments or the effect pigments based thereon is determined depending on the aluminum content with a device from Malvern (device: MALVERN Mastersizer 2000) or a device from Quantachrome (Cilas 1064), in each case according to the manufacturer's instructions.
  • the evaluation of the scattered light signals was carried out according to the Mie theory or
  • Fraunhofer method which also includes refractive and absorption behavior of the metal oxide-containing pigments or the effect pigments based thereon.
  • pigments according to the invention have a D-io value from a range of 1 ⁇ m to 20 ⁇ m, a D 50 value from a range from 2 ⁇ m to 50 ⁇ m and a D 90 value from a range from 10 ⁇ m to 250 ⁇ m, preferably one Dm value from a range of 3 pm to 17 pm, a D 50 value from a range of 7 pm to 43 pm and a D 90 value from a range of 19 pm to 173 pm.
  • effect pigments based on oxidized aluminum and / or aluminum alloy platelets depends on their content metallic aluminum and / or the content of aluminum alloy.
  • Aluminum alloy platelets containing ⁇ 3% by weight of metallic aluminum, based on the total weight of the oxidized aluminum and / or aluminum alloy platelets comprising at least one optically active layer, have a deep gloss typical for pearlescent pigments
  • Aluminum alloy platelets containing from 3 to 18% by weight of metallic aluminum and / or aluminum alloy,
  • oxidized aluminum and / or aluminum alloy platelets preferably from a range of 4 to 15 wt .-%, each based on the total weight of the oxidized aluminum and / or aluminum alloy platelets lose due to their low aluminum or aluminum alloy content the typical metallic luster, but still have a striking opacity.
  • effect pigments comprising oxidized aluminum and / or aluminum alloy platelets containing
  • metallic aluminum and / or aluminum alloy from a range of 3 to 18 wt .-%, preferably from a range of 4 to 15 wt .-%, each based on the total weight of the oxidized aluminum and / or
  • Aluminum alloy platelets, and a preferred aspect ratio within a range of 50 to 2000 has a D 5 o value of 2 to 50 ⁇ m.
  • Aluminum alloy platelets can be used as fillers in cosmetic formulations, textiles, plastics, films, ceramic materials, glasses,
  • Coating compositions such as paints, printing inks, (inkjet) inks, paints or powder coatings are used.
  • Coating compositions and materials also effect pigments based on these oxidized aluminum or aluminum alloy platelets may be used.
  • cosmetic formulations such as e.g. Body powder, face powder, pressed and loose powder, face makeup, powder cream, cream makeup, emulsion makeup, wax makeup, foundation, mousse makeup, cheek rouge, eye makeup such as eye shadow, mascara, eyeliner, liquid eyeliner, eyebrow pencil, lip balm, lipstick, lip gloss, lip liner, hair styling compositions hairspray,
  • Hair mousse, hair gel, hair wax, hair mascara, permanent or semipermanent hair colors, temporary hair colors, skincare compositions such as lotions, gels, emulsions and nail polish compositions, can be used
  • oxidized aluminum or aluminum alloy platelets according to the invention and / or the effect pigments according to the invention with raw materials, auxiliaries and / or active substances which are suitable for the respective application and optionally colorants.
  • Aluminum content less than 3% by weight, based on the total weight of the oxidized aluminum and / or aluminum alloy platelets, are preferably used as fillers, optionally in combination with colorants, in a concentration between 0.001% by weight for rinse-off products and 40% by weight for leave-on products, each based on the total weight of the cosmetic formulation.
  • Oxidized aluminum or aluminum alloy flakes having an aluminum and / or aluminum alloy content in the range from 3 to 18% by weight, based on the total weight of the oxidized aluminum or aluminum alloy flakes or effect pigments based thereon can be dispersed in cosmetic formulations at a concentration between 0.001% by weight for rinse-off products and 40% by weight for leave-on products, in each case based on the total weight of the cosmetic formulation.
  • effect pigments according to the invention can also be used in admixture with further color and / or effect components.
