WO2006116641A2 - Embossed metallic flakes process and product - Google Patents
Embossed metallic flakes process and product Download PDFInfo
- Publication number
- WO2006116641A2 WO2006116641A2 PCT/US2006/016115 US2006016115W WO2006116641A2 WO 2006116641 A2 WO2006116641 A2 WO 2006116641A2 US 2006016115 W US2006016115 W US 2006016115W WO 2006116641 A2 WO2006116641 A2 WO 2006116641A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- flakes
- embossed
- particle size
- microns
- diffraction grating
- Prior art date
Links
Classifications
-
- 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
- A61K8/0258—Layered structure
-
- 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
- A61Q3/00—Manicure or pedicure preparations
- A61Q3/02—Nail coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F3/26—Impregnating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured 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
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
-
- 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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- 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
- C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
- C23C4/185—Separation of the coating from the substrate
-
- 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
- A61K2800/437—Diffractive phenomena; Photonic arrays
-
- 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
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
- Y10T428/24901—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material including coloring matter
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
-
- 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
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
-
- 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.]
Definitions
- This invention relates to a process for producing embossed metal flakes and the use of such of flakes in coatings and printing inks. More particularly, the process involves techniques for producing embossed flakes having high levels of brightness and color intensity when formulated in coatings and printing inks.
- Metallic flakes have been used for many years in decorative coatings to produce different visual effects.
- Metallic flakes are used in metallic automotive paints, for example. These flakes are typically made by vacuum metalizing the smooth surface of a release coat applied to a flexible temporary carrier film, solubilizing the metalized release surface to remove the metal film from the carrier, and breaking up the metal into flakes.
- metallic flakes have been used in other coating compositions, paints, enamels, lacquers, and the like, including coatings that produce a highly reflective metalized surface for metallic-like or mirror-like optical effects.
- small particle size metal flakes below about 50 microns in size can produce good reflectivity along with the opacity necessary to provide complete 100% coverage for the mirror-like effects.
- Larger flakes which may be reflective are usually more spread out when applied as a coating, and therefore, may not produce the necessary opacity or hiding ability for yielding a highly reflective mirror-like surface.
- the small metal flakes also have tended to be more useful in compositions such as printing inks where the larger flake sizes are not as usable in certain types of printing equipment.
- metallic flakes have been produced with embossed patterns in the form of diffraction grating or holographic image patterns. These flakes produce certain iridescent effects when used in coatings or printing inks. These flakes have been made by a process described in U.S. Patent 5,672,410 to Miekka et al., assigned to Avery Dennison Corporation. The entire disclosure of the '410 patent is incorporated herein by reference. In the process of making embossed flakes according to the '410 patent, metallic flakes having a controlled particle size below about 50 microns are produced.
- the metallic flakes can be produced by different embossing techniques followed by metalizing the embossed surface, stripping the metal to form a dispersion of flakes, and then breaking up the metal flakes into smaller size flakes approximately 10 to 50 microns in size.
- the dispersed metal particles are subjected to high speed mixing or ultrasonic mixing which breaks up the particles into the desired size range without destroying the reflectivity of the flakes.
- the metallic film obtained by this process resembles the brilliance, reflective gloss and hiding power of commercial metallic foils. Due to the natural orientation of the single layer leafing flake, even when embossed, small amounts of pigment will cover a very large surface area.
- one embodiment of the present invention comprises a process for making embossed fine particulate thin metallic flakes having high levels of brightness and color intensity.
- the process comprises providing a release surface on a carrier, embossing the release surface with a diffraction grating pattern having an angular ruling pattern greater than 45°, metalizing the embossed release surface with a thin reflective metal film, removing the metal film from the release surface to form a solvent dispersion of embossed metal flakes that have replicated the diffraction grating pattern, and controlling the particle size of the flakes contained in the dispersion to maintain the embossed flakes contained therein at a D50 average particle size at or above 75 microns.
- Another embodiment of the invention comprises reflective metal flakes which have been embossed by replicating a diffraction grating pattern having a monoruled embossing angle above 45°, the particles having a D50 average particle size at or above 75 microns and a flake thickness from about 50 to about 500 angstroms.
