Classifications

• • 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
  • C09C1/62—Metallic pigments or fillers
  • C09C1/627—Copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
• • 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
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
  • C09C3/041—Grinding
• • 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
  • C09C1/62—Metallic pigments or fillers
  • C09C1/622—Comminution, shaping or abrasion of initially uncoated particles, possibly in presence of grinding aids, abrasives or chemical treating or coating agents; Particle solidification from melted or vaporised metal; Classification
  • C09C1/625—Comminution, shaping or abrasion of initially uncoated particles, possibly in presence of grinding aids, abrasives or chemical treating or coating agents; Particle solidification from melted or vaporised metal; Classification the particles consisting of zinc or a zinc alloy
• • 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
  • C09C1/62—Metallic pigments or fillers
  • C09C1/64—Aluminium
• • 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
  • C09C1/66—Copper alloys, e.g. bronze
• • 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
  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
  • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
  • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
  • Y10T428/2995—Silane, siloxane or silicone coating
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
  • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
  • Y10T428/2996—Glass particles or spheres
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
  • Y10T428/2998—Coated including synthetic resin or polymer

Definitions

• Metallic effect pigments are pigments that exhibit specular reflection on flat, oriented particles (DIN 55944).
• the interest in lustrous gold-colored effect pigments is great, particularly in the fields of application of printing, lacquer, paint coating, plastic coloring, cosmetics and glass coloring, since the gold-like products have a high aesthetic quality and impart to such coated, imprinted or colored materials an expensive look.
• the best known genuine-gold flake substitute pigments are the so-called gold bronze powders, which consist predominantly of copper/zinc alloys and, depending on their composition, may have different shades of color ranging from red gold to rich gold (Pigment Handbook, Vol. 1, Second Edition, p. 805 ff, Wiley).
• Gold bronze pigments are produced through atomization of a molten copper/zinc alloy and subsequent grinding of the granules produced by the atomization. During the grinding process, the alloy particles are deformed flake-like and comminuted. In practice gold bronze pigment is predominantly ground dry. To prevent cold welding, a lubricant, such as stearic acid, is added to the utilized granules.
• a post-treatment of the ground product by brushing or gentle milling in special ball mills serves to improve the luster of the metal pigment and is referred to as polishing.
• Irregularities in the surfaces of the metal flakes have a luster-reducing effect. Since the generation of irregularities in the structure of the surfaces of the flakes and different flake thicknesses cannot be avoided during the grinding process, the gold bronze pigments that are produced in this manner do not exhibit the luster that is calculated from the reflectivity of the alloys. Additionally, virtually all gold bronze pigments that are produced via grinding processes display leafing properties, i.e., they float in the medium, which can be attributed to the lubricants added during the grinding process. The manufacture of non-leafing gold bronze pigments requires expensive freeing from lubricant.
• customary vapor deposition methods electron beam technology, resistance radiation heated processes
• a one-layered flake-like metal pigment with plane-parallel planes of reflection that is composed of a copper-based alloy deposited by condensation from the vapor phase.
• Preferred suitable alloy partners are aluminum, but also the metals silver, palladium and silicon, either individually or in combination.
• the coloristics of the novel lustrous gold-colored pigments are determined predominantly by the ratio of copper to the achromatic alloy components. The higher the percentage of copper, the more red gold the flakes are. Silicon increases the color depth of the flakes.
• Typical compositions of flakes with red gold to yellow gold or green gold luster contain, in addition to copper, 1 to 49% aluminum and optionally 0.1-6% silicon.
• the flake thickness is 10-100 nm, preferably 20-60 nm and can be varied without difficulty. Very thin flakes are partially transparent.
• lustrous gold-colored pigments are their perfect plane-parallel surfaces, their undisturbed structural composition and their uniform flake thickness, which permits the highest possible reflection values.
• the most important steps of the manufacturing process are the application of a release coat onto a carrier, condensations of the alloy as a film onto the release coat, stripping of the metallic film, comminuting of the film, and optionally sizing of the pigment particles.
• the vaporizing of the metals in vacuo takes place according to known methods using the ready-made alloys or the individual metals.
• the inventive pigments exhibit the highest degree of brilliance and are sufficiently corrosion-stable in many fields of application. If a special corrosion stability is required it is possible to improve the stability of the highly lustrous pigments through surface coating.
• the surface coatings are generally sufficiently thin and have virtually no impact on the luster behavior of the metal flakes.
• Surface coatings to improve the corrosion behavior may be applied in the vacuum chamber in the course of the metal film deposition, for example through vacuum deposition of SiO x on both sides of the metal film, or via wet-chemical methods during or after comminuting of the film.
• protective coatings of SiO 2 , Al 2 O 3 , phosphate, phosphoric ester, phosphinic acid, silanes, or combinations of these compounds have proven effective.
• the lustrous gold-colored metal flakes are used for lacquers, paints, dyes, printer's inks, plastic coloring, cosmetics, glass and ceramics.
• the present invention relates to a novel effect pigment composed of an alloy.
• An alloy in this context, is understood to mean the solid solution of two or more metals. Surprisingly it is possible to deposit coloristically suitable alloys from the vapor phase in vacuo. Pigments that consist of alloys and are produced by simultaneous condensation of metal vapors have not been known until now.
• Suitable alloys for the development of brilliant genuine-gold substitute pigments via PVD processes are copper-based and contain, for example, as additional alloy components, aluminum and/or silver, palladium and silicon.
• aluminum is the preferred alloy partner of copper, not only because of its superior reflectivity and low specific weight.