  • the color and / or effect components include, for example, in the surrounding medium soluble, black or colored dyes or in the surrounding medium insoluble pigments, such as platelet-shaped metallic effect pigments (for example from the product group Visionaire, Fa. Eckart), pearlescent pigments (for example from the
  • Fig. 1 shows a scanning electron micrograph of a
  • the content of elemental aluminum is 0 wt .-%.
  • the voids produced within the aluminum oxide plate thus produced.
  • the cavities extend within the pigment and are considered dark
  • a platelet-shaped metal oxide-containing pigment was obtained with a metallic aluminum content of ⁇ 0.1% by weight, based on the total weight of aluminum oxide and elemental aluminum.
  • Silvershine S2100 (Eckart) with an aspect ratio of 275 in 900g
  • a platelet-shaped metal oxide-containing pigment was obtained with a metallic aluminum content of 0.23% by weight, based on the total weight of aluminum oxide and elemental aluminum.
  • Metalure A41010 PM (Eckart) presented with an aspect ratio of 244 in 270.0 g of isopropanol and dispersed for 10 min. Subsequently, a mixture of 26.7 g of deionized water and 1.6 g of triethanolamine was added and the suspension was heated to 80.degree. After 2 hours of heating, 133.3 g of isopropanol were added. After 7 h at 80 ° C, the suspension was allowed to cool. The suspension was then sucked off through a Buchner funnel and the filter cake in a
  • Vacuum drying oven dried at 100 ° C for 6 h under N 2 atmosphere.
  • a black powder with silky-matt silvery luster was obtained. There was obtained a platelet-shaped metal oxide-containing pigment with a content of metallic aluminum of 5.7 wt .-%, based on the total weight of aluminum oxide and elemental aluminum.
  • TiO2 coating (interference gold):
  • Example 2 50 g of the wet-chemically oxidized aluminum pigment from Example 1 were suspended in 400 ml of deionized water and heated to 80 ° C. with turbulent stirring. The pH was lowered to 1.9 with dilute hydrochloric acid. Then a layer of SnO 2 M was deposited on the surface, this layer being prepared by adding a solution of 3 g SnCl 4 ⁇ 5 H 2 O (in 10 mL concentrated HCl and 50 mL DI water) with simultaneous addition of 10% by weight. formed NaOH solution.
  • TiO2 coating (interference green):
  • Example 2 50 g of the wet-chemically oxidized aluminum pigment from Example 1 were suspended in 400 ml of deionized water and heated to 80 ° C. with turbulent stirring. The pH was lowered to 1.9 with dilute hydrochloric acid. A layer of SnO 2 M was then deposited on the surface, this layer being prepared by adding a solution of 3 g SnCl 4 ⁇ 5 H 2 O (in 10 mL concentrated HCl and 50 mL DI water) with simultaneous addition of 10% by weight.
  • the pH was then adjusted to pH 1.6 with dilute HCl, then a solution of 1000 ml of TiCl 4 (200 g of / 2 / ⁇ fully demineralized water) and at the same time a 10 wt .-% NaOH solution added to the suspension.
  • a 10 wt .-% NaOH solution added to the suspension.
  • the filter cake was calcined at 800 ° C in a tube furnace. An effect pigment with green interference color and a diameter of 3.2 ⁇ m, a D 50 of 10.3 ⁇ m and a D 90 of 26.2 ⁇ m was obtained.
  • TiO2 coating (interference gold):
  • Example 2 60 g of the wet-chemically oxidized aluminum pigment from Example 2 were suspended in 450 ml of deionized water and heated to 80 ° C. with turbulent stirring. The pH was lowered to 1.9 with dilute hydrochloric acid. Then a layer of SnO 2 M was deposited on the surface, this layer being prepared by adding a solution of 3 g SnCl 4 ⁇ 5 H 2 O (in 10 ml concentrated HCl and 50 ml DI water) with simultaneous addition of a 10 wt.
  • the pH was then brought to pH 1, 6 with dilute HCl, then a solution of 200 ml of TiCl 4 (200 g of / 2 / ⁇ of demineralized water) and, at the same time, a 10% by weight NaOH solution.
  • the mixture was stirred for a further hour, filtered off and the filter cake was washed with demineralized water.
  • the filter cake was calcined in a tubular oven at 800 ° C. This gave an effect pigment with golden interference color and a diameter of 10 , 7 pm, a D 50 of 18.3 pm and a D 90 of 26.9 pm.