- the process of this invention controls the color intensity or chromaticity and brightness of embossed flakes and produces flakes of large particle size with high levels of color intensity and brilliance.
- the embossed flakes of this invention have application to coatings and printing inks that produce extremely high brightness characterized as an optically apparent glitter or sparkle effect in combination with high color intensity or chromaticity.
- the embossed flakes also can be used to produce similar optical effects when used in the decorative layers of multi-layer laminates, including those subjected to thermoforming.
- FIG. 1 is a schematic cross sectional view illustrating an intermediate embossing step in a process according to principles of this invention.
- FIG. 2 is a schematic diagram illustrating diffraction grating embossments formed at a 45° angle.
- FIG. 3 is a schematic diagram illustrating diffraction grating embossments formed at a 60° angle.
- FIG. 4 is a schematic diagram illustrating reflection angles used for measuring color intensity and chromaticity with a multi-angle spectrophotometer.
- a temporary carrier film 10 passes into a coater for applying a release coat 12 to at least one side of the carrier film.
- both sides of the carrier film are coated with a thin film of the release coat material.
- FIG. 1 illustrates one embodiment of the invention which includes embossing the release coat to form a pattern of embossments 14 as described below.
- the embossed carrier is then metalized with a thin reflective metal film as described below.
- the carrier film is preferably a flexible, foldable, heat-resistant polymeric casting film, preferably biaxially oriented PET.
- the polyester films Mylar or Hostaphan from American Hoechst are examples of the preferred casting films.
- the preferred carrier film has an extremely smooth casting surface substantially in the absence of adherent fine particulate materials such as filler particles commonly used for roughening the surface to improve slip properties.
- the carrier film used for this invention preferably has no slip additive.
- Such polyester film is commercially available in different grades.
- the carrier film can be embossed by various techniques, including embossing the release coat applied to the carrier or embossing the metal layer of a metalized carrier film.
- embossing the release coat applied to the carrier or embossing the metal layer of a metalized carrier film.
- the above-mentioned '410 patent describes four separate methods which may be used for forming the embossment pattern.
- the preferred embossing process involves applying a release coat to the carrier and embossing the release coat as follows.
- the release coat material comprises various polymeric materials which can be embossed with accurately formed embossments (described below) and which can be easily solubilized in an organic solvent.
- suitable release coat materials include acrylic resins such as PMMA, acrylic copolymers, PVC, and polystyrene.
- the release coat material is solubilized in a suitable organic solvent and applied to the carrier film by roll coating techniques.
- the coated carrier is then subjected to heat for drying the release coat to produce an extremely smooth release surface.
- the preferred thickness of the release coat is produced by applying the release coat at about 0.8 grams per square meter per side of the carrier, or 1.6 grams per square meter total.
- the release surface is embossed with an embossing roll to form the pattern of embossments 14 on the release surface.
- the embossments are preferably in the form of a diffraction grating pattern formed by embossing closely spaced apart and regularly spaced apart parallel grooves in the release surface.
- the diffraction grating is formed by a regular pattern from 5,000 to less than 14,000 groves per centimeter.
- the diffraction grating structure is from about 10,000 to about 12,500 grooves per centimeter.
- the release coat Prior to embossing, the release coat is allowed to dry or solidify.
- the embossing step is then carried out by heating the release coat to above its softening temperature and then embossing the diffraction grating pattern in the release surface.
- the embossing roll preferably forms the embossments in a monoruled pattern — straight parallel grooves identically shaped and uniformly spaced apart in a single embossing path across the release surface.
- the groove pattern has a wavy or sinusoidal cross-sectional structure such as that shown in FIG. 4.
- the grating structure from which the flakes of this invention are made can have a groove depth from about 125 nm to about 140 nm, and more preferably, from about 130 nm to about 135 nm.
- FIG. 2 illustrates such a monoruled embossment pattern 16 and the 45° ruling angle defined as a line drawn from the base of the groove tangential to the adjacent top portion of the groove.
- the embossing roll forms a diffraction grating pattern by monoruling identically shaped and uniformly spaced-apart parallel grooves each having an embossment angle greater than 45°.