• Silver and palladium percentages in the deposited alloy increase the corrosion stability of the lustrous gold-colored metal flakes, silicon influences the coloristics.
• the metals may be evaporated individually or as previously molten alloys.
• the color-imparting copper plays the main role in this context.
• Coloristically interesting compositions lie, for example, at 90-99% copper, 10-1% aluminum. If very thin flakes are present, they may display partial transparency. Interference effects may have minor impacts on the above-described coloristics.
• the thickness of the lustrous gold-colored metal flakes can be adjusted and controlled without difficulty via the evaporation rate of the metals and via the belt speed.
• the belt speeds are generally selected between 2 and 5 m/sec.
• Metal film thicknesses between 10 and 100 nm may be selected in the process, as desired.
• thicknesses between 20 and 60 nm are of particular interest.
• the particle size is adjusted after stripping the metal films from the carrier sheet through mechanical comminuting of the film fragments. The comminuting may take place with suitable agitators, pumps, or with the aid of ultrasound units of the film fragments that are suspended in a solvent.
• particle sizes between 3 and 150 ⁇ m, preferably between 5 and 50 ⁇ m are of interest.
• the optical appearance may be varied by means of sizing, i.e., setting narrow particle size distributions with different mean diameters.
• the sizing may be performed, for example, in a decanter.
• the characteristic properties of the gold-colored metal flakes are their high reflectability and a very high tinctorial power of the pigment in the application.
• the high reflectability is based on the mirror-smooth undisturbed surfaces and the uniform thickness of the flakes. Potential scatter centers are reduced to a minimum.
• the high tinctorial power of the pigment is based on the low thickness of the individual particles so that a sufficient degree of coverage can be attained already with a comparably small amount of pigment.
• the inventive pigments are produced in such a way that a carrier sheet, for example a PET film or a continuous metal belt is optionally coated with a release coat.
• a carrier sheet for example a PET film or a continuous metal belt is optionally coated with a release coat.
• the coating of the carrier sheet with a soluble resin or wax may be performed via a dipping or imprinting method.
• the appropriate metals are then evaporated individually or as pre-molten alloy for example in one or more evaporators under high vacuum and condensed onto the carrier sheet.
• the metal film is subsequently stripped and comminuted to pigment particle size in a solvent suitable for the application, such as isopropanol, isopropylacetate, ehtylacetate or glycol ether by means of a suitable agitator or a pump that exerts high shearing forces.
• a solvent suitable for the application such as isopropanol, isopropylacetate, ehtylacetate or glycol ether by means of a suitable agitator or a pump that exerts high shearing forces.
• Ultrasound comminuting may be used in addition or alternatively.
• the pigment particles are also sized.
• anticorrosive layers Since these layers are thin and low refracting, they have virtually no influence on the optical behavior of the pigments.
• two methods of applying anticorrosive layers are possible: on one hand by vapor deposition of a double-sided protective layer during the evaporation process, on the other hand by precipitation of a passivating layer during or after comminuting of the film fragments.
• the vapor deposition of protective layers during the evaporating process is performed in the sequence protective layer, alloy film, protective layer, for which low-soluble but easily evaporated materials are generally selected, such as SiO x or MgF 2 .
• the precipitation of a passivation layer is performed as a wet-chemical reaction.
• the precipitation of a thin SiO 2 layer expediently via a sol-gel process through hydrolysis of silanes and subsequent silanol treatment has proven suitable, also the precipitation of aluminum oxide, silicon oxide, phosphate, phosphoric acid, phosphoric esters, phosphinic acid, silanes, organically modified silicates, titanates, zirconates or methacrylate-based polymer layers or combinations of these compounds.
• a PET carrier film of 48 ⁇ m thickness which is coated with a release coat, is coated with a copper/aluminum alloy under high vacuum.
• the release coat consists of acetone-soluble methylmethacrylate resin and is printed on in advance in a separate processing step. The vacuum is adjusted to 5.10 ⁇ 4 mbar.
• the speed with which the carrier film is unwound is 4 m/s.
• the copper/aluminum alloy with a copper content of 92% is evaporated in a boat via resistance heating at a rate that results in a metal film thickness on the moving carrier sheet of 40 nm.
• the roll coater is flooded with nitrogen, the metallized PET roll is removed and treated with acetone in a stripping station. Through dissolving of the release coat the metal film is separated from the carrier film.
• the metallic film fragments are concentrated in a centrifuge and separated from the release-coat containing acetone solution.
• the filter cake is then entered into an isopropanol solution, where the film is comminuted over the course of 20 minutes.
• the suspension in which the metal flakes are present is a 12% suspension.
• the obtained pigment suspension exhibits lustrous gold-colored pigment particles of the highest brilliance.
• the mean particle size of the flakes is 10 ⁇ m (Cilas). Chemical analyses show that the pigment contains 92% copper and 8% aluminum. X-ray analyses reveal that the elements are present in homogenous alloy form.
• a copper-aluminum-silicon film is deposited. This is performed analogous to example 1, with the difference that, in addition to the evporation source for copper/aluminum, an additional one is installed for silicon.
• the copper/aluminum alloy that is made available for the evaporation contains 94% copper.
• the thickness of the film that is precipitated from the vapor phase is set to 45 nm. Stripping of the film and comminuting of the film fragments to pigment size takes place as in example 1.
• the pigment that is obtained in suspension has a deep red golden luster. It contains 2% silicon.
• the mean particle size, according to Cilas measurements, is 11 ⁇ m.
• the metal pigment is then present in a corrosion-stabilized form.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Nanotechnology (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• General Physics & Mathematics (AREA)
• Physics & Mathematics (AREA)
• Composite Materials (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Wood Science & Technology (AREA)
• Crystallography & Structural Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Manufacture Of Metal Powder And Suspensions Thereof (AREA)
• Powder Metallurgy (AREA)
• Conductive Materials (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)
• Other Surface Treatments For Metallic Materials (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

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