  • TiO2 coating (interference green gold):
  • Example 2 60 g of the wet-chemically oxidized aluminum pigment from Example 2 were suspended in 450 ml of deionized water and heated to 80 ° C. with turbulent stirring. The pH was lowered to 1.9 with dilute hydrochloric acid. A layer of SnO 2 M was then deposited on the surface, this layer being prepared by adding a solution of 3 g SnCl 4 ⁇ 5 H 2 O (in 10 mL concentrated HCl and 50 mL DI water) with simultaneous addition of 10% by weight.
  • the pH was then brought to pH 1, 6 with dilute HCl, then a solution of 330 ml of TiCl 4 (200 g of / 2 / ⁇ of demineralized water) and, at the same time, a 10% by weight NaOH solution. Solution is added to the suspension Coating was stirred for 1 h, filtered off and the filter cake washed with deionized water. The filter cake was calcined at 800 ° C in a tube furnace. An effect pigment with green-gold interference color and a diameter of 10.8 ⁇ m, a D 50 of 18.3 ⁇ m and a D 90 of 27.1 ⁇ m was obtained.
  • TiO2 coating (interference blue):
  • a black effect pigment with blue interference color and a diameter of 5.2 ⁇ m, a D 50 of 12.0 ⁇ m and a D 90 of 19.5 ⁇ m was obtained.
  • the platelet-shaped metal oxide-containing pigments were dissolved in 15% strength by weight sodium hydroxide solution.
  • the resulting hydrogen was collected in a gas burette and calculated the metal content gas volumetric.
  • Illb particle size measurement The size distribution curve of the platelet-shaped metal oxide-containing pigments containing elemental aluminum or aluminum alloy from a range of 0 to less than 3% by weight, based on the total weight of aluminum oxide and / or the aluminum alloy and elemental oxide
  • Aluminum and / or the aluminum alloy, as well as the size distribution curve of the effect pigments based thereon were determined using a device from Malvern (device: MALVERN Mastersizer 2000) according to the manufacturer's instructions. For this purpose, about 0.1 g of the platelet-shaped metal oxide-containing pigment or of the effect pigment based thereon was used as aqueous suspension without addition of
  • Dispersing aids with constant stirring by means of a Pasteur pipette in the sample preparation cell of the meter and measured several times. From the individual measurement results, the resulting averages were formed.
  • the evaluation of the scattered light signals was carried out according to the Mie theory, which also includes refractive and absorption behavior of the platelet-shaped metal oxide-containing pigments or of the effect pigment based thereon.
  • Range of 3 to 18 wt .-%, based on the total weight of aluminum oxide and / or the oxide of aluminum alloy and elemental aluminum and / or the aluminum alloy, and the size distribution curve of the effect pigments based thereon were with a device from. Quantachrome (device: Cilas 1064) according to the manufacturer's instructions. For this purpose, about 1, 5g of the corresponding pigment were suspended in isopropanol, treated for 300 seconds in an ultrasonic bath (device: Sonorex IK 52, Fa. Bandelin) and then by means of a
  • Pasteur pipette into the sample preparation cell of the measuring device and measure several times. From the individual results were the
  • D 50 By average size D 50 is in the context of this invention, the D 5 o-value of the cumulative frequency distribution of volumengem ittelten size distribution function, as obtained by laser diffraction methods, understood.
  • the D 5 o value indicates that 50% of the oxidized aluminum or aluminum alloy flakes have a diameter equal to or less than the specified value.
  • the D 9 o value indicates that 90% of the oxidized aluminum or aluminum alloy flakes have a diameter equal to or less than the respective value.
  • the scanning electron micrograph was obtained by cross-sectioning the platelet-shaped metal oxide-containing pigments with the scanning electron microscope Supra 35 (Zeiss).
  • the average thickness of the possibly still present metallic core and the average layer thickness of the aluminum oxide and / or the oxide of the aluminum alloy was determined by means of scanning electron images of
  • Aluminum pigments ie the average layer thickness of the aluminum oxide and the average thickness of the possibly still present metallic core, without a further coating with titanium dioxide.