- the embossment pattern is a monoruled 60° angle diffraction grating pattern 20 as shown in FIG. 3.
- the embossed carrier is passed through a vacuum metalizer for vacuum depositing a metal film on the embossed release coating.
- a vacuum metalizer for vacuum depositing a metal film on the embossed release coating.
- both sides are embossed, and the metal film is vacuum deposited on both sides of the carrier.
- the thickness of the deposited metal monolayer film is from about 50 to 1,000 angstroms (5-100 nm), controlled by the speed of the web and the evaporation rate.
- Suitable bright metals for deposition include aluminum, chromium, copper, indium, steel, silver, gold, nickel or Nichrome. Aluminum is a presently preferred metal film.
- a preferred metal thickness range for a single layer metalized aluminum flake product is from about 50 nm to about 100 nm.
- the desired metal thickness also can be from 1.0 to 3.5 optical density.
- Optical density is measured on a MacBeth TR 927 densitometer.
- the metal coated embossed carrier is then passed through a metal stripping machine for removing the metal from the carrier to form flakes.
- the metalized carrier is passed around a series of rollers in a tank containing a suitable solvent for solubilizing the release coat.
- the preferred solvent is acetone.
- the metal film passes over the rollers and then past a series of doctor blades for removing the metal particles and release coat material from the carrier.
- the dispersion of flakes and release coat polymer in the solvent is then pumped to a slurry tank.
- the resultant dispersion in the slurry tank has a percent solids weight from about 2% to about 4% based on the aluminum flakes and residual polymer solids dispersed in the solvent.
- the flakes contained in the resulting slurry have a desired average particle size at or above about 75 microns. These flakes are maintained at a particle size at or above 75 microns by omitting any high energy mixing or particle sizing steps following the metal stripping process. High energy particle sizing such as centrifuging, sonolater treatment or high shear mixing are avoided. Possibly low shear mixing may be suitable in some instances, but with the object of controlling particle size to at or above about 75 microns. High speed mixing, in addition to reducing particle size, can reduce flake brightness. In one embodiment, single layer aluminum flakes produced by this process had an average (D50) particle size above 75 microns.
- Flakes within a 75 to 200 micron size range can be produced at optical densities within the range of about 1.0 to about 3.5.
- the range of desired particle sizes is generally from about 75 to about 150 microns to produce certain optical effects described below. Such particles have been produced within this size range at an optical density of about 2.0 and by following the process steps described above. Larger particle sizes can be produced with thicker flakes, say greater than about 3.5 optical density.
- the present invention also can produce embossed flakes greater than 200 microns in particle size.
- flakes with a particle size above 200 microns were produced from thicker flakes having an optical density of 3.0 and above.
- Particle size measurements as described herein are made using a Horiba LA 910 instrument.
- Single layer metal flakes having an average D50 particle size greater than 75 microns have been produced using a diffraction grating similar to FIG. 4, to produce flakes having a thickness in the range of 50 nm to 100 nm. In one embodiment, the flake thickness was about 90 nm. These embossed metal flakes have been produced with a diffractive grating pitch of less than 14,000 lines per centimeter. These diffractive flakes, in one embodiment, had a pitch of less than 12,500 lines per centimeter, and in another embodiment, the diffractive pattern was in the range from about 10,900 to less than 12,000 lines per centimeter.
- embossed metal flakes had a groove depth of less than about 140 nm, and in one embodiment, groove depth measured from about 130 nm to about 135 nm. These embossed flakes were characterized by a desired groove depth to flake thickness ratio of greater than 1.0.
- the large embossed flakes produced by this invention can be used in various types of coatings to produce certain controlled optical effects.
- coatings having greater color intensity combined with a glitter or sparkle effect can be produced.
- Embossed particles at about 100 micron size can just start to be seen by non-magnified visual observation, which reveals the glitter or sparkle effect produced by the visually observable embossments.
- the glitter or sparkle effect is produced by the larger particles embossed by the techniques of this invention which produce greater reflectivity than the reflectivity produced by the smaller flakes, say about 50 microns average particle size.
- This comparison is between the larger particles of this invention made by replicating embossments greater than 45°, and in one embodiment, at a 60° angle, when compared with smaller 50 micron flakes made by replicating embossments at a 45° angle.
- the smaller flakes have lower reflectivity, i.e., are not as mirror-like or are less brilliant.
- the increased reflectivity of the larger flakes is produced across all colors of the color spectrum.
- Flakes made with embossments at angles greater than 45° can appear substantially brighter than the same size flake made with embossments at 45°. Flakes made with 60° embossments have been observed to have greater brightness in fluorescent light. The flake made with embossments greater than 45° also had visually observable greater color intensity and color shift. The greater area of the replicated embossments available for reflecting incident light is considered to be a reason for the greater brightness and color effects.
- the glitter or sparkle effect is produced in combination with a greater color intensity when compared with the smaller 50 micron flakes; and the greater color intensity combined with the glitter effect has been observed visually from various coatings as well as demonstrated by numerical data produced by color measurements taken by a multi- angle spectrophotometer as shown in the examples below.
- the larger flakes of this invention can be used to produce the described optical effects in various coating compositions such as paints, inks, enamels and print coats.
- Resinous binders useful with the invention include acrylic and nitrocellulosic resins.
- One application of the invention comprises a nail polish enamel containing embossed flakes greater than 75 microns, which exhibits a brighter glitter or sparkle effect and greater color intensity or color shift at certain observation angles when compared with a nail polish enamel containing the smaller (50 micron) flakes.
- This application of the invention has been observed using a nitrocellulose enamel such as that described in International Patent Publication WO 02/03913 to Kirker Enterprises, Inc., incorporated herein by reference.
- This nail polish enamel was drawndown on a card, dried and observed for its optical effects.
- the application of the larger particle size embossed flake with the extremely thin angstrom level particle thickness produces the glitter or color shift effects in coatings such as enamels with the embossed flake sizes at 75 microns or more.
- the individual particles can just be seen by the naked eye at 100 microns sufficient to observe the glitter or rainbow effects of the embossed particles.
- the ability of these larger embossed flakes to lay down flat in various coatings also enhances the reflected light and color shift effects which are visually observable.
- the larger embossed flakes of this invention are in colored printing inks, inks used in silk screen processes, and cosmetic formulations.
- the larger flakes of this invention can add glitter or sparkle effects to printing inks and dyes.
- the larger flakes of this invention were found to have good orientation in nitrocellulosic coating compositions which can be useful for printing inks as well as nail polish enamel.
- Another application is for producing certain visual effects in print coats used in various multi-layer laminates.
- These can include laminates having a thermoformable polymeric substrate base layer, an opaque pigmented base coat or paint coat applied to the substrate, a metallic print coat applied to the pigmented base coat by various printing techniques for producing a decorative print pattern, and an optional outer clear coat that can be a protective weatherable and abrasion-resistant clear coat.
- the resulting laminate can be thermoformed to form various shapes without degrading the reflective appearance of the metallic print coat.
- the larger metallic flakes also can be used in highly reflective metallic layers contained in similar thermo-formable multi-layer laminates.
- Embossed flakes greater than 75 microns in size were produced according to the previous description.
- a PET carrier was coated with an acrylic release coat, embossed with a diffraction grating pattern having a 60° monoruled embossment pattern as described previously, metalized with a vapor deposited aluminum film, and stripped to form a metal flake dispersion. Layer thickness for the metalized film in these examples was approximately 2.0 optical density.
- the flakes were removed directly after stripping for testing. Particle- sizing such as centrifuging or sonic mixing, that would otherwise reduce particle size, were avoided. The act of centrifuging may not reduce particle size, but running through a pump or high speed mixing will reduce the particle size.
- the embossed particles had a D50 average particle size of about 114 microns.
- a sample was drawndown on the black side of a leneta card. This sample was compared with a similar sample containing 50 micron flakes made by 45° embossing also drawndown on the black side of a leneta card. The larger flakes were visually observed to display a more pronounced color shift and color intensity than the smaller flakes.
- Example 1 The larger particle size flakes of Example 1 were decanted by letting the flakes settle to the bottom of a vessel and removing the resin-rich liquid layer from the top of the vessel.