  • the heavy metal content was determined according to the leaching method.
  • the corresponding pigments were heated to boiling in 0.5 M HCl and the extract was analyzed by means of graphite atomic absorption spectrometry (type 240 Z, Varian.) Or by inductively coupled plasma optical emission spectrometry (type CIROS, Spectro).
  • the titanium and tin content of the pigments used as starting material was determined by means of atomic absorption spectrometer (type: 240FS, Varian.).
  • the opacity of the pigments was determined by means of lacquer applications on black and white cover cards (Byko Chart 2853, Byk Gardner).
  • the respective pigment was stirred into a conventional nitrocellulose lacquer (Dr. Renger Erco Bronzemischlack 2615e, from Morton) at a pigmentation level of 6% by weight (based on the total weight of the wet lacquer.)
  • the respective pigment was initially introduced and then brushed in with a brush
  • the finished varnish was spread on a doctor blade extractor with a
  • the brightness values L * were measured with a measuring geometry of 1 10 °, relative to the angle of reflection of the irradiated at 45 °, based on these paint applications on the black and on the white background of the black and white card with the device BYK-mac, Byk Gardner, presumptuous.
  • the brightness (L * value) was determined by diffuse color measurement of the respective powder beds with a colorimeter CM700d from Konica Minolta.
  • the platelet-shaped metal oxide-containing pigments according to the invention can be used as a filler or as an effect pigment in cosmetic formulations, depending on their proportion of elemental aluminum. If the proportion of metallic aluminum is in a range of 0 to less than 3 wt .-%, based on the total weight of aluminum oxide and elemental aluminum, the platelet-shaped metal oxide-containing pigments are preferably used as a filler. If the proportion of metallic aluminum is in a range of 3 to 18 wt .-%, based on the total weight of aluminum oxide and elemental aluminum, the platelet-shaped metal oxide-containing pigments as
  • the metal oxide-containing pigment according to Example 1 can be used in a range from 0.1 to 8.0% by weight, based on the total weight of the mousse formulation become. Balancing can be done with Dow Corning 9041 Silicone Elastomer Blend.
  • Phase A was mixed and heated until everything had melted.
  • Phase B was weighed separately and mixed with a high speed mixer for 60s at 2400 rpm.
  • Half of the molten phase A was added to phase B and mixed again in the blender at 2400 rpm for 30 seconds.
  • the remaining portion of phase B was also added to phase A and mixed again at 2400 rpm for 30 seconds.
  • phase C is added to phase AB and mixed again at 2400 rpm for 30s in the high speed mixer.
  • the metal oxide-containing pigment according to Example 2 can be used in a range of 0.5-2.5% by weight, based on the total weight of the body lotion formulation.
  • the compensation can be done with water.
  • Phase A was mixed and heated to 75 ° C, Phase B was heated to 70 ° C after mixing, then Phase B slowly added with homogenization Phase A added. While stirring, the emulsion was cooled and placed in an appropriate container.
  • the metal oxide-containing pigment according to Example 1 can be used in a range from 0.1 to 1.0% by weight, based on the total weight of the foundation formulation.
  • the compensation can be done with water.
  • Phase A and Phase B were weighed separately. Phase A was heated to 70 ° C with stirring and Phase B added with stirring. Phase C was mixed well until Aristoflex was dissolved and then also heated to 70 ° C. Phase C was added to Phase AB and after cooling to 40 ° C, Phase D was added.
  • the metal oxide-containing pigment according to Example 3 can be used in a range of 5.0-40.0% by weight, based on the total weight of the eye shadow formulation.
  • the compensation can be done with Tale.
  • Phase A was mixed for 30s at 2500 rpm in a high speed mixer. Subsequently, phase B was added and the mixture was mixed for 60 s at 3000 rpm in the same mixer. Finally, the powder mixture by means of a
  • Eyeshadow press pressed at 150 bar for 30s in the form.
  • the metal oxide-containing pigment according to Example 1 can be used in a range of 0.5-5.0% by weight, based on the total weight of the face cream formulation.
  • the compensation can be done with water.
  • Rhodicare from phase B was sprinkled into the water with stirring.