- the clear liquid was at 2.4% resin solids (when measured by drying and reporting weight difference).
- the decanted sample contained 4.1% solids by weight. The test data showed that the flakes were brighter with more intense color than the sample that was not decanted.
- Example 1 The larger particle size flakes of Example 1 were added to the 50 micron flakes (10 parts 50 micron flakes to 2 parts 100 micron flakes) contained in a lacquer and drawndown on a leneta card, both sides. These samples were compared with a similar drawdown of the 50 micron flakes of Example 1. The results showed improved color intensity with the addition of the larger flakes.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Metallurgy (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
- Powder Metallurgy (AREA)
- Diffracting Gratings Or Hologram Optical Elements (AREA)
Abstract
Description
Claims
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2006800183114A CN101184565B (en) | 2005-04-26 | 2006-04-26 | Embossed metallic flakes process and product |
DE602006007356T DE602006007356D1 (en) | 2005-04-26 | 2006-04-26 | METHOD FOR PRODUCING PRESENTED METAL FLAKES AND PRODUCT |
AU2006239328A AU2006239328A1 (en) | 2005-04-26 | 2006-04-26 | Embossed metallic flakes process and product |
JP2008509147A JP2008539322A (en) | 2005-04-26 | 2006-04-26 | Embossed metal flakes, methods and products |
US11/792,470 US20080274354A1 (en) | 2005-04-26 | 2006-04-26 | Embossed Metallic Flakes Process and Product |
AT06758706T ATE433812T1 (en) | 2005-04-26 | 2006-04-26 | METHOD FOR PRODUCING EMBOSSED METAL FLAKES AND PRODUCT |
MX2007013332A MX2007013332A (en) | 2005-04-26 | 2006-04-26 | Embossed metallic flakes process and product. |
EP06758706A EP1901870B1 (en) | 2005-04-26 | 2006-04-26 | Embossed metallic flakes process and product |
BRPI0607670-0A BRPI0607670A2 (en) | 2005-04-26 | 2006-04-26 | process for producing fine enhanced fine particle metal flakes having brightness and color intensity, first coating process containing enhanced flakes, reflective metal flakes, multilayer laminate and resin coating |
US13/794,959 US20130192789A1 (en) | 2005-04-26 | 2013-03-12 | Embossed Metallic Flakes Process And Product |
US14/147,146 US20140154520A1 (en) | 2005-04-26 | 2014-01-03 | Embossed Metallic Flakes Process And Product |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US67480805P | 2005-04-26 | 2005-04-26 | |
US60/674,808 | 2005-04-26 |
Related Child Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/792,470 A-371-Of-International US20080274354A1 (en) | 2005-04-26 | 2006-04-26 | Embossed Metallic Flakes Process and Product |
US13/794,959 Division US20130192789A1 (en) | 2005-04-26 | 2013-03-12 | Embossed Metallic Flakes Process And Product |
US14/147,146 Continuation US20140154520A1 (en) | 2005-04-26 | 2014-01-03 | Embossed Metallic Flakes Process And Product |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2006116641A2 true WO2006116641A2 (en) | 2006-11-02 |
WO2006116641A3 WO2006116641A3 (en) | 2007-02-22 |
Family
ID=36691829
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2006/016115 WO2006116641A2 (en) | 2005-04-26 | 2006-04-26 | Embossed metallic flakes process and product |
Country Status (13)
Country | Link |
---|---|
US (3) | US20080274354A1 (en) |
EP (1) | EP1901870B1 (en) |
JP (1) | JP2008539322A (en) |
KR (1) | KR100979219B1 (en) |
CN (1) | CN101184565B (en) |
AT (1) | ATE433812T1 (en) |
AU (1) | AU2006239328A1 (en) |
BR (1) | BRPI0607670A2 (en) |
DE (1) | DE602006007356D1 (en) |
MX (1) | MX2007013332A (en) |
RU (1) | RU2007143487A (en) |
WO (1) | WO2006116641A2 (en) |
ZA (1) | ZA200709543B (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2349527A1 (en) * | 2009-03-31 | 2011-01-04 | Tecser Print. S.L.L. | Procedure for printing with bright effect (Machine-translation by Google Translate, not legally binding) |
WO2011021007A1 (en) | 2009-08-21 | 2011-02-24 | Qinetiq Limited | Production of flake particles |
WO2014042639A1 (en) * | 2012-09-13 | 2014-03-20 | Eckart America Corporation | Methods for producing platelet materials |
ITRM20120659A1 (en) * | 2012-12-21 | 2014-06-22 | Alessandro Panzani | PAINTING COMPOSITIONS. |
US9856385B2 (en) | 2008-12-19 | 2018-01-02 | Basf Se | Thin aluminium flakes |
WO2021198121A1 (en) | 2020-03-30 | 2021-10-07 | Basf Coatings Gmbh | Retroreflective pigments and paints |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20100024295A (en) * | 2008-08-25 | 2010-03-05 | 주식회사 잉크테크 | Preparation method of metal flake |
KR101130101B1 (en) * | 2009-09-09 | 2012-03-28 | 금호타이어 주식회사 | Tire sidewall rubber composition |
US20110091644A1 (en) * | 2009-10-16 | 2011-04-21 | Vacumet Corp. | Water release silver and holographic metal flake and method of manufacturing metal flake |
US20110150793A1 (en) * | 2009-12-17 | 2011-06-23 | Avon Products, Inc. | Clear or Translucent Composition |
JP5877892B2 (en) * | 2011-04-05 | 2016-03-08 | エイボン プロダクツ インコーポレーテッド | Lipstick |
WO2013028970A1 (en) * | 2011-08-24 | 2013-02-28 | Eckart America Corporation | Ionic liquid release coat for use in metal flake manufacture |
CN102974839B (en) * | 2012-12-04 | 2015-05-20 | 中山大学 | Method for preparing nanometer flake silver powder through chemical deposition |
KR101665475B1 (en) | 2014-12-26 | 2016-10-12 | 박대용 | Mold appartus for manufacturing waterway pipe and method produced thereby |
KR101655843B1 (en) | 2014-12-26 | 2016-09-08 | 박대용 | Mold appartus for manufacturing waterway pipe |
EP3442491B1 (en) | 2016-04-15 | 2021-02-24 | ECKART GmbH | Surface modified effect pigment and nail varnish composition |
WO2019038910A1 (en) | 2017-08-25 | 2019-02-28 | 福田金属箔粉工業株式会社 | Evaluation method of powder for laminate molding, and powder for laminate molding |
EP3791853A1 (en) | 2017-10-18 | 2021-03-17 | ECKART GmbH | Surface-modified embossed effect pigments |
US20210244634A1 (en) | 2018-07-16 | 2021-08-12 | Eckart Gmbh | Pvd-aluminum pigment dispersion and cosmetic formulations |
EP4127079A1 (en) * | 2020-03-30 | 2023-02-08 | BASF Coatings GmbH | Paints having enhanced reflectivity |
CN114891367A (en) | 2021-01-26 | 2022-08-12 | 中钞特种防伪科技有限公司 | Flaky optical pigment, preparation method thereof and anti-counterfeiting element |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4116710A (en) * | 1973-10-24 | 1978-09-26 | The Dow Chemical Company | Metallic particulate |
US5672410A (en) * | 1992-05-11 | 1997-09-30 | Avery Dennison Corporation | Embossed metallic leafing pigments |
WO2003046245A2 (en) * | 2001-11-29 | 2003-06-05 | Avery Dennison Corporation | Process for making angstrom scale and high aspect functional platelets |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4321087A (en) * | 1978-12-21 | 1982-03-23 | Revlon, Inc. | Process for making metallic leafing pigments |
US5084351A (en) * | 1979-12-28 | 1992-01-28 | Flex Products, Inc. | Optically variable multilayer thin film interference stack on flexible insoluble web |
US5569535A (en) * | 1979-12-28 | 1996-10-29 | Flex Products, Inc. | High chroma multilayer interference platelets |
JPH0694543B2 (en) * | 1987-01-09 | 1994-11-24 | 三菱自動車工業株式会社 | Paint |
US5549774A (en) * | 1992-05-11 | 1996-08-27 | Avery Dennison Corporation | Method of enhancing the visibility of diffraction pattern surface embossment |