  • Phase B was heated to 80 ° C
  • Phase A was heated to 80 ° C after mixing and then Phase A was added to Phase B with stirring. Subsequently, the mass was cooled to 35 ° C and stirred until a homogeneous appearance was achieved.
  • the metal oxide-containing pigment according to Example 2 can be used in a range from 0.2 to 5.0% by weight, based on the total weight of the body powder formulation.
  • the compensation can be done with Mica.
  • Phase A was mixed, then Phase B was added to Phase A. After mixing, the body powder was filled into a suitable container.
  • the resulting effect pigments can be obtained, for example, in the following cosmetic
  • Example 4 The effect pigment according to Example 4 can be used in a range of 0.01-5.0% by weight, based on the total weight of the lipstick formulation.
  • the compensation can be made with Paraffinum Liquidum.
  • Phase A was heated to 85 ° C, then Phase B was added to Phase A and mixed. Subsequently, the mixture was filled at a temperature of 75 ° C in a lipstick form.
  • the effect pigment according to Example 6 can be used in a range of 0.5-2.5% by weight, based on the total weight of the body lotion formulation.
  • the compensation can be done with water.
  • Phase A was mixed and heated to 75 ° C, Phase B heated to 70 ° C after mixing, then Phase B was slowly added to Phase A with homogenization. While stirring, the emulsion was cooled and placed in an appropriate container.
  • Example 17 Cream Eyeshadow
  • the effect pigment according to Example 8 can be used in a range of 0, 1 to 5.0 wt .-%, based on the total weight of the eye shadow formulation.
  • the compensation can be made with Castor Oil.
  • Phase A was mixed and heated to 85 ° C, Phase B was also mixed and then added to Phase A with stirring. After filling into a corresponding container, the mixture is cooled to room temperature.
  • Example 18 shower gel
  • the effect pigment according to Example 5 can be used in a range of 0.01-1.0% by weight, based on the total weight of the shower gel formulation.
  • the compensation can be done with water.
  • Carbopol was dispersed in phase A, stirred for 15 minutes and heated to 65 ° C. Thereafter, the ingredients of Phase B were sequentially under slow
  • the effect pigment according to Example 6 can be used in a range of 0.1-1.0% by weight, based on the total weight of the foundation formulation.
  • the compensation can be done with water.
  • Phase A and Phase B were weighed separately. Phase A was heated to 70 ° C with stirring and Phase B added with stirring. Phase C was mixed well until Aristoflex was dissolved and then also heated to 70 ° C. Phase C was added to Phase AB and after cooling to 40 ° C, Phase D was added.
  • Example 20 Pressed eye shadow
  • the effect pigment according to Example 8 can be used in a range of 5.0-40.0% by weight, based on the total weight of the eye shadow formulation.
  • the compensation can be done with Tale.
  • Phase A was mixed for 30s at 2500 rpm in a high speed mixer. Subsequently, phase B was added and the mixture was mixed for 60 s at 3000 rpm in the same mixer. Finally, the powder mixture by means of a
  • Eyeshadow press pressed at 150 bar for 30s in the form.
  • the effect pigment according to Example 8 can be used in a range of 0.5-5.0% by weight, based on the total weight of the hair mascara formulation.
  • the compensation can be done with water from phase A.
  • Phase A and Phase B were separately heated to 80 ° C, after which Phase B was added slowly to Phase A.
  • Phase B was added slowly to Phase A.
  • Klucel and Veegum were added to Phase C water.
  • phase AB was cooled to 40 ° C and added during cooling phases C and D with stirring.
  • Citric Acid Citric Acid 0, 10 VWR
  • Triethanolamine Triethanolamine 1 20 VWR
  • the effect pigment according to Example 8 can be used in a range of 0.01-0.5 wt .-%, based on the total weight of the Haargel formulation.
  • the compensation can be done with water.
  • the pigment was stirred with the water from Phase A, Aristoflex AVP and Citric Acid were added with stirring and mixed at a speed of 800 rpm for 15 minutes.
  • the ingredients of Phase B were dissolved until a homogeneous solution formed, then Phase B was added to Phase A and mixed.
  • the effect pigment according to Example 6 can be used in a range from 0.2 to 5.0% by weight, based on the total weight of the body powder formulation.