US5424517A (en) * | 1993-10-27 | 1995-06-13 | James River Paper Company, Inc. | Microwave impedance matching film for microwave cooking |
TW265421B (en) * | 1993-11-23 | 1995-12-11 | Commw Scient Ind Res Org | |
JPH117231A (en) * | 1997-06-17 | 1999-01-12 | Tsuchihashi Kinpun Kogyo Kk | Brilliant decorative powder and its manufacture |
JP3449215B2 (en) * | 1997-07-07 | 2003-09-22 | トヨタ自動車株式会社 | Metal fine piece with embossed pattern and method for producing the same |
US6112388A (en) * | 1997-07-07 | 2000-09-05 | Toyota Jidosha Kabushiki Kaisha | Embossed metallic flakelets and method for producing the same |
US6168100B1 (en) * | 1997-10-23 | 2001-01-02 | Toyota Jidosha Kabushiki Kaisha | Method for producing embossed metallic flakelets |
US6863851B2 (en) * | 1998-10-23 | 2005-03-08 | Avery Dennison Corporation | Process for making angstrom scale and high aspect functional platelets |
US6242510B1 (en) * | 1999-04-02 | 2001-06-05 | Green Bay Packaging, Inc. | Label adhesive with dispersed refractive particles |
US6761959B1 (en) * | 1999-07-08 | 2004-07-13 | Flex Products, Inc. | Diffractive surfaces with color shifting backgrounds |
JP2001058154A (en) * | 1999-08-24 | 2001-03-06 | Nippon Paint Co Ltd | Method for forming brilliant coating film brilliant coating composition and coated article |
US6565835B1 (en) * | 2000-07-07 | 2003-05-20 | Kirker Enterprises, Inc. | Nail enamel compositions containing aluminum platelets |
US6749936B2 (en) * | 2001-12-20 | 2004-06-15 | Flex Products, Inc. | Achromatic multilayer diffractive pigments and foils |
US6692830B2 (en) * | 2001-07-31 | 2004-02-17 | Flex Products, Inc. | Diffractive pigment flakes and compositions |
JP2003096403A (en) * | 2001-09-27 | 2003-04-03 | Nippon Paint Co Ltd | Powder coating composition forming coated film changing color by viewing angle and method for forming the film |
JP4302385B2 (en) * | 2001-10-22 | 2009-07-22 | 三星電子株式会社 | Liquid crystal display device for improving reflectivity and manufacturing method thereof |
JP2004099801A (en) * | 2002-09-11 | 2004-04-02 | Hakko Koyu Kk | Coloring rope oil agent |
CN1253251C (en) * | 2004-06-09 | 2006-04-26 | 远东技术学院 | Producingm ethod for sheet aluminium powder |
-
2006
- 2006-04-26 JP JP2008509147A patent/JP2008539322A/en active Pending
- 2006-04-26 MX MX2007013332A patent/MX2007013332A/en unknown
- 2006-04-26 CN CN2006800183114A patent/CN101184565B/en active Active
- 2006-04-26 DE DE602006007356T patent/DE602006007356D1/en active Active
- 2006-04-26 RU RU2007143487/02A patent/RU2007143487A/en not_active Application Discontinuation
- 2006-04-26 EP EP06758706A patent/EP1901870B1/en active Active
- 2006-04-26 BR BRPI0607670-0A patent/BRPI0607670A2/en not_active Application Discontinuation
- 2006-04-26 AT AT06758706T patent/ATE433812T1/en active
- 2006-04-26 WO PCT/US2006/016115 patent/WO2006116641A2/en active Application Filing
- 2006-04-26 AU AU2006239328A patent/AU2006239328A1/en not_active Abandoned
- 2006-04-26 US US11/792,470 patent/US20080274354A1/en not_active Abandoned
- 2006-04-26 KR KR1020077027184A patent/KR100979219B1/en active IP Right Grant
-
2007
- 2007-11-06 ZA ZA200709543A patent/ZA200709543B/en unknown
-
2013
- 2013-03-12 US US13/794,959 patent/US20130192789A1/en not_active Abandoned
-
2014
- 2014-01-03 US US14/147,146 patent/US20140154520A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4116710A (en) * | 1973-10-24 | 1978-09-26 | The Dow Chemical Company | Metallic particulate |
US5672410A (en) * | 1992-05-11 | 1997-09-30 | Avery Dennison Corporation | Embossed metallic leafing pigments |
WO2003046245A2 (en) * | 2001-11-29 | 2003-06-05 | Avery Dennison Corporation | Process for making angstrom scale and high aspect functional platelets |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9856385B2 (en) | 2008-12-19 | 2018-01-02 | Basf Se | Thin aluminium flakes |
ES2349527A1 (en) * | 2009-03-31 | 2011-01-04 | Tecser Print. S.L.L. | Procedure for printing with bright effect (Machine-translation by Google Translate, not legally binding) |
WO2011021007A1 (en) | 2009-08-21 | 2011-02-24 | Qinetiq Limited | Production of flake particles |
WO2014042639A1 (en) * | 2012-09-13 | 2014-03-20 | Eckart America Corporation | Methods for producing platelet materials |
CN104736645A (en) * | 2012-09-13 | 2015-06-24 | 爱卡美国公司 | Methods for producing platelet materials |
ITRM20120659A1 (en) * | 2012-12-21 | 2014-06-22 | Alessandro Panzani | PAINTING COMPOSITIONS. |
WO2021198121A1 (en) | 2020-03-30 | 2021-10-07 | Basf Coatings Gmbh | Retroreflective pigments and paints |
CN115362221A (en) * | 2020-03-30 | 2022-11-18 | 巴斯夫涂料有限公司 | Retroreflective pigments and paints |
Also Published As
Publication number | Publication date |
---|---|
CN101184565B (en) | 2012-04-25 |
AU2006239328A1 (en) | 2006-11-02 |
RU2007143487A (en) | 2009-06-10 |
KR20080003919A (en) | 2008-01-08 |
ZA200709543B (en) | 2008-10-29 |
ATE433812T1 (en) | 2009-07-15 |
EP1901870B1 (en) | 2009-06-17 |
MX2007013332A (en) | 2008-01-18 |
WO2006116641A3 (en) | 2007-02-22 |
KR100979219B1 (en) | 2010-08-31 |
US20130192789A1 (en) | 2013-08-01 |
US20140154520A1 (en) | 2014-06-05 |
US20080274354A1 (en) | 2008-11-06 |
DE602006007356D1 (en) | 2009-07-30 |
EP1901870A2 (en) | 2008-03-26 |
JP2008539322A (en) | 2008-11-13 |
CN101184565A (en) | 2008-05-21 |
BRPI0607670A2 (en) | 2009-09-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1901870B1 (en) | Embossed metallic flakes process and product | |
US7241489B2 (en) | Opaque flake for covert security applications | |
US9856385B2 (en) | Thin aluminium flakes | |
EP1414913B1 (en) | Diffractive pigment flakes and compositions | |
CA2917599C (en) | Magnetic or magnetisable pigment particles and optical effect layers | |
TW567343B (en) | Achromatic multilayer diffractive pigments and foils | |
TWI262323B (en) | Chromatic diffractive pigments and foils | |
JP6587449B2 (en) | PVD metallic effect pigment having a gradient with respect to nanoscale metal particles, process for its production and use thereof | |
EP0227423A2 (en) | Optical thin film flakes, replicated optical coatings and coatings and inks incorporating the same and method | |
AU2002254497A1 (en) | Diffractive pigment flakes and compositions | |
KR20060121734A (en) | Producing two distinct flake products using a single substrate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200680018311.4 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/a/2007/013332 Country of ref document: MX |
|
ENP | Entry into the national phase |
Ref document number: 2008509147 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2006239328 Country of ref document: AU |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2006758706 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2006239328 Country of ref document: AU Date of ref document: 20060426 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020077027184 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007143487 Country of ref document: RU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11792470 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: PI0607670 Country of ref document: BR Kind code of ref document: A2 |