  • the compensation can be done with Mica. Phase A was mixed, then Phase B was added to Phase A. After mixing, the body powder was filled into a suitable container.
  • the effect pigment according to Example 4 can be used in a range of 0.01-0.50 wt .-%, based on the total weight of the lip gloss formulation. Compensation can be done with Versagel ME 750.
  • Phase A was heated to 85 ° C, then the Phase B ingredients were added individually to Phase A, stirred until a uniform consistency was obtained and then filled into a Lip Gloss tube.
  • the effect pigment according to Example 6 can be used in a range of 0.5-10% by weight, based on the total weight of the lip liner formulation.
  • the balance can be made with other pigments, but the total pigmentation should be maintained at 25% by weight based on the total weight of the lip liner formulation.
  • Phase A was heated to 85 ° C and then Phase B added to Phase A with stirring until a uniform mass resulted. Thereafter, the mixture was poured hot into a stick form.
  • the effect pigment according to Example 4 can be used in a range of 0.5-10.0% by weight, based on the total weight of the lipstick formulation.
  • the compensation can be done with other pigments, the
  • total pigmentation level should be 21% by weight, based on the
  • Phase A was heated to 85 ° C, then Phase B was added to Phase A and mixed. Subsequently, the mixture was filled at a temperature of 75 ° C in a lipstick form.
  • the effect pigment according to Example 7 can be used in a range of 0.5-8.0% by weight, based on the total weight of the eyeliner formulation.
  • the compensation can be done with water.
  • phase A was dispersed in phase A and stirred for 15 minutes, after which phase B was added to phase A, then phase C to phase AB and stirred again for 10 minutes. Subsequently, Phase D was added to Phase ABC and heated to 75 ° C, Phase E was also heated to 75 ° C and then added to Phase ABCD. After cooling to 60 ° C, phase F was added and filled into a suitable vessel.
  • the effect pigment according to Example 6 can be used in a range from 0.1 to 8.0% by weight, based on the total weight of the mousse formulation. Balance with Dow Corning Silicone 9041 Elastomer Blend.
  • Phase A was mixed and heated until all components had melted.
  • Phase B was sold separately in a high speed mixer for 60s at 2400 rpm mixed.
  • Half of the molten phase A was added to phase B and mixed again in the blender at 2400 rpm for 30 seconds.
  • the remaining portion of phase A was added to the aforementioned mixture of phase A and phase B and mixed again at 2400 rpm for 30 seconds.
  • phase C is added to phase AB and mixed again at 2400 rpm for 30s in the high speed mixer.
  • the effect pigment according to Example 7 can be used in a range from 0.1 to 10.0% by weight, based on the total weight of the nail varnish formulation.
  • the compensation can be made with International Lacquers Nailpolish.
  • Phase A and Phase B were mixed and then filled into an appropriate container.
  • the effect pigment according to Example 8 can be used in a range of 0, 1 to 10.0 wt .-%, based on the total weight of the nail polish formulation.
  • the compensation can be made with International Lacquers Nailpolish.
  • the effect pigment according to Example 5 can be used in a range from 0.5 to 5.0% by weight, based on the total weight of the sunscreen formulation.
  • the compensation can be done with water.
  • Phase A was mixed and heated to 80 ° C, phase B was also heated after mixing to 80 ° C, then phase A was slowly under
  • phase B Homogenization added to Phase B. While stirring, the emulsion was cooled, added phase C at 45 ° C and filled into an appropriate container.

Abstract

L'invention concerne un pigment lamellaire contenant de l'oxyde métallique. Le pigment contenant de l'oxyde métallique présente un noyau métallique en aluminium élémentaire et/ou en alliage d'aluminium. Le noyau métallique est présent dans une proportion pondérale de l'ordre de 0 à 18 % en poids, par rapport au poids total d'aluminium et/ou d'alliage d'aluminium et d'oxyde métallique sous la forme d'oxyde d'aluminium et/ou d'oxyde de l'alliage d'aluminium. L'aluminium et/ou l'alliage d'aluminium forment un noyau enveloppé d'oxyde d'aluminium et/ou de l'oxyde de l'alliage d'aluminium, à condition que l'alliage d'aluminium présente une teneur en aluminium d'au moins 60 % en poids par rapport au poids total de l'alliage d'aluminium. L'invention concerne également un procédé de fabrication de ces pigments ainsi que leur utilisation.
PCT/EP2012/053104 2011-02-23 2012-02-23 Pigment lamellaire contenant de l'oxyde métallique, son procédé de fabrication et son utilisation comme pigment à effet et/ou comme substrat pour pigments à effet WO2012113886A1 (fr)

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EP12708100.8A EP2678393A1 (fr) 2011-02-23 2012-02-23 Pigment lamellaire contenant de l'oxyde métallique, son procédé de fabrication et son utilisation comme pigment à effet et/ou comme substrat pour pigments à effet

Applications Claiming Priority (2)

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DE201110012214 DE102011012214A1 (de) 2011-02-23 2011-02-23 Plättchenförmiges metalloxidhaltiges Pigment, Verfahren zu dessen Herstellung und Verwendung desselben als Effektpigment und/oder als Substrat für Effektpigmente
DE102011012214.1 2011-02-23

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Cited By (3)

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EP3080209B1 (fr) 2013-12-11 2017-10-18 Eckart GmbH Pigments métalliques pourvue d'un revêtement, procédé pour leur fabrication et leur utilisation, compositions de revêtement et objet
KR20190125393A (ko) * 2017-03-01 2019-11-06 비아비 솔루션즈 아이엔씨. 라멜라 입자 및 제조 방법
WO2021154123A1 (fr) 2020-01-28 2021-08-05 Общество С Ограниченной Ответственностью "Суал Пм" Pigments métalliques avec revêtements anti-corrosion

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DE102013008926A1 (de) 2013-05-24 2014-11-27 Schlenk Metallic Pigments Gmbh Verwendung von modifizierten Effektpigmenten in strahlenhärtbaren Beschichtungszusammensetzungen
FR3028753B1 (fr) * 2014-11-24 2018-01-05 L'oreal Gel aqueux ou hydroalcoolique de phyllosilicates synthetiques a titre d'agent viscosant, matifiant et/ou homogeneisant d'application
FR3028751B1 (fr) * 2014-11-24 2018-01-05 L'oreal Phyllosilicate synthetique sous forme de poudre a titre d'agent matifiant et/ou homogeneisant d'application
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.
SI3034563T1 (sl) 2014-12-19 2019-06-28 Eckart Gmbh Zlato obarvani efektni pigmenti z visoko kromo in visokim sijajem, postopek za njihovo pripravo in njihova uporaba
ES2733082T3 (es) 2014-12-19 2019-11-27 Eckart Gmbh Pigmentos de efecto de color rojo con croma alto y brillo alto, procedimiento para su preparación y uso de los mismos
PL3034564T3 (pl) 2014-12-19 2018-07-31 Eckart Gmbh Pigmenty efektowe o wysokiej transparentności, wysokim nasyceniu i wysokiej czystości barwy, sposób ich wytwarzania i ich zastosowanie
PL3034566T3 (pl) * 2014-12-19 2019-08-30 Eckart Gmbh Metaliczne pigmenty efektowe o wysokim nasyceniu barwy i wysokim połysku, sposób ich wytwarzania oraz ich zastosowanie

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EP3080209B1 (fr) 2013-12-11 2017-10-18 Eckart GmbH Pigments métalliques pourvue d'un revêtement, procédé pour leur fabrication et leur utilisation, compositions de revêtement et objet
KR20190125393A (ko) * 2017-03-01 2019-11-06 비아비 솔루션즈 아이엔씨. 라멜라 입자 및 제조 방법
CN113321946A (zh) * 2017-03-01 2021-08-31 唯亚威通讯技术有限公司 层状颗粒及制造方法
KR102403177B1 (ko) 2017-03-01 2022-05-27 비아비 솔루션즈 아이엔씨. 라멜라 입자 및 제조 방법
WO2021154123A1 (fr) 2020-01-28 2021-08-05 Общество С Ограниченной Ответственностью "Суал Пм" Pigments métalliques avec revêtements anti-corrosion

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